CN111162262B - Preparation method of high-rate lithium ion battery positive electrode slurry - Google Patents
Preparation method of high-rate lithium ion battery positive electrode slurry Download PDFInfo
- Publication number
- CN111162262B CN111162262B CN202010050291.0A CN202010050291A CN111162262B CN 111162262 B CN111162262 B CN 111162262B CN 202010050291 A CN202010050291 A CN 202010050291A CN 111162262 B CN111162262 B CN 111162262B
- Authority
- CN
- China
- Prior art keywords
- slurry
- graphene
- stirring
- lithium ion
- ion battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000011267 electrode slurry Substances 0.000 title claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 106
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 73
- 239000002002 slurry Substances 0.000 claims abstract description 67
- 238000003756 stirring Methods 0.000 claims abstract description 55
- 239000007788 liquid Substances 0.000 claims abstract description 39
- 239000006185 dispersion Substances 0.000 claims abstract description 35
- 229920000297 Rayon Polymers 0.000 claims abstract description 26
- 239000007787 solid Substances 0.000 claims abstract description 23
- 239000000853 adhesive Substances 0.000 claims abstract description 21
- 230000001070 adhesive effect Effects 0.000 claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 238000000498 ball milling Methods 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000006256 anode slurry Substances 0.000 claims abstract description 13
- 239000011230 binding agent Substances 0.000 claims abstract description 11
- 239000013543 active substance Substances 0.000 claims abstract description 9
- 239000002131 composite material Substances 0.000 claims abstract description 7
- 238000007873 sieving Methods 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 25
- 239000002033 PVDF binder Substances 0.000 claims description 19
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 18
- 239000006258 conductive agent Substances 0.000 claims description 17
- 239000002041 carbon nanotube Substances 0.000 claims description 14
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 14
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 claims description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical group O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 230000007306 turnover Effects 0.000 claims description 5
- 239000011324 bead Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000007774 positive electrode material Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 239000003292 glue Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000002048 multi walled nanotube Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 2
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000006183 anode active material Substances 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000006257 cathode slurry Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of graphene, and discloses a preparation method of high-rate lithium ion battery anode slurry, which comprises the following steps: a. dissolving a binder in a solvent NMP, stirring and dispersing by double planets to prepare a viscose solution; b. adding the graphene dispersion liquid into the viscose solution, performing ball milling and mixing by using a planetary ball mill to obtain graphene viscose solution A, and sieving and storing the graphene viscose solution A; c. adding the carbon tube conductive slurry into part of the graphene adhesive liquid A, stirring and mixing by using a high-speed dispersion machine, and homogenizing by using a high-pressure homogenizer to obtain composite slurry B; d. adding the positive active substance into the composite slurry B twice, and stirring and dispersing by double planets to obtain slurry C; e. adding the residual graphene viscose liquid A into the slurry C, stirring and dispersing by double planets to obtain a slurry D, adding a solvent NMP to adjust the viscosity and determine the solid content, and filtering and defoaming in vacuum when the solid content meets the requirement to prepare the high-rate lithium ion battery slurry; the positive electrode slurry disclosed by the invention is uniformly dispersed, has good conductivity and is suitable for high-rate charge and discharge.
Description
Technical Field
The invention relates to the technical field of graphene, in particular to a preparation method of high-rate lithium ion battery slurry.
Background
Compared with the traditional energy supply mode based on fossil fuel, the appearance of the lithium battery breaks through the traditional carbon-based energy supply mode, reduces the carbon emission and provides a new path for sustainable development. Since the last 90 s, lithium batteries began to enter the market and became the power choice for electrical appliances and IT terminals. The lithium battery has smaller volume, more stable performance and better cyclicity, so that the lithium battery gradually spreads all aspects of daily life of people, and the lithium battery can help people to make an important step towards the cleaning world.
