WO2022170299A2 - Flame-resistant quasi-solid and solid-state electrolytes, lithium batteries and manufacturing method - Google Patents
Flame-resistant quasi-solid and solid-state electrolytes, lithium batteries and manufacturing method Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present disclosure provides a fire/flame-resistant electrolyte and lithium batteries (lithium-ion and lithium metal batteries) containing such an electrolyte.
- lithium-ion and lithium metal batteries e.g., lithium-sulfur, lithium selenium, and Li metal-air batteries
- EV electric vehicle
- HEV hybrid electric vehicle
- portable electronic devices such as lap-top computers and mobile phones.
- Lithium as a metal element has the highest lithium storage capacity (3,861 mAh/g) compared to any other metal or metal-intercalated compound as an anode active material (except Li4.4Si, which has a specific capacity of 4,200 mAh/g).
- Li metal batteries having a lithium metal anode
- Li-ion batteries having a graphite anode
- the electrolytes used for lithium-ion batteries and all lithium metal secondary batteries pose some safety concerns.
- Most of the organic liquid electrolytes can cause thermal runaway or explosion problems.
- Ionic liquids (ILs) are a new class of purely ionic, salt-like materials that are liquid at unusually low temperatures.
- ILs are ionic compounds which are liquid below 100°C”.
- a particularly useful and scientifically interesting class of ILs is the room temperature ionic liquid (RTIL), which refers to the salts that are liquid at room temperature or below.
- RTILs are also referred to as organic liquid salts or organic molten salts.
- An accepted definition of an RTIL is any salt that has a melting temperature lower than ambient temperature.
- ILs were suggested as a potential electrolyte for rechargeable lithium batteries due to their non-flammability, conventional ionic liquid compositions have not exhibited satisfactory performance when used as an electrolyte likely due to several inherent drawbacks: (a) ILs have relatively high viscosity at room or lower temperatures; thus being considered as not amenable to lithium ion transport; (b) For Li-S cell uses, ILs are capable of dissolving lithium polysulfides at the cathode and allowing the dissolved species to migrate to the anode (i.e., the shuttle effect remains severe); and (c) For lithium metal secondary cells, most of the ILs strongly react with lithium metal at the anode, continuing to consume Li and deplete the electrolyte itself during repeated charges and discharges.
- Solid state electrolytes are commonly believed to be safe in terms of fire and explosion proof. Solid state electrolytes can be divided into organic, inorganic, organic-inorganic composite electrolytes.
- organic polymer solid state electrolytes such as poly(ethylene oxide) (PEO), polypropylene oxide (PPO), poly(ethylene glycol) (PEG), and poly(acrylonitrile) (PAN)
- PEO poly(ethylene oxide)
- PPO polypropylene oxide
- PEG poly(ethylene glycol)
- PAN poly(acrylonitrile)
- the conductivity of organic polymer solid state electrolytes is typically low ( ⁇ 10 ⁇ 5 S/cm).
- the inorganic solid-state electrolyte e.g., garnet-type and metal sulfide-type
- the interfacial impedance or resistance between the inorganic solid-state electrolyte and the electrode (cathode or anode) is high.
- the traditional inorganic ceramic electrolyte is very brittle and has poor film-forming ability and poor mechanical properties.
- QSSE quasi-solid state electrolytes
- a small amount of liquid electrolyte may be present to help improving the physical and ionic contact between the electrolyte and the electrode, thus reducing the interfacial resistance. Examples of QSSEs are disclosed in the following: Hui He, et al.
- Lithium Secondary Batteries Containing a Non-flammable Quasi-solid Electrolyte US Patent Application No. 13/986,814 (06/10/2013); US Patent No. 9,368,831 (06/14/2016); US Patent No. 9,601,803 (03/21/2017); US Patent No. 9,601,805 (03/21/2017); US Patent No. 9,059,481 (06/16/2015).
- the presence of certain liquid electrolytes may cause some problems, such as liquid leakage, gassing, and low resistance to high temperature. Therefore, a novel electrolyte system that obviates all or most of these issues is needed.
- a general object of the present disclosure is to provide a safe, flame/fire-resistant, quasi-solid or solid-state electrolyte system for a rechargeable lithium cell that is compatible with existing battery production facilities.
- a rechargeable lithium battery comprising an anode, a cathode, and a quasi-solid or solid-state electrolyte in ionic communication with the anode and the cathode, wherein the electrolyte comprises a polymer, which is a polymerization or crosslinking product of a reactive additive, wherein the reactive additive comprises at least one polymerizable liquid solvent (itself being a monomer), a lithium salt dissolved in the polymerizable liquid solvent, and a crosslinking agent and/or an initiator; wherein the polymerizable liquid solvent is selected from the group consisting of fluorinated monomers having unsaturation (double bonds or triple bonds) in the backbone or cyclic structure (e.g., fluorinated vinyl carbonates, fluorin
- liquid solvents listed above are commonly used as a solvent to dissolve a lithium salt therein and the resulting solutions are used as a liquid electrolyte.
- These liquid solvents are not known to be polymerizable and a separate polymer or monomer is typically used in the industry to prepare a gel polymer electrolyte or solid polymer electrolyte. It is uniquely advantageous to be able to polymerize the liquid solvent once injected into a battery cell. With such a novel strategy, one can readily reduce the liquid solvent or completely eliminate the liquid solvent all together. This is of significant utility value since most of the organic solvents are known to be volatile and flammable, posing a fire and explosion danger.
- the lithium salt occupies 0.1%-30% by weight
- the polymerizable liquid solvent occupies 1%-90% by weight
- the crosslinking agent and/or initiator occupies 0.1- 90% (preferably ⁇ 50%) by weight, all based on the total weight of the lithium salt, the crosslinking agent and/or initiator, and the polymerizable liquid solvent combined.
- the polymer electrolyte exhibits a vapor pressure less than 0.001 kPa when measured at 20°C, a vapor pressure less than 10% of the vapor pressure of said liquid solvent and lithium salt alone without the polymerization, a flash point at least 100 degrees Celsius higher than a flash point of said liquid solvent alone, a flash point higher than 200°C, or no measurable flash point and wherein the polymer has a lithium ion conductivity from 10 -8 S/cm to 10 -2 S/cm at room temperature.
- the reactive additive comprises a first polymerizable liquid solvent and a second liquid solvent and wherein the second liquid solvent either is not polymerizable or is polymerizable but polymerized to a lesser extent as compared to the first polymerizable liquid solvent.
- the presence of this second liquid solvent is designed to impart certain desired properties to the polymerized electrolyte, such as lithium ion conductivity, flame retardancy, ability of the electrolyte to permeate into the electrode (anode and/or cathode) to properly wet the surfaces of the anode active material and/or the cathode active material.
- the second liquid solvent is selected from a fluorinated carbonate, hydrofluoroether, fluorinated ester, sulfone, nitrile, phosphate, phosphite, alkyl phosphonate, phosphazene, sulfate, siloxane, silane, 1,3-dioxolane (DOL), 1,2-dimethoxyethane (DME), tetraethylene glycol dimethylether (TEGDME), poly(ethylene glycol) dimethyl ether (PEGDME), diethylene glycol dibutyl ether (DEGDBE), 2-ethoxyethyl ether (EEE), sulfone, sulfolane, ethylene carbonate (EC), dimethyl carbonate (DMC), methylethyl carbonate (MEC), diethyl carbonate (DEC), ethyl propionate, methyl propionate, propylene carbonate (PC), gamma.-butyrolactone ( ⁇
- Desirable polymerizable liquid solvents include fluorinated monomers having unsaturation (double bonds or triple bonds that can be opened up for polymerization); e.g., fluorinated vinyl carbonates, fluorinated vinyl monomers, fluorinated esters, fluorinated vinyl esters, and fluorinated vinyl ethers).
- fluorinated vinyl carbonates are given below: These liquid solvents, as a monomer, can be cured in the presence of an initiator (e.g., 2- Hydroxy-2-methyl-1-phenyl-propan-1-one, Ciba DAROCUR-1173, which can be activated by UV or electron beam):
- an initiator e.g., 2- Hydroxy-2-methyl-1-phenyl-propan-1-one, Ciba DAROCUR-1173, which can be activated by UV or electron beam
- the fluorinated carbonate is selected from vinyl- or double bond- containing variants of fluoroethylene carbonate (FEC), DFDMEC, FNPEC, a combination thereof, or a combination thereof with hydrofluoro ether (HFE), trifluoro propylene carbonate (FPC), or methyl nonafluorobutyl ether (MFE), wherein the chemical formulae for FEC, DFDMEC, and FNPEC, respectively are shown below: (FEC) (DFDMEC
- Effective anionic-type catalysts or initiators are n-BuLi, ZnEt2, LiN(CH2)2, NaNH2, and complexes of n-LiBu with ZnEt2 or AlEh.
- a second solvent such as pyridine, sulfolane, toluene or benzene, can be used to dissolve alkyl vinyl sulfones, aryl vinyl sulfones, and other larger sulfone molecules.
- Poly(sulfone)s have high oxygen indices and low smoke emission on burning. Poly(sulfone)s are inherently self-extinguishing materials owing to their highly aromatic character.
- a hydroxy-terminated copoly(ester sulfone) synthesized by melt polycondensation of the diethylene glycol and 4,4-dihydroxydiethoxydiphenyl sulfone with adipic acid can be used as a flame retardant.
- the sulfone is selected from TrMS, MTrMS, TMS, or vinyl or double bond-containing variants of TrMS, MTrMS, TMS, EMS, MMES, EMES, EMEES, or a combination thereof; their chemical formulae being given below: (MMES) (EMES) (EMEES)
- MMES MMES
- EMES EMEES
- the cyclic structure, such as TrMS, MTrMS, and TMS, can be polymerized via ring-opening polymerization with the assistance of an ionic type initiator.
- the nitrile may be selected from dinitriles, such as AND, GLN, and SEN, which have the following chemical formulae: (AND) (GLN) (SEN)
- the phosphate, phosphonate, phosphazene, phosphite, or sulfate is selected from tris(trimethylsilyl)phosphite (TTSPi), alkyl phosphate, triallyl phosphate (TAP), ethylene sulfate (DTD), a combination thereof.
- TTSPi tris(trimethylsilyl)phosphite
- TAP triallyl phosphate
- DTD ethylene sulfate
- the phosphate, alkyl phosphonate, or phosphazene may be selected from the following:
- the phosphate, alkyl phosphonate, phosphonic acid, and phosphazene, upon polymerization, are found to be essentially non-flammable. Good examples include diethyl vinylphosphonate, dimethyl vinylphosphonate, vinylphosphonic acid, diethyl allyl phosphate, and diethyl allylphosphonate:
- Initiators for these phosphazene derivatives can be those of Lewis acids, SbCl3, AlCl3, or sulfur compounds.
- the siloxane or silane may be selected from alkylsiloxane (Si-O), alkyylsilane (Si-C), liquid oligomeric silaxane (-Si-O-Si-), or a combination thereof.
- the reactive additive may further comprise an amide group selected from N,N- dimethylacetamide, N,N-diethylacetamide, N,N-dimethylformamide, N,N-diethylformamide, or a combination thereof.
- the crosslinking agent comprises a compound having at least one reactive group selected from a hydroxyl group, an amino group, an imino group, an amide group, an acrylic amide group, an amine group, an acrylic group, an acrylic ester group, or a mercapto group in the molecule.
- the crosslinking agent is selected from poly(diethanol) diacrylate, poly(ethyleneglycol)dimethacrylate, poly(diethanol) dimethylacrylate, poly(ethylene glycol) diacrylate, lithium hexafluorophosphate (LiPF6), lithium borofluoride (LiBF4), lithium hexafluoroarsenide (LiAsF6), lithium trifluoro-methanesulfonate (LiCF3SO3), bis-trifluoromethyl sulfonylimide lithium (LiN(CF 3 SO 2 ) 2 ), lithium bis(oxalato)borate (LiBOB), lithium oxalyldifluoroborate (LiBF2C2O4), lithium oxalyldifluoroborate (LiBF2C2O4), or a combination thereof.
- the initiator may be selected from an azo compound (e.g., azodiisobutyronitrile, AIBN), azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, benzoyl peroxide tert- butyl peroxide and methyl ethyl ketone peroxide, benzoyl peroxide (BPO), bis(4-tert- butylcyclohexyl)peroxydicarbonate, t-amyl peroxypivalate, 2,2′-azobis-(2,4- dimethylvaleronitrile), 2,2′-azobis-(2-methylbutyronitrile), 1,1-azobis(cyclohexane-1- carbonitrile, benzoylperoxide (BPO), hydrogen peroxide, dodecamoyl peroxide, isobutyryl peroxide, cumene hydroperoxide, tert-butyl peroxypivalate, diis
- the lithium salt may be selected from lithium perchlorate (LiClO 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium borofluoride (LiBF 4 ), lithium hexafluoroarsenide (LiAsF6), lithium trifluoro-methanesulfonate (LiCF3SO3), bis-trifluoromethyl sulfonylimide lithium (LiN(CF3SO2)2), lithium bis(oxalato)borate (LiBOB), lithium oxalyldifluoroborate (LiBF 2 C 2 O 4 ), lithium nitrate (LiNO 3 ), Li-fluoroalkyl-phosphates (LiPF3(CF2CF3)3), lithium bisperfluoro-ethylsulfonylimide (LiBETI), lithium bis(trifluoromethanesulphonyl)imide, lithium bis(fluorosul
- the cathode in the disclosed lithium cell typically comprises particles of a cathode active material and the electrolyte permeates into the cathode and is in physical contact with substantially all the cathode active material particles.
- the battery cell contains substantially no liquid solvent left therein (substantially all of the liquid solvent being polymerized to become a polymer).
- it is essential to initially include a liquid solvent in the cell enabling the lithium salt to get dissociated into lithium ions and anions. A majority (>50%, preferably > 70%) or substantially all of the liquid solvents is then cured (polymerized or crosslinked). With substantially 0% liquid solvent, the resulting electrolyte is a solid-state electrolyte.
- the crosslinking agent preferably comprises a compound having at least one reactive group selected from a hydroxyl group, an amino group, an imino group, an amide group, an amine group, an acrylic group, or a mercapto group in the molecule.
- the crosslinking agent may be selected from a chemical species represented by Chemical formula 1 below: where R 4 and R 5 are each independently hydrogen or methyl group, and n is an integer from 3 to 30, wherein R' is C 1 ⁇ C 5 alkyl group.
- the crosslinking agent may be selected from N,N-methylene bisacrylamide, epichlorohydrin, 1,4-butanediol diglycidyl ether, tetrabutylammonium hydroxide, cinnamic acid, ferric chloride, aluminum sulfate octadecahydrate, diepoxy, dicarboxylic acid compound, poly(potassium 1-hydroxy acrylate) (PKHA), glycerol diglycidyl ether (GDE), ethylene glycol, polyethylene glycol, polyethylene glycol diglycidyl ether (PEGDE), citric acid, acrylic acid, methacrylic acid, a derivative compound of acrylic acid, a derivative compound of methacrylic acid, glycidyl functions, N,N'-Methylenebisacrylamide (MBAAm), Ethylene glycol dimethacrylate (EGDMAAm), isobomyl methacrylate, poly (acrylic acid) (PAA), methyl
- the electrolyte further comprises a flame-retardant additive selected from a halogenated flame retardant, phosphorus-based flame retardant, melamine flame retardant, metal hydroxide flame retardant, silicon-based flame retardant, phosphate flame retardant, biomolecular flame retardant, or a combination thereof.
