JP6922355B2 - Electrolyte for aqueous solution-based lithium secondary battery and aqueous solution-based lithium secondary battery - Google Patents
Electrolyte for aqueous solution-based lithium secondary battery and aqueous solution-based lithium secondary battery Download PDFInfo
- Publication number
- JP6922355B2 JP6922355B2 JP2017073742A JP2017073742A JP6922355B2 JP 6922355 B2 JP6922355 B2 JP 6922355B2 JP 2017073742 A JP2017073742 A JP 2017073742A JP 2017073742 A JP2017073742 A JP 2017073742A JP 6922355 B2 JP6922355 B2 JP 6922355B2
- Authority
- JP
- Japan
- Prior art keywords
- electrolyte
- secondary battery
- lithium secondary
- aqueous solution
- aqueous
- 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.)
- Expired - Fee Related
Links
Images
Classifications
-
- 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
- Secondary Cells (AREA)
Description
本明細書で開示する発明は、水溶液系リチウム二次電池用電解液及び水溶液系リチウム二次電池に関する。 The invention disclosed in the present specification relates to an aqueous electrolytic solution for an aqueous lithium secondary battery and an aqueous lithium secondary battery.
リチウムイオン電池の課題のひとつとして、電解液の不燃化が挙げられる。水は安全で安価な液体であるが、電気化学的に安定な電位の範囲（電位窓）は、１．２３Ｖであり、非水系電解液の溶媒として広く用いられているカーボネート系溶媒の約１／３である。このため、エネルギー密度の高い水溶液系リチウムイオン電池の実現はこれまで困難であった。近年、水溶液系リチウムイオン電池の電解液の研究が行われており、高濃度に調製した水溶液系電解液の電位窓が３．０Ｖ以上に拡張されたものが報告されている（例えば、非特許文献１，２参照）。これらの電解液を用いた一有無イオン二次電池では、２．０Ｖ〜３．１Ｖの電圧で作動するとしている。 One of the problems with lithium-ion batteries is to make the electrolytic solution incombustible. Water is a safe and inexpensive liquid, but the electrochemically stable potential range (potential window) is 1.23 V, which is about 1 of the carbonate-based solvents widely used as solvents for non-aqueous electrolyte solutions. / 3. For this reason, it has been difficult to realize an aqueous solution-based lithium-ion battery having a high energy density. In recent years, research on the electrolytic solution of an aqueous solution-based lithium-ion battery has been carried out, and it has been reported that the potential window of the aqueous solution-based electrolytic solution prepared at a high concentration is expanded to 3.0 V or more (for example, non-patent). Refer to Documents 1 and 2). It is said that the one-presence / absence ion secondary battery using these electrolytes operates at a voltage of 2.0V to 3.1V.
しかしながら、上述の非特許文献１、２では、電位窓拡張効果は、電解質のアニオン構造が無機酸の一つであるフルオロスルホニルイミド構造を有するリチウム塩、リチウムビス（トリフルオロメタンスルホニル）イミド、リチウムビス（ペンタフルオロエチルスルホニル）イミド、あるいはこれらの混合物のみに限定して確認されている。これらのイミド構造を有するリチウム塩以外に、電位窓の拡張効果を有する新規な電解質が求められていた。 However, in Non-Patent Documents 1 and 2 described above, the potential window expansion effect is a lithium salt having a fluorosulfonylimide structure in which the anionic structure of the electrolyte is one of the inorganic acids, lithium bis (trifluoromethanesulfonyl) imide, and lithium bis. It has been confirmed to be limited to (pentafluoroethylsulfonyl) imide or a mixture thereof. In addition to these lithium salts having an imide structure, a novel electrolyte having an effect of expanding the potential window has been required.
本開示は、このような課題に鑑みなされたものであり、水溶液系の電解液において、電位窓を拡張する新規な水溶液系リチウム二次電池用電解液及び水溶液系リチウム二次電池を提供することを主目的とする。 The present disclosure has been made in view of such a problem, and provides a novel electrolytic solution for an aqueous solution-based lithium secondary battery and an aqueous solution-based lithium secondary battery that expands a potential window in an aqueous solution-based electrolytic solution. Is the main purpose.