Nowadays, lithium ion batteries are more widely developed and applied, and face a few challenges, for example, in the actual use process of new lithium battery energy vehicles, there are still problems of low energy density, long charging time, low discharge power, etc., and there is a need for continuous improvement of the process design of lithium ion batteries and continuous innovation in the field of new materials.
The preparation method of the ternary material lithium ion anode slurry commonly used at present comprises the following steps: mixing and stirring a binder PVDF and a solvent NMP to prepare an adhesive solution, and then uniformly mixing and stirring nickel cobalt lithium manganate and a conductive agent (such as conductive carbon black, graphite, carbon fiber and the like) to prepare a corresponding electrode slurry. The prior art uses wet mixing, and has the advantages that the adhesive solution is completely dissolved, and relatively uniform slurry can be obtained.
However, the conductive agent has different characteristics, conductivity and liquid absorption, has different combination degree with PVDF glue, is not easy to disperse uniformly, and cannot be mixed with the positive electrode material fully by one-time addition. Meanwhile, in order to reduce the resistance, the addition amount of the conductive agent is large, which is not favorable for the stability and uniformity of the positive electrode slurry and influences the gram volume performance.
Disclosure of Invention
The invention aims to provide a preparation method of a high-capacity and high-rate positive electrode conductive slurry of a nickel-cobalt-manganese ternary lithium battery, which solves the problems of uniformity and stability existing in the existing preparation method of a lithium ion positive electrode slurry, and improves the conductivity and the gram capacity.
The technical scheme of the invention is as follows:
a preparation method of high-rate lithium ion battery anode slurry comprises the following steps:
a. dissolving a binder in a solvent NMP, stirring and dispersing by double planets to prepare a viscose solution;
b. adding the graphene dispersion liquid into the viscose solution, performing ball milling and mixing by using an all-dimensional planetary ball mill to obtain graphene viscose solution A, and sieving and storing the graphene viscose solution A;
c. adding the carbon tube conductive slurry into part of the graphene adhesive liquid A, stirring and mixing by using a high-speed dispersion machine, and homogenizing by using a high-pressure homogenizer to obtain composite slurry B;
d. adding the positive active substance into the composite slurry B twice, and stirring and dispersing by double planets to obtain slurry C;
e. adding the residual graphene viscose solution A into the slurry C, stirring and dispersing by double planets to obtain a slurry D, adding a solvent NMP according to the material condition to adjust the viscosity and measure the solid content, and filtering and defoaming in vacuum when the solid content meets the requirement to prepare the high-rate lithium ion battery slurry.
Preferably, in the step a, the binder is polyvinylidene fluoride, and the solvent NMP is N-methylpyrrolidone; and d, taking the nickel cobalt lithium manganate as the positive active material in the step d.
Preferably, the graphene dispersion liquid in the step b comprises 3 parts of graphene and 97 parts of N-methyl pyrrolidone, the solid content of the graphene dispersion liquid is 1% -5%, the sheet diameter of graphene contained in the graphene dispersion liquid is 10-40um, and the thickness of graphene is 3-10 nm.
Preferably, the carbon tube conductive slurry in the step c comprises 3% -5% of a conductive agent, 1% -2% of a binder and 93% -96% of a solvent NMP, and the prepared carbon tube conductive slurry has a solid content of 4% -6%.
Preferably, the conductive agent comprises carbon nanotubes and graphene, wherein the content of the carbon nanotubes is 40-80%, and the content of the graphene is 20-60%; the diameter of the carbon nano tube is 5-20nm, and the length of the carbon tube is 5-20 um.
Preferably, the mass fraction of the positive electrode active material in the step d is 96-98%.
Preferably, the mass ratio of the viscose solution to the graphene dispersion liquid in the step b is 1.0:0.6-1.0, a planetary ball mill is used for mixing treatment, the forward rotation speed is 200-500rpm, and the time is 30 min; after pausing for 5min, reversing the operation speed to be 100-500rpm for 30min, and repeating the forward and reverse rotation operation for 3 times; during the operation, the vertical direction 360 is always kept o Tipping bucket type turning at 5-10rpm, and ball milling medium is zirconia beads.