- the flame-retardant additive may be in a form of encapsulated particles comprising the additive encapsulated by a shell of a substantially lithium ion-impermeable and liquid electrolyte-impermeable coating material, wherein said shell is breakable when exposed to a temperature higher than a threshold temperature.
- the flame-retardant additive-to-liquid solvent ratio in the mixture is from 1/95 to 50/50 by weight, preferably from 15/85 to 40/60 by weight, further preferably from 20/80 to 30/70 by weight.
- the polymer in the electrolyte may form a mixture, copolymer, semi-interpenetrating network, or simultaneous interpenetrating network with a second polymer selected from poly(ethylene oxide), polypropylene oxide, poly(ethylene glycol), poly(acrylonitrile), poly(methyl methacrylate), poly(vinylidene fluoride), poly bis-methoxy ethoxyethoxide- phosphazene, polyvinyl chloride, polydimethylsiloxane, poly(vinylidene fluoride)- hexafluoropropylene, cyanoethyl poly(vinyl alcohol), a pentaerythritol tetraacrylate-based polymer, an aliphatic polycarbonate,
- This second polymer may be pre-mixed into an anode and/or an cathode. Alternatively, this second polymer may be dissolved in the liquid solvent where appropriate or possible to form a solution prior to being injected into the battery cell.
- the electrolyte further comprises particles of an inorganic solid electrolyte material having a particle size from 2 nm to 30 ⁇ m, wherein the particles of inorganic solid electrolyte material are dispersed in the polymer or chemically bonded by the polymer.
- the particles of inorganic solid electrolyte material are preferably selected from an oxide type, sulfide type, hydride type, halide type, borate type, phosphate type, lithium phosphorus oxynitride (LiPON), garnet-type, lithium superionic conductor (LISICON) type, sodium superionic conductor (NASICON) type, or a combination thereof.
- the present disclosure further provides a rechargeable lithium battery, including a lithium metal secondary cell, a lithium-ion cell, a lithium-sulfur cell, a lithium-ion sulfur cell, a lithium- selenium cell, or a lithium-air cell. This battery features a non-flammable, safe, and high- performing electrolyte as herein disclosed.
- the rechargeable lithium cell may further comprise a separator disposed between the anode and the cathode.
- the separator comprises a quasi-solid or solid-state electrolyte as herein disclosed.
- the polymerizable may be initially in a liquid monomer state, which can be injected into the battery cell and then cured (polymerized and/or crosslinked) in situ inside the cell.
- the reactive liquid solvent (along with the needed initiator and/or crosslinking agent) may be mixed with an electrode active material (e.g. cathode active material particles, such as NCM, NCA and lithium iron phosphate), a conducting additive (e.g.
- a reactive slurry or paste is then made into a desired electrode shape (e.g. cathode electrode), possibly supported on a surface of a current collector (e.g. an Al foil as a cathode current collector).
- a desired electrode shape e.g. cathode electrode
- a current collector e.g. an Al foil as a cathode current collector.
- An anode of a lithium-ion cell may be made in a similar manner using an anode active material (e.g. particles of graphite, Si, SiO, etc.).
- the anode electrode, a cathode electrode, and an optional separator are then combined to form a battery cell.
- the reactive solvent inside the cell is then polymerized and/or crosslinked in situ inside the battery cell.
- the electrolyte composition is designed to permeate into the internal structure of the cathode and to be in physical contact or ionic contact with the cathode active material in the cathode, and to permeate into the anode electrode to be in physical contact or ionic contact with the anode active material where/if present.
- the flash point of the quasi-solid electrolyte is typically at least 100 degrees higher than the flash point of the same organic liquid solvent without being polymerized. In most of the cases, either the flash point is higher than 200°C or no flash point can be detected. The electrolyte just would not catch on fire or get ignited.
- Still another preferred embodiment of the present disclosure is a rechargeable lithium- sulfur cell or lithium-ion sulfur cell containing a sulfur cathode having sulfur or lithium polysulfide as a cathode active material.
- the anode current collector may comprise a foil, perforated sheet, or foam of a metal having two primary surfaces wherein at least one primary surface is coated with or protected by a layer of lithiophilic metal (a metal capable of forming a metal-Li solid solution or is wettable by lithium ions), a layer of graphene material, or both.
- the metal foil, perforated sheet, or foam is preferably selected from Cu, Ni, stainless steel, Al, graphene-coated metal, graphite-coated metal, carbon-coated metal, or a combination thereof.
- the lithiophilic metal is preferably selected from Au, Ag, Mg, Zn, Ti, K, Al, Fe, Mn, Co, Ni, Sn, V, Cr, an alloy thereof, or a combination thereof.
- an anode active material for a lithium ion battery featuring the presently disclosed electrolyte, there is no particular restriction on the selection of an anode active material.
- the anode active material may be selected from the group consisting of: (a) silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), phosphorus (P), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), nickel (Ni), cobalt (Co), and cadmium (Cd); (b) alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Ni, Co, or Cd with other elements; (c) oxides, carbides, nitrides, sulfides, phosphides, selenides, and tellurides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Fe, Ni, Co, V, or Cd, and their mixtures, composites, or lithium-containing composites; (d) salts and hydroxides of Sn; (e) lithium titanate, lithium manganate, lithium alumina
- the separator may comprise the presently disclosed electrolyte. In certain embodiments, the separator comprises polymeric fibers, ceramic fibers, glass fibers, or a combination thereof.
- These fibers may be stacked together in such a manner that there are pores that allow for permeation of lithium ions, but not for penetration of any potentially formed lithium dendrites.
- These fibers may be dispersed in a matrix material or bonded by a binder material.
- This matrix or binder material may contain a ceramic or glass material.
- the polymer electrolyte may serve as the matrix material or binder material that helps to hold these fibers together.
- the separator may contain particles of a glass or ceramic material (e.g. metal oxide, metal carbide, metal nitride, metal boride, etc.).
- the rechargeable lithium cell may further comprise a cathode current collector selected from aluminum foil, carbon- or graphene-coated aluminum foil, stainless steel foil or web, carbon- or graphene-coated steel foil or web, carbon or graphite paper, carbon or graphite fiber fabric, flexible graphite foil, graphene paper or film, or a combination thereof.
- a web means a screen-like structure or a metal foam, preferably having interconnected pores or through- thickness apertures.
- the present disclosure also provides a method of producing the disclosed rechargeable lithium cell, the method comprising: (a) Combining an anode, an optional separator layer, a cathode, and a protective housing to form a cell; (b) Introducing a reactive liquid electrolyte composition into the cell, wherein the reactive liquid electrolyte composition comprises at least a first polymerizable liquid solvent, a lithium salt dissolved in the first polymerizable liquid solvent, a crosslinking agent and/or an initiator and wherein the polymerizable liquid solvent is selected from the group consisting of fluorinated carbonates, hydrofluoroethers, fluorinated esters, sulfones, nitriles, phosphates, phosphites, alkyl phosphonates, phosphazenes, sulfates, siloxanes, silanes, and combinations thereof; and (c) Partially or totally polymerizing the liquid solvent to obtain a quasi-solid or solid-state electrolyte where
- the reactive liquid electrolyte composition may further comprise a second liquid solvent (polymerizable or non-polymerizable) and step (c) either does not polymerize the second liquid solvent or polymerizes the second liquid solvent to a different extent as compared to the first polymerizable liquid solvent.
- a second liquid solvent polymerizable or non-polymerizable
- the disclosure further provides a method of producing the rechargeable lithium cell, the method comprising: (A) Mixing particles of a cathode active material, an optional conductive additive, an optional binder, a reactive additive, and a lithium salt to form a cathode, wherein the reactive additive comprises at least a first polymerizable liquid solvent and a crosslinking agent or initiator; (B) providing an anode; (C) combining the cathode and the anode to form a cell; and (D) partially or totally polymerizing the first polymerizable solvent, prior to or after step (C), to produce the rechargeable lithium cell, wherein at least 30% by weight of the first liquid solvent is polymerized.
- the anode may be prepared in a similar manner, wherein step (B) may comprise a procedure of mixing particles of an anode active material, an optional conductive additive, an optional binder, a reactive additive, and a lithium salt to form an anode, wherein the reactive additive comprises at least a polymerizable liquid solvent and a crosslinking agent or initiator and wherein the method further comprises polymerizing and/or crosslinking the reactive additive, prior to or after step (C), to produce the rechargeable lithium cell.
- step (A) may further comprise adding particles of an inorganic solid electrolyte powder in the cathode or in the anode.
- step (E) of injecting a second liquid solvent into the cell.
- This second liquid solvent may be polymerizable or non-polymerizable.
- the disclosure provides yet another method of producing a rechargeable lithium cell, the method comprising: (A) combining an anode, an optional separator layer, a cathode, and a protective housing to form a cell; (B) introducing a reactive additive into the anode, the cathode or substantially the entire cell, wherein the reactive additive comprises at least one polymerizable liquid solvent, a second liquid solvent, and a crosslinking agent or initiator for the first and/or the second solvent; and (C) partially or totally polymerizing and/or crosslinking the reactive additive to produce the rechargeable lithium cell, wherein the first liquid solvent and the second solvent are polymerized or crosslinked to different extents.
- the first liquid solvent and the second liquid solvent typically are polymerized and/or crosslinked to different extents even under the same conditions.
- the second liquid solvent may be chosen to be non-polymerizable.
- the procedure of polymerizing and/or crosslinking may comprise exposing the reactive additive to heat, UV, high-energy radiation, or a combination thereof.
- the high-energy radiation may be selected from electron beam, Gamma radiation, X-ray, neutron radiation, etc. Electron beam irradiation is particularly useful.
- the present disclosure provides a rechargeable lithium battery comprising an anode, a cathode, and a quasi-solid or solid-state electrolyte in ionic communication with the anode and the cathode, wherein the electrolyte comprises a polymer, which is a polymerization or crosslinking product of a reactive additive, wherein the reactive additive comprises (i) a first liquid solvent that is polymerizable, (ii) an initiator or curing agent, (iii) a lithium salt, and (iv) a second liquid solvent; wherein the first liquid solvent occupies from 1% to 99% by weight and the second liquid electrolyte occupies from 0.1% to 99% by weight based on the total weight of the reactive additive; wherein the first liquid solvent has a lower flash point (higher flammability), a higher vapor pressure, a higher dielectric constant (hence, more capable of dissolving a lithium salt), or a higher solubility of the lithium salt as compared with the second liquid solvent; and where
- the polymerizable first liquid solvent is polymerized; more preferably > 50%, further preferably >70%, and most preferably >99% is polymerized.
- the first liquid solvent is selected from vinylene carbonate, fluoro-ethylene carbonate (FEC), ethylene carbonate, vinyl sulfite, vinyl ethylene sulfite, vinyl ethylene carbonate, 1,3-propyl sultone, 1,3- acrylic-sultones, methyl ethylene sulfone, methyl vinyl sulfone, ethyl vinyl sulfone, methyl methacrylate, vinyl acetate, acrylamide, 1,3-dioxolane (DOL), a fluorinated vinyl ester, a fluorinated vinyl ether, or a combination thereof.
- FEC fluoro-ethylene carbonate
- DOL 1,3-dioxolane
- liquid solvents tend to have a relatively low flash points, high flammability, but good ability to dissolve a lithium salt.
- the liquid solvents listed above are commonly used as a solvent to dissolve a lithium salt therein and the resulting solutions are used as a liquid electrolyte.
- These liquid solvents have a relatively high dielectric constant and are capable of dissolving a high amount of a lithium salt; however, they are typically highly volatile, having a low flash point and being highly flammable.
- liquid solvents are generally not known to be polymerizable, with or without the presence of a second liquid solvent, and a separate or different polymer or monomer is typically used in the industry to prepare a gel polymer electrolyte or solid polymer electrolyte. It is uniquely advantageous to be able to polymerize the liquid solvent once the liquid electrolyte (having a lithium salt dissolved in the first liquid solvent) is injected into a battery cell. With such a novel strategy, one can readily reduce the liquid solvent or completely eliminate the volatile liquid solvent all together. A desired amount of a second liquid solvent, preferably a flame-resistant liquid solvent, may be retained in the battery cell to improve the lithium ion conductivity of the electrolyte.
- a second liquid solvent preferably a flame-resistant liquid solvent
- the second liquid solvent comprises a flame retardant selected from an organic phosphorus compound, an inorganic phosphorus compound, a halogenated derivative thereof, or a combination thereof.
- the organic phosphorus compound or the inorganic phosphorus compound preferably is selected from the group consisting of phosphates, phosphonates, phosphonic acids, phosphorous acids, phosphites, phosphoric acids, phosphinates, phosphines, phosphine oxides, phosphazene compounds, derivatives thereof, and combinations thereof.
- the second liquid solvent is selected from the group consisting of fluorinated ethers, fluorinated esters, sulfones, sulfides, nitriles, sulfates, siloxanes, silanes, combinations thereof, and combinations with phosphates, phosphonates, phosphinates, phosphines, phosphine oxides, phosphonic acids, phosphorous acid, phosphites, phosphoric acids, phosphazene compounds, derivatives thereof, and combinations thereof.
- the second liquid solvent is selected from a phosphate, phosphonate, phosphinate, phosphine, or phosphine oxide having the structure of: wherein R 10 , R 11 , and R 12 , are independently selected from the group consisting of alkyl, aryl, heteroalkyl, heteroaryl, halogen substituted alkyl, halogen substituted aryl, halogen substituted heteroalkyl, halogen substituted heteroaryl, alkoxy, aryloxy, heteroalkoxy, heteroaryloxy, halogen substituted alkoxy, halogen substituted aryloxy, halogen substituted heteroalkoxy, and halogen substituted heteroaryloxy functional groups, and the second liquid solvent is stable under an applied electrical potential no less than 4 V.
- the second liquid solvent comprises a phosphoranimine having the structure of: wherein R 1 , R 2 , and R 3 are independently selected from the group consisting of alkyl, aryl, heteroalkyl, heteroaryl, halogen substituted alkyl, halogen substituted aryl, halogen substituted heteroalkyl, halogen substituted heteroaryl, alkoxy, aryloxy, heteroalkoxy, heteroaryloxy, halogen substituted alkoxy, halogen substituted aryloxy, halogen substituted heteroalkoxy, and halogen substituted heteroaryloxy functional groups, wherein R 1 , R 2 , and R 3 are represented by at least two different substituents and wherein X is selected from the group consisting of an organosilyl group or a tert-butyl group.
- the R 1 , R 2 , and R 3 may be each independently selected from the group consisting of an alkoxy group, and an aryloxy group.
- the lithium salt occupies 0.1%-30% by weight and the crosslinking agent and/or initiator occupies 0.1-50% by weight of the reactive additive.
- the polymer electrolyte exhibits a vapor pressure less than 0.001 kPa when measured at 20°C, a vapor pressure less than 10% of the vapor pressure of the combined first liquid solvent and lithium salt alone without the polymerization, a flash point at least 100 degrees Celsius higher than a flash point of the liquid solvent alone, a flash point higher than 200°C, or no measurable flash point and wherein the polymer has a lithium ion conductivity from 10 -8 S/cm to 10 -2 S/cm at room temperature.
- the reactive additive comprises a polymerizable first liquid solvent and a second liquid solvent and wherein the second liquid solvent either is not polymerizable or is polymerizable but polymerized to a lesser extent as compared to the first liquid solvent.
- the presence of this second liquid solvent is designed to impart certain desired properties to the polymerized electrolyte, such as lithium ion conductivity, flame retardancy, and the ability of the electrolyte to permeate into the electrode (anode and/or cathode) to properly wet the surfaces of the anode active material and/or the cathode active material.
