CN106058319A - Electrolyte with polyanion functional group and preparation method and application thereof - Google Patents
Electrolyte with polyanion functional group and preparation method and application thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—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
- H01M10/0568—Liquid materials characterised by the solutes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses an electrolyte with a polyanion functional group and a preparation method and application thereof, and relates to a nonaqueous secondary battery electrolyte. For example, the preparation method of Li[PF2(PO2F2)2(C2O4)] comprises the following steps: (1) dissolving Li3PO4 into dimethyl carbonate, adding LiPF6, and recycling a settled solution for recrystallization after reaction so as to obtain LiPO2F2; (2) dissolving the LiPO2F2 obtained in the first step into dimethyl ether, then introducing PF5 gas, and recycling a settled solution for recrystallization so as to obtain LiPF4(PO2F2)2; and (3) under an inert atmosphere condition, dissolving the LiPF4(PO2F2)2 obtained in the second step into the dimethyl ether, then adding oxalic acid, and reacting to obtain the product LiPF2(PO2F2)2(C2O4). The electrolyte with the polyanion functional group can be used in the preparation of a nonaqueous electrolyte and a nonaqueous secondary battery.
Description
Technical field
The present invention relates to non-aqueous secondary batteries electrolyte, especially relate to a class and there is the electrolyte of polyanionic functional group
And preparation method and application.
Background technology
Reduce fossil class energy resource consumption, reduce the discharge of carbon dioxide isothermal chamber gas, become the current whole mankind and the most urgently solve
One of problem certainly.In today that energy environment is continuous worsening, lithium ion battery industry is in new energy field role day
Benefit highlights, Development of EV, with battery provide power replace oil be a practicable method, it is ensured that energy security and
The important channel of development low-carbon economy.
At present, China and world's Main Developed Countries have all put into effect the policy of a lot of support new-energy automobile, new forms of energy vapour
Car is classified as one of seven big novel industries by country, will promote China's Development of Electric Vehicles further from policy aspect, and by electronic
Automobile is as main development direction, and along with the development of New Energy Industry, its demand, by increasing, is expected at electronic vapour
Car field presents explosive growth.
Power lithium-ion battery and coupling electrolyte are core and the development bottlenecks of electric automobile.Electrolyte is lithium-ion electric
One of big critical material in pond four, formulated by non-aqueous organic solvent, electrolyte lithium salt (lithium hexafluoro phosphate etc.), additive etc..
Electrolyte lithium salt is not only the supplier of lithium ion in electrolyte, and its anion is also to determine electrolyte process based prediction model
Principal element.The electrolyte lithium salt obtaining widespread commercialization application at present is LiPF6.But LiPF6Meet water to be easier to decompose, relatively
Under high-temperature or rugged environment, produce the free acids such as HF (Fluohydric acid .), so that electrolyte acidifying, ultimately result in electrode material
Damage and the drastically deterioration of battery performance；Seek to substitute LiPF6Performance more preferable novel electrolytes lithium salts become and grind
One of emphasis studied carefully.
LiPOxFyOften it is considered LiPF6Inorganic constituents in negative pole SEI, adds use in the electrolytic solution, is just deposited on
Negative terminal surface, suppresses LiPF6Decompose side reaction, simultaneously LiPO at interfacexFyLead lithium performance and can effectively reduce in battery
Resistance；Japanese Patent Laid-Open 2014-62036 reports the synthetic method of a kind of difluorophosphate, uses LiPF6Mix with LiCl,
The method then passing to steam obtains, but reacts wayward, and by-product is numerous, and the part chloride ion of residual affects battery
Performance.Pyrosulfate and fluorine gas are reacted generation mixed gas by Wang Hai etc., then by anhydrous by LiF of prepared mixed gas
In hydrogen fluoride solution, reaction obtains difluorophosphate product, and this electrolyte can be substantially improved the capacity restoration rate of battery, low temperature
Discharge performance and cycle performance (Chinese patent CN104445133A).
It is pointed out that POxFy -Group radius is less, be relatively difficult to resolve in non-aqueous organic solvent from, no matter as electrolysis
The main salt of matter or assisted electrolysis matter use, and the ionic conductivity of electrolyte all can be caused to reduce, make battery capacity and coulombic efficiency
Become impact.