上述した目的を達成するために鋭意研究したところ、本発明者らは、ジカルボン酸２リチウム塩を電解質として用いると、水溶液が電気化学的に安定し、電位窓をより拡張することができることを見いだし、本明細書で開示する発明を完成するに至った。 As a result of diligent research to achieve the above-mentioned object, the present inventors have found that the use of the dicarboxylic acid dilithium salt as an electrolyte makes the aqueous solution electrochemically stable and the potential window can be further expanded. , The invention disclosed in the present specification has been completed.
即ち、本明細書で開示する水溶液系リチウム二次電池用電解液は、
正極と、負極とを備えた水溶液系リチウム二次電池に用いられる電解液であって、
水溶性の２価の有機酸構造を有する２リチウム塩を電解質とし、０．５ｍｏｌ／Ｌ以上の濃度で該電解質を溶解した水溶液であるものである。
That is, the electrolytic solution for an aqueous solution-based lithium secondary battery disclosed in the present specification is
An electrolytic solution used in an aqueous lithium secondary battery having a positive electrode and a negative electrode.
It is an aqueous solution in which a dilithium salt having a water-soluble divalent organic acid structure is used as an electrolyte and the electrolyte is dissolved at a concentration of 0.5 mol / L or more.
本明細書で開示する水溶液系リチウム二次電池は、
正極と、
負極と、
上述した水溶液系リチウム二次電池用電解液と、
を備えたものである。
The aqueous solution-based lithium secondary battery disclosed in the present specification includes
With the positive electrode
With the negative electrode
With the above-mentioned electrolyte for aqueous lithium secondary batteries,
It is equipped with.
本開示は、電位窓を拡張する新規な水溶液系リチウム二次電池用電解液及び水溶液系リチウム二次電池を提供することができる。このような効果が得られる理由は、以下のように推測される。例えば、ジカルボン酸２リチウムは、水中でリチウムイオン及び水分子を含む錯体を形成しやすい構造であり、これを用いることにより、水分子の電極上での酸化や還元による分解反応の反応速度を低下させ、溶液の分解反応が抑制されることにより、電位窓の拡張効果が得られるものと推察される。 The present disclosure can provide a novel electrolyte for an aqueous solution-based lithium secondary battery and an aqueous solution-based lithium secondary battery that expand the potential window. The reason why such an effect is obtained is presumed as follows. For example, dilithium dicarboxylate has a structure that easily forms a complex containing lithium ions and water molecules in water, and by using this, the reaction rate of the decomposition reaction by oxidation or reduction of water molecules on the electrode is reduced. It is presumed that the effect of expanding the potential window can be obtained by suppressing the decomposition reaction of the solution.
（水溶液系電解液）
本開示の水溶液系リチウム二次電池用電解液は、水溶液系リチウム二次電池に用いられる電解液である。この電解液は、水溶性の２価の有機酸構造を有する２リチウム塩を電解質とし、０．５ｍｏｌ／Ｌ（Ｍ）以上の濃度で電解質を溶解した水溶液である。
(Aqueous electrolyte)
The electrolytic solution for an aqueous solution-based lithium secondary battery of the present disclosure is an electrolytic solution used for an aqueous solution-based lithium secondary battery. This electrolytic solution is an aqueous solution in which a dilithium salt having a water-soluble divalent organic acid structure is used as an electrolyte, and the electrolyte is dissolved at a concentration of 0.5 mol / L (M) or more.
