CN102324566B - Preparation method for ionic liquid electrolyte - Google Patents
Preparation method for ionic liquid electrolyte Download PDFInfo
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- CN102324566B CN102324566B CN2011102784274A CN201110278427A CN102324566B CN 102324566 B CN102324566 B CN 102324566B CN 2011102784274 A CN2011102784274 A CN 2011102784274A CN 201110278427 A CN201110278427 A CN 201110278427A CN 102324566 B CN102324566 B CN 102324566B
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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
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- 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
Abstract
The present invention discloses a preparation method for an ionic liquid electrolyte. According to the method, a lithium salt, a carbonate, ionic liquid, 12-crown-4 and a 12-crown-4 derivative, a polymethacrylic acid long chain alkyl ester, a polyacrylic acid long chain alkyl ester and a fire retardant agent are adopted as raw materials. The preparation method comprises: mixing the raw materials according to a certain ratio, wherein the raw materials comprise, by mass, 0.001-95% of the lithium salt, 0.001-95% of the carbonate, 0.001-95% of the ionic liquid, 0.001-95% of the 12-crown-4 and the 12-crown-4 derivative, 0.001-15% of the polymethacrylic acid long chain alkyl ester, 0.001-15% of the polyacrylic acid long chain alkyl ester and 0.001-15% of the fire retardant agent; carrying out stirring until all the materials are completely dissolved to obtain the ionic liquid electrolyte.
Description
Technical field
The present invention relates to a kind of preparation method of il electrolyte, belong to the lithium ion battery material field.
Background technology
The advantages such as lithium ion battery has that operating voltage is high, energy density is large, temperature limit is wide, self-discharge rate is low, has extended cycle life, memory-less effect.Along with increasingly sharpening of world energy sources crisis and environmental crisis; lithium ion battery is compared the extensive concern that has advantage significantly and be subject to countries in the world with conventional batteries; be described as one of environmental protection energy of 21 century; this makes lithium ion battery develop rapidly becomes a huge industry, occupies an important position in global economy and acts on.
At present; lithium ion battery has been widely used in pocket household electrical appliance as in portable computer and mobile phone; in Aeronautics and Astronautics, artificial satellite and military domain of communication equipment, also be widely applied; especially in recent years the application in the electric bicycle field has obtained developing rapidly; following lithium ion battery will be brought into play as electrokinetic cell the effect that conventional batteries is difficult to substitute in auto industry; make automobile become the vehicles of clean environment firendly, will play an important role for the protection world environments.
Electrolyte is one of large critical material of lithium ion battery four (positive electrode, negative material, barrier film, electrolyte), be " blood " of lithium ion battery, playing the effect of conduction electron in lithium ion battery between both positive and negative polarity, is the assurance that lithium ion battery obtains the performances such as high voltage, high specific energy.At present, lithium-ion battery electrolytes is generally by highly purified organic solvent, electrolyte lithium salt, other necessary raw material such as additive, under certain condition, formulated by a certain percentage.Organic solvent adopts carbonic ester series high-purity organic solvent more, as ethylene carbonate, propene carbonate, butylene, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, methyl carbonic acid propylene, ethyl carbonate propylene etc., electrolyte lithium salt is actual, and what use is mainly lithium hexafluoro phosphate.
Lithium hexafluoro phosphate exists the problems such as preparation process complexity, process conditions be harsh, expensive, particularly has the problems such as thermal stability is poor, poor water resistance.When lithium hexafluoro phosphate is met water or steam, decomposition reaction occurs rapidly generate phosphorus pentafluoride, phosphorus pentafluoride is colourless foul gas at normal temperatures and pressures, skin, eyes, mucous membrane are had to intense stimulus, in humid air or meet water and can generate severe toxicity and the extremely strong hydrogen fluoride of corrosivity by vigorous reaction, this has had a strong impact on stability and the safety in utilization of lithium ion battery.
