CN109494405A - A kind of lithium-ion battery electrolytes additive and electrolyte - Google Patents
A kind of lithium-ion battery electrolytes additive and electrolyte Download PDFInfo
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- CN109494405A CN109494405A CN201811087402.4A CN201811087402A CN109494405A CN 109494405 A CN109494405 A CN 109494405A CN 201811087402 A CN201811087402 A CN 201811087402A CN 109494405 A CN109494405 A CN 109494405A
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- ion
- lithium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention provides a kind of lithium-ion battery electrolytes additive and contain the electrolyte of additive, the electrolysis additive is the salt compounds that halide anion and metal cation are constituted, and the halide anion is halogen anion and/or pseudohalogen anion；The metal cation is one or more of alkali metal cation, alkaline earth metal cation, transition-metal cation, main group metal cation and metalloid cation.Compared with prior art; with lithium ion anode material cobalt acid lithium specific physical and chemical reaction can occur for the electrolysis additive that the present invention uses during circulating battery; stable protective film is generated in electrode interface; prevent the avalanche of cathode material structure; to improve the coulombic efficiency, cyclical stability and discharge capacity of lithium ion battery, and substantially prolong cycle life.
Description
Technical field
The present invention relates to technical field of lithium ion more particularly to a kind of lithium-ion battery electrolytes additive and electrolysis
Liquid.
Background technique
Since commercial Li-ion battery comes out since 1991, in fields such as smart phone, wearable device, electric cars
Extensive utilization has been obtained, the important component in people's daily life is become.Electrolyte is referred to as lithium ion battery
" blood " has the interface of vital influence, especially electrode and electrolyte on the performance of lithium ion battery (LIBs)
Structure and properties.With the fast development of pure electric automobile (EVs) and hybrid-electric car (HEVs), people are to lithium ion battery
Energy density, cycle life and security requirement be continuously improved.However, positive electrode exists in traditional electrolyte liquid system
Violent structure change and interface side reaction easily occur in cyclic process, brings huge challenge to practical application.Exploitation adaptation
Electrolysis additive improves electrode and electrolyte interface structure, is to improve the most economical effective side of lithium ion battery chemical property
One of method, the extensive concern by all circles.
LiCoO2Since being developed since 1991 by Sony company, since it is simple with synthesis technology, charging/discharging voltage is flat
Platform stablizes the advantages that high with theoretical capacity and occupies very big one piece of share in anode material for lithium-ion batteries market.However due to
When cobalt acid lithium height takes off lithium, material has strong oxidizing property, can decompose electrolyte, therefore its in practical application only has 140mAh/g
The specific discharge capacity of left and right, and that there are capacity attenuations is rapid, coulombic efficiency is low and recycles the problems such as unstable.Currently, solution party
There are mainly two types of methods: on the one hand, improving or develop new electrode material；On the other hand, the lithium cobaltate cathode material electricity of adaptation is developed
Solve solution additive.
Vinylene carbonate (VC) is developed by the Sanyo Electric Company company of Japan earliest, with dielectric
The characteristics such as constant is high, viscosity is low, are a kind of most common electrolysis additives.Battery performance is improved about VC
The generally existing two kinds of viewpoints of main cause: a kind of to think that VC is reduced to form more stable SEI film in cathode, another kind thinks it
The catholyte interfacial film (SEI) that polymerization reaction is formed, which occurs, reduces the rate of positive electrode surface electrolyte oxidation.VC conduct
Electrolysis additive is relatively not added on battery coulombic efficiency really and increases, but the discharge capacity for adding battery after VC declines
The rate of deceleration does not have significant change.
Since F atom has strong electronegativity and a low pole, thus fluorinated solvents and its additive have lower freezing point,
The advantages that higher flash-point, oxidation stability are high and compatibility between electrolyte and electrode is strong, excellent performance and latent
Business application by all circles' extensive concern.At present, F includes fluoro lactone, fluoric cyclic carbonate, fluoro carboxylic for solvent
Acid, fluoro linear carbonates and fluoro-ether etc..But fluoro reagent is used as electrolyte solvent and has dosage big, it is at high cost etc. to ask
Topic, and can it is micro use and obtain remarkable result the metal halide salt additives including metal fluoride salt etc. it is rare
People refers to.