Preferably, the mass ratio of the graphene viscose liquid to the carbon tube conductive slurry in the step c is 1.0:0.8-1.2, a high-pressure homogenizer is used for dispersion treatment, the homogenization pressure is 1000-2000bar, and the circulation treatment is performed for 3-5 times.
Preferably, when the solvent is used for adjusting the viscosity in the step e, the stirring revolution speed is 10-20rpm, the rotation speed is 1000-1500rpm, the stirring time is 0.5h after each solvent addition, and then the solid content is measured until the solid content of the slurry reaches a set value of 62%, so that the high-rate lithium ion battery anode slurry is prepared.
Compared with the prior art, the invention has the beneficial effects that:
the conductive agent used in the application is carbon nanotubes and graphene, the carbon nanotubes have good electronic conductivity, a fibrous structure can form a continuous conductive network in an electrode active material, the graphene conducts electricity through point-surface contact, the liquid absorption capacity is relatively weak and easy to disperse, the graphene and the carbon nanotubes are compounded and matched, a complete three-dimensional conductive network structure can be formed, compared with the traditional conductive agent such as conductive carbon black and the like, the conductive agent has higher electronic conductivity, the required using amount is relatively low, and the addition amount of the conductive agent is only 0.5% -2%.
The graphene dispersion liquid and the viscose liquid are mixed by using an all-directional ball mill, a ball milling tank not only has revolution motion in the horizontal direction, but also has tipping bucket type turnover in the vertical direction, and materials are mixed more fully; in addition, the ball milling mixing can be used for processing materials with higher viscosity, and as the viscosity of the PVDF glue and the graphene dispersion liquid is higher, the stirring and mixing action force is weaker, and the ball milling dispersion can be more uniform.
According to the application, the carbon tube conductive slurry and the graphene dispersion liquid are subjected to homogenization treatment, so that on one hand, interlayer stripping of graphene is more thorough, and the graphene is fully coated by PVDF (polyvinylidene fluoride) glue; on the other hand, the carbon tubes and the graphene are mutually permeated and mixed in a high-pressure homogeneous state, so that a compact and uniform three-dimensional conductive network can be formed; after the composite slurry is mixed with the anode active material, the carbon nano tube can completely cover the anode active material due to the high surface area and the super-large length-diameter ratio of the carbon nano tube, so that a short-distance conductive network is realized, the specific surface area of the anode material is improved, and the anode material can absorb electrolyte.
The graphene viscose is used for adjusting the viscosity of the positive electrode slurry, a long-range conductive network is built by large-area coverage and flexibility of graphene, the internal resistance of the positive electrode piece is greatly reduced, and high-rate charge and discharge performance is facilitated.
The graphene adhesive is prepared by mixing the graphene and the PVDF adhesive, so that the adhesion of a current collector and positive electrode slurry is facilitated, meanwhile, the connection of a graphene network and the current collector is guaranteed, and the electronic conductivity of the positive electrode is improved.
Drawings
FIG. 1 is a scanning electron microscope image of a high-magnification lithium ion battery cathode slurry coated on an aluminum foil.
Detailed Description
The following describes the embodiment of the present invention in detail with reference to fig. 1.
The first embodiment is as follows:
a preparation method of high-rate lithium ion battery anode slurry comprises the following steps:
1. the preparation method comprises the following steps of (1) taking a multi-wall carbon nano tube as a conductive agent, polyvinylidene fluoride as a binder and N-methyl pyrrolidone as a solvent, wherein the three components are as follows: polyvinylidene fluoride: conductive agent = 94: 1: 5, preparing carbon tube conductive slurry; and preparing graphene dispersion liquid by taking 3 parts of graphene and 97 parts of N-methyl pyrrolidone.