Summary of the invention
It is an object of the invention to provide class electrolyte with polyanionic functional group and preparation method thereof.
The electrolyte that another object of the present invention is to provide a class to have polyanionic functional group is preparing non-aqueous solution electrolysis
Application in liquid and non-aqueous secondary batteries.
The general structure of the electrolyte that a described class has polyanionic functional group is as follows:
Wherein, A+For alkali metal ion；M is (III A) race in the periodic table of elements or (V A) element, is (III A) race at M
Time, m1Value is 0～4, m2It is 0～2；When M is (V A) race, m1Value is 0～6, m2It is 0～3；R1、R2It is each independently selected from halogen
Element, C1-C10Itrile group, haloalkyl, C6-C20Aryl or halogenated aryl, R3And R4It is each independently selected from C0-C8Alkyl,
Thiazolinyl, alkynyl and phenyl ring thereof etc..X1、X2、X3、X4It is each independently selected from IV race's element.
Described A+It is selected from Li+、Na+、K+One in Deng；M can be the one in B, P, Al, Sb etc.；X1、X2Can be C, Si
In any one；R1、R2、R3Can be F, CF3, one in fluorophenyl etc..Wherein anionicsiteIt is selected from [PF2(PO2F2)2(C2O4)]-、[P(PO2F2)2(C2O4)2]-、
{PF2(C2O4)[PO2(CF3)2]}-、{P[PO2(CF3)6]}-、[PF2(Si2O4)(PO2F2)2]、[P(Si2O4)2(PO2F2)2]-、[B
(PO2F2)4]-、[B(C2O4)(PO2F2)2]-At least one in Deng.
A described class has the electrolyte preparation method of polyanionic functional group, with Li [PF2(PO2F2)2(C2O4)] it is
Example, comprises the following steps:
1) under inert atmosphere conditions, by Li3PO4It is dissolved in dimethyl carbonate (DMC), is subsequently adding according to stoichiometry
Than the LiPF weighed6, reclaim settled solution recrystallization after reaction, obtain LiPO2F2；
2) under inert atmosphere conditions, by step 1) prepare LiPO2F2It is dissolved in dimethyl ether (DME), then passes to by change
Learn metering and compare PF5Gas, reclaims settled solution recrystallization, obtains LiPF4(PO2F2)2；
3) under inert atmosphere conditions, by step 2) LiPF that obtains4(PO2F2)2It is dissolved in dimethyl ether (DME), then adds
Enter oxalic acid (H2C2O4), react and i.e. obtain product LiPF2(PO2F2)2(C2O4)。
A described class has the electrolyte of polyanionic functional group and can apply in preparing nonaqueous electrolytic solution.
Described nonaqueous electrolytic solution includes that a class has the electrolyte of polyanionic functional group, non-aqueous organic solvent and interpolation
Agent, it is 0.01～3mol/ that the electrolyte that a described class has polyanionic functional group accounts for the molar concentration scope of nonaqueous electrolytic solution
L；
Described electrolyte is using on the basis of said structure compound, it is possible to select lithium hexafluoro phosphate, LiBF4,
In two (trifluoromethane sulfonic acid) imine lithium, double (fluorine sulphonyl) imine lithium, difluorine oxalic acid boracic acid lithium, di-oxalate lithium borate etc. at least
A kind of.
Described non-aqueous organic solvent is selected from carbonates non-aqueous organic solvent, fluoro ethers non-aqueous organic solvent, sulfone class
At least one in non-aqueous organic solvent, carboxylic acid esters non-aqueous organic solvent etc..
Described carbonates non-aqueous organic solvent is selected from ethylene carbonate, Allyl carbonate, Ethyl methyl carbonate, carbonic acid two
Methyl ester, diethyl carbonate, methyl propyl carbonate, fluorinated ethylene carbonate, fluoro Ethyl methyl carbonate, fluoropropylene carbonate, double fluorine
For at least one in ethylene carbonate, methyl trifluoro ethyl carbonate ester, three (trifluoroethyl) carbonic ester etc..