- the second liquid solvent is selected from a fluorinated carbonate, hydrofluoroether, fluorinated ester, sulfone, nitrile, phosphate, phosphite, alkyl phosphonate, phosphazene, sulfate, siloxane, silane, 1,3-dioxolane (DOL), 1,2-dimethoxyethane (DME), tetraethylene glycol dimethylether (TEGDME), poly(ethylene glycol) dimethyl ether (PEGDME), diethylene glycol dibutyl ether (DEGDBE), 2-ethoxyethyl ether (EEE), sulfone, sulfolane, dimethyl carbonate (DMC), methylethyl carbonate (MEC), ethyl propionate, methyl propionate, propylene carbonate (PC), gamma.-butyrolactone ( ⁇ -BL), acetonitrile (AN), ethyl
- High-viscosity solvents such as ethylene carbonate (EC) and low dielectric constant solvents such as diethyl carbonate (DEC) are not desirable second liquid solvent for use in the presently disclosed electrolyte.
- the first or the second liquid solvents may include fluorinated monomers having unsaturation (double bonds or triple bonds that can be opened up for polymerization); e.g., fluorinated vinyl carbonates, fluorinated vinyl monomers, fluorinated esters, fluorinated vinyl esters, and fluorinated vinyl ethers).
- fluorinated vinyl carbonates are given below: These liquid solvents can be cured in the presence of an initiator (e.g., 2-Hydroxy-2- methyl-1-phenyl-propan-1-one, Ciba DAROCUR-1173, which can be activated by UV or electron beam) if so desired:
- the fluorinated carbonate is selected from vinyl- or double bond- containing variants of fluoroethylene carbonate (FEC), DFDMEC, FNPEC, hydrofluoro ether (HFE), trifluoro propylene carbonate (FPC), methyl nonafluorobutyl ether (MFE), or a combination thereof, wherein the chemical formulae for FEC, DFDMEC, and FNPEC, respectively are shown below:
- FEC fluoroethylene carbonate
- DFDMEC DFDMEC
- FNPEC hydrofluoro ether
- Desirable sulfones as a first or second liquid solvent include, but not limited to, alkyl and
- Effective anionic-type catalysts or initiators are n-BuLi, ZnEt2, LiN(CH 2 ) 2 , NaNH 2 , and complexes of n-LiBu with ZnEt2 or AlEh.
- a second solvent such as pyridine, sulfolane, toluene or benzene, can be used to dissolve alkyl vinyl sulfones, aryl vinyl sulfones, and other larger sulfone molecules.
- Poly(sulfone)s have high oxygen indices and low smoke emission on burning. Poly(sulfone)s are inherently self-extinguishing materials owing to their highly aromatic character.
- the sulfone as a first or the second liquid solvent is selected from TrMS, MTrMS, TMS, or vinyl or double bond-containing variants of TrMS, MTrMS, TMS, EMS, MMES, EMES, EMEES, or a combination thereof; their chemical formulae being given below: (MMES) (EMES) (EMEES)
- MMES MMES
- EMES EMEES
- the cyclic structure, such as TrMS, MTrMS, and TMS, can be polymerized via ring-opening polymerization with the assistance of an ionic type initiator.
- the first or the second liquid solvent may be a nitrile preferably selected from dinitriles, such as AND, GLN, and SEN, which have the following chemical formulae: 22 (AND) (GLN) (SEN)
- the phosphate, phosphonate, phosphazene, phosphite, or sulfate as a first liquid solvent or in the second liquid solvent, is selected from tris(trimethylsilyl) phosphite (TTSPi), alkyl phosphate, triallyl phosphate (TAP), ethylene sulfate (DTD), a combination thereof.
- TTSPi tris(trimethylsilyl) phosphite
- TAP triallyl phosphate
- DTD ethylene sulfate
- the phosphate, alkyl phosphonate, or phosphazene may be selected from the following: .
- the phosphate, alkyl phosphonate, phosphonic acid, and phosphazene are flame-resistant. Good examples include diethyl vinylphosphonate, dimethyl vinylphosphonate, vinylphosphonic acid, diethyl allyl phosphate, and diethyl allylphosphonate:
- the siloxane or silane in the second liquid solvent may be selected from alkylsiloxane (Si-O), alkyylsilane (Si-C), liquid oligomeric silaxane (-Si-O-Si-), or a combination thereof.
- the reactive additive may further comprise an amide group selected from N,N- dimethylacetamide, N,N-diethylacetamide, N,N-dimethylformamide, N,N-diethylformamide, or a combination thereof.
- the crosslinking agent comprises a compound having at least one reactive group selected from a hydroxyl group, an amino group, an imino group, an amide group, an acrylic amide group, an amine group, an acrylic group, an acrylic ester group, or a mercapto group in the molecule.
- the crosslinking agent is selected from poly(diethanol) diacrylate, poly(ethyleneglycol)dimethacrylate, poly(diethanol) dimethylacrylate, poly(ethylene glycol) diacrylate, lithium hexafluorophosphate (LiPF6), lithium borofluoride (LiBF4), lithium hexafluoroarsenide (LiAsF6), lithium trifluoro-metasulfonate (LiCF3SO3), bis-trifluoromethyl sulfonylimide lithium (LiN(CF 3 SO 2 ) 2 ), lithium bis(oxalato)borate (LiBOB), lithium oxalyldifluoroborate (LiBF 2 C 2 O 4 ), lithium oxalyldifluoroborate (LiBF 2 C 2 O 4 ), or a combination thereof.
- the initiator may be selected from an azo compound (e.g., azodiisobutyronitrile, AIBN), azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, benzoyl peroxide tert- butyl peroxide and methyl ethyl ketone peroxide, benzoyl peroxide (BPO), bis(4-tert- butylcyclohexyl)peroxydicarbonate, t-amyl peroxypivalate, 2,2′-azobis-(2,4- dimethylvaleronitrile), 2,2′-azobis-(2-methylbutyronitrile), 1,1-azobis(cyclohexane-1- carbonitrile, benzoylperoxide (BPO), hydrogen peroxide, dodecamoyl peroxide, isobutyryl peroxide, cumene hydroperoxide, tert-butyl peroxypivalate, diis
- the lithium salt may be selected from lithium perchlorate (LiClO4), lithium hexafluorophosphate (LiPF6), lithium borofluoride (LiBF4), lithium hexafluoroarsenide (LiAsF6), lithium trifluoro-metasulfonate (LiCF3SO3), bis-trifluoromethyl sulfonylimide lithium (LiN(CF 3 SO 2 ) 2 ), lithium bis(oxalato)borate (LiBOB), lithium oxalyldifluoroborate (LiBF2C2O4), lithium oxalyldifluoroborate (LiBF2C2O4), lithium nitrate (LiNO3), Li-Fluoroalkyl-Phosphates (LiPF3(CF2CF3)3), lithium bisperfluoro-ethysulfonylimide (LiBETI), lithium bis(LiClO4), lithium
- the cathode in the disclosed lithium cell typically comprises particles of a cathode active material and the electrolyte permeates into the cathode to come in physical contact with substantially all the cathode active material particles.
- the battery cell contains substantially no liquid solvent left therein (substantially > 99% of the liquid solvent being polymerized to become a polymer).
- it is essential to initially include a liquid solvent in the cell enabling the lithium salt to get dissociated into lithium ions and anions.
- a majority (>50%, preferably > 70%) or substantially all of the liquid solvents is then cured (polymerized or crosslinked). With less than 1% liquid solvent, the resulting electrolyte is a solid-state electrolyte.
- the crosslinking agent preferably comprises a compound having at least one reactive group selected from a hydroxyl group, an amino group, an imino group, an amide group, an amine group, an acrylic group, or a mercapto group in the molecule.
- the crosslinking agent may be selected from a chemical species represented by Chemical formula 1 below: (Chemical Formula 1) where R 4 and R 5 are each independently hydrogen or methyl group, and n is an integer from 3 to 30, wherein R' is C1 ⁇ C5 alkyl group.
- the crosslinking agent may be selected from N,N-methylene bisacrylamide, epichlorohydrin, 1,4-butanediol diglycidyl ether, tetrabutylammonium hydroxide, cinnamic acid, ferric chloride, aluminum sulfate octadecahydrate, diepoxy, dicarboxylic acid compound, poly(potassium 1-hydroxy acrylate) (PKHA), glycerol diglycidyl ether (GDE), ethylene glycol, polyethylene glycol, polyethylene glycol diglycidyl ether (PEGDE), citric acid, acrylic acid, methacrylic acid, a derivative compound of acrylic acid, a derivative compound of methacrylic acid, glycidyl functions, N,N'-Methylenebisacrylamide (MBAAm), Ethylene glycol dimethacrylate (EGDMAAm), isobomyl methacrylate, poly (acrylic acid) (PAA), methyl
- the polymer in the electrolyte may form a mixture, copolymer, semi-interpenetrating network, or simultaneous interpenetrating network with a second polymer selected from poly(ethylene oxide), polypropylene oxide, poly(ethylene glycol), poly(acrylonitrile), poly(methyl methacrylate), poly(vinylidene fluoride), poly bis-methoxy ethoxyethoxide- phosphazenex, polyvinyl chloride, polydimethylsiloxane, poly(vinylidene fluoride)- hexafluoropropylene, cyanoethyl poly(vinyl alcohol), a pentaerythritol tetraacrylate-based polymer, an aliphatic polycarbonate, a single Li-ion conducting solid polymer electrolyte with a carboxylate anion, a sulfonylimide anion, or sulfonate anion, a crosslinked electrolyte of poly(ethylene
- This second polymer may be pre-mixed into an anode and/or a cathode. Alternatively, this second polymer may be dissolved in the liquid solvent where appropriate or possible to form a solution prior to being injected into the battery cell.
- the electrolyte further comprises particles of an inorganic solid electrolyte material having a particle size from 2 nm to 30 ⁇ m, wherein the particles of inorganic solid electrolyte material are dispersed in the polymer or chemically bonded by the polymer.
- the particles of inorganic solid electrolyte material are preferably selected from an oxide type, sulfide type, hydride type, halide type, borate type, phosphate type, lithium phosphorus oxynitride (LiPON), garnet-type, lithium superionic conductor (LISICON) type, sodium superionic conductor (NASICON) type, or a combination thereof.
- the present disclosure further provides a rechargeable lithium battery, including a lithium metal secondary cell, a lithium-ion cell, a lithium-sulfur cell, a lithium-ion sulfur cell, a lithium- selenium cell, or a lithium-air cell. This battery features a non-flammable, safe, and high- performing electrolyte as herein disclosed.
- the rechargeable lithium cell may further comprise a separator disposed between the anode and the cathode.
- the separator comprises a quasi-solid or solid-state electrolyte as herein disclosed.
- the polymerizable first liquid solvent may be initially in a liquid monomer state, which can be injected into the battery cell and then cured (polymerized and/or crosslinked) in situ inside the cell.
- the reactive liquid solvent (along with the needed initiator and/or crosslinking agent) may be mixed with an electrode active material (e.g., cathode active material particles, such as NCM, NCA and lithium iron phosphate), a conducting additive (e.g., carbon black, carbon nanotubes, expanded graphite flakes, or graphene sheets), and an optional flame- retardant agent and/or optional particles of an inorganic solid electrolyte to form a reactive slurry or paste.
- the slurry or paste is then made into a desired electrode shape (e.g., cathode electrode), possibly supported on a surface of a current collector (e.g., an Al foil as a cathode current collector).
- a desired electrode shape e.g., cathode electrode
- a current collector e.g., an Al foil as a cathode current collector
- An anode of a lithium-ion cell may be made in a similar manner using an anode active material (e.g., particles of graphite, Si, SiO, etc.).
- the anode electrode, a cathode electrode, and an optional separator are then combined to form a battery cell.
- the reactive solvent inside the cell is then polymerized and/or crosslinked in situ inside the battery cell.
- the electrolyte composition is designed to permeate into the internal structure of the cathode and to be in physical contact or ionic contact with the cathode active material in the cathode, and to permeate into the anode electrode to be in physical contact or ionic contact with the anode active material where/if present.
- the flash point of the quasi-solid electrolyte is typically at least 100 degrees higher than the flash point of the same organic liquid solvent without being polymerized. In most of the cases, either the flash point is higher than 200°C or no flash point can be detected. The electrolyte just would not catch on fire or get ignited. Any accidentally initiated flame does not sustain for longer than a few seconds. This is a highly significant discovery, considering the notion that fire and explosion concern has been a major impediment to widespread acceptance of battery-powered electric vehicles. This new technology could potentially reshape the landscape of EV industry.
- the present disclosure also provides a reactive electrolyte composition
- a reactive electrolyte composition comprising (i) a first liquid solvent that is polymerizable, (ii) an initiator or curing agent, (iii) a lithium salt, and (iv) a second liquid solvent; wherein the first liquid solvent occupies from 1% to 99% by weight and the second solvent occupies from 0.1% to 99% by weight based on the total weight of the reactive electrolyte composition; wherein the first liquid solvent has a lower flash point, a higher vapor pressure, a higher dielectric constant, or a higher solubility of the lithium salt as compared with the second liquid solvent.
- the first liquid solvent is preferably selected from vinylene carbonate, ethylene carbonate, fluoro-ethylene carbonate, vinyl sulfite, vinyl ethylene sulfite, vinyl ethylene carbonate, 1,3-propyl sultone, 1,3- acrylic-sultones, methyl ethylene sulfone, methyl vinyl sulfone, ethyl vinyl sulfone, methyl methacrylate, vinyl acetate, acrylamide, 1,3-dioxolane (DOL), a fluorinated vinyl carbonate, fluorinated vinyl monomer, fluorinated ester, fluorinated vinyl ester, fluorinated vinyl ether, or a combination thereof.
- DOL 1,3-dioxolane
- the second liquid solvent in this reactive electrolyte composition is preferably selected from the group consisting of fluorinated ethers, fluorinated esters, sulfones, sulfides, nitriles, sulfates, siloxanes, silanes, combinations thereof, and combinations with phosphates, phosphonates, phosphinates, phosphines, phosphine oxides, phosphonic acids, phosphorous acid, phosphites, phosphoric acids, phosphazene compounds, derivatives thereof, and combinations thereof.
- the present disclosure also provides a method of producing the disclosed rechargeable lithium cell, the method comprising: (a) combining an anode, an optional separator layer, a cathode, and a protective housing to form a cell; (b) introducing a reactive liquid electrolyte composition into the cell, wherein the reactive liquid electrolyte composition comprises at least a polymerizable first liquid solvent, a lithium salt dissolved in the first liquid solvent, a crosslinking agent and/or an initiator, and a second liquid solvent, wherein the first liquid solvent occupies from 1% to 99% by weight and the second liquid solvent occupies from 0.1% to 99% by weight based on the total weight of the reactive liquid electrolyte composition and the first liquid solvent has a lower flash point (higher flammability), a higher vapor pressure, a higher dielectric constant, or a higher solubility of the lithium salt as compared with the second liquid solvent; and (c) partially or totally polymerizing the first liquid solvent to obtain a quasi-solid or solid-state electroly
- the first liquid solvent is selected from vinylene carbonate, ethylene carbonate, vinyl sulfite, vinyl ethylene sulfite, vinyl ethylene carbonate, 1,3-propyl sultone, 1,3- acrylic-sultones, methyl ethylene sulfone, methyl vinyl sulfone, ethyl vinyl sulfone, methyl methacrylate, vinyl acetate, acrylamide, 1,3-dioxolane (DOL), or a combination thereof.
- Step (c) either does not polymerize the second liquid solvent or polymerizes the second liquid solvent to a different extent as compared to the polymerizable first liquid solvent.