この電解質は、脂肪族及び芳香族のジカルボン酸２リチウム塩のうち１以上を含むものとしてもよい。脂肪族のジカルボン酸２リチウム塩としては、例えば、炭素数１〜６の炭素鎖の末端にカルボキシ基が結合したリチウム塩としてもよい。このような電解質としては、例えば、マロン酸２リチウムなどが挙げられる。芳香族のジカルボン酸２リチウム塩としては、２以上の芳香環構造を有する場合、例えば、ビフェニルなど２以上の芳香環が結合した芳香族多環化合物としてもよいし、ナフタレンやアントラセン、ピレンなど２以上の芳香環が縮合した縮合多環化合物としてもよい。この芳香環は、五員環や六員環、八員環としてもよく、六員環が好ましい。また、芳香環は、２以上５以下とするのが好ましい。このような電解質としては、例えば、ナフタレンジカルボン酸２リチウムなどが挙げられる。また、ナフタレンジカルボン酸２リチウムとしては、例えば、２，６−ナフタレンジカルボン酸２リチウムであるものとしてもよい。 The electrolyte may contain one or more of the aliphatic and aromatic dicarboxylic acid dilithium salts. The aliphatic dicarboxylic acid dilithium salt may be, for example, a lithium salt in which a carboxy group is bonded to the end of a carbon chain having 1 to 6 carbon atoms. Examples of such an electrolyte include dilithium malonic acid. The aromatic dicarboxylic acid dilithium salt may be an aromatic polycyclic compound having two or more aromatic rings, such as biphenyl, or an aromatic polycyclic compound having two or more aromatic rings bonded thereto, or may be an aromatic polycyclic compound having two or more aromatic rings, such as naphthalene, anthracene, and pyrene. A condensed polycyclic compound obtained by condensing the above aromatic rings may be used. This aromatic ring may be a five-membered ring, a six-membered ring, or an eight-membered ring, and a six-membered ring is preferable. The aromatic ring is preferably 2 or more and 5 or less. Examples of such an electrolyte include dilithium naphthalenedicarboxylic acid. Further, the dilithium naphthalene dicarboxylic acid may be, for example, dilithium 2,6-naphthalenedicarboxylic acid.
この電解液は、電解質を０．５Ｍ以上含むものとすればよいが、リチウムイオンの伝導を考慮すると、電解質の濃度はできるだけ多いことが望ましく、電解質を飽和濃度で含むことが好ましい。上述した２価の有機酸構造を有する２リチウム塩は、水への溶解度ができるだけ高いことが望ましい。 This electrolytic solution may contain an electrolyte of 0.5 M or more, but considering the conduction of lithium ions, it is desirable that the concentration of the electrolyte is as high as possible, and it is preferable that the electrolyte is contained in a saturated concentration. It is desirable that the above-mentioned dilithium salt having a divalent organic acid structure has as high a solubility in water as possible.
（水溶液系リチウム二次電池）
本開示の水溶液系リチウム二次電池は、正極と、負極と、上述した水溶液系電解液とを備えている。水溶液系電解液は、正極と負極との間に介在し、リチウムイオンを伝導するものである。
(Aqueous solution lithium secondary battery)
The aqueous solution-based lithium secondary battery of the present disclosure includes a positive electrode, a negative electrode, and the above-mentioned aqueous solution-based electrolytic solution. The aqueous electrolytic solution is interposed between the positive electrode and the negative electrode and conducts lithium ions.
正極は、正極活物質を有するものとしてもよい。この正極は、例えば正極活物質と導電材と結着材とを混合し、適当な溶剤を加えてペースト状の正極合材としたものを、集電体の表面に塗布乾燥し、必要に応じて電極密度を高めるべく圧縮して形成してもよい。正極活物質としては、例えば、スピネル構造のリチウムマンガン複合酸化物や層状構造のリチウムマンガン複合酸化物、欠損型層状構造のリチウムマンガン複合酸化物、オリビン構造のリチウムリン酸化合物等を正極活物質とすることが好ましい。正極活物質は、水の電気分解による酸素が生じない電位範囲において、可逆的にできるだけ大量のリチウムイオンの吸蔵・放出が可能であることが好ましい。こうした観点から、正極活物質は、Ｌｉ及びＦｅを金属元素の主成分とするオリビン構造のリチウムリン酸化合物（ＬｉＦｅＰＯ4）であるものとしてもよい。 The positive electrode may have a positive electrode active material. For this positive electrode, for example, a positive electrode active material, a conductive material, and a binder are mixed, and an appropriate solvent is added to form a paste-like positive electrode mixture, which is applied and dried on the surface of the current collector, and if necessary. It may be formed by compression in order to increase the electrode density. Examples of the positive electrode active material include a lithium manganese composite oxide having a spinel structure, a lithium manganese composite oxide having a layered structure, a lithium manganese composite oxide having a defective layered structure, and a lithium phosphoric acid compound having an olivine structure. It is preferable to do so. It is preferable that the positive electrode active material can reversibly occlude and release as much lithium ion as possible in a potential range in which oxygen is not generated by electrolysis of water. From this point of view, the positive electrode active material may be a lithium phosphoric acid compound (LiFePO 4 ) having an olivine structure containing Li and Fe as main components of the metal element.