Described fluoro ethers non-aqueous organic solvent be selected from oxolane, 1,3-dioxolanes, 1,2-dimethoxy,
Diethylene glycol dimethyl ether, ethylene-propylene ether, methyl perfluoro for butyl ether, ethylperfluoro in fluoro-ethers such as butyl ether, fluoro ethylene-propylene ether etc.
At least one.
Described sulfone class non-aqueous organic solvent be selected from sulfolane, dimethyl sulfoxide, positive fourth sulfone, dimethyl sulfone, benzene sulfone, first and second
At least one in base sulfone etc..
Described additive is selected from succinonitrile, adiponitrile, hexamethylene dicyanide, hexane three nitrile, vinylethylene carbonate, carbonic acid Asia second
Alkene ester, propylene sulfite, dimethyl sulfite, sulfuric acid vinyl ester, methane-disulfonic acid methylene ester, n-pro-pyl phosphoric anhydride, triolefin
At least one in propyl phosphate, succinic anhydride, pyrovinic acid acid anhydride etc..
A described class has the electrolyte of polyanionic functional group and can apply in preparing non-aqueous secondary batteries.
Described non-aqueous secondary batteries, including positive pole, negative pole, barrier film and nonaqueous electrolytic solution, barrier film be located at positive pole and negative pole it
Between, described nonaqueous electrolytic solution includes that a class has the electrolyte of polyanionic functional group, non-aqueous organic solvent and additive.
The present invention utilizes a described class to have the excellent electrochemical performance of electrolyte of polyanionic functional group, is used for preparing
Nonaqueous electrolytic solution and nonaqueous electrolytic solution secondary battery, the electrolyte that a described class has polyanionic functional group substitutes or part
Substitute LiPF6, make up or suppress LiPF6Meet water and easily decompose the secondary cell caused with poor heat stability at high temperature cycle performance
Deterioration, internal resistance rise the problem that high aspect exists, thus improve the overall function of electrolyte, meet the high energy to secondary cell
The demand that metric density grows to even greater heights.
Two kinds of electrolytic anion structure of functional groups are organically combined by the present invention, utilize [PO2R2]-Functional group can suppress
The HF corrosion to interfacial film in electrolyte.Additionally, the distribution dispersion of this electrolyte charge delocalization, reduce the lattice energy of lithium salts, reduce
The effect of zwitterion also increases lithium salts dissolubility, thus improves electrochemistry and the thermal stability of lithium salts.The anion increased
Group occurs electrochemical decomposition to react, with PO during initial charge2F2Mutual form stable and densification lead lithium protective layer,
The increase of molecular structure, it is possible to more efficient protection interface.
Accompanying drawing explanation
Fig. 1 is embodiment 1 and comparative example 1 high temperature circulation capability retention curve.
Fig. 2 is embodiment 1 and comparative example 1 room temperature circulation volume conservation rate curve.
Fig. 3 is capability retention and recovery rate after comparative example and embodiment high temperature storage.
Detailed description of the invention
The present invention is described in further detail with embodiment below in conjunction with the accompanying drawings, but embodiments of the present invention do not limit
In implementation below.
The nonaqueous electrolytic solution of embodiment of the present invention, comprises the chemical combination of non-aqueous organic solvent, additive and below formula
Thing, here, be exemplified below out LiP (C2O4)F2(PO2F2)2、LiBC2O4PO2F2、LiB(PO2CF3)4、Li[PF2(PO2F2)2
(C2O4)]-、Li[P(PO2F2)2(C2O4)2]-、Li{PF2(C2O4)[PO2(CF3)2]}-、Li[PF2(Si2O4)(PO2F2)2]、Li[P
(Si2O4)2(PO2F2)2]-、Li[B(PO2F2)4]-、Li[B(C2O4)(PO2F2)2]-(seeing table 1).
Table 1
Embodiment 1
1) prepared by electrolyte
Preparing electrolyte in glove box, be full of high-purity argon gas in glove box, moisture Control is at below 5ppm, and temperature is room
Temperature.Ethylene carbonate (EC), dimethyl carbonate (DEC), Ethyl methyl carbonate (EMC) are distinguished purification by the mass ratio of 30 30 40
Rear mixing, and remove impurity obtains mixed solvent system, then by the lithium hexafluoro phosphate (LiPF of 1mol/L except water6) add mixed solvent
Middle dissolving, is simultaneously introduced 1%VC and 1% compound 1 i.e. can get electrolyte, tests electrolytic conductivity.