- the disclosure further provides a method of producing the rechargeable lithium cell, the method comprising: (A) mixing particles of a cathode active material, an optional conductive additive, an optional binder, and a reactive additive to form a cathode, wherein the reactive additive comprises (i) a first liquid solvent that is polymerizable, (ii) an initiator or curing agent, (iii) a lithium salt, and (iv) a second liquid solvent; wherein the first liquid solvent occupies from 1% to 99% by weight based on the total weight of the reactive additive and wherein the first liquid solvent has a lower flash point, a higher vapor pressure, a higher dielectric constant, or a higher solubility of the lithium salt as compared with the second liquid solvent; (B) providing an anode; (C) combining the cathode, a separator, and the anode to form a cell; and (D) partially or totally polymerizing the first solvent, prior to or after step (C), to produce the rechargeable lithium cell,
- step (B) comprises a procedure of mixing particles of an anode active material, an optional conductive additive, an optional binder, a reactive additive, and a lithium salt to form an anode, wherein the reactive additive comprises at least a polymerizable liquid solvent, a crosslinking agent or initiator, and a second liquid solvent and wherein the method further comprises polymerizing and/or crosslinking the reactive additive, prior to or after step (C), to produce the rechargeable lithium cell.
- Step (A) may further comprise adding particles of an inorganic solid electrolyte powder in the cathode or in the anode.
- FIG. 1(A) A process flow chart to illustrate a method of producing a lithium metal battery comprising a substantially solid-state electrolyte according to some embodiments of the present disclosure
- FIG. 1(B) A process flow chart to illustrate the method of producing a reactive electrolyte composition according to some embodiments of the present disclosure
- FIG. 1(C) A process flow chart to illustrate a method of producing a lithium metal battery comprising a substantially solid-state electrolyte according to some embodiments of the present disclosure
- FIG. 1(D) A process flow chart to illustrate a method of producing a lithium metal battery comprising a substantially solid-state electrolyte according to some embodiments of the present disclosure.
- FIG. 1(A) A process flow chart to illustrate a method of producing a lithium metal battery comprising a substantially solid-state electrolyte according to some embodiments of the present disclosure
- FIG. 1(B) A process flow chart to illustrate the method of producing a reactive electrolyte composition according to some embodiments of the present disclosure
- DETAILED DESCRIPTION The present disclosure provides a safe and high-performing lithium battery, which can be any of various types of lithium-ion cells or lithium metal cells. A high degree of safety is imparted to this battery by a novel and unique electrolyte that is highly flame-resistant and would not initiate a fire or sustain a fire and, hence, would not pose explosion danger. This disclosure has solved the very most critical issue that has plagued the lithium-metal and lithium-ion industries for more than two decades.
- the present disclosure provides a rechargeable lithium battery comprising an anode, a cathode, and a quasi-solid or solid-state electrolyte in ionic communication with the anode and the cathode, wherein the electrolyte comprises a polymer, which is a polymerization or crosslinking product of a reactive additive, wherein the reactive additive comprises at least one polymerizable liquid solvent (itself being a monomer), a lithium salt dissolved in the polymerizable liquid solvent, and a crosslinking agent and/or an initiator; wherein the polymerizable liquid solvent is selected from the group consisting of fluorinated carbonates, hydrofluoroethers, fluorinated esters, sulfones, sulfides, nitriles, phosphates, phosphites, alkyl phosphonate, phosphazene, sulfates, siloxanes, silanes, and combinations thereof; and wherein at least 20% by weight or by volume of the
- the lithium salt occupies 0.1%-30% by weight
- the polymerizable liquid solvent occupies 1%-90% by weight
- the crosslinking agent and/or initiator occupies 1-90% by weight, all based on the total weight of the lithium salt, the crosslinking agent and/or initiator, and the polymerizable liquid solvent combined.
- the liquid solvents e.g., those listed above
- these liquid solvents are not known to be polymerizable and a separate polymer or monomer is typically used in the industry to prepare a gel polymer electrolyte or solid polymer electrolyte.
- the present disclosure provides a rechargeable lithium battery comprising an anode, a cathode, and a quasi-solid or solid-state electrolyte in ionic communication with the anode and the cathode, wherein the electrolyte comprises a polymer, which is a polymerization or crosslinking product of a reactive additive, wherein the reactive additive comprises (i) a first liquid solvent that is polymerizable, (ii) an initiator or curing agent, (iii) a lithium salt, and (iv) a second liquid solvent; wherein the first liquid solvent occupies from 1% to 99% by weight and the second liquid electrolyte occupies from 0.1% to 99% by weight based on the total weight of the reactive additive; wherein the first liquid solvent has a lower flash point (higher flammability), a higher vapor pressure, a higher dielectric constant (hence, more capable of dissolving a lithium salt), or a higher solubility of the lithium salt as compared with the second liquid solvent; and where
- the polymerizable first liquid solvent is polymerized; more preferably > 50%, further preferably >70%, and most preferably >99% is polymerized.
- the first liquid solvent is selected from vinylene carbonate, ethylene carbonate, fluoroethylene carbonate, vinyl sulfite, vinyl ethylene sulfite, vinyl ethylene carbonate, 1,3-propyl sultone, 1,3- acrylic-sultones, methyl ethylene sulfone, methyl vinyl sulfone, ethyl vinyl sulfone, methyl methacrylate, vinyl acetate, acrylamide, 1,3-dioxolane (DOL), or a combination thereof.
- DOL 1,3-dioxolane
- liquid solvents listed above are commonly used as a solvent to dissolve a lithium salt therein and the resulting solutions are used as a liquid electrolyte.
- These liquid solvents have a relatively high dielectric constant and are capable of dissolving a high amount of a lithium salt; however, they are typically highly volatile, having a low flash point and being highly flammable.
- these liquid solvents are generally not known to be polymerizable, with or without the presence of a second liquid solvent, and a separate or different polymer or monomer is typically used in the industry to prepare a gel polymer electrolyte or solid polymer electrolyte.
- a second liquid solvent preferably a flame-resistant liquid solvent
- Desirable flame retardant-type second liquid solvents are, as examples, alkyl phosphates, alkyl phosphonates, phosphazenes, hydrofluoroethers, fluorinated ethers, and fluorinated esters.
- This strategy enables us to achieve several desirable features of the resultant electrolytes and batteries: a) no liquid electrolyte leakage issue (the in situ cured polymer being capable of holding the remaining liquid together to form a gel); b) adequate lithium salt amount can be dissolved in the electrolyte, enabling a good lithium ion conductivity; c) reduced or eliminated flammability (only a solid polymer and a non-flammable second liquid are retained in the cell); d) good ability of the electrolyte to wet on anode/cathode active material surfaces (hence, significantly reduced interfacial impedance and internal resistance); e) processing ease and compatibility with current lithium-ion battery production processes and equipment, etc.; and f) enabling a high cathode active material proportion in the cathode electrode (typically 75- 97%, in contrast to typically less than 75% by weight of the cathode active material when working with a conventional solid polymer electrolyte or inorganic solid electrolyte.
- the electrolyte is a quasi-solid or substantially solid-state electrolyte that has the following highly desirable and advantageous features: (i) good electrolyte-electrode contact and interfacial stability (minimal solid electrode-electrolyte interfacial impedance) commonly enjoyed by a liquid electrolyte; (ii) good processibility and ease of battery cell production; (iii) highly resistant to flame and fire.
- the second liquid solvent comprises a flame-resisting or flame retardant liquid selected from an organic phosphorus compound, an inorganic phosphorus compound, a halogenated derivative thereof, or a combination thereof.
- the organic phosphorus compound or the inorganic phosphorus compound preferably is selected from the group consisting of phosphates, phosphonates, phosphonic acids, phosphorous acids, phosphites, phosphoric acids, phosphinates, phosphines, phosphine oxides, phosphazene compounds, derivatives thereof, and combinations thereof.
- the second liquid solvent is selected from the group consisting of fluorinated ethers, fluorinated esters, sulfones, sulfides, nitriles, sulfates, siloxanes, silanes, phosphates, phosphonates, phosphinates, phosphines, phosphine oxides, phosphonic acids, phosphorous acid, phosphites, phosphoric acids, phosphazene compounds, derivatives thereof, and combinations thereof.
- the second liquid solvent is selected from a phosphate, phosphonate, phosphinate, phosphine, or phosphine oxide having the structure of: wherein R 10 , R 11 , and R 12 , are independently selected from the group consisting of alkyl, aryl, heteroalkyl, heteroaryl, halogen substituted alkyl, halogen substituted aryl, halogen substituted heteroalkyl, halogen substituted heteroaryl, alkoxy, aryloxy, heteroalkoxy, heteroaryloxy, halogen substituted alkoxy, halogen substituted aryloxy, halogen substituted heteroalkoxy, and halogen substituted heteroaryloxy functional groups, and the second liquid solvent is stable under an applied electrical potential no less than 4 V.
- the second liquid solvent comprises a phosphoranimine having the structure of: wherein R 1 , R 2 , and R 3 are independently selected from the group consisting of alkyl, aryl, heteroalkyl, heteroaryl, halogen substituted alkyl, halogen substituted aryl, halogen substituted heteroalkyl, halogen substituted heteroaryl, alkoxy, aryloxy, heteroalkoxy, heteroaryloxy, halogen substituted alkoxy, halogen substituted aryloxy, halogen substituted heteroalkoxy, and halogen substituted heteroaryloxy functional groups, wherein R 1 , R 2 , and R 3 are represented by at least two different substituents and wherein X is selected from the group consisting of an organosilyl group or a tert-butyl group.
- the R 1 , R 2 , and R 3 may be each independently selected from the group consisting of an alkoxy group, and an aryloxy group.
- the polymer electrolyte typically has a lithium ion conductivity typically from 10 -8 S/cm to 10 -2 S/cm at room temperature.
- the rechargeable lithium cell comprises: (a) a cathode that may contain a cathode active material (along with an optional conductive additive and an optional resin binder) and an optional cathode current collector (such as Al foil) supporting the cathode active material; (b) an anode that may contain an anode current collector, with or without an anode active material in the beginning, when the cell is made.
- anode-less lithium cell (It may be noted that if no conventional anode active material, such as graphite, Si, SiO, Sn, and conversion-type anode materials, and no lithium metal is present in the cell when the cell is made and before the cell begins to charge and discharge, the battery cell is commonly referred to as an “anode-less” lithium cell.)
- an optional porous separator (a lithium ion-permeable membrane) electronically separating the anode and the cathode; and
- an electrolyte comprising (i) a lithium salt and (ii) a polymer, which is a polymerization or crosslinking product of a reactive additive, wherein the reactive additive comprises at least one polymerizable liquid solvent and a crosslinking agent and/or initiator, wherein the polymerizable liquid solvent is selected from the group consisting of fluorinated carbonates, hydrofluoroethers, fluorinated esters, sulfones, nitriles, phosphates
- the battery cell contains substantially no (volatile) liquid solvent therein after polymerization. However, it is essential to initially include a liquid solvent in the cell, enabling the lithium salt to get dissociated into lithium ions and anions. A majority (>50%, preferably > 70%) or substantially all of the liquid solvent (particularly the organic solvent) is then removed just before or after curing of the reactive additive.
- the resulting electrolyte is a solid-state electrolyte. With less than 30% liquid solvent, we have a quasi-solid electrolyte. Both are highly flame-resistant.
- the electrolyte exhibits a vapor pressure less than 0.001 kPa when measured at 20°C, a vapor pressure less than 60% of the vapor pressure of the combined (first) liquid solvent and lithium salt alone without the polymer (or prior to polymerization), a flash point at least 100 degrees Celsius higher than a flash point of the liquid solvent prior to polymerization, a flash point higher than 200°C, or no measurable flash point and wherein the polymer has a lithium ion conductivity from 10 -8 S/cm to 10 -2 S/cm at room temperature.
- the reactive additive comprises a first polymerizable liquid solvent and a second liquid solvent and wherein the second liquid solvent either is not polymerizable or is polymerizable but polymerized to a lesser extent as compared to the first polymerizable liquid solvent.
- this second liquid solvent is designed to impart certain desired properties to the polymerized electrolyte, such as lithium ion conductivity, flame retardancy, ability of the electrolyte to permeate into the electrode (anode and/or cathode) to properly wet the surfaces of the anode active material and/or the cathode active material.
- the second liquid solvent is selected from a fluorinated carbonate, hydrofluoroether, fluorinated ester, sulfone, nitrile, phosphate, phosphite, alkyl phosphonate, phosphazene, sulfate, siloxane, silane, 1,3-dioxolane (DOL), 1,2-dimethoxyethane (DME), tetraethylene glycol dimethylether (TEGDME), poly(ethylene glycol) dimethyl ether (PEGDME), diethylene glycol dibutyl ether (DEGDBE), 2-ethoxyethyl ether (EEE), sulfone, sulfolane, ethylene carbonate (EC), dimethyl carbonate (DMC), methylethyl carbonate (MEC), diethyl carbonate (DEC), ethyl propionate, methyl propionate, propylene carbonate (PC), gamma.-butyrolactone (
- Desirable polymerizable liquid solvents include fluorinated monomers having unsaturation (double bonds or triple bonds) in the backbone or cyclic structure (e.g., fluorinated vinyl carbonates, fluorinated vinyl monomers, fluorinated esters, fluorinated vinyl esters, and fluorinated vinyl ethers).
- fluorinated vinyl carbonates are given below: These liquid solvents, as a monomer, can be cured in the presence of an initiator (e.g., 2- Hydroxy-2-methyl-1-phenyl-propan-1-one, Ciba DAROCUR-1173, which can be activated by UV or electron beam):
- an initiator e.g., 2- Hydroxy-2-methyl-1-phenyl-propan-1-one, Ciba DAROCUR-1173, which can be activated by UV or electron beam
- the fluorinated carbonate is selected from vinyl- or double bond- containing variants of fluoroethylene carbonate (FEC), DFDMEC, FNPEC, a combination thereof, or a combination thereof with hydrofluoro ether (HFE), trifluoro propylene carbonate (FPC), or methyl nonafluorobutyl ether (MFE), wherein the chemical formulae for FEC, DFDMEC, and FNPEC, respectively (all polymerizable via ring-opening
- R NH2, NO2 or Br
- phenyl and methyl vinyl sulfones can be polymerized with several anionic-type initiators.
- Effective anionic-type catalysts or initiators are n-BuLi, ZnEt2, LiN(CH2)2, NaNH2, and complexes of n-LiBu with ZnEt2 or AlEh.
- a second solvent such as pyridine, sulfolane, toluene or benzene, can be used to dissolve alkyl vinyl sulfones, aryl vinyl sulfones, and other larger sulfone molecules.
- Poly(sulfone)s have high oxygen indices and low smoke emission on burning. Poly(sulfone)s are inherently self-extinguishing materials owing to their highly aromatic character.
- a hydroxy-terminated copoly(ester sulfone) synthesized by melt polycondensation of the diethylene glycol and 4,4-dihydroxydiethoxydiphenyl sulfone with adipic acid can be used as a flame retardant.
- Some examples are difunctional ⁇ -allyl sulfones and 4,4 ⁇ -(m-phenylene- dioxy)bis(benzenesulfonyl chloride): Bisphenol S (BPS) and 4,4′-Dichlorodiphenyl sulfone (DCDPS) are additional examples that can be a part of a polymer structure.
- BPS Bisphenol S
- DCDPS 4,4′-Dichlorodiphenyl sulfone
- the sulfone is selected from TrMS, MTrMS, TMS, or vinyl or double bond-containing variants of TrMS, MTrMS, TMS, EMS, MMES, EMES, EMEES, or a combination thereof; their chemical formulae being given below: (MMES) (EMES) (EMEES)
- the cyclic structure, such as TrMS, MTrMS, and TMS, can be polymerized via ring-opening polymerization with the assistance of an ionic type initiator.