負極は、負極活物質を有するものとしてもよい。この負極は、例えば負極活物質と導電材と結着材とを混合し、適当な溶剤を加えてペースト状の負極合材としたものを、集電体の表面に塗布乾燥し、必要に応じて電極密度を高めるべく圧縮して形成してもよい。負極活物質としては、リン化合物やリチウムイオンを吸蔵・放出可能な炭素質材料、導電性ポリマーなどが挙げられる。このうち、リン化合物が好ましく、チタン及びリンを含む複合化合物がより好ましい。この負極活物質は、チタン及びリン酸を含む複合化合物として、例えばＡxＴｉ2（ＰＯ4）3（Ａはアルカリ金属及びアルカリ土類金属から選ばれる１種以上であり、Ｘは０以上３以下である）を含むものがより好ましい。このＡは、リチウムであることが好ましい。例えば、負極活物質は、複合化合物として組成式ＬｉＴｉ2（ＰＯ4）3を含むものが更に好ましい。また、この負極活物質は、ＬｉＭ1-xＴｉx（ＰＯ4）3（Ｍは遷移金属、Ｘは正数）のように１つの遷移金属を他の遷移金属で置換したものを含むものとしてもよい。 The negative electrode may have a negative electrode active material. For this negative electrode, for example, a negative electrode active material, a conductive material, and a binder are mixed, and an appropriate solvent is added to form a paste-like negative electrode mixture, which is applied and dried on the surface of the current collector, and if necessary. It may be formed by compression in order to increase the electrode density. Examples of the negative electrode active material include a carbonaceous material capable of occluding and releasing phosphorus compounds and lithium ions, and a conductive polymer. Of these, a phosphorus compound is preferable, and a composite compound containing titanium and phosphorus is more preferable. This negative electrode active material is, for example, A x Ti 2 (PO 4 ) 3 (A is one or more selected from alkali metals and alkaline earth metals, and X is 0 or more 3 as a composite compound containing titanium and phosphoric acid. The following) is more preferable. This A is preferably lithium. For example, the negative electrode active material is more preferably one containing the composition formula LiTi 2 (PO 4 ) 3 as a composite compound. Further, this negative electrode active material includes one in which one transition metal is replaced with another transition metal, such as LiM 1-x Ti x (PO 4 ) 3 (M is a transition metal and X is a positive number). May be good.