2) prepared by anode pole piece
Quality according to 95 32 is than mixed cathode active material LiNi1/3Co1/3Mn1/3O2, conductive agent Super-P is with viscous
Knot agent PVDF (HSV900), then by they in solvent NMP dispersed, obtain anode sizing agent.Slurry is coated uniformly on
On the two sides of aluminum foil current collector, through drying, rolling and be vacuum dried, after welding aluminum lug, obtain anode pole piece, pole piece face
Density is 15～30mg/cm2。
3) preparation of cathode pole piece
Mass ratio according to 94 1 2.5 2.5 is by negative electrode active material Delanium, conductive agent Super-P and binding agent
Butadiene-styrene rubber (SBR) and thickening agent hydroxymethyl cellulose (CMC), then by they in solvent deionized water dispersed,
To cathode size.Slurry is coated uniformly on the two sides of copper foil current collector, through drying, rolling and be vacuum dried, welds nickel
Obtaining cathode pole piece after lug processed, pole piece surface density is 10～20mg/cm2。
4) prepared by battery core
Between anode pole piece and cathode pole piece, place the polyethene microporous membrane of 20 μm as isolating membrane, then carried out
Winding, is assembled into 2.5Ah flexible packaged battery core, treats fluid injection after baking.
5) battery core fluid injection and chemical conversion
In the environment that dew point controls below-40 DEG C, prepare after electrolyte injection is toasted in battery core by above-mentioned, electrolyte
Reservoir quantity controls 2.5～5g/Ah, then according to following steps are melted into: 0.05C constant-current charge 30min, and 0.2C constant current is filled
Electricity is to 3.9V, and after shelving 10h, with 0.5C constant-current charge to 4.2V, constant-voltage charge to electric current is 0.05C, then with 0.5C electric current
Constant-current discharge is to 3.0V.
6) room temperature loop test
With 1C constant-current charge to 4.2V at room temperature 25 DEG C, constant-voltage charge to electric current is 0.05C, then with 1C electric current constant current
It is discharged to 3.0V, circulates 800 weeks, record the discharge capacity of first week and the discharge capacity of the 800th week, test thickness, interior simultaneously
The data variation such as resistance.
7) high temperature circulation test
With 1C constant-current charge to 4.2V at 55 DEG C, constant-voltage charge to electric current is 0.05C, then with 1C electric current constant-current discharge
To 3.0V, circulate 800 weeks, record the discharge capacity of first week and the discharge capacity of the 800th week, test thickness, internal resistance etc. simultaneously
Data.
8) high-temperature storage performance test
At room temperature with 1C constant-current charge to 4.2V, then constant-voltage charge to electric current is 0.05C, the thickness of test battery,
Then battery is held in 80 DEG C of baking ovens of constant temperature storage 48h, be cooled to after taking-up room temperature test cell thickness, discharge capacity,
The data such as internal resistance.
Embodiment 2
Being changed into by 1% compound 1 in prepared by electrolyte in addition to the compound 2 of 1%, other are same as in Example 1, survey
Examination room temperature circulation, high temperature circulation and the data of high temperature storage.
Embodiment 3
Being changed into by 1% compound 1 in prepared by electrolyte in addition to the compound 3 of 1%, other are same as in Example 1, survey
Examination room temperature circulation, high temperature circulation and the data of high temperature storage.
Embodiment 4
Being changed into by 1% compound 1 in prepared by electrolyte in addition to the compound 4 of 1%, other are same as in Example 1, survey
Examination room temperature circulation, high temperature circulation and the data of high temperature storage.
Embodiment 5
Being changed into by 1% compound 1 in prepared by electrolyte in addition to the compound 5 of 1%, other are same as in Example 1, survey
Examination room temperature circulation, high temperature circulation and the data of high temperature storage.
Embodiment 6
Being changed into by 1% compound 1 in prepared by electrolyte in addition to the compound 6 of 1%, other are same as in Example 1, survey
Examination room temperature circulation, high temperature circulation and the data of high temperature storage.