- the nitrile may be selected from AND, GLN, SEN, or a combination thereof and their chemical formulae are given below: (AND) (GLN) (SEN)
- the phosphate (including various derivatives of phosphoric acid), alkyl phosphonate, phosphazene, phosphite, or sulfate is selected from tris(trimethylsilyl) phosphite (TTSPi), alkyl phosphate, triallyl phosphate (TAP), ethylene sulfate (DTD), a combination thereof, or a combination with 1,3-propane sultone (PS) or propene sultone (PES).
- the phosphate, alkyl phosphonate, or phosphazene may be selected from the following:
- R H, NH2, or C1 -C6 alkyl.
- Phosphonate moieties can be readily introduced into vinyl monomers to produce allyl- type, vinyl-type, styrenic-type and (meth)acrylic-type monomers bearing phosphonate groups (e.g., either mono or bisphosphonate).
- These liquid solvents may serve as a first or a second liquid solvent in the electrolyte composition.
- the phosphate, alkyl phosphonate, phosphonic acid, and phosphazene, upon polymerization, are found to be essentially non-flammable.
- Initiators for these phosphazene derivatives can be those of Lewis acids, SbCl 3 , AlCl 3 , or sulfur compounds.
- initiator compounds that can be used in the polymerization of vinylphosphonic acid are peroxides such as benzoyl peroxide, toluy peroxide, di-tert.butyl peroxide, chloro benzoyl peroxide, or hydroperoxides such as methylethyl ketone peroxide, tert.
- butyl hydroperoxide cumene hydroperoxide, hydrogen Superoxide, or azo-bis-iso-butyro nitrile, or sulfinic acids such as p-methoxyphenyl-sulfinic acid, isoamyl-sulfinic acid, benzene-sulfinic acid, or combinations of various of such catalysts with one another and/or combinations for example, with formaldehyde sodium sulfoxylate or with alkali metal sulfites.
- the siloxane or silane may be selected from alkylsiloxane (Si-O), alkyylsilane (Si-C), liquid oligomeric silaxane (-Si-O-Si-), or a combination thereof.
- the reactive additive may further comprise an amide group selected from N,N- dimethylacetamide, N,N-diethylacetamide, N,N-dimethylformamide, N,N-diethylformamide, or a combination thereof.
- the crosslinking agent comprises a compound having at least one reactive group selected from a hydroxyl group, an amino group, an imino group, an amide group, an acrylic amide group, an amine group, an acrylic group, an acrylic ester group, or a mercapto group in the molecule.
- the crosslinking agent is selected from poly(diethanol) diacrylate, poly(ethyleneglycol)dimethacrylate, poly(diethanol) dimethylacrylate, poly(ethylene glycol) diacrylate, lithium hexafluorophosphate (LiPF 6 ), lithium borofluoride (LiBF 4 ), lithium hexafluoroarsenide (LiAsF 6 ), lithium trifluoro-metasulfonate (LiCF 3 SO 3 ), bis-trifluoromethyl sulfonylimide lithium (LiN(CF3SO2)2), lithium bis(oxalato)borate (LiBOB), lithium oxalyldifluoroborate (LiBF2C2O4), lithium oxalyldifluoroborate (LiBF2C2O4), or a combination thereof.
- the initiator may be selected from an azo compound (e.g., azodiisobutyronitrile, AIBN), azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate, benzoyl peroxide tert- butyl peroxide and methyl ethyl ketone peroxide, benzoyl peroxide (BPO), bis(4-tert- butylcyclohexyl)peroxydicarbonate, t-amyl peroxypivalate, 2,2′-azobis-(2,4- dimethylvaleronitrile), 2,2′-azobis-(2-methylbutyronitrile), 1,1-azobis(cyclohexane-1- carbonitrile, benzoylperoxide (BPO), hydrogen peroxide, dodecamoyl peroxide, isobutyryl peroxide, cumene hydroperoxide, tert-butyl peroxypivalate, diis
- the lithium salt may be selected from lithium perchlorate (LiClO 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium borofluoride (LiBF 4 ), lithium hexafluoroarsenide (LiAsF6), lithium trifluoro-metasulfonate (LiCF3SO3), bis-trifluoromethyl sulfonylimide lithium (LiN(CF3SO2)2), lithium bis(oxalato)borate (LiBOB), lithium oxalyldifluoroborate (LiBF2C2O4), lithium nitrate (LiNO3), Li-fluoroalkyl-phosphates (LiPF 3 (CF 2 CF 3 ) 3 ), lithium bisperfluoro-ethylsulfonylimide (LiBETI), lithium bis(trifluoromethanesulphonyl)imide, lithium bis(fluoros), lithium perchlorate (Li
- the crosslinking agent preferably comprises a compound having at least one reactive group selected from a hydroxyl group, an amino group, an imino group, an amide group, an amine group, an acrylic group, or a mercapto group in the molecule.
- the amine group is preferably selected from Chemical Formula 2: (Chemical Formula 2).
- the reactive additive may further comprise a chemical species represented by Chemical Formula 3 or a derivative thereof and the crosslinking agent comprises a chemical species represented by Chemical Formula 4 or a derivative thereof: (Chemical Formula 4) where R1 is hydrogen or methyl group, and R2 and R3 are each independently one selected from the group consisting of hydrogen, methyl, ethyl, propyl, dialkylaminopropyl (--C3 H6 N(R')2) and hydroxyethyl (CH 2 CH 2 OH) groups, and R 4 and R 5 are each independently hydrogen or methyl group, and n is an integer from 3 to 30, wherein R' is C 1 ⁇ C 5 alkyl group.
- Suitable vinyl monomers having Chemical formula 3 include acrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N-isopropylacrylamide, N,N-dimethylamino- propylacrylamide, and N-acryloylmorpholine. Among these species, N-isopropylacrylamide and N-acryloylmorpholine are preferred.
- the crosslinking agent is preferably selected from N,N-methylene bisacrylamide, epichlorohydrin, 1,4-butanediol diglycidyl ether, tetrabutylammonium hydroxide, cinnamic acid, ferric chloride, aluminum sulfate octadecahydrate, diepoxy, dicarboxylic acid compound, poly(potassium 1-hydroxy acrylate) (PKHA), glycerol diglycidyl ether (GDE), ethylene glycol, polyethylene glycol, polyethylene glycol diglycidyl ether (PEGDE), citric acid (Formula 4 below), acrylic acid, methacrylic acid, a derivative compound of acrylic acid, a derivative compound of methacrylic acid (e.g.
- polyhydroxyethylmethacrylate polyhydroxyethylmethacrylate), glycidyl functions, N,N'- Methylenebisacrylamide (MBAAm), Ethylene glycol dimethacrylate (EGDMAAm), isobomyl methacrylate, poly (acrylic acid) (PAA), methyl methacrylate, isobomyl acrylate, ethyl methacrylate, isobutyl methacrylate, n-Butyl methacrylate, ethyl acrylate, 2-Ethyl hexyl acrylate, n-Butyl acrylate, a diisocyanate (e.g.
- the electrolyte may further comprise a flame-retardant additive, different in composition than the liquid solvent.
- Flame-retardant additives are intended to inhibit or stop polymer pyrolysis and electrolyte combustion processes by interfering with the various mechanisms involved—heating, ignition, and propagation of thermal degradation.
- the flame-retardant additive may be selected from a halogenated flame retardant, phosphorus-based flame retardant, melamine flame retardant, metal hydroxide flame retardant, silicon-based flame retardant, phosphate flame retardant, biomolecular flame retardant, or a combination thereof.
- flame retardant that can be physically or chemically incorporated into the elastic polymer.
- the main families of flame retardants are based on compounds containing: Halogens (Bromine and Chlorine), Phosphorus, Nitrogen, Intumescent Systems, Minerals (based on aluminum and magnesium), and others (e.g., Borax, Sb2O3, and nanocomposites).
- Antimony trioxide is a good choice, but other forms of antimony such as the pentoxide and sodium antimonate may also be used.
- reactive polysiloxane can chemically react with EPDM type elastic polymer and become part of the crosslinked network polymer.
- flame-retarding group modified polysiloxane itself is an elastic polymer composite containing a flame retardant according to an embodiment of instant disclosure. Both reactive and additive types of flame retardants can be further separated into several different classes: 1) Minerals: Examples include aluminum hydroxide (ATH), magnesium hydroxide (MDH), huntite and hydromagnesite, various hydrates, red phosphorus and boron compounds (e.g. borates).
- Organo-halogen compounds This class includes organochlorines such as chlorendic acid derivatives and chlorinated paraffins; organobromines such as decabromodiphenyl ether (decaBDE), decabromodiphenyl ethane (a replacement for decaBDE), polymeric brominated compounds such as brominated polystyrenes, brominated carbonate oligomers (BCOs), brominated epoxy oligomers (BEOs), tetrabromophthalic anyhydride, tetrabromobisphenol A (TBBPA), and hexabromocyclododecane (HBCD).
- organochlorines such as chlorendic acid derivatives and chlorinated paraffins
- organobromines such as decabromodiphenyl ether (decaBDE), decabromodiphenyl ethane (a replacement for decaBDE)
- polymeric brominated compounds such as brominated polystyrenes, bromin
- Organophosphorus compounds This class includes organophosphates such as triphenyl phosphate (TPP), resorcinol bis(diphenylphosphate) (RDP), bisphenol A diphenyl phosphate (BADP), and tricresyl phosphate (TCP); phosphonates such as dimethyl methylphosphonate (DMMP); and phosphinates such as aluminum diethyl phosphinate.
- TPP triphenyl phosphate
- RDP resorcinol bis(diphenylphosphate)
- BADP bisphenol A diphenyl phosphate
- TCP tricresyl phosphate
- phosphonates such as dimethyl methylphosphonate (DMMP)
- phosphinates such as aluminum diethyl phosphinate.
- compounds contain both phosphorus and a halogen.
- Such compounds include tris(2,3-dibromopropyl) phosphate (brominated tris) and chlorinated organophosphates such as tris(1,3-dichloro- 2-propyl)phosphate (chlorinated tris or TDCPP) and tetrakis(2-chlorethyl) dichloroisopentyldiphosphate (V6).
- Organic compounds such as carboxylic acid and dicarboxylic acid
- the mineral flame retardants mainly act as additive flame retardants and do not become chemically attached to the surrounding system (the polymer). Most of the organohalogen and organophosphate compounds also do not react permanently to attach themselves into the polymer.
- the flame-retardant additive is in a form of encapsulated particles comprising the additive encapsulated by a shell of coating material that is breakable or meltable when exposed to a temperature higher than a threshold temperature (e.g., flame or fire temperature induced by internal shorting).
- the encapsulating material is a substantially lithium ion-impermeable and liquid electrolyte-impermeable coating material.
- the encapsulating or micro-droplet formation processes The flame-retardant additive-to-liquid solvent ratio in the mixture is from 1/95 to 99/1 by weight, preferably from 10/85 to 80/20 by weight, further preferably from 20/80 to 70/20 by weight, and most preferably from 35/65 to 65/35 by weight.
- the polymer in the electrolyte may form a mixture, copolymer, semi-interpenetrating network, or simultaneous interpenetrating network with a second polymer selected from poly(ethylene oxide), polypropylene oxide, poly(ethylene glycol), poly(acrylonitrile), poly(methyl methacrylate), poly(vinylidene fluoride), poly bis-methoxy ethoxyethoxide- phosphazene, polyvinyl chloride, polydimethylsiloxane, poly(vinylidene fluoride)- hexafluoropropylene, cyanoethyl poly(vinyl alcohol), a pentaerythritol tetraacrylate-based polymer, an aliphatic polycarbonate, a single Li-ion conducting solid polymer electrolyte with a carboxylate anion, a sulfonylimide anion, or sulfonate anion, a crosslinked electrolyte of poly(ethylene
- the electrolyte further comprises particles of an inorganic solid electrolyte material having a particle size from 2 nm to 30 ⁇ m, wherein the particles of inorganic solid electrolyte material are dispersed in the polymer or chemically bonded by the polymer.
- the particles of inorganic solid electrolyte material are preferably selected from an oxide type, sulfide type, hydride type, halide type, borate type, phosphate type, lithium phosphorus oxynitride (LiPON), garnet-type, lithium superionic conductor (LISICON) type, sodium superionic conductor (NASICON) type, or a combination thereof.
- the inorganic solid electrolytes that can be incorporated into an elastic polymer protective layer (or into the electrolyte) include, but are not limited to, perovskite-type, NASICON-type, garnet-type and sulfide-type materials.
- a representative and well-known perovskite solid electrolyte is Li 3x La 2/3 ⁇ x TiO 3 , which exhibits a lithium-ion conductivity exceeding 10 ⁇ 3 S/cm at room temperature.
- This material has been deemed unsuitable in lithium batteries because of the reduction of Ti 4+ on contact with lithium metal. However, we have found that this material, when dispersed in an elastic polymer, does not suffer from this problem.
- the sodium superionic conductor (NASICON)-type compounds include a well-known Na 1 + x Zr 2 Si x P 3 ⁇ x O 12 . These materials generally have an AM 2 (PO 4 ) 3 formula with the A site occupied by Li, Na or K. The M site is usually occupied by Ge, Zr or Ti.
- LiTi 2 (PO 4 ) 3 system has been widely studied as a solid state electrolyte for the lithium-ion battery.
- the Li 1 + x Al x Ge 2 ⁇ x (PO 4 ) 3 system is also an effective solid state due to its relatively wide electrochemical stability window.
- NASICON-type materials are considered as suitable solid electrolytes for high-voltage solid electrolyte batteries.
- Garnet-type materials have the general formula A 3 B 2 Si 3 O 12 , in which the A and B cations have eightfold and sixfold coordination, respectively.
- the Li 6.5 La 3 Zr 1.75 Te 0.25 O 12 compounds have a high ionic conductivity of 1.02 ⁇ 10 ⁇ 3 S/cm at room temperature.
- the sulfide-type solid electrolytes include the Li2S–SiS2 system.
- the highest reported conductivity in this type of material is 6.9 ⁇ 10 ⁇ 4 S/cm, which was achieved by doping the Li 2 S– SiS 2 system with Li 3 PO 4 .
- the sulfide type also includes a class of thio-LISICON ( lithium superionic conductor) crystalline material represented by the Li2S–P2S5 system.
- the chemical stability of the Li 2 S–P 2 S 5 system is considered as poor, and the material is sensitive to moisture (generating gaseous H 2 S).
- the stability can be improved by the addition of metal oxides.
- the stability is also significantly improved if the Li2S–P2S5 material is dispersed in an elastic polymer.
- the polymer has a lithium ion conductivity no less than 10 -5 S/cm, more preferably no less than 10 -4 S/cm, and further preferably no less than 10 -3 S/cm.
- the disclosed lithium battery can be a lithium-ion battery or a lithium metal battery, the latter having lithium metal as the primary anode active material.
- the lithium metal battery can have lithium metal implemented at the anode when the cell is made. Alternatively, the lithium may be stored in the cathode active material and the anode side is lithium metal-free initially.
- the anode-less lithium cell is in an as-manufactured or fully discharged state according to certain embodiments of the present disclosure.
- the cell comprises an anode current collector 12 (e.g., Cu foil), a separator, a cathode layer 16 comprising a cathode active material, an optional conductive additive (not shown), an optional resin binder (not shown), and an electrolyte (dispersed in the entire cathode layer and in contact with the cathode active material), and a cathode current collector 18 that supports the cathode layer 16.