Lithium ion battery relies on the comprehensive advantage of himself coming into a more huge industrial colony---automobile power cell field.In order to adapt to this huge industrial colony, the development trend in lithium-ion battery electrolytes material future will mainly concentrate on the aspects such as ionic liquid, new lithium salts.Therefore, the electrolyte material that the positive and negative electrode material of research and development and lithium ion battery is complementary, to make lithium ion battery safer, there is higher power and larger capacity, be applied to electric motor car, energy storage, space flight and field widely with finally making the lithium ion battery safe ready, significant to promoting the lithium ion battery industrial expansion.
Ionic liquid (Ionic Liquids) is exactly ion, to consist of fully, the salt be in a liquid state under low temperature (<100 ℃), and also referred to as low temperature molten salt, it generally is comprised of organic cation and inorganic anion.The material consisted of ion be in a liquid state at room temperature or near room temperature temperature, be called ionic liquid at room temperature, generally referred to as ionic liquid.Because ionic liquid has good conductivity, difficult volatilizees, do not burn, electrochemical window is more much bigger than other electrolyte aqueous solution, ionic liquid is applied to battery and can alleviates self discharge, ionic liquid is applied to manufacture novel high-performance battery, solar cell and capacitor etc. as electrolyte and all has significant advantage.Therefore, ionic liquid, as lithium-ion battery electrolytes, not only can be widened the serviceability temperature scope of lithium ion battery, and can improve the fail safe of lithium ion battery under high-energy-density, the desirable electrolyte of following power lithium-ion battery, thereby, be subject in recent years extensive concern.
The present invention is with lithium salts, carbonic ester, ionic liquid, 12-crown-4 and derivative thereof, the polymethylacrylic acid long-chain alkyl groups, polyacrylic acid long-chain alkyl groups and fire retardant etc. are raw material, the preparation steam forces down, thermally-stabilised good, chemical stability is good, electrochemical window is wide, clean, environmental protection, the il electrolyte of safety and excellent performance, to substitute the lithium hexafluorophosphate electrolyte solution that contains of current lithium ion battery use, fundamentally solve the existing poor water resistance of traditional organic electrolyte, the problems such as poor heat stability, improve the capacity of lithium ion battery, the performance such as cryogenic property and battery cycle life.
Adopt il electrolyte cheap, the Chemical Physics stable performance, substitute the lithium hexafluorophosphate electrolyte solution of lithium ion battery in the market, it is one of inexorable trend of lithium ion battery industrial development, to be conducive to significantly reduce the production cost of lithium ion battery, improve the performance of lithium ion battery, very favourable to large tracts of land developing lithium ion battery produce market.
Summary of the invention
The preparation method of a kind of il electrolyte of the present invention, provide that a kind of to take lithium salts, carbonic ester, ionic liquid, 12-crown-4 and derivative thereof, polymethylacrylic acid long-chain alkyl groups, polyacrylic acid long-chain alkyl groups and fire retardant be raw material, according to certain mass percent, the method for preparation lithium-ion battery electrolytes.
The preparation method of a kind of il electrolyte of the present invention adopts following technical scheme:
According to lithium salts, carbonic ester, ionic liquid, 12-crown-4 and derivative thereof, the polymethylacrylic acid long-chain alkyl groups, the mass percent of polyacrylic acid long-chain alkyl groups and fire retardant is (0.001%～95%): (0.001%～95%): (0.001%～95%): (0.001%～95%): (0.001%～15%): (0.001%～15%): the ratio of (0.001%～15%), by lithium salts, carbonic ester, ionic liquid, 12-crown-4 and derivative thereof, the polymethylacrylic acid long-chain alkyl groups, polyacrylic acid long-chain alkyl groups and fire retardant mix, after being stirred to all materials and dissolving fully, obtain il electrolyte.