正極や負極に用いられる導電材や結着材、集電体などは、一般的な水溶液系リチウム二次電池に用いられるものを採用することができる。例えば、導電材としては、炭素材料などが挙げられ、電子伝導性及び塗工性の観点より、例えば、カーボンブラック、アセチレンブラック及びケッチェンブラックなどが好ましい。結着材としては、水溶性及び／又は水分散性を有する水系高分子を用いることができる。集電体は、水溶液系電解液に対して安定であるものであれば特に限定されず、例えば、アルミニウム、ニッケル、チタン及び貴金属から選ばれる少なくとも１種を含むものとしてもよい。集電体の形状については、箔状、フィルム状、シート状、ネット状、パンチ又はエキスパンドされたもの、ラス体、多孔質体、発泡体、繊維群の形成体などが挙げられる。集電体の厚さは、例えば１〜５００μｍとすることができる。 As the conductive material, the binder, the current collector, and the like used for the positive electrode and the negative electrode, those used for a general aqueous solution-based lithium secondary battery can be adopted. For example, examples of the conductive material include a carbon material, and from the viewpoint of electron conductivity and coatability, for example, carbon black, acetylene black, and Ketjen black are preferable. As the binder, an aqueous polymer having water solubility and / or water dispersibility can be used. The current collector is not particularly limited as long as it is stable to the aqueous electrolyte solution, and may contain at least one selected from, for example, aluminum, nickel, titanium, and a noble metal. Examples of the shape of the current collector include a foil shape, a film shape, a sheet shape, a net shape, a punched or expanded body, a lath body, a porous body, a foam body, and a fiber group forming body. The thickness of the current collector can be, for example, 1 to 500 μm.
この水溶液系リチウム二次電池は、正極と負極との間にセパレータを備えていてもよい。このセパレータには、水溶液系の電解液が浸透してイオンが透過しやすいように、親水処理を施したり微多孔化を施すのが好ましい。セパレータとしては、水溶液系リチウム二次電池の使用範囲に耐えうる組成であれば特に限定されないが、例えば、ポリプロピレン製不織布やポリフェニレンスルフィド製不織布などの高分子不織布、ポリエチレンやポリプロピレンなどのオレフィン系樹脂の薄い微多孔膜が挙げられる。これらは単独で用いてもよいし、複数を混合して用いてもよい。 This aqueous solution-based lithium secondary battery may include a separator between the positive electrode and the negative electrode. It is preferable that the separator is subjected to hydrophilic treatment or microporous treatment so that the aqueous electrolytic solution permeates and ions easily permeate. The separator is not particularly limited as long as it has a composition that can withstand the range of use of the aqueous lithium secondary battery, and is, for example, a polymer non-woven fabric such as a polypropylene non-woven fabric or a polyphenylene sulfide non-woven fabric, or an olefin resin such as polyethylene or polypropylene. Examples include thin microporous membranes. These may be used alone or in combination of two or more.
この水溶液系リチウム二次電池の形状は、特に限定されないが、例えばコイン型、ボタン型、シート型、積層型、円筒型、偏平型、角型などが挙げられる。また、電気自動車等に用いる大型のものなどに適用してもよい。図１は、本明細書で開示する水溶液系リチウム二次電池２０の一例を示す模式図である。この水溶液系リチウム二次電池２０は、カップ形状の電池ケース２１と、正極活物質を有しこの電池ケース２１の下部に設けられた正極２２と、負極活物質を有し正極２２に対してセパレータ２４を介して対向する位置に設けられた負極２３と、絶縁材により形成されたガスケット２５と、電池ケース２１の開口部に配設されガスケット２５を介して電池ケース２１を密封する封口板２６と、を備えている。この水溶液系リチウム二次電池２０は、正極２２と負極２３との空間にリチウム塩を溶解した水溶液系電解液２７が満たされている。
The shape of the aqueous solution-based lithium secondary battery is not particularly limited, and examples thereof include a coin type, a button type, a sheet type, a laminated type, a cylindrical type, a flat type, and a square type. Further, it may be applied to a large-sized vehicle used for an electric vehicle or the like. FIG. 1 is a schematic view showing an example of the aqueous solution-based lithium
なお、本開示は上述した実施形態に何ら限定されることはなく、本開示の技術的範囲に属する限り種々の態様で実施し得ることはいうまでもない。 It goes without saying that the present disclosure is not limited to the above-described embodiment, and can be implemented in various embodiments as long as it belongs to the technical scope of the present disclosure.
以下には、本明細書で開示する水溶液系電解液を具体的に作製した例を実施例として説明する。 Hereinafter, an example in which the aqueous electrolytic solution disclosed in the present specification is specifically prepared will be described as an example.