- anode current collector 12 e.g., Cu foil
- separator e.g., a separator
- a cathode layer 16 comprising a cathode active material
- an optional conductive additive not shown
- an optional resin binder not shown
- electrolyte electrolyte
- the cell comprises an anode current collector 12, lithium metal 20 plated on a surface (or two surfaces) of the anode current collector 12 (e.g., Cu foil), a separator 15, a cathode layer 16, and a cathode current collector 18 supporting the cathode layer.
- the lithium metal comes from the cathode active material (e.g., LiCoO2 and LiMn2O4) that contains Li element when the cathode is made.
- the cathode active material e.g., LiCoO2 and LiMn2O4
- anode-less lithium cell One unique feature of the presently disclosed anode-less lithium cell is the notion that there is substantially no anode active material and no lithium metal is present when the battery cell is made.
- the commonly used anode active material such as an intercalation type anode material (e.g., graphite, carbon particles, Si, SiO, Sn, SnO2, Ge, etc.), P, or any conversion-type anode material, is not included in the cell.
- the anode only contains a current collector or a protected current collector.
- lithium metal e.g., Li particle, surface-stabilized Li particle, Li foil, Li chip, etc.
- cathode e.g., Li element in LiCoO2, LiMn2O4, lithium iron phosphate, lithium polysulfides, lithium polyselenides, etc.
- a housing e.g., a stainless steel hollow cylinder or an Al/plastic laminated envelop
- lithium ions are released from these Li-containing compounds (cathode active materials) in the cathode, travel through the electrolyte/separator into the anode side, and get deposited on the surfaces of an anode current collector.
- anode-less cell is much simpler and more cost-effective to produce since there is no need to have a layer of anode active material (e.g., graphite particles, along with a conductive additive and a binder) pre-coated on the Cu foil surfaces via the conventional slurry coating and drying procedures.
- anode active material e.g., graphite particles, along with a conductive additive and a binder
- the anode materials and anode active layer manufacturing costs can be saved.
- the weight and volume of the cell can be significantly reduced, thereby increasing the gravimetric and volumetric energy density of the cell.
- the anode current collector may be selected from a foil, perforated sheet, or foam of Cu, Ni, stainless steel, Al, graphene, graphite, graphene-coated metal, graphite-coated metal, carbon- coated metal, or a combination thereof.
- the current collector is a Cu foil, Ni foil, stainless steel foil, graphene-coated Al foil, graphite-coated Al foil, or carbon-coated Al foil.
- the anode current collector typically has two primary surfaces. Preferably, one or both of these primary surfaces is deposited with multiple particles or coating of a lithium-attracting metal (lithiophilic metal), wherein the lithium-attracting metal, preferably having a diameter or thickness from 1 nm to 10 ⁇ m, is selected from Au, Ag, Mg, Zn, Ti, K, Al, Fe, Mn, Co, Ni, Sn, V, Cr, an alloy thereof, or a combination thereof.
- a lithium-attracting metal preferably having a diameter or thickness from 1 nm to 10 ⁇ m
- This deposited metal layer may be further deposited with a layer of graphene that covers and protects the multiple particles or coating of the lithiophilic metal.
- the graphene layer may comprise graphene sheets selected from single-layer or few- layer graphene, wherein the few-layer graphene sheets are commonly defined to have 2-10 layers of stacked graphene planes having an inter-plane spacing d002 from 0.3354 nm to 0.6 nm as measured by X-ray diffraction.
- the single-layer or few-layer graphene sheets may contain a pristine graphene material having essentially zero % of non-carbon elements, or a non-pristine graphene material having 0.001% to 45% by weight of non-carbon elements.
- the non-pristine graphene may be selected from graphene oxide, reduced graphene oxide, graphene fluoride, graphene chloride, graphene bromide, graphene iodide, hydrogenated graphene, nitrogenated graphene, doped graphene, chemically functionalized graphene, or a combination thereof.
- the graphene layer may comprise graphene balls and/or graphene foam.
- the graphene layer has a thickness from 1 nm to 50 ⁇ m and/or has a specific surface area from 5 to 1000 m 2 /g (more preferably from 10 to 500 m 2 /g).
- the anode active material may be selected from the group consisting of: (a) silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), phosphorus (P), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), nickel (Ni), cobalt (Co), and cadmium (Cd); (b) alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Ni, Co, or Cd with other elements; (c) oxides, carbides, nitrides, sulfides, phosphides, selenides, and tellurides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Fe, Ni, Co, V, or Cd, and their mixtures, composites, or lithium-
- a solid-like or quasi-solid electrolyte e.g., first electrolyte in the cathode.
- a quasi-solid electrolyte exhibits a vapor pressure less than 0.01 kPa and often less than 0.001 kPa (when measured at 20°C) and less than 0.1 kPa and often less than 0.01 kPa (when measured at 100°C).
- the vapor molecules are practically too few to be detected.
- a highly significant observation is that the polymer derived (polymerized) from an otherwise volatile solvent (monomer) can dramatically curtail the amount of volatile solvent molecules that can escape into the vapor phase in a thermodynamic equilibrium condition. In many cases, this has effectively prevented any flammable gas molecules from initiating a flame even at an extremely high temperature.
- the flash point of the quasi-solid or solid-state electrolyte is typically at least 100 degrees (often > 150 degrees) higher than the flash point of the neat organic solvent without polymerization.
- the interfacial impedance can be significantly reduced. Additionally, the local high viscosity induced by presence of a polymer can increase the pressure from the electrolyte to inhibit dendrite growth, potentially resulting in a more uniform deposition of lithium ions on the surface of the anode. The high viscosity could also limit anion convection near the deposition area, promoting more uniform deposition of Li ions.
- this electrolyte is capable of inhibiting lithium polysulfide dissolution at the cathode and migration to the anode of a Li-S cell, thus overcoming the polysulfide shuttle phenomenon and allowing the cell capacity not to decay significantly with time. Consequently, a coulombic efficiency nearing 100% along with long cycle life can be achieved.
- a concentrated electrolyte and a crosslinked polymer is used, the solubility of lithium polysulfide will be reduced significantly.
- the lithium salt may be selected from lithium perchlorate (LiClO4), lithium hexafluorophosphate (LiPF6), lithium borofluoride (LiBF4), lithium hexafluoroarsenide (LiAsF6), lithium trifluoro-methanesulfonate (LiCF 3 SO 3 ), bis-trifluoromethyl sulfonylimide lithium (LiN(CF3SO2)2), lithium bis(oxalato)borate (LiBOB), lithium oxalyldifluoroborate (LiBF2C2O4), lithium nitrate (LiNO3), Li-fluoroalkyl-phosphates (LiPF3(CF2CF3)3), lithium bisperfluoro- ethylsulfonylimide (LiBETI), lithium bis(trifluoromethanesulphonyl)imide, lithium bis(fluorosulphonyl)imide, lithium trifluorome
- the ionic liquid is composed of ions only.
- Ionic liquids are low melting temperature salts that are in a molten or liquid state when above a desired temperature. For instance, an ionic salt is considered as an ionic liquid if its melting point is below 100°C. If the melting temperature is equal to or lower than room temperature (25oC), the salt is referred to as a room temperature ionic liquid (RTIL).
- RTIL room temperature ionic liquid
- the IL-based lithium salts are characterized by weak interactions, due to the combination of a large cation and a charge-delocalized anion. This results in a low tendency to crystallize due to flexibility (anion) and asymmetry (cation).
- ILs may be used as a co-solvent (not as a salt) to work with the first organic solvent of the present disclosure.
- a well-known ionic liquid is formed by the combination of a 1-ethyl-3- methyl-imidazolium (EMI) cation and an N,N-bis(trifluoromethane)sulphonamide (TFSI) anion.
- EMI 1-ethyl-3- methyl-imidazolium
- TFSI N,N-bis(trifluoromethane)sulphonamide
- This combination gives a fluid with an ionic conductivity comparable to many organic electrolyte solutions, a low decomposition propensity and low vapor pressure up to ⁇ 300-400°C. This implies a generally low volatility and non-flammability and, hence, a much safer electrolyte solvent for batteries.
- Ionic liquids are basically composed of organic or inorganic ions that come in an unlimited number of structural variations owing to the preparation ease of a large variety of their components.
- various kinds of salts can be used to design the ionic liquid that has the desired properties for a given application. These include, among others, imidazolium, pyrrolidinium and quaternary ammonium salts as cations and bis(trifluoromethanesulphonyl) imide, bis(fluorosulphonyl)imide and hexafluorophosphate as anions.
- Useful ionic liquid-based lithium salts may be composed of lithium ions as the cation and bis(trifluoromethanesulphonyl)imide, bis(fluorosulphonyl)imide and hexafluorophosphate as anions.
- lithium trifluoromethanesulfonimide LiTFSI
- ionic liquids come in different classes that include three basic types: aprotic, protic and zwitterionic types, each one suitable for a specific application.
- RTILs room temperature ionic liquids
- RTILs include, but are not limited to, tetraalkylammonium, di, tri, and tetra-alkylimidazolium, alkylpyridinium, dialkyl-pyrrolidinium, dialkylpiperidinium, tetraalkylphosphonium, and trialkylsulfonium.
- RTILs include, but are not limited to, BF 4 -, B(CN) 4 -, CH 3 BF 3 -, CH 2 CHBF 3 -, CF 3 BF 3 -, C 2 F 5 BF 3 -, n- C 3 F 7 BF 3 -, n-C 4 F 9 BF 3 -, PF 6 -, CF 3 CO 2 -, CF 3 SO 3 -, N(SO 2 CF 3 ) 2 -, N(COCF 3 )(SO 2 CF 3 )-, N(SO 2 F) 2 -, N(CN)2-, C(CN)3-, SCN-, SeCN-, CuCl2-, AlCl4-, F(HF)2.3-, etc.
- RTILs with good working conductivities.
- RTILs can possess archetypical properties such as high intrinsic ionic conductivity, high thermal stability, low volatility, low (practically zero) vapor pressure, non-flammability, the ability to remain liquid at a wide range of temperatures above and below room temperature, high polarity, high viscosity, and wide electrochemical windows.
- the cathode active material may contain lithium polysulfide or sulfur. If the cathode active material includes lithium-containing species (e.g., lithium polysulfide) when the cell is made, there is no need to have a lithium metal pre- implemented in the anode. There are no particular restrictions on the types of cathode active materials that can be used in the presently disclosed lithium battery, which can be a primary battery or a secondary battery.
- the rechargeable lithium metal or lithium-ion cell may preferably contain a cathode active material selected from, as examples, a layered compound LiMO 2 , spinel compound LiM2O4, olivine compound LiMPO4, silicate compound Li2MSiO4, Tavorite compound LiMPO4F, borate compound LiMBO3, or a combination thereof, wherein M is a transition metal or a mixture of multiple transition metals.
- the cathode active material may be selected from a metal oxide, a metal oxide-free inorganic material, an organic material, a polymeric material, sulfur, lithium polysulfide, selenium, or a combination thereof.
- the metal oxide-free inorganic material may be selected from a transition metal fluoride, a transition metal chloride, a transition metal dichalcogenide, a transition metal trichalcogenide, or a combination thereof.
- the cathode active material is selected from FeF 3 , FeCl 3 , CuCl 2 , TiS 2 , TaS 2 , MoS 2 , NbSe 3 , MnO 2 , CoO 2 , an iron oxide, a vanadium oxide, or a combination thereof, if the anode contains lithium metal as the anode active material.
- the vanadium oxide may be preferably selected from the group consisting of VO2, LixVO2, V2O5, LixV2O5, V3O8, LixV3O8, Li x V 3 O 7 , V 4 O 9 , Li x V 4 O 9 , V 6 O 13 , Li x V 6 O 13 , their doped versions, their derivatives, and combinations thereof, wherein 0.1 ⁇ x ⁇ 5.
- a lithium source implemented in the cathode side to begin with. This can be any compound that contains a high lithium content, or a lithium metal alloy, etc.
- the cathode active material may be selected to contain a layered compound LiMO2, spinel compound LiM2O4, olivine compound LiMPO 4 , silicate compound Li 2 MSiO 4 , Tavorite compound LiMPO 4 F, borate compound LiMBO 3 , or a combination thereof, wherein M is a transition metal or a mixture of multiple transition metals.
- cathode active materials comprise lithium nickel manganese oxide (LiNi a Mn 2-a O 4 , 0 ⁇ a ⁇ 2), lithium nickel manganese cobalt oxide (LiNi n Mn m Co 1-n-m O 2 , 0 ⁇ n ⁇ 1, 0 ⁇ m ⁇ 1, n+m ⁇ 1), lithium nickel cobalt aluminum oxide (LiNicCodAl1-c-dO2, 0 ⁇ c ⁇ 1, 0 ⁇ d ⁇ 1, c+d ⁇ 1), lithium manganate (LiMn2O4), lithium iron phosphate (LiFePO4), lithium manganese oxide (LiMnO 2 ), lithium cobalt oxide (LiCoO 2 ), lithium nickel cobalt oxide (LiNi p Co 1-p O 2 , 0 ⁇ p ⁇ 1), or lithium nickel manganese oxide (LiNiqMn2-qO4, 0 ⁇ q ⁇ 2).
- the cathode active material preferably contains an inorganic material selected from: (a) bismuth selenide or bismuth telluride, (b) transition metal dichalcogenide or trichalcogenide, (c) sulfide, selenide, or telluride of niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, cobalt, manganese, iron, nickel, or a transition metal; (d) boron nitride, or (e) a combination thereof.
- an inorganic material selected from: (a) bismuth selenide or bismuth telluride, (b) transition metal dichalcogenide or trichalcogenide, (c) sulfide, selenide, or telluride of niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, cobalt, manganese, iron, nickel, or a transition metal; (
- the cathode active material contains an organic material or polymeric material selected from Poly(anthraquinonyl sulfide) (PAQS), lithium oxocarbons (including squarate, croconate, and rhodizonate lithium salts), oxacarbon (including quinines, acid anhydride, and nitrocompound), 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA), poly(anthraquinonyl sulfide), pyrene-4,5,9,10-tetraone (PYT), polymer-bound PYT, Quino(triazene), redox-active organic material (redox-active structures based on multiple adjacent carbonyl groups (e.g., “C 6 O 6 ”-type structure, oxocarbons), Tetracyanoquinodimethane (TCNQS), Li oxocarbons (including squarate, croconate, and rho
- the thioether polymer may be selected from Poly[methanetetryl-tetra(thiomethylene)] (PMTTM), Poly(2,4-dithiopentanylene) (PDTP), or Poly(ethene-1,1,2,2-tetrathiol) (PETT) as a main-chain thioether polymer, in which sulfur atoms link carbon atoms to form a polymeric backbones.
- the side-chain thioether polymers have polymeric main-chains that consist of conjugating aromatic moieties, but having thioether side chains as pendants.
- Poly(2-phenyl-1,3-dithiolane) PPDT
- Poly(1,4-di(1,3-dithiolan-2-yl)benzene) PPDTB
- poly(tetrahydrobenzodithiophene) PTHBDT
- poly[1,2,4,5-tetrakis(propylthio)benzene] PEDTT
- PEDTT poly[3,4(ethylenedithio)thiophene]
- PEDTT has polythiophene backbone, linking cyclo-thiolane on the 3,4- position of the thiophene ring.
- the cathode active material contains a phthalocyanine compound selected from copper phthalocyanine, zinc phthalocyanine, tin phthalocyanine, iron phthalocyanine, lead phthalocyanine, nickel phthalocyanine, vanadyl phthalocyanine, fluorochromium phthalocyanine, magnesium phthalocyanine, manganous phthalocyanine, dilithium phthalocyanine, aluminum phthalocyanine chloride, cadmium phthalocyanine, chlorogallium phthalocyanine, cobalt phthalocyanine, silver phthalocyanine, a metal-free phthalocyanine, a chemical derivative thereof, or a combination thereof.