The problems such as lithium ion battery lithium cobaltate cathode capacity attenuation is serious, and coulombic efficiency is low is solved from the root, it is necessary to
Develop novel electrolysis additive that is cheap and being commercially easy to get.And metal halide salt additives are since it is to lithium cobaltate cathode material
Material has fabulous suitability, and stable protective film can be formed at interface, improves electrode with electrolyte interface structure to improve
Coulombic efficiency, cyclical stability and the discharge capacity of lithium ion battery, and effectively extend cycle life, this is to long circulating, Gao An
The lithium ion battery development of total stability is of great significance.
Summary of the invention
Present invention solves the technical problem that being to provide a kind of lithium-ion battery electrolytes additive, lithium ion battery is improved
Coulombic efficiency, cyclical stability and discharge capacity, and effectively extend cycle life, the present invention also provides one kind contain above-mentioned lithium
The electrolyte of ion battery electrolysis additive.
In view of this, the present invention provides a kind of lithium-ion battery electrolytes additives, which is characterized in that for halogen yin from
The salt compounds that son and metal cation are constituted, the halide anion be halogen anion and/or pseudohalogen yin from
Son；The metal cation is alkali metal cation, alkaline earth metal cation, transition-metal cation, main group metal cation
One or more of with metalloid cation.
Preferably, the halogen anion is one in fluorine ion, chloride ion, bromide ion, iodide ion and astatine ion
Kind is several.
Preferably, the pseudohalogen anion includes one of sulphur cyanogen, selenium cyanogen, oxygen cyanogen and the corresponding anion of cyanogen or several
Kind.
Preferably, the alkali metal cation is in lithium ion, sodium ion, potassium ion, rubidium ion, cesium ion and francium ion
One or more.
Preferably, the alkaline earth metal cation is one in beryllium ion, magnesium ion, calcium ion, strontium ion and barium ions
Kind is several.
Preferably, the transition-metal cation is one of titanium ion, zirconium ion, rhodium ion and manganese ion or several
Kind.
Preferably, the main group metal cation is aluminium ion, gallium ion, indium ion, tin ion, thallium ion, lead ion
One or more of with bismuth ion.
Preferably, the metalloid cation be boron ion, silicon ion, germanium ion, arsenic ion, antimony ion, tellurium ion and
One or more of polonium ion.
Correspondingly, containing lithium-ion battery electrolytes additive described in above-mentioned technical proposal the present invention also provides a kind of
Electrolyte, including lithium-ion battery electrolytes additive described in base fluid and above-mentioned technical proposal, the base fluid is with ethylene carbonate
One of ester, dimethyl carbonate, diethyl carbonate, 1,3- dioxolane, glycol dimethyl ether and fluorinated ethylene carbonate or
Several is solvent, with bis- (trifluoromethanesulp-onyl -onyl imide) lithiums or LiPF6For electrolytic salt.
Preferably, it is applied to lithium ion cell positive to protect, positive electrode is the cobalt acid lithium and/or de- lithium state of embedding lithium state
Cobalt dioxide.
The present invention provides a kind of lithium-ion battery electrolytes additive and contain the electrolyte of additive, the electrolyte
Additive is the salt compounds that halide anion and metal cation are constituted, and the halide anion is halogen anion
And/or pseudohalogen anion；The metal cation be alkali metal cation, alkaline earth metal cation, transition-metal cation,
One or more of main group metal cation and metalloid cation.Compared with prior art, the electrolyte that the present invention uses
With lithium ion anode material cobalt acid lithium specific physical and chemical reaction can occur for additive during circulating battery, look unfamiliar in sector electrode
At stable protective film, it is therefore prevented that the avalanche of cathode material structure, so that it is steady to improve the coulombic efficiency of lithium ion battery, circulation
Qualitative and discharge capacity, and substantially prolong cycle life.
Detailed description of the invention
Fig. 1 is the cycle performance figure of the battery prepared in embodiment 1 with blank electrolysis liquid 233；
Fig. 2 is the first all discharge curves of battery 0.1C of the electrolyte preparation after adding KF in embodiment 1；
Fig. 3 is the cycle performance figure of the electrolyte 0.1C after 1 blank electrolysis liquid 233 of embodiment and addition KF；
Fig. 4 is the cycle performance figure of the electrolyte 0.1C after 2 blank electrolysis liquid 233 of embodiment and addition KF；
Fig. 5 is the cycle performance figure of the electrolyte 0.5C after 3 blank electrolysis liquid 233 of embodiment and addition KF.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still
It should be appreciated that these descriptions are only further explanation the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.