The preparation method of a kind of il electrolyte of the present invention has following features:
1, use fluorocarboxylic acid lithium salts and fluoro sulfonic acid lithium salts, as trifluoroacetic acid lithium, five fluorine propionic acid lithiums and trifluoromethanesulfonic acid lithium, can effectively improve the conductivity of il electrolyte;
2, substitute lithium hexafluoro phosphate with ionic liquid, both can reduce the production cost of il electrolyte, can eliminate again the problem of electrolyte poor water resistance, also can effectively improve the conductivity of il electrolyte;
3, because 12-crown-4 and derivative thereof can form complex compound with the lithium ion complexing, thereby increase the degree of dissociation of lithium salts, reduce the interaction between lithium ion and solvent molecule, realized effective separation that the lithium salts zwitterion is right, therefore, use 12-crown-4 and derivative thereof as complexing agent, can further improve the conductivity of il electrolyte;
4, use polymethylacrylic acid long-chain alkyl groups and polyacrylic acid long-chain alkyl groups can effectively reduce the solidifying point of il electrolyte, make the serviceability temperature scope of il electrolyte become wider, be conducive to widen its application;
5, the organic solvent in lithium-ion battery electrolytes can be vaporized, lithium ion battery in the situation that excessively discharge and recharge, short circuit and large electric current work long hours and emit a large amount of heat, cause flammable electrolyte to have potential safety hazard, even cause battery to be blasted, the purpose of using fire retardant is to make inflammable organic electrolyte become difficult combustion or non-flammable electrolyte, avoid battery burn under overheated condition or explode, eliminate the potential safety hazard of electrolyte.
The preparation method of a kind of il electrolyte of the present invention, lithium salts used is any one or more in trifluoroacetic acid lithium, five fluorine propionic acid lithiums and trifluoromethanesulfonic acid lithium.
The preparation method of a kind of il electrolyte of the present invention, carbonic ester used is any one or more in ethylene carbonate, propene carbonate, butylene, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, methyl carbonic acid propylene and ethyl carbonate propylene.
The preparation method of a kind of il electrolyte of the present invention, ionic liquid used is 1-methyl-3-ethyl imidazol(e) hexafluorophosphate, 1-methyl-3-ethyl imidazol(e) tetrafluoroborate, 1-methyl-3-butyl imidazole hexafluorophosphate, 1-methyl-3-butyl imidazole tetrafluoroborate, 1-methyl-3-hexyl imidazoles hexafluorophosphate, 1-methyl-3-hexyl tetrafluoroborate, 1, 2-dimethyl-3-ethyl imidazol(e) hexafluorophosphate, 1, 2-dimethyl-3-ethyl imidazol(e) tetrafluoroborate, 1, 2-dimethyl-3-butyl imidazole hexafluorophosphate, 1, 2-dimethyl-3-butyl imidazole tetrafluoroborate, 1, 2-dimethyl-3-hexyl imidazoles hexafluorophosphate, 1, 2-dimethyl-3-hexyl tetrafluoroborate, N-ethylpyridine hexafluorophosphate, N-ethylpyridine tetrafluoroborate, N-butyl-pyridinium hexafluorophosphate, N-butyl-pyridinium tetrafluoroborate, any one or more in N-hexyl pyridine hexafluorophosphate and N-hexyl pyridinium tetrafluoroborate salt.
The preparation method of a kind of il electrolyte of the present invention, 12-crown-4 used and derivative thereof are 12-crown-4, phendioxin 2-hat-4,2-methylol-12-crown-4,1, any one or more in 2-cyclohexyl-12-crown-4 and 4-methyl benzo 12-crown-4.
The preparation method of a kind of il electrolyte of the present invention, polymethylacrylic acid long-chain alkyl groups used is any one or more in polymethylacrylic acid n-tetradecane base ester, polymethylacrylic acid dodecyl ester, polymethylacrylic acid n-octyl.
The preparation method of a kind of il electrolyte of the present invention, polyacrylic acid long-chain alkyl groups used is any one or more in polyacrylic acid n-tetradecane base ester, polyacrylic acid dodecyl ester, polyacrylic acid n-octyl.
The preparation method of a kind of il electrolyte of the present invention, fire retardant used is any one or more in deca-BDE, pentabromotoluene, HBCD, triphenyl phosphate, tricresyl phosphate.
Embodiment
It is below the preparation method's of a kind of il electrolyte of the present invention non-limiting example.Providing of these examples is only for illustrative purposes, can not be interpreted as limitation of the invention.Because without departing from the spirit and scope of the present invention, can carry out many conversion to the present invention.In these embodiments, unless stated otherwise, all percentage all refers to mass percent.