2. Dissolving polyvinylidene fluoride in N-methyl pyrrolidone 13 times of the weight of polyvinylidene fluoride, dispersing at high speed for 4h under vacuum condition, stirring and revolving at 18rpm and dispersing at 1200rpm to obtain viscose liquid.
3. Adding the weighed graphene dispersion liquid and the viscose liquid with the same mass into a ball milling tank, putting 1.0mm of zirconia beads into the ball milling tank, and rotating forward at the speed of 300rpm for 30 min; after pausing for 5min, the operation speed is reversed again to 300rpm for 30min, and the forward and reverse rotation operations are repeated for 3 times. During the operation, the vertical direction 360 is always kept o Tipping bucket type turnover, and the rotating speed is 5 rpm. And sieving for later use to obtain the graphene adhesive liquid A.
4. And weighing half of the graphene adhesive A, adding the carbon nano tube conductive slurry into the graphene adhesive A, and stirring the mixture for 30min under a vacuum condition at the stirring speed of 1500 rpm. And then using a high-pressure homogenizer for processing, wherein the homogenizing pressure is 1200bar, and circularly processing for 5 times to obtain the slurry B.
5. Adding an active substance lithium nickel cobalt manganese oxide into the slurry B twice, wherein 50% of the total addition amount of the lithium nickel cobalt manganese oxide is added for the first time, the revolution speed is 20rpm, and the stirring time is 0.5 h; and adding the rest of the nickel cobalt lithium manganate for the second time, wherein the revolution speed is 20rpm, the dispersion speed is 1300rpm, the stirring time is 3 hours, and the slurry C is prepared after the stirring is finished.
6. And adding the residual graphene adhesive A into the slurry C, stirring and dispersing for 3 hours in vacuum, wherein the stirring revolution speed is 25rpm, the dispersion speed is 1200rpm, and stirring is finished to obtain a slurry D.
7. After stirring is finished, when the temperature of the slurry D is cooled to 25 ℃, the viscosity of the slurry is tested, N-methyl pyrrolidone is added according to a test result to adjust the viscosity, the solid content is measured, the stirring revolution speed is 10rpm after the addition, the dispersion speed is 1000rpm, the stirring time is 30min, the viscosity condition and the solid content of the adjusted slurry are required to be measured every time the viscosity is adjusted, and the high-rate lithium ion battery anode slurry is prepared until the solid content of the prepared slurry is 62%.
The slurry was applied to an aluminum foil and subjected to scanning electron microscopy, the scan being shown in FIG. 1.
Example two:
a preparation method of high-rate lithium ion battery anode slurry comprises the following steps:
1. the preparation method comprises the following steps of (1) taking a multi-wall carbon nano tube as a conductive agent, polyvinylidene fluoride as a binder and N-methyl pyrrolidone as a solvent, wherein the three components are as follows: polyvinylidene fluoride: conductive agent = 94: 1: 5, preparing carbon tube conductive slurry; and preparing graphene dispersion liquid by taking 3 parts of graphene and 97 parts of N-methyl pyrrolidone.
2. Dissolving polyvinylidene fluoride in N-methyl pyrrolidone 13 times of the weight of the polyvinylidene fluoride, dispersing for 4 hours at a high speed under a vacuum condition, and stirring at a revolution speed of 18rpm and a dispersion speed of 1200rpm to prepare the viscose liquid.
3. Adding the graphene dispersion liquid and the viscose liquid which are weighed to be equal in mass into a ball milling tankIn the process, zirconia balls with the diameter of 1.0mm are placed into a ball milling tank, the forward rotation speed is 200rpm, and the time is 30 min; after pausing for 5min, the operation speed is reversed again to 100rpm for 30min, and the forward and reverse rotation operations are repeated for 3 times. During the operation, the vertical direction 360 is always kept o Tipping bucket type turnover, and the rotating speed is 8 rpm. And sieving for later use to obtain the graphene adhesive liquid A.