［実施例１］
２，６−ナフタレンジカルボン酸２リチウムを電解質とする飽和水溶液を調製した。電解質の濃度は、約０．５Ｍと見積もられた。これを電解液としてサイクリックボルタモグラムを測定した。作用極、対極は、ステンレス鋼（ＳＵＳ３１６）の金網とし、参照極には、銀−塩化銀電極を用いた。図２は、実施例１の水溶液系電解液のサイクリックボルタモグラムである。図２に示すように、実施例１では、−１．１Ｖから１．２Ｖの範囲で水の酸化分解反応、あるいは、還元分解反応を示す電流は測定されなかった。このことから、実施例１の水溶液系電解液は、この電位範囲で電気化学的に安定であり、電位窓が２．３Ｖである好適な電解液であることがわかった。
[Example 1]
A saturated aqueous solution using dilithium 2,6-naphthalenedicarboxylic acid as an electrolyte was prepared. The electrolyte concentration was estimated to be about 0.5M. Using this as an electrolytic solution, a cyclic voltammogram was measured. The working electrode and the counter electrode were made of stainless steel (SUS316) wire mesh, and the reference electrode was a silver-silver chloride electrode. FIG. 2 is a cyclic voltammogram of the aqueous electrolyte solution of Example 1. As shown in FIG. 2, in Example 1, the current showing the oxidative decomposition reaction or the reduction decomposition reaction of water was not measured in the range of −1.1 V to 1.2 V. From this, it was found that the aqueous electrolyte solution of Example 1 is a suitable electrolyte solution that is electrochemically stable in this potential range and has a potential window of 2.3 V.
［実施例２］
マロン酸２リチウムを電解質とする飽和水溶液を調製した。電解質の濃度は、約２Ｍと見積もられた。これを電解液として実施例１と同様にサイクリックボルタモグラムを測定した。図３は、実施例２の水溶液系電解液のサイクリックボルタモグラムである。図３に示すように、実施例２では、−１．１Ｖから１．２Ｖの範囲で水の酸化分解反応、あるいは、還元分解反応を示す電流は測定されなかった。このことから、実施例２の水溶液系電解液は、この電位範囲で電気化学的に安定であり、電位窓が２．３Ｖである好適な電解液であることがわかった。
[Example 2]
A saturated aqueous solution using dilithium malonic acid as an electrolyte was prepared. The electrolyte concentration was estimated to be about 2M. Using this as an electrolytic solution, a cyclic voltamogram was measured in the same manner as in Example 1. FIG. 3 is a cyclic voltammogram of the aqueous electrolyte solution of Example 2. As shown in FIG. 3, in Example 2, the current showing the oxidative decomposition reaction or the reduction decomposition reaction of water was not measured in the range of −1.1 V to 1.2 V. From this, it was found that the aqueous electrolyte solution of Example 2 is a suitable electrolyte solution that is electrochemically stable in this potential range and has a potential window of 2.3 V.
［実施例３］
マロン酸２リチウムを電解質とし、電解質の濃度を０．５Ｍとした水溶液系電解液を調製した。図４は、実施例３の水溶液系電解液のサイクリックボルタモグラムである。図４に示すように、実施例３では、−１．１Ｖから１．２Ｖの範囲で水の酸化分解反応、あるいは、還元分解反応を示す電流は測定されなかった。このことから、実施例３の水溶液系電解液は、この電位範囲で電気化学的に安定であり、電位窓が２．３Ｖである好適な電解液であることがわかった。
[Example 3]
An aqueous electrolytic solution was prepared using dilithium malonic acid as an electrolyte and having an electrolyte concentration of 0.5 M. FIG. 4 is a cyclic voltammogram of the aqueous electrolyte solution of Example 3. As shown in FIG. 4, in Example 3, the current showing the oxidative decomposition reaction or the reduction decomposition reaction of water was not measured in the range of −1.1 V to 1.2 V. From this, it was found that the aqueous electrolyte solution of Example 3 is a suitable electrolyte solution that is electrochemically stable in this potential range and has a potential window of 2.3 V.