Embodiment 1
Trifluoroacetic acid lithium: 8%
Ethylene carbonate: 40%
Ethyl carbonate propylene: 15%
1-methyl-3-ethyl imidazol(e) hexafluorophosphate: 15%
N-hexyl pyridinium tetrafluoroborate salt: 5%
12-crown-4: 15%
Polymethylacrylic acid n-tetradecane base ester: 0.3%
Polyacrylic acid n-octyl: 0.2%
Deca-BDE: 1.5%
Preparing process: according to above-mentioned mass percent, trifluoroacetic acid lithium, ethylene carbonate, ethyl carbonate propylene, 1-methyl-3-ethyl imidazol(e) hexafluorophosphate, N-hexyl pyridinium tetrafluoroborate salt, 12-crown-4, polymethylacrylic acid n-tetradecane base ester, polyacrylic acid n-octyl and deca-BDE are mixed, after being stirred to all materials and dissolving fully, obtain il electrolyte.
Embodiment 2
Trifluoromethanesulfonic acid lithium: 10%
Propene carbonate: 31%
Butylene: 26%
1-methyl-3-ethyl imidazol(e) tetrafluoroborate: 12%
N-hexyl pyridine hexafluorophosphate: 7%
Phendioxin 2-hat-4:12%
Polymethylacrylic acid dodecyl ester: 0.2%
Polyacrylic acid dodecyl ester: 0.1%
Pentabromotoluene: 1.7%
Preparing process: according to above-mentioned mass percent, trifluoromethanesulfonic acid lithium, propene carbonate, butylene, 1-methyl-3-ethyl imidazol(e) tetrafluoroborate, N-hexyl pyridine hexafluorophosphate, phendioxin 2-hat-4, polymethylacrylic acid dodecyl ester, polyacrylic acid dodecyl ester and pentabromotoluene are mixed, after being stirred to all materials and dissolving fully, obtain il electrolyte.
Embodiment 3
Trifluoroacetic acid lithium: 11%
Butylene: 50%
1-methyl-3-butyl imidazole hexafluorophosphate: 6%
N-butyl-pyridinium tetrafluoroborate: 13%
2-methylol-12-crown-4: 18%
Polymethylacrylic acid n-octyl: 0.2%
Polyacrylic acid n-tetradecane base ester: 0.2%
HBCD: 1.6%
Preparing process: according to above-mentioned mass percent, trifluoroacetic acid lithium, butylene, 1-methyl-3-butyl imidazole hexafluorophosphate, N-butyl-pyridinium tetrafluoroborate, 2-methylol-12-crown-4, polymethylacrylic acid n-octyl, polyacrylic acid n-tetradecane base ester and HBCD are mixed, after being stirred to all materials and dissolving fully, obtain il electrolyte.
Embodiment 4
Trifluoromethanesulfonic acid lithium: 9%
Dimethyl carbonate: 45%
Butylene: 10%
1-methyl-3-butyl imidazole tetrafluoroborate: 7%
N-butyl-pyridinium hexafluorophosphate: 11%
1,2-cyclohexyl-12-crown-4: 15.5%
Polymethylacrylic acid n-tetradecane base ester: 0.1%
Polyacrylic acid n-octyl: 0.5%
Triphenyl phosphate: 1.9%
Preparing process: according to above-mentioned mass percent, by trifluoromethanesulfonic acid lithium, dimethyl carbonate, butylene, 1-methyl-3-butyl imidazole tetrafluoroborate, N-butyl-pyridinium hexafluorophosphate, 1,2-cyclohexyl-12-crown-4, polymethylacrylic acid n-tetradecane base ester, polyacrylic acid n-octyl and triphenyl phosphate mix, after being stirred to all materials and dissolving fully, obtain il electrolyte.