4. And weighing half of the graphene adhesive A, adding the carbon nano tube conductive slurry into the graphene adhesive A, and stirring the mixture for 30min under a vacuum condition at a stirring speed of 1500 rpm. And then using a high-pressure homogenizer for processing, wherein the homogenizing pressure is 1000bar, and circularly processing for 5 times to obtain the slurry B.
5. Adding an active substance of nickel cobalt lithium manganate into the slurry B twice, wherein the adding amount of the active substance of nickel cobalt lithium manganate is 50% of the total adding amount of the nickel cobalt lithium manganate for the first time, the revolution speed is 20rpm, and the stirring time is 0.5 h; and adding the rest of the nickel cobalt lithium manganate for the second time, wherein the revolution speed is 20rpm, the dispersion speed is 1300rpm, the stirring time is 3 hours, and the slurry C is prepared after the stirring is finished.
6. And adding the residual graphene adhesive A into the slurry C, stirring and dispersing for 3 hours in vacuum, wherein the stirring revolution speed is 25rpm, the dispersion speed is 1000rpm, and stirring is finished to obtain slurry D.
7. After stirring is finished, when the temperature of the slurry D is cooled to 25 ℃, the viscosity of the slurry is tested, N-methyl pyrrolidone is added according to a test result to adjust the viscosity, the solid content is measured, the stirring revolution speed is 10rpm after the addition, the dispersion speed is 1200rpm, the stirring time is 30min, the viscosity condition and the solid content of the adjusted slurry are required to be measured every time the viscosity is adjusted, and the high-rate lithium ion battery anode slurry is prepared until the solid content of the prepared slurry is 62%.
Example three:
a preparation method of high-rate lithium ion battery anode slurry comprises the following steps:
1. the preparation method comprises the following steps of (1) taking a multi-wall carbon nano tube as a conductive agent, polyvinylidene fluoride as a binder and N-methyl pyrrolidone as a solvent, wherein the three components are as follows: polyvinylidene fluoride: conductive agent = 94: 1: 5, preparing carbon tube conductive slurry; and preparing graphene dispersion liquid by taking 3 parts of graphene and 97 parts of N-methyl pyrrolidone.
2. Dissolving polyvinylidene fluoride in N-methyl pyrrolidone 13 times of the weight of polyvinylidene fluoride, dispersing at high speed for 4h under vacuum condition, stirring and revolving at 18rpm and dispersing at 1200rpm to obtain viscose liquid.
3. Adding the weighed graphene dispersion liquid and the viscose liquid with the same mass into a ball milling tank, putting 1.0mm of zirconia beads into the ball milling tank, and rotating forward at the speed of 500rpm for 30 min; after pausing for 5min, the operation speed is reversed again to be 500rpm for 30min, and the forward and reverse rotation operation is repeated for 3 times. During the operation, the vertical direction 360 is always kept o Tipping bucket type turnover, and the rotating speed is 10 rpm. And sieving for later use to obtain the graphene adhesive liquid A.
4. And weighing half of the graphene adhesive A, adding the carbon nano tube conductive slurry into the graphene adhesive A, and stirring the mixture for 30min under a vacuum condition at the stirring speed of 1500 rpm. And (5) processing by using a high-pressure homogenizer with the homogenizing pressure of 2000bar, and circularly processing for 5 times to obtain the slurry B.
5. Adding an active substance of nickel cobalt lithium manganate into the slurry B twice, wherein the adding amount of the active substance of nickel cobalt lithium manganate is 50% of the total adding amount of the nickel cobalt lithium manganate for the first time, the revolution speed is 10rpm, and the stirring time is 0.5 h; and adding the rest of the nickel cobalt lithium manganate for the second time, wherein the revolution speed is 10rpm, the dispersion speed is 1500rpm, the stirring time is 3 hours, and obtaining the slurry C after the stirring is finished.
6. And adding the residual graphene adhesive A into the slurry C, stirring and dispersing for 3 hours in vacuum, wherein the stirring revolution speed is 25rpm, the dispersion speed is 1200rpm, and stirring is finished to obtain slurry D.