［比較例１］
グリシンリチウムを電解質とする飽和水溶液を調製した。電解質の濃度は、約０．５Ｍと見積もられた。図５は、比較例１の水溶液系電解液のサイクリックボルタモグラムである。図５に示すように、比較例１では、モノカルボン酸を電解質としたため、電位窓が１．８Ｖであり、実施例１〜３に比して低かった。
[Comparative Example 1]
A saturated aqueous solution using lithium glycine as an electrolyte was prepared. The electrolyte concentration was estimated to be about 0.5M. FIG. 5 is a cyclic voltammogram of the aqueous electrolyte solution of Comparative Example 1. As shown in FIG. 5, in Comparative Example 1, since the monocarboxylic acid was used as the electrolyte, the potential window was 1.8 V, which was lower than that of Examples 1 to 3.
なお、本開示は上述した実施例に何ら限定されることはなく、本開示の技術的範囲に属する限り種々の態様で実施し得ることはいうまでもない。 It should be noted that the present disclosure is not limited to the above-described examples, and it goes without saying that the present disclosure can be carried out in various aspects as long as it belongs to the technical scope of the present disclosure.
本明細書で開示する水溶液系リチウム二次電池用電解液及び水溶液系リチウム二次電池は、エネルギー産業、例えば電池産業の分野に利用可能である。 The electrolytic solution for an aqueous solution-based lithium secondary battery and the aqueous solution-based lithium secondary battery disclosed in the present specification can be used in the fields of the energy industry, for example, the battery industry.
２０ 水溶液系リチウム二次電池、２１ 電池ケース、２２ 正極、２３ 負極、２４
セパレータ、２５ ガスケット、２６ 封口板、２７ 水溶液系電解液。
20 aqueous solution lithium secondary battery, 21 battery case, 22 positive electrode, 23 negative electrode, 24
Separator, 25 gasket, 26 sealing plate, 27 aqueous electrolyte.
Claims (4)
水溶性の２価の有機酸構造を有する２リチウム塩を電解質とし、０．５ｍｏｌ／Ｌ以上の濃度で該電解質を溶解した水溶液であり、
前記電解質は、脂肪族及び芳香族のジカルボン酸２リチウム塩のうち１以上を含む、
水溶液系リチウム二次電池用電解液。 An electrolytic solution used in an aqueous lithium secondary battery having a positive electrode and a negative electrode.
The dilithium salt having a divalent organic acid structure of soluble and electrolyte, Ri aqueous der dissolving the electrolyte at a concentration of at least 0.5 mol / L,
The electrolyte comprises one or more of the aliphatic and aromatic dicarboxylic acid dilithium salts.
Electrolyte for aqueous lithium secondary batteries.
負極と、
請求項１〜３のいずれか１項に記載の水溶液系リチウム二次電池用電解液と、
を備えた水溶液系リチウム二次電池。 With the positive electrode
With the negative electrode
The electrolytic solution for an aqueous solution-based lithium secondary battery according to any one of claims 1 to 3.