- a phthalocyanine compound selected from copper phthalocyanine, zinc phthalocyanine, tin phthalocyanine, iron phthalocyanine, lead phthalocyanine, nickel phthalocyanine, vanadyl phthalocyanine, fluorochromium phthalocyanine,
- the present disclosure also provides an electrolyte composition
- a first solution comprising at least a polymerizale liquid solvent
- a second solution comprising an initiator and/or crosslinking agent, a lithium salt, and a second non-aqueous liquid solvent (e.g., an organic solvent or ionic liquid solvent); wherein the first solution and the second solution are stored separately before the first solution and the second solution are mixed to form the electrolyte.
- a first solution comprising at least a polymerizale liquid solvent
- a second solution comprising an initiator and/or crosslinking agent, a lithium salt, and a second non-aqueous liquid solvent (e.g., an organic solvent or ionic liquid solvent)
- a second non-aqueous liquid solvent e.g., an organic solvent or ionic liquid solvent
- the first liquid solvent may have a lower flash point (higher flammability), a higher vapor pressure, a higher dielectric constant, or a higher solubility of the lithium salt as compared with the second liquid solvent. Further, the lithium salt may be dissolved in the first solvent, the second solvent, or both.
- the disclosure further provides a method of producing a rechargeable lithium cell (as illustrated in FIG.1(A)), the method comprising: (a) providing a cathode; (b) providing an anode; (c) combining the cathode and the anode to form a dry cell; and (d) introducing (e.g., injecting) the presently disclosed electrolyte composition into the dry cell and polymerizing and/or crosslinking the reactive additive to produce the rechargeable lithium cell.
- Step (d) may comprise partially or totally removing any un-polymerized liquid solvent, if so desired.
- step (a) may be selected from any commonly used cathode production process.
- the process may include (i) mixing particles of a cathode active material, a conductive additive, an optional resin binder, optional particles of a solid inorganic electrolyte powder, and an optional flame retardant in a liquid medium (e.g., an organic solvent, such as NMP) to form a slurry; and (ii) coating the slurry on a cathode current collector (e.g., an Al foil) and removing the solvent.
- a liquid medium e.g., an organic solvent, such as NMP
- a cathode current collector e.g., an Al foil
- the anode in step (b) may be produced in a similar manner, but using particles of an anode active material (e.g., particles of Si, SiO, Sn, SnO 2 , graphite, and carbon).
- Step (c) may entail combining the anode, a porous separator, the cathode, along with their respective current collectors, to form a unit cell which is enclosed in a protective housing to form a dry cell. As illustrated in FIG.
- the disclosure also provides a method of producing the disclosed rechargeable lithium cell, the method comprising: (A) mixing particles of a cathode active material, an optional conductive additive (typically required in the cathode), an optional binder (optional but not required since, upon polymerization and/or crosslinking, the reactive additive becomes a binder that bonds the solid particles in the electrode together), an optional flame retardant, optional particles of an inorganic solid electrolyte powder, a reactive additive, and a lithium salt to form a cathode, wherein the reactive additive comprises at least one polymerizable solvent and a curing agent or initiator; (B) providing an anode; (C) combining the cathode and the anode to form a cell; and (D) polymerizing and/or crosslinking the reactive additive, prior to or after step (C), to produce the rechargeable lithium cell.
- A mixing particles of a cathode active material, an optional conductive additive (typically required in the cathode), an optional binder
- particles of a cathode active material, an optional conductive additive, an optional binder, an optional flame retardant, a lithium salt, and optional particles of an inorganic solid electrolyte powder may be dissolved or dispersed in a reactive additive (containing at least a polymerizable liquid solvent) to form a slurry.
- a reactive additive containing at least a polymerizable liquid solvent
- the slurry is attached to or coated on a primary surface or both primary surfaces of a cathode current collector (e.g., Al foil) to form a cathode.
- step (B) comprises a procedure of mixing particles of an anode active material, an optional conductive additive (not required if the anode active material is a carbon or graphite material), an optional binder (not required since, upon polymerization and/or crosslinking, the reactive additive becomes a binder that bonds the solid particles in the electrode together), an optional flame retardant, optional particles of an inorganic solid electrolyte powder, a reactive additive (the same or different reactive as used in the cathode, and a lithium salt to form an anode.
- the method further comprises polymerizing and/or crosslinking the reactive additive, prior to or after step (C), to produce the rechargeable lithium cell.
- step (A) further comprises adding particles of an inorganic solid electrolyte powder in the cathode.
- Step (B) may further comprise adding particles of an inorganic solid electrolyte powder in the anode. Illustrated in FIG. 1(D) is yet another embodiment of the present disclosure, which is a method of producing the disclosed rechargeable lithium cell.
- the method comprises: (A) mixing particles of a cathode active material, an optional conductive additive (typically required in the cathode), an optional binder (not required since the reactive additive becomes a binder upon polymerization and/or crosslinking), an optional flame retardant, optional particles of an inorganic solid electrolyte powder, and a reactive additive to form a cathode (preferably containing at least one cathode active material layer supported on a current collector), wherein the reactive additive comprises at least one polymerizable liquid solvent; (B) providing an anode; (C) combining the cathode, an optional separator, the anode, and a protective housing to form a cell; and (D) injecting a liquid mixture of a lithium salt, an initiator or crosslinking agent, an optional flame retardant (if in a liquid state) and a second non-aqueous liquid solvent into the cell and polymerizing and/or crosslinking the reactive additive to produce the rechargeable lithium cell.
- A mixing particles of a
- step (B) may comprise mixing particles of an anode material (e.g., Si, SiO, graphite, carbon particles, etc.), an optional conductive additive, an optional binder, an optional flame retardant, optional particles of an inorganic solid electrolyte powder, and a reactive additive to form at least one anode active layer supported on an anode current collector (e.g., Cu foil).
- anode material e.g., Si, SiO, graphite, carbon particles, etc.
- an optional conductive additive e.g., Si, SiO, graphite, carbon particles, etc.
- an optional binder e.g., an optional flame retardant
- optional particles of an inorganic solid electrolyte powder e.g., Cu foil
- EXAMPLE 1a Lithium metal cell featuring an in situ polymerized FVC and PEGDA
- fluorinated vinylene carbonate (FVC) and poly(ethyleneglycol) diacrylate (PEGDA) were stirred under the protection of argon gas until a homogeneous solution was obtained.
- lithium hexafluoro phosphate was then added and dissolved in the above solution to obtain a reactive mixture solution, wherein the weight fractions of fluorinated vinylene carbonate, polyethyleneglycol diacrylate, and lithium hexafluoro phosphate were 85wt%, 10wt%, and 5wt%, respectively.
- This cell was then injected with the reactive solution mixture (10% by weight based on the total cell weight). The cell was then irradiated with electron beam at room temperature until a total dosage of 40 Gy was reached. In-situ polymerization of the polymerizable liquid solvent in the battery cell was accomplished.
- EXAMPLE 1b Similar procedure as in Example 1a was followed, but the polymerizable solvent was a fluorinated vinyl carbonate, given below: which was cured with an initiator, 2-Hydroxy-2-methyl-1-phenyl-propan-1-one (Ciba DAROCUR-1173), with the assistance of electron beam irradiation.
- EXAMPLE 2a Lithium-ion cell featuring an in situ polymerized phenyl vinyl sulfide
- the lithium-ion cells prepared in this example comprise an anode of meso-carbon micro- beads (MCMB, an artificial graphite supplied from China Steel Chemical Co. Taiwan), a cathode of NCM-622 particles, and a porous PE/PP membrane as a separator.
- MCMB meso-carbon micro- beads
- NCM-622 particles a cathode of NCM-622 particles
- a porous PE/PP membrane as a separator.
- EXAMPLE 2b Lithium-ion cell featuring an in situ polymerized ethyl vinyl sulfone In situ reaction of vinyl sulfones (e.g., ethyl vinyl sulfone, EVS), acrylates (e.g.
- hexanethiol, HA) and/or 1-Hexanethiol (HT) as a co-reactant or curing agent, and triethylamine (TEA) as an initiator was investigated.
- Hexanethiol (HT), ethyl vinyl sulfone (EVS) and hexyl acrylate (HA) were prepared at a molar ratio from 1 : 1 : 0.1 (no unreacted HA) to 1: 1 :0.3 (20% of HA remained unreacted).
- LiCF3SO3 lithium trifluoro- methanesulfonate
- Varying stoichiometric amounts of vinyl sulfone and acrylate were added to the mixture, which was mixed vigorously and then introduced into a battery cell to start the thiol–Michael addition reaction. With a 2.0% TEA initiator, the reaction can be concluded in approximately 20-40 minutes, generating a network of crosslinked chains.
- the use of acrylates via thiol–Michael addition reaction in ternary systems was used to control gelation behavior in crosslinked polymer networks formed by thiol–Michael addition reactions.
- the lithium-ion cells prepared in this example comprise an anode of meso-carbon micro- beads (MCMB, an artificial graphite), a cathode of NCM-622 particles, and a porous PE/PP membrane as a separator.
- MCMB meso-carbon micro- beads
- PE/PP membrane a porous PE/PP membrane as a separator.
- EXAMPLE 2c Lithium-ion cell featuring an in situ polymerized phenyl vinyl sulfone
- the lithium-ion cells prepared in this example comprise an anode of graphene-protected Si particles, a cathode of NCM-622 particles, and a porous PE/PP membrane as a separator.
- Phenyl vinyl sulfone can be polymerized with several anionic-type initiators; e.g., n-BuLi, ZnEt2, LiN(CH2)2, and NaNH2.
- the second solvent may be selected from pyridine, sulfolane, toluene or benzene, which may be removed before or after polymerization.
- a mixture of PVS, n-BuLi (1.0%), LiBF 4 (0.5 M), and sulfolane was thoroughly mixed and injected into the battery cell, which was maintained at 30°C overnight to cure the polymer.
- EXAMPLE 3 Quasi-solid and solid-state electrolytes from vinylphosphonic acid (VPA) and triethylene glycol dimethacrylate (TEGDA) or acrylic acid (AA)
- VPA vinylphosphonic acid
- TAGDA triethylene glycol dimethacrylate
- acrylic acid (AA) acrylic acid
- AA vinylphosphonic acid
- benzoyl peroxide benzoyl peroxide
- a vessel provided with a reflux condenser 150 parts vinylphosphonic acid were dissolved in 150 parts isopropanol and heated for 5 hours at 90°C together with 0.75 parts benzoyl peroxide and 20 parts of lithium bis(oxalato)borate (LiBOB). A very viscous clear solution of polyvinylphosphonic acid was obtained.
- a similar reactive mixture was added with a desirable amount (e.g., 10-50 parts) of AA or TEGDA as a co-monomer.
- a desirable amount e.g. 10-50 parts
- For the preparation of lithium cells dry cells were injected with the reactive mass, followed by removal of most of the isopropanol.
- a solid electrolyte separator to be disposed between an anode and a cathode layer.
- a lithium-ion cell a natural graphite- based anode, a solid electrolyte separator, and a LiCoO 2 -based cathode were combined.
- a solid electrolyte separator layer is implemented between a Cu foil and a LiCoO 2 -based cathode layer. Electrochemical measurements (CV curves) were carried out in an electrochemical workstation at a scanning rate of 1-100 mV/s.
- the electrochemical performance of the cells was evaluated by galvanostatic charge/discharge cycling at a current density of 50-500 mA/g using an Arbin electrochemical workstation. Testing results indicate that the cells containing quasi- solid or solid-state electrolytes obtained by in situ curing perform very well. These cells are flame resistant and relatively safe.
- EXAMPLE 4 In situ cured diethyl vinylphosphonate and diisopropyl vinylphosphonate polymer electrolytes in a lithium/NCM-532 cell (initially the cell being lithium-free) and lithium- ion cell containing a Si-based anode and a NCM-532 cathode Both diethyl vinylphosphonate and diisopropyl vinylphosphonate were polymerized by a peroxide initiator (di-tert-butyl peroxide), along with LiBF 4 , to clear, light ⁇ yellow polymers of low molecular weight.
- a peroxide initiator di-tert-butyl peroxide
- diethyl vinylphosphonate or diisopropyl vinylphosphonate (being a liquid at room temperature) is added with di-tert-butyl peroxide (0.5- 2% by weight) and LiBF 4 (5-10% by weight) to form a reactive solution.
- the solution was heated to 45°C and injected into a dry battery cell. Bulk polymerization was allowed to proceed for 2-12 hours.
- a graphene-coated Si particle-based anode, a porous separator, and a NCM-532–based cathode were stacked and housed in a plastic/Al laminated envelop to form a cell.
- a Cu foil anode current collector, a porous separator, and a NCM-532–based cathode were stacked and housed in a plastic/Al laminated envelop to form a cell. Additionally, layers of diethyl vinylphosphonate and diisopropyl vinylphosphonate polymer electrolytes were cast on glass surfaces and polymerized under comparable conditions. The lithium ion conductivity of these solid-state electrolytes was measured.
- the lithium ion conductivity of diethyl vinylphosphonate derived polymers was found to be in the range from 5.4 ⁇ 10 ⁇ 5 S/cm – 7.3 x 10 ⁇ 4 S/cm and that of diisopropyl vinylphosphonate polymer electrolytes in the range from 6.6 ⁇ 10 ⁇ 5 S/cm – 8.4 x 10 ⁇ 4 S/cm. Both are solid state electrolytes that are highly flame resistant. In some samples, a desired amount (5% by weight based on a total electrode weight) of a flame retardant (e.g.
- decabromodiphenyl ethane DBDPE
- brominated poly(2,6-dimethyl-1,4- phenylene oxide) BPPO
- melamine-based flame retardant separately; the latter from Italmatch Chemicals
- DBDPE decabromodiphenyl ethane
- BPPO brominated poly(2,6-dimethyl-1,4- phenylene oxide)
- melamine-based flame retardant separately; the latter from Italmatch Chemicals
- EXAMPLE 5 Solid state electrolytes via in situ curing of cyclic esters of phosphoric acid
- polymers from phosphates five ⁇ membered cyclic esters of phosphoric acid of the general formula: -CH 2 CH(R)OP(O) ⁇ (OR′)O- were polymerized to solid, soluble polymers of high molecular weight by using n ⁇ C 4 H 9 Li, (C 5 H 5 ) 2 Mg, or (i ⁇ C 4 H 9 ) 3 Al as initiators.
- Temperature or a second solvent may be used to adjust the viscosity of the reactant mixture, where necessary.
- the mixture was introduced into a battery cell and the anionic polymerization was allowed to proceed at room temperature (or lower) overnight to produce a solid state electrolyte in situ.
- the room temperature lithium ion conductivities of this series of solid electrolytes are in the range from 2.5 ⁇ 10 ⁇ 5 S/cm – 1.6 x 10 ⁇ 3 S/cm.
- EXAMPLE 6 Li metal cells and Li-ion cells containing an in situ cured polymer from a dinitrile monomer A monomer solvent 4,4’-(1,4-Butylenedioxy)dibenzonitrile (BDDN) was used, along with trifluoromethanesulfonic acid (CF3SO3H) as an initiator dissolved in o-dichlorobenzene (o- DCB) in the polymerization reaction.
- BDDN monomer solvent 4,4’-(1,4-Butylenedioxy)dibenzonitrile
- CF3SO3H trifluoromethanesulfonic acid
- o- DCB o-dichlorobenzene
- Both cells comprise NCA particles as the cathode active material.