Comparative example 1
In addition in electrolyte preparation without compound 1, other are same as in Example 1, test electrolytic conductivity,
The data such as the circulation of battery room temperature, high temperature circulation and high temperature storage are tested after fluid injection.
Comparative example 2
Without compound 1 in preparing except electrolyte, add 1%LiPO in the electrolytic solution2F2Outside, other and enforcement
Example 1 is identical, tests electrolytic conductivity, tests the data such as the circulation of battery room temperature, high temperature circulation and high temperature storage after fluid injection.
Comparative example and embodiment battery data see table 2.
Table 2
Embodiment 1 and comparative example 1 high temperature circulation capability retention curve see Fig. 1.Embodiment 1～6 is prepared
Compare with comparative example 1～2 for the lithium secondary battery electrolyte containing described structural compounds: the data such as table 2 and Fig. 3 can
To find out, the battery room temperature circulation obtained by the electrolyte embodiment containing present configuration formula compound, high temperature cyclic performance
Substantially being optimized with high-temperature storage performance, especially Fig. 2 embodiment 1 and comparative example 1 room temperature circulate, high-temperature cycle life ratio
Relatively curve is it can be seen that the battery cycle life containing this structural compounds is improved significantly, for being used at electrokinetic cell
For aspect, it it is the electrolyte lithium salt of a kind of very advantageous.
Claims (10)
1. a class has the electrolyte of polyanionic functional group, it is characterised in that its general structure is as follows:
Wherein, A+For alkali metal ion；M is (III A) race in the periodic table of elements or (V A) element, when M is (III A) race, and m1
Value is 0～4, m2It is 0～2；When M is (V A) race, m1Value is 0～6, m2It is 0～3；R1、R2Be each independently selected from halogen,
C1-C10Itrile group, haloalkyl, C6-C20Aryl or halogenated aryl, R3And R4It is each independently selected from C0-C8Alkyl, alkene
Base, alkynyl and phenyl ring thereof；X1、X2、X3、X4It is each independently selected from IV race's element.
A class the most as claimed in claim 1 has the electrolyte of polyanionic functional group, it is characterised in that described A+Selected from Li+、Na+、K+In one；M is the one in B, P, Al, Sb；X1、X2For any one in C, Si；R1、R2、R3For F, CF3, in fluorophenyl
One.
A class the most as claimed in claim 1 has the electrolyte of polyanionic functional group, it is characterised in that its anionicsiteSelected from [PF2(PO2F2)2(C2O4)]-、[P(PO2F2)2(C2O4)2]-、{PF2
(C2O4)[PO2(CF3)2]}-、{P[PO2(CF3)6]}-、[PF2(Si2O4)(PO2F2)2]、[P(Si2O4)2(PO2F2)2]-、[B
(PO2F2)4]-、[B(C2O4)(PO2F2)2]-In at least one.
4. a class has the electrolyte preparation method of polyanionic functional group, it is characterised in that comprise the following steps:
1) under inert atmosphere conditions, by Li3PO4It is dissolved in dimethyl carbonate, is subsequently adding according to stoichiometric proportion weighing
LiPF6, reclaim settled solution recrystallization after reaction, obtain LiPO2F2；
2) under inert atmosphere conditions, by step 1) prepare LiPO2F2It is dissolved in dimethyl ether, then passes to stoichiometrically
PF5Gas, reclaims settled solution recrystallization, obtains LiPF4(PO2F2)2；
3) under inert atmosphere conditions, by step 2) LiPF that obtains4(PO2F2)2It is dissolved in dimethyl ether, is subsequently adding oxalic acid, instead
Should i.e. obtain product LiPF2(PO2F2)2(C2O4)。
A class the most as claimed in claim 1 has the electrolyte of polyanionic functional group and applies in preparing nonaqueous electrolytic solution.
Apply the most as claimed in claim 5, it is characterised in that described nonaqueous electrolytic solution includes that a class has polyanionic functional group
Electrolyte, non-aqueous organic solvent and additive, the electrolyte that a described class has polyanionic functional group accounts for nonaqueous electrolytic solution
Molar concentration scope be 0.01～3mol/L.