The embodiment of the invention discloses a kind of lithium-ion battery electrolytes additives, are halide anion and metal cation
The salt compounds of composition, the halide anion are halogen anion and/or pseudohalogen anion；The metal sun from
Son is in alkali metal cation, alkaline earth metal cation, transition-metal cation, main group metal cation and metalloid cation
One or more.
Preferably, the halogen anion is fluorine ion, chloride ion, bromide ion, iodide ion and astatine ion
One or more of.The pseudohalogen anion includes sulphur cyanogen (SCN)2, selenium cyanogen (SeCN)2, oxygen cyanogen (OCN)2With cyanogen (CN)2
One or more of corresponding anion.The alkali metal cation be lithium ion, sodium ion, potassium ion, rubidium ion, caesium from
One or more of son and francium ion.The alkaline earth metal cation is beryllium ion, magnesium ion, calcium ion, strontium ion and barium
One or more of ion.The transition-metal cation be one of titanium ion, zirconium ion, rhodium ion and manganese ion or
It is several.The main group metal cation is in aluminium ion, gallium ion, indium ion, tin ion, thallium ion, lead ion and bismuth ion
One or more.The metalloid cation is boron ion, silicon ion, germanium ion, arsenic ion, antimony ion, tellurium ion and polonium
One or more of ion.
Lithium-ion battery electrolytes additive provided by the invention has different dissolubilities in the electrolytic solution, including readily soluble
(20 DEG C of solubility s>10g), solvable (s>1g), slightly soluble (s>0.01g) and indissoluble (s<0.01g).
Correspondingly, containing lithium-ion battery electrolytes additive described in above-mentioned technical proposal the present invention also provides a kind of
Electrolyte, including lithium-ion battery electrolytes additive described in base fluid and above-mentioned technical proposal, the base fluid is with ethylene carbonate
Ester (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), 1,3- dioxolane (DOL), glycol dimethyl ether (DME), fluorine
It is solvent for one or more of ethylene carbonate (FEC), with bis- (trifluoromethanesulp-onyl -onyl imide) lithiums (LiTFSI) or LiPF6
For electrolytic salt.Preferably, the electrolyte is protected applied to lithium ion cell positive, and positive electrode is embedding lithium state
The cobalt dioxide of cobalt acid lithium and/or de- lithium state.
Preferably, the electrolysis additive anion selects fluorine ion；Metal cation selects potassium ion, that is, adds
Agent is potassium fluoride salt (KF).Electrolyte system selection has preferable deliquescent FEC/EC/DMC-LiPF to KF6Combination solution；Electricity
Pond electrode uses lithium cobaltate cathode/graphite cathode.
Further preferably, FEC:EC:DMC=3:1:4, LiF additive amount are 0.5wt%.The lithium ion battery point
It is not tested under 0.05C and 0.1C multiplying power.
From above scheme as can be seen that the present invention provides a kind of lithium-ion battery electrolytes additive and containing additive
Electrolyte can form stable protective film at lithium ion cell anode material lithium cobaltate interface, improve electrode and electrolyte interface
Structure effectively extends cycle life to improve the coulombic efficiency, cyclical stability and discharge capacity of lithium ion battery.Through trying
Issue after examination and approval existing: control blank electrolysis liquid, after auxiliary agent is added, first discharge specific capacity, first charge-discharge efficiency gets a promotion；Auxiliary agent
Addition greatly reduces the decaying of specific capacity, and 10 enclose, and specific capacity keeps still extending battery 98% or more and following after 20 circles
The ring service life.
For a further understanding of the present invention, technical solution provided by the invention is carried out specifically below with reference to embodiment
Bright, protection scope of the present invention is not limited by the following examples.
Raw material and chemical reagent used in the embodiment of the present invention are commercially available.
Embodiment 1
In 1M LiPF6Fluorinated ethylene carbonate (FEC)/ethylene carbonate (EC)/dimethyl carbonate (DMC) (3:1:4,
Volume ratio) electrolyte (233) in be added mass fraction be 0.5% potassium fluoride (KF) additive (233+ auxiliary agent), obtain electricity
Solve liquid.
Using graphite as cathode, cobalt acid lithium is anode, respectively to be helped with blank electrolysis liquid 233 and addition manufactured in the present embodiment
The electrolyte (233+ auxiliary agent) of agent is assembled into the button cell of 2032 models in the glove box that argon gas is protected.