- EXAMPLE 7 Preparation of solid electrolyte powder, lithium nitride phosphate compound (LIPON) for use as a solid filler or additive Particles of Li 3 PO 4 (average particle size 4 ⁇ m) and urea were prepared as raw materials; 5 g each of Li 3 PO 4 and urea was weighed and mixed in a mortar to obtain a raw material composition. Subsequently, the raw material composition was molded into 1 cm x 1 cm x 10 cm rod with a molding machine, and the obtained rod was put into a glass tube and evacuated.
- LIPON lithium nitride phosphate compound
- Li10GeP2S12 LGPS
- EXAMPLE 9 Preparation of garnet-type solid electrolyte powder The synthesis of the c-Li 6.25 Al 0.25 La 3 Zr 2 O 12 was based on a modified sol–gel synthesis- combustion method, resulting in sub-micron-sized particles after calcination at a temperature of 650°C (J. van den Broek, S. Afyon and J. L. M. Rupp, Adv. Energy Mater., 2016, 6, 1600736).
- the garnet-type solid electrolyte with a composition of c-Li 6.25 Al 0.25 La 3 Zr 2 O 12 (LLZO) in a powder form was dispersed in several electric, ion-conducting polymers discussed earlier.
- EXAMPLE 10 Preparation of sodium superionic conductor (NASICON) type solid electrolyte powder
- the procedure employed includes two sequential steps. Firstly, solid solutions of alkaline earth metal oxides (MO) and ZrO 2 were synthesized by high energy ball milling at 875 rpm for 2 h.
- MO alkaline earth metal oxides
- ZrO 2 ZrO 2
- EXAMPLE 11 Lithium metal cell featuring an in situ polymerized VC or FEC as the first liquid solvent and TEP as a second liquid solvent
- VC vinylene carbonate
- FEC fluoroethylene carbonate
- PEGDA poly(ethylene glycol) diacrylate
- the TEP has the following chemical structure: Subsequently, lithium hexafluoro phosphate, as a lithium salt, was added and dissolved in the above solution to obtain a reactive mixture solution, wherein the weight fractions of VC or FEC, TEP, polyethylene glycol diacrylate, and lithium hexafluoro phosphate were 80 wt%, 5 wt%, 10 wt%, and 5 wt%, respectively.
- This cell was then injected with the reactive solution mixture (10% by weight based on the total cell weight). The cell was then irradiated with electron beam at room temperature until a total dosage of 40 Gy was reached.
- EXAMPLE 13 VC or FEC as the first liquid solvent and Trifluoro-Phosphate (TFP) as the second liquid solvent
- TFP Trifluoro-Phosphate
- VC or FEC was used as the first liquid solvent
- azodiisobutyronitrile (AIBN) as the initiator
- LiDFOB lithium difluoro(oxalate) borate
- TFP has the following chemical structure: Solutions containing 1.5 M LiDFOB in VC and FEC, respectively, and 0.2 wt % AIBN (vs VC or FEC) were prepared.
- TFP TFP/VC or TFP/FEC ratios being from 10/90 to 50/50
- the electrolyte solutions were separately injected into different dry battery cells, allowing the electrolyte solution to permeate into the anode (wetting out the anode active material; e.g., graphite particles), into the cathode (wetting out the cathode active material; e.g., NCM-532 particles), and into the porous separator layer (porous PE/PP film or nonwoven of electro-spun PAN nano-fibers).
- the battery cells were stored at 60°C for 24 h and then 80°C for another 2 h to obtain polymerized VC or polymerized FEC that contained TFP in their matrix of polymer chains.
- the polymerization scheme of VC is shown below (Reaction scheme 1): (Reaction scheme 1). It may be noted that presumably FEC inside the cell may be naturally converted to VC according to the following reaction and the resulting VC can be polymerized according to the following Reaction scheme 2: (Reaction scheme 2).
- the resultant VC is then polymerized according to Reaction scheme 1 shown above.
- the HF can help form a LiF-rich solid electrolyte interface layer on Li anode or graphite anode material surface for improved cycling performance.
- EXAMPLE 14 Vinyl ethylene sulfite (VES) as the first solvent and hydrofluoro ether (HFE) as the second solvent Under the protection of an argon gas atmosphere, vinyl ethylene sulfite (VES), hydrofluoro ether (HFE), and tetra(ethylene glycol) diacrylates were stirred evenly to form a solution. Bis trifluoromethyl sulfimide lithium was then dissolved in the solution to obtain a solution mixture. In this solution mixture, the weight fractions for the four ingredients were VEC (40%), HFE (20%), tetra(ethylene glycol) diacrylates (20%), and bis trifluoromethyl sulfimide (10%).
- the mixed solution was added to a lithium-ion cell having an NCM cathode, graphite anode, and porous PE/PP membrane. After the mixed solution was injected, the mixed solution accounted for 3% of the total cell weight. The cell was exposed to electron beam at 50°C until a dosage of 20 kGy was reached. VEC was polymerized and crosslinked to become a solid polymer, but HFE remained as a liquid.
- the lithium-ion cells prepared in this example comprise an anode of meso-carbon micro- beads (MCMB, an artificial graphite supplied from China Steel Chemical Co. Taiwan), a cathode of NCM-622 particles, and a porous PE/PP membrane as a separator.
- MCMB meso-carbon micro- beads
- NCM-622 particles a cathode of NCM-622 particles
- a porous PE/PP membrane as a separator.
- Phenyl vinyl sulfide first liquid solvent
- TMS second solvent
- CTA chain transfer agent, shown below
- AIBN initiator, 1.0%)
- LiCF 3 SO 3 lithium trifluoro- metasulfonate
- EXAMPLE 16 Lithium-ion cell featuring an in situ polymerized phenyl vinyl sulfone
- the lithium-ion cells prepared in this example comprise an anode of graphene-protected Si particles, a cathode of NCM-622 particles, and a porous PE/PP membrane as a separator.
- Phenyl vinyl sulfone (PVS) can be polymerized with several anionic-type initiators; e.g., n-BuLi, ZnEt2, LiN(CH2)2, and NaNH2.
- the second solvent may be selected from pyridine, sulfolane, Trimethyl phosphate (TMP), Trifluoro-Phosphate (TFP), etc.
- Trimethyl phosphate has the following chemical structure: A mixture of PVS, TFP, n-BuLi (1.0% relative to PVS), and LiBF4 (0.5 M) was thoroughly mixed and injected into the battery cell, which was maintained at 30°C overnight to cure the polymer.
- EXAMPLE 17 Quasi-solid and solid-state electrolytes from vinylphosphonic acid (VPA) The free radical polymerization of vinylphosphonic acid (VPA) can be catalyzed with benzoyl peroxide as the initiator. In a procedure, 150 parts vinylphosphonic acid, 0.75 parts benzoyl peroxide, and 20 parts of lithium bis(oxalato)borate (LiBOB) were dissolved in 150 parts isopropanol.
- a solid electrolyte separator to be disposed between an anode and a cathode layer.
- a lithium-ion cell a natural graphite- based anode, a solid electrolyte separator, and a LiCoO2-based cathode were combined.
- a solid electrolyte separator layer is implemented between a Cu foil and a LiCoO 2 -based cathode layer. Electrochemical measurements (CV curves) were carried out in an electrochemical workstation at a scanning rate of 1-100 mV/s.
- the electrochemical performance of the cells was evaluated by galvanostatic charge/discharge cycling at a current density of 50-500 mA/g using an Arbin electrochemical workstation. Testing results indicate that the cells containing quasi- solid or solid-state electrolytes obtained by in situ curing perform very well. These cells are flame resistant and relatively safe.
- EXAMPLE 18 In situ cured diethyl vinylphosphonate and diisopropyl vinylphosphonate polymer electrolytes in a lithium/NCM-532 cell (initially the cell being lithium-free) and lithium- ion cell containing a Si-based anode and an NCM-532 cathode
- Both diethyl vinylphosphonate and diisopropyl vinylphosphonate can be polymerized by a peroxide initiator (di-tert-butyl peroxide), along with LiBF4, to clear, light ⁇ yellow polymers of low molecular weight.
- a peroxide initiator di-tert-butyl peroxide
- a graphene-coated Si particle-based anode, a porous separator, and a NCM-532–based cathode were stacked and housed in a plastic/Al laminated envelop to form a cell.
- a Cu foil anode current collector, a porous separator, and a NCM-532–based cathode were stacked and housed in a plastic/Al laminated envelop to form a cell.
- layers of diethyl vinylphosphonate and diisopropyl vinylphosphonate polymer electrolytes were cast on glass surfaces and polymerized under comparable conditions.
- the lithium ion conductivity of these solid-state electrolytes was measured.
- the lithium ion conductivity of diethyl vinylphosphonate derived polymers was found to be in the range of 5.4 ⁇ 10 ⁇ 5 S/cm – 7.3 x 10 ⁇ 4 S/cm and that of diisopropyl vinylphosphonate polymer electrolytes in the range of 6.6 ⁇ 10 ⁇ 5 S/cm – 8.4 x 10 ⁇ 4 S/cm without a second solvent. Both are solid state electrolytes that are highly flame resistant. The presence of phosphazene liquid was found to increase the lithium ion conductivity by 3-5 times.
- EXAMPLE 19 Solid state electrolytes via in situ curing of cyclic esters of phosphoric acid
- polymers from phosphates five ⁇ membered cyclic esters of phosphoric acid of the general formula: -CH 2 CH(R)OP(O) ⁇ (OR′)O- were polymerized to solid, soluble polymers of high molecular weight by using n ⁇ C 4 H 9 Li, (C 5 H 5 ) 2 Mg, or (i ⁇ C 4 H 9 ) 3 Al as initiators.
- a second solvent, DMMP, having the following structure, was used to adjust the viscosity of the reactant mixture: The mixture was introduced into a battery cell and the anionic polymerization was allowed to proceed at room temperature (or lower) overnight to produce a solid state electrolyte in situ.
- the room temperature lithium ion conductivities of this series of solid electrolytes are in the range of 2.5 ⁇ 10 ⁇ 5 S/cm – 1.6 x 10 ⁇ 3 S/cm.
- Both Li metal cells containing a lithium foil as an anode material
- Li-ion cells containing artificial graphite particles as an anode active material
- Both cells comprise NCA particles as the cathode active material.
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| KR1020237027576A KR20230134521A (en) | 2021-01-22 | 2022-01-24 | Flame-retardant quasi-solid and solid-state electrolytes, lithium batteries and manufacturing methods |
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| PCT/US2022/070314 Ceased WO2022170299A2 (en) | 2021-01-22 | 2022-01-24 | Flame-resistant quasi-solid and solid-state electrolytes, lithium batteries and manufacturing method |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP2024504703A (en) |
| KR (1) | KR20230134521A (en) |
| WO (1) | WO2022170299A2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115312835A (en) * | 2022-08-25 | 2022-11-08 | 浙江吉利控股集团有限公司 | Gel electrolyte, preparation method thereof and lithium ion battery |
| CN115692834A (en) * | 2022-10-20 | 2023-02-03 | 天津大学 | Polyester quasi-solid electrolyte and preparation method and application thereof |
| CN116365054A (en) * | 2023-06-01 | 2023-06-30 | 蓝固(常州)新能源有限公司 | Aqueous solid electrolyte slurry, solid electrolyte membrane and secondary battery |
| CN116454374A (en) * | 2023-05-06 | 2023-07-18 | 苏州纤锋纳米科技有限公司 | Polymer electrolyte based on bis (vinyl sulfonyl) methane and preparation method thereof |
| CN119029290A (en) * | 2023-05-24 | 2024-11-26 | 张家港市国泰华荣化工新材料有限公司 | Semi-solid electrolyte and lithium ion battery and preparation method thereof |
| WO2025169052A1 (en) * | 2024-02-09 | 2025-08-14 | Novac S.R.L. | Electric energy storage device comprising an in-situ polymerized solid-state electrolyte |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2025084789A1 (en) * | 2023-10-17 | 2025-04-24 | 주식회사 솔리텍 | All-solid-state battery comprising porous composite anode current collector |
| WO2025110679A1 (en) * | 2023-11-24 | 2025-05-30 | 주식회사 엘지에너지솔루션 | Lithium secondary battery |
| KR20250173271A (en) * | 2024-06-03 | 2025-12-10 | 에스케이이노베이션 주식회사 | Monomer for electrolyte, electrolyte for secondary battery including the same, method of preparing the same and lithium secondary battery including the same |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100261252B1 (en) * | 1996-07-30 | 2000-07-01 | 윤종용 | Polymer solid electrolyte and lithium secondary battery employing the same |
| CN104871362B (en) * | 2012-12-13 | 2018-09-04 | 艾利电力能源有限公司 | The manufacturing method of non-aqueous electrolyte secondary battery |
| WO2016011613A1 (en) * | 2014-07-23 | 2016-01-28 | Basf Corporation | Electrolytes for lithium transition metal phosphate batteries |
| KR101715845B1 (en) * | 2014-09-26 | 2017-03-27 | 삼성전자주식회사 | Electrolyte, preparing method thereof, and secondary battery comprising the electrolyte |
| EP3353844B1 (en) * | 2015-03-27 | 2022-05-11 | Mason K. Harrup | All-inorganic solvents for electrolytes |
| CN111326789B (en) * | 2020-03-09 | 2021-08-13 | 天津中电新能源研究院有限公司 | Semi-interpenetrating network flame-retardant solid lithium ion electrolyte, solid lithium battery and preparation method |
-
2022
- 2022-01-24 WO PCT/US2022/070314 patent/WO2022170299A2/en not_active Ceased
- 2022-01-24 KR KR1020237027576A patent/KR20230134521A/en active Pending
- 2022-01-24 JP JP2023544264A patent/JP2024504703A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115312835A (en) * | 2022-08-25 | 2022-11-08 | 浙江吉利控股集团有限公司 | Gel electrolyte, preparation method thereof and lithium ion battery |
| CN115312835B (en) * | 2022-08-25 | 2024-11-01 | 浙江吉利控股集团有限公司 | Gel electrolyte, preparation method thereof and lithium ion battery |
| CN115692834A (en) * | 2022-10-20 | 2023-02-03 | 天津大学 | Polyester quasi-solid electrolyte and preparation method and application thereof |
| CN116454374A (en) * | 2023-05-06 | 2023-07-18 | 苏州纤锋纳米科技有限公司 | Polymer electrolyte based on bis (vinyl sulfonyl) methane and preparation method thereof |
| CN119029290A (en) * | 2023-05-24 | 2024-11-26 | 张家港市国泰华荣化工新材料有限公司 | Semi-solid electrolyte and lithium ion battery and preparation method thereof |
| CN119029290B (en) * | 2023-05-24 | 2025-10-03 | 张家港市国泰华荣化工新材料有限公司 | Semi-solid electrolyte and lithium ion battery and preparation method thereof |
| CN116365054A (en) * | 2023-06-01 | 2023-06-30 | 蓝固(常州)新能源有限公司 | Aqueous solid electrolyte slurry, solid electrolyte membrane and secondary battery |
| CN116365054B (en) * | 2023-06-01 | 2023-08-18 | 蓝固(常州)新能源有限公司 | Aqueous solid electrolyte slurry, solid electrolyte membrane and secondary battery |
| WO2025169052A1 (en) * | 2024-02-09 | 2025-08-14 | Novac S.R.L. | Electric energy storage device comprising an in-situ polymerized solid-state electrolyte |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2022170299A3 (en) | 2022-11-03 |
| JP2024504703A (en) | 2024-02-01 |
| KR20230134521A (en) | 2023-09-21 |
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