Embodiment 5
Trifluoromethanesulfonic acid lithium: 3%
Trifluoroacetic acid lithium: 7%
Diethyl carbonate: 20%
Propene carbonate: 31%
1-methyl-3-hexyl imidazoles hexafluorophosphate: 10%
N-ethylpyridine tetrafluoroborate: 10%
4-methyl benzo 12-crown-4: 17%
Polymethylacrylic acid dodecyl ester: 0.2%
Polyacrylic acid dodecyl ester: 0.2%
Tricresyl phosphate: 1.6%
Preparing process: according to above-mentioned mass percent, trifluoromethanesulfonic acid lithium, trifluoroacetic acid lithium, diethyl carbonate, propene carbonate, 1-methyl-3-hexyl imidazoles hexafluorophosphate, N-ethylpyridine tetrafluoroborate, 4-methyl benzo 12-crown-4, polymethylacrylic acid dodecyl ester, polyacrylic acid dodecyl ester and tricresyl phosphate are mixed, after being stirred to all materials and dissolving fully, obtain il electrolyte.
Embodiment 6
Trifluoromethanesulfonic acid lithium: 12%
Methyl ethyl carbonate: 17%
Propene carbonate: 30%
1-methyl-3-hexyl tetrafluoroborate: 6%
N-ethylpyridine hexafluorophosphate: 11%
Phendioxin 2-hat-4:21%
Polymethylacrylic acid n-octyl: 0.3%
Polyacrylic acid n-tetradecane base ester: 0.3%
Deca-BDE: 2.4%
Preparing process: according to above-mentioned mass percent, trifluoromethanesulfonic acid lithium, methyl ethyl carbonate, propene carbonate, 1-methyl-3-hexyl tetrafluoroborate, N-ethylpyridine hexafluorophosphate, phendioxin 2-hat-4, polymethylacrylic acid n-octyl, polyacrylic acid n-tetradecane base ester and deca-BDE are mixed, after being stirred to all materials and dissolving fully, obtain il electrolyte.
Embodiment 7
Five fluorine propionic acid lithiums: 13%
Methyl propyl carbonate: 28%
Methyl ethyl carbonate: 19%
1,2-dimethyl-3-ethyl imidazol(e) hexafluorophosphate: 7%
1-methyl-3-butyl imidazole hexafluorophosphate: 8%
2-methylol-12-crown-4: 23%
Polymethylacrylic acid n-tetradecane base ester: 0.1%
Polyacrylic acid n-octyl: 0.3%
Pentabromotoluene: 1.7%
Preparing process: according to above-mentioned mass percent, by five fluorine propionic acid lithiums, methyl propyl carbonate, methyl ethyl carbonate, 1,2-dimethyl-3-ethyl imidazol(e) hexafluorophosphate, 1-methyl-3-butyl imidazole hexafluorophosphate, 2-methylol-12-crown-4, polymethylacrylic acid n-tetradecane base ester, polyacrylic acid n-octyl and pentabromotoluene mix, after being stirred to all materials and dissolving fully, obtain il electrolyte.
Embodiment 8
Trifluoroacetic acid lithium: 5%
Five fluorine propionic acid lithiums: 7%
Methyl carbonic acid propylene: 13%
Dimethyl carbonate: 38%
1,2-dimethyl-3-butyl imidazole hexafluorophosphate: 9%
1-methyl-3-ethyl imidazol(e) tetrafluoroborate: 6%
1,2-cyclohexyl-12-crown-4: 19%
Polymethylacrylic acid n-octyl: 0.2%
Polyacrylic acid dodecyl ester: 0.4%
HBCD: 2.3%
Preparing process: according to above-mentioned mass percent, by trifluoroacetic acid lithium, five fluorine propionic acid lithiums, methyl carbonic acid propylene, dimethyl carbonate, 1,2-dimethyl-3-butyl imidazole hexafluorophosphate, 1-methyl-3-ethyl imidazol(e) tetrafluoroborate, 1,2-cyclohexyl-12-crown-4, polymethylacrylic acid n-octyl, polyacrylic acid dodecyl ester and HBCD mix, after being stirred to all materials and dissolving fully, obtain il electrolyte.