Apply the most as claimed in claim 5, it is characterised in that described electrolyte selected from lithium hexafluoro phosphate, LiBF4, two (three
Methyl fluoride sulfonic acid) imine lithium, double (fluorine sulphonyl) imine lithium, difluorine oxalic acid boracic acid lithium, at least one in di-oxalate lithium borate.
Apply the most as claimed in claim 5, it is characterised in that described non-aqueous organic solvent selected from carbonates non-aqueous organic solvent,
At least one in fluoro ethers non-aqueous organic solvent, sulfone class non-aqueous organic solvent, carboxylic acid esters non-aqueous organic solvent；
Described carbonates non-aqueous organic solvent is selected from ethylene carbonate, Allyl carbonate, Ethyl methyl carbonate, carbonic acid diformazan
Ester, diethyl carbonate, methyl propyl carbonate, fluorinated ethylene carbonate, fluoro Ethyl methyl carbonate, fluoropropylene carbonate, double fluoro
At least one in ethylene carbonate, methyl trifluoro ethyl carbonate ester, three (trifluoroethyl) carbonic ester；
Described fluoro ethers non-aqueous organic solvent is selected from oxolane, 1,3-dioxolanes, 1,2-dimethoxy, two sweet
Diethylene glycol dimethyl ether, ethylene-propylene ether, methyl perfluoro for butyl ether, ethylperfluoro at least in butyl ether, fluoro ethylene-propylene ether fluoro-ether
Kind；
Described sulfone class non-aqueous organic solvent is selected from sulfolane, dimethyl sulfoxide, positive fourth sulfone, dimethyl sulfone, benzene sulfone, first ethyl sulfone
In at least one；
Described additive is selected from succinonitrile, adiponitrile, hexamethylene dicyanide, hexane three nitrile, vinylethylene carbonate, vinylene carbonate
Ester, propylene sulfite, dimethyl sulfite, sulfuric acid vinyl ester, methane-disulfonic acid methylene ester, n-pro-pyl phosphoric anhydride, three allyls
At least one in base phosphate ester, succinic anhydride, pyrovinic acid acid anhydride.
A class the most as claimed in claim 1 has the electrolyte of polyanionic functional group and applies in preparing non-aqueous secondary batteries.
Apply the most as claimed in claim 9, it is characterised in that described non-aqueous secondary batteries, including positive pole, negative pole, barrier film and non-
Water electrolysis liquid, barrier film is located between positive pole and negative pole, and described nonaqueous electrolytic solution includes that a class has the electricity of polyanionic functional group
Xie Zhi, non-aqueous organic solvent and additive.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106848404A (en) * | 2017-02-22 | 2017-06-13 | 中航锂电（洛阳）有限公司 | A kind of lithium-ion battery electrolytes functional additive, lithium-ion battery electrolytes and lithium ion battery |
| CN107863556A (en) * | 2017-10-24 | 2018-03-30 | 湛江市金灿灿科技有限公司 | The lithium ion battery and its electrolyte that a kind of high-nickel material is positive pole, silicon carbon material is negative pole |
| CN109133023A (en) * | 2017-06-27 | 2019-01-04 | 天津金牛电源材料有限责任公司 | The circulation utilization method of nonaqueous solvents in a kind of difluorophosphate preparation process |
| CN110416487A (en) * | 2018-04-27 | 2019-11-05 | 宁德时代新能源科技股份有限公司 | Lithiated polyacrylonitrile sulfide, process for producing the same, positive electrode sheet and lithium-sulfur secondary battery |
| CN110994028A (en) * | 2019-12-25 | 2020-04-10 | 香河昆仑化学制品有限公司 | Electrolyte applied to high-energy-density lithium ion battery and preparation method thereof |
| CN111740161A (en) * | 2018-09-21 | 2020-10-02 | 宁德新能源科技有限公司 | Electrolyte and electrochemical device comprising the same |
| US11444330B2 (en) * | 2019-05-23 | 2022-09-13 | Ningde Amperex Technology Limited | Electrolytic solution and electrochemical device using the same |
| CN116581387A (en) * | 2023-07-11 | 2023-08-11 | 宁德时代新能源科技股份有限公司 | Electrolyte, battery and electric equipment |
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