Aqueous lithium secondary battery equipped with.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017073742A JP6922355B2 (en) | 2017-04-03 | 2017-04-03 | Electrolyte for aqueous solution-based lithium secondary battery and aqueous solution-based lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017073742A JP6922355B2 (en) | 2017-04-03 | 2017-04-03 | Electrolyte for aqueous solution-based lithium secondary battery and aqueous solution-based lithium secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2018181420A JP2018181420A (en) | 2018-11-15 |
| JP6922355B2 true JP6922355B2 (en) | 2021-08-18 |
Family
ID=64275831
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2017073742A Expired - Fee Related JP6922355B2 (en) | 2017-04-03 | 2017-04-03 | Electrolyte for aqueous solution-based lithium secondary battery and aqueous solution-based lithium secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6922355B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11817561B2 (en) | 2018-05-21 | 2023-11-14 | Panasonic Intellectual Property Management Co., Ltd. | Electrolyte and secondary battery |
| KR102803146B1 (en) * | 2021-06-23 | 2025-05-07 | 컨템포러리 엠퍼렉스 테크놀로지 (홍콩) 리미티드 | Method for producing SEI membrane component-like additives and electrolyte, lithium ion battery, battery module, battery pack and power consumption device |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013146792A1 (en) * | 2012-03-28 | 2013-10-03 | 国立大学法人信州大学 | Hybrid capacitor |
| EP3486992B1 (en) * | 2013-06-28 | 2020-09-23 | Positec Power Tools (Suzhou) Co., Ltd | Battery |
| JP6650701B2 (en) * | 2014-09-29 | 2020-02-19 | 東ソー・ファインケム株式会社 | Method for improving electrochemical stability of aqueous electrolyte, electrolyte with improved electrochemical stability, aqueous sodium ion battery and aqueous lithium ion battery using the same |
| DE112016000412T8 (en) * | 2015-01-14 | 2017-11-09 | The University Of Tokyo | AQUEOUS ELECTROLYTE SOLUTION FOR THE ENERGY STORAGE DEVICE AND THE ENERGY STORAGE DEVICE CONTAINING THE AQUEOUS ELECTROLYTE SOLUTION |
| JP6565323B2 (en) * | 2015-05-19 | 2019-08-28 | 株式会社豊田中央研究所 | Non-aqueous secondary battery |
| CN105047932B (en) * | 2015-08-31 | 2017-10-27 | 张家港智电芳华蓄电研究所有限公司 | A kind of aquo-lithium ion battery quinones negative material and aquo-lithium ion battery |
-
2017
- 2017-04-03 JP JP2017073742A patent/JP6922355B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2018181420A (en) | 2018-11-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Suriyakumar et al. | Metal-organic frameworks based membrane as a permselective separator for lithium-sulfur batteries | |
| CA2962296C (en) | Electrode materials for rechargeable zinc cells and batteries produced therefrom | |
| Luo et al. | An interwoven MoO 3@ CNT scaffold interlayer for high-performance lithium–sulfur batteries | |
| KR102658785B1 (en) | Electrodes and electrolytes for water-soluble electrochemical energy storage devices | |
| Chang et al. | Green energy storage chemistries based on neutral aqueous electrolytes | |
| JP6423453B2 (en) | Aqueous electrolyte for power storage device and power storage device including the aqueous electrolyte | |
| JP6613474B2 (en) | Aqueous electrolyte for power storage device and power storage device including the aqueous electrolyte | |
| JP5383954B1 (en) | Metal oxygen battery | |
| JP6361599B2 (en) | Power storage device | |
| CN102918614B (en) | Capacitor and manufacture method thereof | |
| JP5202767B2 (en) | Metal oxygen battery | |
| JP5263115B2 (en) | Aqueous secondary battery | |
| KR20120080199A (en) | Material consisting of composite oxide particles, method for preparing same, and use thereof as electrode active material | |
| TWI542534B (en) | Composite material, negative electrode, and sodium secondary battery | |
| JP6394253B2 (en) | Non-aqueous secondary battery electrode, method for producing the same, and non-aqueous secondary battery | |
| Hara et al. | Emergent electrochemical functions and future opportunities of hierarchically constructed metal–organic frameworks and covalent organic frameworks | |
| JP2015079685A (en) | Aqueous solution-based secondary battery | |
| JP5187350B2 (en) | Aqueous secondary battery | |
| JP6922355B2 (en) | Electrolyte for aqueous solution-based lithium secondary battery and aqueous solution-based lithium secondary battery | |
| JP5493330B2 (en) | Water-based lithium secondary battery | |
| WO2018147404A1 (en) | Metal air battery | |
| JP2019186266A (en) | Electricity storage device | |
| JP5220211B1 (en) | Metal oxygen battery | |
| JP2019079617A (en) | Electrolyte, power storage device and production method of the power storage device | |
| JP6863347B2 (en) | Aqueous solution secondary battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20200312 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20201216 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20210126 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20210226 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20210629 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20210712 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6922355 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| LAPS | Cancellation because of no payment of annual fees |