Assemble the test condition of obtained battery are as follows: the test of 0.05C/0.1C perseverance rate charge-discharge, 233 is different for electrolyte
The cycle performance figure of multiplying power is referring to Fig. 1, and lithium cobaltate cathode capacity attenuation in 233 electrolyte of non-adding assistant is fast as shown in Figure 1
Speed；Add the first all discharge curves of 0.1C after KF additive to see Fig. 2, KF additive is added in control blank electrolysis liquid as shown in Figure 2
Afterwards, first discharge specific capacity, first charge-discharge efficiency have certain promotion；The cycle performance of two kinds of electrolyte 0.1C as shown in figure 3,
The addition for knowing KF auxiliary agent greatly reduces the decaying of cobalt acid lithium specific capacity, and 10 enclose, and specific capacity is kept still 98% after 20 circles
More than.Extend battery cycle life.
Embodiment 2
In 1M LiPF6Ethylene carbonate (EC)/dimethyl carbonate (DMC) (1:1, volume ratio) electrolyte in be added
Potassium fluoride (KF) additive (blank+auxiliary agent) preparation that mass fraction is 0.5% obtains composite electrolyte.
Using lithium piece as cathode, nickel ion doped is anode, respectively to use blank electrolysis liquid and addition manufactured in the present embodiment
The electrolyte (blank+auxiliary agent) of auxiliary agent is assembled into the button cell of 2032 models in the glove box that argon gas is protected.
The test of 0.1C perseverance rate charge-discharge, nickel ion doped anode holds in the blank electrolysis liquid of non-adding assistant as shown in Figure 4
It measures lower；Significantly decay when circulation 70 is enclosed.After adding KF additive, blank electrolysis liquid, first discharge specific capacity are compareed
There is certain promotion, and greatly reduce the decaying of cobalt acid lithium specific capacity, specific capacity just starts to be remarkably decreased after 90 circles.Extend electricity
Pond cycle life.
Embodiment 3
In 1.1M LiPF6Ethylene carbonate (EC)/methyl ethyl carbonate (EMC)/diethyl carbonate (DEC) (12:16:9,
Volume ratio) electrolyte EED in be added mass fraction be 0.5% potassium fluoride (KF) additive (EED+ auxiliary agent) preparation answered
Close electrolyte.
Using lithium piece as cathode, nickel ion doped is anode, respectively using the electrolyte (EED+ of EED electrolyte and addition auxiliary agent
Auxiliary agent) button cell of 2032 models is assembled into the glove box of argon gas protection.
The test of 0.5C perseverance rate charge-discharge significantly extends circulating battery as shown in Figure 5 using the electrolyte of addition auxiliary agent
Service life.
The above description of the embodiment is only used to help understand the method for the present invention and its core ideas.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvements and modifications, these improvements and modifications also fall within the scope of protection of the claims of the present invention.
Claims (10)
1. a kind of lithium-ion battery electrolytes additive, which is characterized in that the salt constituted for halide anion and metal cation
Class compound, the halide anion are halogen anion and/or pseudohalogen anion；The metal cation is alkali gold
Belong to that cation, alkaline earth metal cation, transition-metal cation, main group metal be cationic and one of metalloid cation or
It is several.
2. lithium-ion battery electrolytes additive according to claim 1, which is characterized in that the halogen anion
For one or more of fluorine ion, chloride ion, bromide ion, iodide ion and astatine ion.
3. lithium-ion battery electrolytes additive according to claim 1, which is characterized in that the pseudohalogen anion is
One or more of sulphur cyanogen, selenium cyanogen, oxygen cyanogen and the corresponding anion of cyanogen.
4. lithium-ion battery electrolytes additive according to claim 1, which is characterized in that the alkali metal cation is
One or more of lithium ion, sodium ion, potassium ion, rubidium ion, cesium ion and francium ion.
5. lithium-ion battery electrolytes additive according to claim 1, which is characterized in that the alkaline earth metal cation
For one or more of beryllium ion, magnesium ion, calcium ion, strontium ion and barium ions.
6. lithium-ion battery electrolytes additive according to claim 1, which is characterized in that the transition-metal cation
For one or more of titanium ion, zirconium ion, rhodium ion and manganese ion.
7. lithium-ion battery electrolytes additive described in -6 any one according to claim 1, which is characterized in that the main group
Metal cation is one or more of aluminium ion, gallium ion, indium ion, tin ion, thallium ion, lead ion and bismuth ion.