7. After stirring is finished, when the temperature of the slurry D is cooled to 25 ℃, the viscosity of the slurry is tested, N-methyl pyrrolidone is added according to a test result to adjust the viscosity, the solid content is measured, the stirring revolution speed is 10rpm after the addition, the dispersion speed is 2000rpm, the stirring time is 30min, the viscosity condition and the solid content of the adjusted slurry are required to be measured every time the viscosity is adjusted, and the high-rate lithium ion battery anode slurry is prepared until the solid content of the prepared slurry is 62%.
The foregoing is merely a preferred embodiment of the invention and all such equivalent alterations and permutations and derivations thereof are intended to be included within the scope of the invention.
Claims (8)
1. A preparation method of high-rate lithium ion battery anode slurry is characterized by comprising the following steps:
a. dissolving a binder in a solvent NMP, stirring and dispersing by double planets to prepare a viscose solution;
b. adding the graphene dispersion liquid into the viscose solution, performing ball milling and mixing by using an all-directional planetary ball mill to obtain graphene viscose solution A, and sieving and storing the graphene viscose solution A, wherein the mass ratio of the viscose solution to the graphene dispersion liquid is 1.0: 0.6-1.0;
c. taking 50% of graphene adhesive liquid A by mass, adding the carbon tube conductive slurry into the graphene adhesive liquid A, stirring and mixing the mixture by using a high-speed dispersion machine, and homogenizing the mixture by using a high-pressure homogenizer to obtain composite slurry B, wherein the mass ratio of the graphene adhesive liquid A to the carbon tube conductive slurry is 1.0: 0.8-1.2;
d. adding the positive active substance into the composite slurry B twice, and stirring and dispersing by double planets to obtain a slurry C, wherein the mass fraction of the positive active substance is 96-98%;
e. adding the remaining 50% mass fraction of graphene viscose solution A into the slurry C, stirring and dispersing with double planets to obtain a slurry D, adding a solvent NMP according to the material condition to adjust the viscosity and measure the solid content, and filtering and vacuum defoaming when the solid content meets the requirement to obtain the high-rate lithium ion battery anode slurry.
2. The preparation method of the high-rate lithium ion battery positive electrode slurry according to claim 1, characterized by comprising the following steps:
in the step a, the binder is polyvinylidene fluoride, and the solvent NMP is N-methyl pyrrolidone; and d, taking the nickel cobalt lithium manganate as the positive active material in the step d.
3. The preparation method of the high-rate lithium ion battery positive electrode slurry according to claim 1, characterized by comprising the following steps:
the graphene dispersion liquid in the step b comprises 3 parts of graphene and 97 parts of N-methyl pyrrolidone, the solid content of the graphene dispersion liquid is 1% -5%, the sheet diameter of graphene contained in the graphene dispersion liquid is 10-40um, and the thickness of the graphene is 3-10 nm.
4. The preparation method of the high-rate lithium ion battery positive electrode slurry according to claim 1, characterized by comprising the following steps:
the carbon tube conductive slurry in the step c comprises 3-5% of a conductive agent, 1-2% of a binder and 93-96% of a solvent NMP, and the prepared carbon tube conductive slurry has a solid content of 4-6%.
5. The preparation method of the high-rate lithium ion battery positive electrode slurry according to claim 4, characterized by comprising the following steps:
the conductive agent comprises carbon nano tubes and graphene, wherein the content of the carbon nano tubes is 40-80%, and the content of the graphene is 20-60%; the diameter of the carbon nano tube is 5-20nm, and the length of the carbon tube is 5-20 um.