Claims (1)
1. the preparation method of an il electrolyte is characterized in that:
The preparing process of il electrolyte is according to lithium salts, carbonic ester, ionic liquid, 12-crown-4 and derivative thereof, the polymethylacrylic acid long-chain alkyl groups, the mass percent of polyacrylic acid long-chain alkyl groups and fire retardant is (0.001%～95%): (0.001%～95%): (0.001%～95%): (0.001%～95%): (0.001%～15%): (0.001%～15%): the ratio of (0.001%～15%), by lithium salts, carbonic ester, ionic liquid, 12-crown-4 and derivative thereof, the polymethylacrylic acid long-chain alkyl groups, polyacrylic acid long-chain alkyl groups and fire retardant mix, after being stirred to all materials and dissolving fully, obtain il electrolyte, preparation il electrolyte lithium salts used is any one or more in trifluoroacetic acid lithium, five fluorine propionic acid lithiums and trifluoromethanesulfonic acid lithium, preparation il electrolyte carbonic ester used is any one or more in ethylene carbonate, propene carbonate, butylene, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, methyl carbonic acid propylene and ethyl carbonate propylene, preparation il electrolyte ionic liquid used is 1-methyl-3-ethyl imidazol(e) hexafluorophosphate, 1-methyl-3-ethyl imidazol(e) tetrafluoroborate, 1-methyl-3-butyl imidazole hexafluorophosphate, 1-methyl-3-butyl imidazole tetrafluoroborate, 1-methyl-3-hexyl imidazoles hexafluorophosphate, 1-methyl-3-hexyl tetrafluoroborate, 1, 2-dimethyl-3-ethyl imidazol(e) hexafluorophosphate, 1, 2-dimethyl-3-ethyl imidazol(e) tetrafluoroborate, 1, 2-dimethyl-3-butyl imidazole hexafluorophosphate, 1, 2-dimethyl-3-butyl imidazole tetrafluoroborate, 1, 2-dimethyl-3-hexyl imidazoles hexafluorophosphate, 1, 2-dimethyl-3-hexyl tetrafluoroborate, N-ethylpyridine hexafluorophosphate, N-ethylpyridine tetrafluoroborate, N-butyl-pyridinium hexafluorophosphate, N-butyl-pyridinium tetrafluoroborate, any one or more in N-hexyl pyridine hexafluorophosphate and N-hexyl pyridinium tetrafluoroborate salt, the derivative of the 12-crown-4 that the preparation il electrolyte is used is phendioxin 2-hat-4,2-methylol-12-crown-4,1, any one or more in 2-cyclohexyl-12-crown-4 and 4-methyl benzo 12-crown-4, preparation il electrolyte polymethylacrylic acid long-chain alkyl groups used is any one or more in polymethylacrylic acid n-tetradecane base ester, polymethylacrylic acid dodecyl ester, polymethylacrylic acid n-octyl, preparation il electrolyte polyacrylic acid long-chain alkyl groups used is any one or more in polyacrylic acid n-tetradecane base ester, polyacrylic acid dodecyl ester, polyacrylic acid n-octyl, preparation il electrolyte fire retardant used is any one or more in deca-BDE, pentabromotoluene, HBCD, triphenyl phosphate, tricresyl phosphate.
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| CN102912383B (en) * | 2012-10-31 | 2015-02-25 | 南京工业大学 | Method for manufacturing porous nickel powder by electro-deposition of Ni-Al-Mg-Li alloy |
| WO2015042851A1 (en) * | 2013-09-27 | 2015-04-02 | 惠州亿纬锂能股份有限公司 | Electrolyte for lithium battery and lithium battery using same |
| CN103756754B (en) * | 2014-02-19 | 2015-08-19 | 南京林业大学 | A kind ofly add lubricating oil of modified Nano zinc powder and ionic liquid and preparation method thereof |
| RU2592646C2 (en) * | 2014-11-14 | 2016-07-27 | Открытое Акционерное Общество " Научно-исследовательский и проектно-технологический институт электроугольных изделий" | Low-temperature lithium-fluocarbon element |
| WO2018096889A1 (en) * | 2016-11-24 | 2018-05-31 | 日本電気株式会社 | Non-aqueous electrolyte solution and lithium ion secondary battery |
| CN107946646A (en) * | 2017-04-14 | 2018-04-20 | 云南锡业集团（控股）有限责任公司 | A kind of square low-temperature lithium ion battery and preparation method thereof |
| CN111293356A (en) * | 2018-12-10 | 2020-06-16 | 张家港市国泰华荣化工新材料有限公司 | Crown ether electrolyte and application thereof |
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