8. lithium-ion battery electrolytes additive described in -6 any one according to claim 1, which is characterized in that the eka-gold
Belonging to cation is one or more of boron ion, silicon ion, germanium ion, arsenic ion, antimony ion, tellurium ion and polonium ion.
9. a kind of electrolyte, which is characterized in that be electrolysed including lithium ion battery described in base fluid and claim 1-8 any one
Solution additive, the base fluid is with ethylene carbonate, dimethyl carbonate, diethyl carbonate, 1,3- dioxolane, glycol dimethyl ether
It is solvent with one or more of fluorinated ethylene carbonate, with bis- (trifluoromethanesulp-onyl -onyl imide) lithiums or LiPF6For electrolyte
Salt.
10. electrolyte according to claim 9, which is characterized in that it is applied to lithium ion cell positive and protects, positive electrode
For the cobalt acid lithium of embedding lithium state and/or the cobalt dioxide of de- lithium state.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811087402.4A CN109494405A (en) | 2018-09-18 | 2018-09-18 | A kind of lithium-ion battery electrolytes additive and electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811087402.4A CN109494405A (en) | 2018-09-18 | 2018-09-18 | A kind of lithium-ion battery electrolytes additive and electrolyte |
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| CN201811087402.4A Withdrawn CN109494405A (en) | 2018-09-18 | 2018-09-18 | A kind of lithium-ion battery electrolytes additive and electrolyte |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3719908A1 (en) * | 2019-04-04 | 2020-10-07 | Toyota Jidosha Kabushiki Kaisha | Liquid electrolyte and fluoride-ion battery comprising the same |
| CN112670574A (en) * | 2020-12-22 | 2021-04-16 | 同济大学 | Electrolyte for metal battery and metal battery |
| CN113851622A (en) * | 2021-09-14 | 2021-12-28 | 厦门大学 | Protective layer of battery system and electrochemical device |
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| JP2014067587A (en) * | 2012-09-26 | 2014-04-17 | Sanyo Electric Co Ltd | Nonaqueous electrolyte secondary battery |
| KR20150014074A (en) * | 2013-07-29 | 2015-02-06 | 상명대학교서울산학협력단 | Electrolyte for high voltage lithium secondary battery and high voltage lithium secondary battery using the electrolyte |
| KR20150042352A (en) * | 2013-10-10 | 2015-04-21 | 재단법인대구경북과학기술원 | Nonaqueous electrolyte comprising fluoride and electrochimical device using the same |
| CN106129471A (en) * | 2016-08-29 | 2016-11-16 | 无锡市宝来电池有限公司 | The lithium battery electrolytes that a kind of compatibility is good |
| CN108417895A (en) * | 2018-03-20 | 2018-08-17 | 成都新柯力化工科技有限公司 | A kind of liquefaction gaseous state electrolyte for lithium battery under cryogenic conditions |
-
2018
- 2018-09-18 CN CN201811087402.4A patent/CN109494405A/en not_active Withdrawn
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014067587A (en) * | 2012-09-26 | 2014-04-17 | Sanyo Electric Co Ltd | Nonaqueous electrolyte secondary battery |
| KR20150014074A (en) * | 2013-07-29 | 2015-02-06 | 상명대학교서울산학협력단 | Electrolyte for high voltage lithium secondary battery and high voltage lithium secondary battery using the electrolyte |
| KR20150042352A (en) * | 2013-10-10 | 2015-04-21 | 재단법인대구경북과학기술원 | Nonaqueous electrolyte comprising fluoride and electrochimical device using the same |
| CN106129471A (en) * | 2016-08-29 | 2016-11-16 | 无锡市宝来电池有限公司 | The lithium battery electrolytes that a kind of compatibility is good |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3719908A1 (en) * | 2019-04-04 | 2020-10-07 | Toyota Jidosha Kabushiki Kaisha | Liquid electrolyte and fluoride-ion battery comprising the same |
| CN111799510A (en) * | 2019-04-04 | 2020-10-20 | 丰田自动车株式会社 | Electrolyte and fluoride ion battery |
| CN112670574A (en) * | 2020-12-22 | 2021-04-16 | 同济大学 | Electrolyte for metal battery and metal battery |
| CN113851622A (en) * | 2021-09-14 | 2021-12-28 | 厦门大学 | Protective layer of battery system and electrochemical device |
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