6. The preparation method of the high-rate lithium ion battery positive electrode slurry according to claim 1, characterized by comprising the following steps:
in the step b, an omnibearing planetary ball mill is used for ball milling and mixing treatment, the forward rotation running speed is 200-500rpm, and the time is 30 min; after pausing for 5min, reversing the running speed to be 100-500rpm for 30min, and repeating the forward and reverse rotation operation for 3 times; in the operation process, the tipping bucket type turnover in the vertical direction is always kept at 360 degrees, the rotating speed is 5-10rpm, and the ball milling medium is zirconia beads.
7. The preparation method of the high-rate lithium ion battery positive electrode slurry according to claim 1, characterized by comprising the following steps:
and c, homogenizing by using a high-pressure homogenizer at the homogenizing pressure of 1000-2000bar, and circularly treating for 3-5 times.
8. The preparation method of the high-rate lithium ion battery positive electrode slurry according to claim 1, characterized by comprising the following steps:
and e, when the solvent is used for adjusting the viscosity in the step e, the stirring revolution speed is 10-20rpm, the rotation speed is 1000-1500rpm, the stirring time is 0.5h after the solvent is added each time, and then the solid content is measured until the solid content of the slurry reaches a set value of 62%, so that the high-rate lithium ion battery anode slurry is prepared.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010050291.0A CN111162262B (en) | 2020-01-17 | 2020-01-17 | Preparation method of high-rate lithium ion battery positive electrode slurry |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010050291.0A CN111162262B (en) | 2020-01-17 | 2020-01-17 | Preparation method of high-rate lithium ion battery positive electrode slurry |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111162262A CN111162262A (en) | 2020-05-15 |
| CN111162262B true CN111162262B (en) | 2022-09-09 |
Family
ID=70563700
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010050291.0A Active CN111162262B (en) | 2020-01-17 | 2020-01-17 | Preparation method of high-rate lithium ion battery positive electrode slurry |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111162262B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112121660B (en) * | 2020-08-26 | 2022-08-23 | 风帆有限责任公司 | Method for preparing anode slurry of lithium ion battery |
| CN112234199A (en) * | 2020-09-15 | 2021-01-15 | 深圳市拓邦锂电池有限公司 | Lithium ion battery positive electrode slurry, preparation method thereof and lithium ion battery positive electrode plate |
| CN112271285A (en) * | 2020-11-02 | 2021-01-26 | 江西安驰新能源科技有限公司 | Preparation process of lithium ion battery anode slurry |
| CN112786828A (en) * | 2021-02-22 | 2021-05-11 | 宁波容百新能源科技股份有限公司 | Prussian positive plate with high compaction density and high rate performance, preparation method of prussian positive plate and sodium ion battery |
| TWI851949B (en) * | 2021-12-17 | 2024-08-11 | 亞福儲能股份有限公司 | Dispersion method of slurry for alluminum battery |
| CN114242992B (en) * | 2021-12-21 | 2024-06-25 | 深圳市和盈新能电子有限公司 | Preparation method of carbon-silicon negative electrode slurry, carbon-silicon negative electrode slurry and lithium ion battery |
| CN116230870B (en) * | 2023-02-27 | 2025-10-24 | 天能电池集团股份有限公司 | A method for preparing anode slurry for solid-state battery, cathode sheet and battery |
| CN117039125B (en) * | 2023-08-10 | 2024-03-29 | 广东钠壹新能源科技有限公司 | Sodium ion battery, sodium ion battery anode slurry and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107464934A (en) * | 2016-06-06 | 2017-12-12 | 深圳格林德能源有限公司 | One kind is based on graphene/carbon nano-tube combined conductive agent anode sizing agent preparation method |
| JP2019052083A (en) * | 2017-09-13 | 2019-04-04 | 東レ株式会社 | Graphene powder, graphene powder / organic solvent dispersion, graphene-electrode active material composite particles, electrode paste, and electrode |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105406070B (en) * | 2015-12-18 | 2018-06-08 | 山东精工电子科技有限公司 | A kind of lithium ion battery anode glue size preparation method |
| JP7028164B2 (en) * | 2016-06-13 | 2022-03-02 | 日本電気株式会社 | Lithium ion secondary battery |
| CN106410188A (en) * | 2016-12-06 | 2017-02-15 | 先进储能材料国家工程研究中心有限责任公司 | Lithium ion battery positive electrode slurry and preparation method thereof |
| CN107706422A (en) * | 2017-07-14 | 2018-02-16 | 常州第六元素材料科技股份有限公司 | Composite mortar of graphene and CNT and preparation method thereof, anode sizing agent and its method |
| CN109346240B (en) * | 2018-09-10 | 2021-02-02 | 明德润和新材料(珠海)有限公司 | Preparation method of graphene conductive slurry |
-
2020
- 2020-01-17 CN CN202010050291.0A patent/CN111162262B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107464934A (en) * | 2016-06-06 | 2017-12-12 | 深圳格林德能源有限公司 | One kind is based on graphene/carbon nano-tube combined conductive agent anode sizing agent preparation method |
| JP2019052083A (en) * | 2017-09-13 | 2019-04-04 | 東レ株式会社 | Graphene powder, graphene powder / organic solvent dispersion, graphene-electrode active material composite particles, electrode paste, and electrode |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111162262A (en) | 2020-05-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111162262B (en) | Preparation method of high-rate lithium ion battery positive electrode slurry | |
| CN103280566B (en) | Preparation method of positive and negative electrode slurry of lithium ion battery | |
| US9166231B2 (en) | Lead acid battery electrode comprising a porous carbon material layer and a lead acid battery | |
| CN110492105B (en) | Positive electrode material, positive electrode plate prepared from positive electrode material and lithium ion battery obtained from positive electrode plate | |
| CN105406070A (en) | Preparation method of lithium ion battery positive pole size | |
| CN102683644A (en) | Preparation method of anode slurry of lithium ion battery | |
| CN113036085A (en) | Positive pole piece and preparation method and application thereof | |
| CN107204446B (en) | Lithium ion battery anode material and preparation method thereof | |
| CN112271285A (en) | Preparation process of lithium ion battery anode slurry | |
| CN111883736A (en) | Preparation method of lithium ion battery anode slurry | |
| Yang et al. | Poly (acrylic acid) locally enriched in slurry enhances the electrochemical performance of the SiO x lithium-ion battery anode | |
| CN111525137B (en) | Positive electrode slurry and application thereof in battery | |
| CN117832510B (en) | Primer slurry and its preparation method, composite current collector, positive electrode sheet and lithium battery | |
| WO2023248980A1 (en) | Carbon nanotube dispersed liquid, electrode mixture slurry, electrode film, and secondary battery | |
| CN118156458A (en) | Lithium iron phosphate positive electrode material, lithium iron phosphate positive electrode sheet, preparation method of lithium iron phosphate positive electrode sheet and lithium ion battery | |
| CN116960282A (en) | A lithium iron manganese phosphate mixed with high nickel ternary material cathode slurry formula and its homogenization method | |
| KR102725891B1 (en) | Method for manufacturing high conductive electrode | |
| CN113809331A (en) | A kind of multifunctional additive for positive electrode of lithium ion battery and preparation method thereof, and lithium ion battery | |
| CN113257584B (en) | Preparation method of hard carbon slurry for lithium ion capacitor | |
| CN120015801A (en) | A heterostructure composite material of electronegative carbon nanotube modified manganese oxide and preparation method thereof, positive electrode sheet and zinc ion battery | |
| CN118335964A (en) | Negative electrode slurry and preparation method thereof | |
| CN117208889A (en) | A kind of double ion doped hard carbon composite material and its preparation method and application | |
| CN115986092B (en) | A method for preparing a lithium-ion battery | |
| CN116565211B (en) | Negative plate, energy storage device and electric equipment | |
| Hidayat et al. | Li 2 CO 3-incorporated PVDF nanofiber network as lithium host enabling low N/P ratio lithium metal batteries |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |