CN110518284A - A kind of nonaqueous electrolytic solution, battery and electric vehicle containing the nonaqueous electrolytic solution - Google Patents
A kind of nonaqueous electrolytic solution, battery and electric vehicle containing the nonaqueous electrolytic solution Download PDFInfo
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- CN110518284A CN110518284A CN201810493336.4A CN201810493336A CN110518284A CN 110518284 A CN110518284 A CN 110518284A CN 201810493336 A CN201810493336 A CN 201810493336A CN 110518284 A CN110518284 A CN 110518284A
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- electrolytic solution
- nonaqueous electrolytic
- battery
- additive
- carbonate
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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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- 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
Abstract
Battery and electric vehicle the invention discloses a kind of nonaqueous electrolytic solution, containing the nonaqueous electrolytic solution, the nonaqueous electrolytic solution includes lithium salts, organic solvent and dislikes the oxide-based additive of thiazole containing two, the electrolyte is applied to battery, the additive has good positive filming performance, it effectively hinders, positive electrode and organic electrolyte is inhibited to react, cycle performance of the positive active material at high voltage 4.4V is improved, it is final to improve cycle life of lithium ion battery and high rate performance.
Description
Technical field
The present invention relates to nonaqueous electrolytic solution fields, and in particular, to a kind of nonaqueous electrolytic solution contains the nonaqueous electrolytic solution
Battery and electric vehicle containing the battery.
Background technique
Film for additive is very important one kind in current electrolysis solution additive.Carbonic acid second in cathode film formation additive
Enester, fluorinated ethylene carbonate etc. use comparative maturity.It is later to the understanding of positive film for additive, it is now recognized that right
Anode film forming effective mainly some benzene compounds and heterocyclic compound and silane etc..But really realize that industrialization is answered
Almost without.In recent years having been reported that propylene sulfite (PS) has certain filming function in positive and negative anodes, but cell body
System is also only capable of stablizing being unable to satisfy the durability requirements to positive electrode under high potential in 4.35V.
Summary of the invention
To solve the above problems, the nonaqueous electrolytic solution contains lithium salts, You Jirong this application provides a kind of nonaqueous electrolytic solution
Agent and additive, the additive have structural formula shown in formula (1):
Formula (1),
In formula, R is selected from alkyl, aminoalkyl, amino, alkoxy, phenyl, dimethoxy alkyl, hydroxyl, amide groups, acyloxy
One of with carboxymethyl group.
Preferably, it is 1-5's that R, which is selected from aminoalkyl, carbon atom number that alkyl, carbon atom that carbon atom number is 1-5 are 1-5,
One of alkoxy, the dimethoxy alkyl that carbon atom number is 1-5 and phenyl.
Preferably, the phenyl is selected from、WithIn one
Kind, wherein X be hydrogen atom, alkyl, alkoxy, aminoalkyl, amino, dimethoxy alkyl, hydroxyl, amide groups, acyloxy and
One of carboxymethyl group.
Preferably, the X is selected from the alkoxy, carbon atom that hydrogen atom, the alkyl that carbon atom number is 1-5, carbon atom are 1-5
One of dimethoxy alkyl or amino that aminoalkyl that number is 1-5, carbon atom number are 1-5.
Preferably, R is in aminoalkyl, amino, amide groups, aminophenyl, aminoalkyl phenyl, amidophenyl
It is a kind of.
Preferably, the additive includes 5- amino -1,3, and 2,4- bis- dislike thiazole -2- oxides, 5- phenyl -1,3, and 2,4-
Two dislike thiazole -2- oxide, 5- aminophenyl -1,3,2,4- two dislikes thiazole -2- oxide, p-methoxyphenyl -1,3,2 5-,
4- bis- dislikes thiazole -2- oxide, 5- methyl-1, and 3,2,4- bis- dislikes thiazole -2- oxide, 5- amino-ethyl -1,3,2,4- two is disliked
One of thiazole -2- oxide is a variety of.
Preferably, on the basis of the gross mass of the nonaqueous electrolytic solution, the content of the additive is 0.05%-20%.
Preferably, on the basis of the gross mass of the nonaqueous electrolytic solution, the content of the additive is 0.2%-10%.
Preferably, the nonaqueous electrolytic solution also contains auxiliary additive, and the auxiliary additive includes in 1,3 propane sulphurs
Ester, 1,4 butane sultones, acrylic -1,3- sultones, sulfuric acid vinyl ester, sulfuric acid acrylic ester, butylene sulfite, carbonic acid
In vinylene, fluorinated ethylene carbonate, double oxalic acid boric acid and one or more of double fluorine sulfimide lithiums.
Preferably, on the basis of the gross mass of the nonaqueous electrolytic solution, the content of the auxiliary additive is 0.05%-
20%。
Preferably, the organic solvent is selected from dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, carbon
Sour dipropyl, ethylene carbonate, propene carbonate, vinylene carbonate, gamma-butyrolacton, sultone, ethylene sulfite, Asia
One in sulfuric acid acrylic ester, methyl sulfide, diethyl sulfite, methyl formate, methyl acrylate, methyl butyrate and ethyl acetate
Kind is several.
Preferably, the lithium salts is selected from LiBOB, LiPF6, LiBF4, LiSbF6, LiClO4, LiCF3SO3, Li
(CF3SO2) one of 2N, LiC4F9SO3, LiAlO4, LiAsF6, LiAlCl4, LiCl, LiI and low fatty acid lithium carbonate or
Several, the concentration of the lithium salts is 0.3-3 mol/L.
The present invention also provides a kind of battery, the battery includes battery case and is sealed in the intracorporal battery core of battery case
And nonaqueous electrolytic solution, the battery core include anode, cathode and diaphragm, which is characterized in that the nonaqueous electrolytic solution is above-mentioned provides
Nonaqueous electrolytic solution.
The present invention also provides a kind of electric vehicle, which contains the battery of above-mentioned offer.
Present inventor chances in an experiment, and the additive of herein described structure has lower oxidation electricity
Position, adds it in electrolyte, which is applied to battery, which can send out prior to the solvent in electrolyte
Raw oxidation, resulting product are adsorbed on positive electrode surface to form densification and stable protective layer, i.e., one layer stable SEI film
(stationary electrolyte interfacial film, Solid Electrolyte Interface), effectively hinder, inhibit positive electrode with it is organic
Electrolyte reacts, to prevent positive active material decaying, loss, improves positive active material at high voltage 4.4V
Cycle performance, it is final to improve cycle life of lithium ion battery and high rate performance.
Specific embodiment
Disclosing benzene compounds, heterocyclic compound and silane etc. in the related technology can form a film in positive electrode surface, inhibit
Side reaction occurs between positive electrode and electrolyte, but there is a problem of it is various, such as register in recent years added with sulfurous
The performance sharp-decay of acid propylene ester battery when battery system is more than 4.35V, is unable to satisfy to positive electrode under high potential
Durability requirements.
For the present invention in view of the above-mentioned problems, providing a kind of nonaqueous electrolytic solution, which contains lithium salts, organic solvent
And additive, the additive have structural formula shown in formula (1):
Formula (1), in formula, R be selected from alkyl, aminoalkyl, amino, alkoxy, phenyl, dimethoxy alkyl, hydroxyl, amide groups,
One of acyloxy and carboxymethyl group.
When R is alkyl, the alkyl of chain can be, be also possible to cyclic alkyl, chain-like alkyl can be that straight chain can also
To contain branch；Preferably, R is the alkyl for being 1-5 selected from carbon atom number, and present inventor has found by many experiments,
When R is the alkyl that carbon atom number is 1-5, the additive has optimal film-formation result.
As the example for the alkyl that carbon atom number is 1-5, it is specifically as follows methyl, ethyl, n-propyl, isopropyl, positive fourth
Base, sec-butyl, n-pentyl, isopentyl etc..
When R is aminoalkyl, it can be the aminoalkyl of chain, be also possible to cyclic aminoalkyl, chain amino alkane
Base for straight chain or can contain branch；Preferably, select carbon atom number for the aminoalkyl of 1-5, present inventor
It is found by many experiments, when R is the aminoalkyl that carbon atom number is 1-5, the additive has preferably film-formation result.
As the example for the aminoalkyl that carbon atom number is 1-5, it is specifically as follows amino methyl, 2- amino-ethyl, 3- ammonia
Base n-propyl, 2-amino isopropyls, 4-amino normal-butyls, 3-amino sec-butyls, 5-amino n-pentyls, 4-amino isoamyls
Base etc..
When R is alkoxy, it can be the alkoxy of chain, be also possible to cyclic alkoxy, chain alkoxy can be
Straight chain can also contain branch；Preferably, it selects, present inventor has found by many experiments, when R is that carbon atom number is
When the alkoxy of 1-5, the additive has preferably film-formation result.
As the example for the alkoxy that carbon atom number is 1-5, it is specifically as follows methoxyl group, ethyoxyl, positive propoxy, isopropyl
Oxygroup, n-butoxy, sec-butoxy, n-pentyloxy, isoamoxy etc..
When R is phenyl, the phenyl is selected from,WithIn
One kind, it is preferred that wherein, X be selected from hydrogen atom, alkyl, alkoxy, aminoalkyl, amino, dimethoxy alkyl, hydroxyl,
One of amide groups, acyloxy and carboxymethyl group, present inventor by many experiments find, when X be selected from hydrogen atom,
One of aminoalkyl or amino that alkoxy that alkyl that carbon atom number is 1-5, carbon atom are 1-5, carbon atom number are 1-5
When, the additive dissolubility is preferable, and has optimal positive film-formation result.
As the specific example of phenyl, specific R can for phenyl ring, p-aminophenyl, p-methylphenyl, to ethylphenyl,
To n-propyl phenyl, p-isopropyl phenyl, to n-butylphenyl, to n-butylphenyl, to secondary butyl phenenyl, to n-amylbenzene
Base, to isopentyl phenyl, p-methoxyphenyl, to ethoxyl phenenyl, to positive propoxy phenyl, to isopropyl phenyl, to just
Butoxy phenyl, to n-butoxyphenyl, to sec-butoxy phenyl, to n-pentyloxy phenyl, to isoamoxy phenyl, to amino
One of aminomethyl phenyl may be that ortho position substitution or meta position replace to the substitution of phenyl in above-mentioned group.
Description above is referred to when X is alkyl, alkoxy, aminoalkyl, amino, dimethoxy alkyl.
According to nonaqueous electrolytic solution provided by the present application, it is preferred that R be selected from aminoalkyl, amino, amide groups, aminophenyl,
One kind of aminoalkyl phenyl, amidophenyl, present inventor chance in an experiment, when R is selected from above-mentioned group
One of when, the oxidizing potential of the additive, can be in non-aqueous solution electrolysis significantly lower than the oxidizing potential of solvent in electrolyte
Preferential oxidation before aoxidizing occurs for organic solvent in liquid, and products therefrom is deposited on positive electrode surface, forms fine and close and stable film,
It effectively hinders, positive electrode and organic electrolyte is inhibited to react, to prevent positive active material decaying, loss.
Thiazole -2- oxides, 5- phenyl -1,3 are disliked specifically, the additive includes 5- amino -1,3,2,4- bis-, 2,4-
Two dislike thiazole -2- oxide, 5- aminophenyl -1,3,2,4- two dislikes thiazole -2- oxide, p-methoxyphenyl -1,3,2 5-,
4- bis- dislikes thiazole -2- oxide, 5- methyl-1, and 3,2,4- bis- dislikes thiazole -2- oxide, 5- amino-ethyl -1,3,2,4- two is disliked
One of thiazole -2- oxide is a variety of.
Above-mentioned additive, e.g., 5- phenyl -1,3,2,4- bis- dislike thiazole -2- oxide (No. CAS: 19279-25-5) can be with
Commercially available voluntarily to synthesize, other additives are referred to 5- phenyl -1,3, and 2,4- bis- dislike the preparation side of thiazole -2- oxide
Method is prepared.
The above-mentioned additive with formula (1) structure is added to electrolyte, because additive has lower oxidizing potential, In
It is easier to form a film in positive electrode surface because oxidation occurs prior to the organic solvent in nonaqueous electrolytic solution in battery charge and discharge process,
Formed film can effectively avoid reacting between positive electrode and electrolyte under high potential, so that the structure of positive electrode is more
Stablize, the high-temperature behavior and high-voltage performance of battery significantly improve.
The nonaqueous electrolytic solution proposed according to the present invention can be in the nonaqueous electrolytic solution and individually add a kind of above-mentioned addition
Agent is also possible to add a variety of above-mentioned additives simultaneously.Wherein, described on the basis of the gross mass of the nonaqueous electrolytic solution
The content of additive be 0.05%-20%, it is preferred that the content of the additive is 0.2%-10%, adds this in electrolyte and contains
The application additive of amount can reach good film-formation result, and will not cause large effect to the performance of battery.
Nonaqueous electrolytic solution according to the present invention, it is preferable that the nonaqueous electrolytic solution also contains auxiliary additive, the auxiliary
Additive includes 1,3 propane sultones, 1,4 butane sultones, acrylic -1,3- sultones, sulfuric acid vinyl ester, sulfuric acid propylene
In ester, butylene sulfite, vinylene carbonate, fluorinated ethylene carbonate, double oxalic acid boric acid, in double fluorine sulfimide lithiums extremely
Few one kind.Auxiliary additive and film for additive of the invention are jointly used in electrolyte, enable to the stability of battery
It is more excellent.
The nonaqueous electrolytic solution proposed according to the present invention, wherein described auxiliary on the basis of the gross mass of the nonaqueous electrolytic solution
The content for helping additive can be 0.05%-20% parts by weight, which can promote additive described herein to exist
Negative terminal surface forms one layer of stable SEI film, plays a protective role to cathode, improves the cycle performance of battery into one, but should
The consumption that excessively will cause excessive active lithium is added in auxiliary additive.
The nonaqueous electrolytic solution of offer according to the present invention, it is normal that those skilled in the art can be used in first organic solvent
The nonaqueous solvents used is advised, such as may include dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, carbonic acid
Dipropyl, ethylene carbonate, propene carbonate, vinylene carbonate, gamma-butyrolacton, sultone, ethylene sulfite, sulfurous
One of acid propylene ester, methyl sulfide, diethyl sulfite, methyl formate, methyl acrylate, methyl butyrate and ethyl acetate
Or it is several.
Nonaqueous electrolytic solution according to the present invention, wherein the selection of the lithium salts does not require particularly, can be non-aqueous electricity
Conventional use of lithium salts in liquid is solved, such as may include LiBOB, LiPF6、LiBF4、LiSbF6、LiClO4、LiCF3SO3、Li
(CF3SO2)2N、LiC4F9SO3、LiAlO4、LiAsF6、LiAlCl4, one of LiCl, LiI and low fatty acid lithium carbonate or several
Kind.The concentration of lithium salts is it is known to those skilled in the art that generally 0.3-3mol/L, preferably 0.8-1.2 mol/L.
The preparation method of nonaqueous electrolytic solution provided by the invention is the conventional use of method of those skilled in the art, i.e., will
Each component (including lithium salts, organic solvent and additive) is uniformly mixed, and is not had to mixed mode and the sequence present invention
Particular determination.Such as be now uniformly mixed organic solvent, lithium salts is then added and is uniformly mixed, it is equal to add the additive mixing
Even, the auxiliary additive can be added together with the additive.
The present invention also provides a kind of battery, the battery include battery case and be sealed in the intracorporal battery core of battery case and
Nonaqueous electrolytic solution.
Wherein, the nonaqueous electrolytic solution is nonaqueous electrolytic solution as described above；The battery core include anode, cathode and every
Film.Since the present invention pertains only to the improvement to prior art battery nonaqueous electrolytic solution, to other the Nomenclature Composition and Structure of Complexes of battery
There is no particular limitation, other the Nomenclature Composition and Structure of Complexes of battery are well known for the person skilled in the art, and details are not described herein.
Invention further provides a kind of electric vehicle, which contains above-mentioned battery.
The present invention will the present invention is further described in detail by following embodiment.
Implement 1
(1) preparation of nonaqueous electrolytic solution
Electrolyte is configured in glove box, controls the oxygen content in glove box, and < 2ppm is full of nitrogen and is controlled in glove box
In glove box the purity of nitrogen be 99.999%, by ethylene carbonate (EC), methyl ethyl carbonate (EMC) according to mass ratio EC:EMC=
3:7 is uniformly mixed, and obtains organic solvent, suitable electric conducting lithium salt LiPF6 is added into above-mentioned solution, the concentration of the lithium salts is
1.0mol/L is stirred evenly, and is added on the basis of the gross mass of nonaqueous electrolytic solution (including lithium salts, additive and organic solvent)
The fluorinated ethylene carbonate of the ethylene carbonate (VC) of 2.5wt.%, vinylethylene carbonate (VEC) and 3wt.% of 1.5wt.%
(FEC) it and is cleaned, except water process, obtains basic electrolyte；On the basis of the gross mass of the nonaqueous electrolytic solution, it is added
The additive of the present invention of 2wt%, obtained electrolyte are denoted as C1, wherein and it is described to be added to 5- amino -1,3,2,4-
Two dislike thiazole -2- oxide, structural formula are as follows:
(2) preparation of battery
By positive active material cobalt acid lithium, acetylene black, Kynoar, 90:5:5 is suppressed after mixing in aluminium foil according to the ratio
On, obtain positive plate；Using graphite as negative electrode tab；Using PE/PP composite diaphragm as amberplex, using the non-aqueous of the present embodiment
Electrolyte C1 is made into button cell S1 using conventional method in that art.
Embodiment 2
Nonaqueous electrolytic solution C2 and battery S2 are prepared using method same as Example 1, the difference is that preparing non-aqueous solution electrolysis
When liquid, added additive of the present invention is 5- phenyl -1,3, and 2,4- bis- dislike thiazole -2- oxide, and structural formula is
Embodiment 3
Nonaqueous electrolytic solution C3 and battery S3 are prepared using method same as Example 1, the difference is that preparing non-aqueous solution electrolysis
When liquid, added additive of the present invention is 5- aminophenyl -1,3, and 2,4- bis- dislike thiazole -2- oxide, structure
Formula is
Embodiment 4
Nonaqueous electrolytic solution C4 and battery S4 are prepared using method same as Example 1, the difference is that preparing non-aqueous solution electrolysis
When liquid, added additive of the present invention is 5- p-methoxyphenyl -1,3, and 2,4- bis- dislike thiazole -2- oxide,
Structural formula is
Embodiment 5
Nonaqueous electrolytic solution C5 and battery S5 are prepared using method same as Example 1, the difference is that preparing non-aqueous solution electrolysis
When liquid, added additive of the present invention is 5- methyl-1, and 3,2,4- bis- dislike thiazole -2- oxide, and structural formula is
Embodiment 6
Nonaqueous electrolytic solution C6 and battery S6 are prepared using method same as Example 1, the difference is that preparing non-aqueous solution electrolysis
When liquid, added additive of the present invention is 5- amino-ethyl -1,3, and 2,4- bis- dislike thiazole -2- oxide, structure
Formula is
Embodiment 7
Nonaqueous electrolytic solution C7 and battery S7 are prepared using method same as Example 1, the difference is that preparing non-aqueous solution electrolysis
When liquid, added additive of the present invention is 5- dimethoxy-methyl -1,3, and 2,4- bis- dislike thiazole -2- oxide,
Structural formula is
Embodiment 8
Nonaqueous electrolytic solution C8 and battery S8 are prepared using method same as Example 1, except that preparing non-aqueous solution electrolysis
When liquid, added additive of the present invention is 5- n-hexyl -1,3, and 2,4- bis- dislike thiazole -2- oxide.
Embodiment 9
Nonaqueous electrolytic solution C9 and battery S9 are prepared using method same as Example 1, except that preparing non-aqueous solution electrolysis
When liquid, added additive of the present invention is 5- n-hexane Oxy-1, and 3,2,4- bis- dislike thiazole -2- oxide, knot
Structure formula is
Embodiment 10
Nonaqueous electrolytic solution C10 and battery S10 are prepared using method same as Example 1, except that preparing non-water power
When solving liquid, the additive amount of added additive of the present invention is 0.2wt%.
Embodiment 11
Nonaqueous electrolytic solution C11 and battery S11 are prepared using method same as Example 1, except that preparing non-water power
When solving liquid, the additive amount of added additive of the present invention is 10wt%.
Embodiment 12
Nonaqueous electrolytic solution C12 and battery S12 are prepared using method same as Example 1, except that preparing non-water power
When solving liquid, the additive amount of added additive of the present invention is 0.05wt%.
Embodiment 13
Nonaqueous electrolytic solution C13 and battery S13 are prepared using method same as Example 1, except that preparing non-water power
When solving liquid, the additive amount of added additive of the present invention is 20wt%.
Control experiment
Comparative example 1
Nonaqueous electrolytic solution DC1 and battery DS1 are prepared using method same as Example 1, except that preparing non-water power
When solving liquid, additive of the present invention is not added.
Comparative example 2
Nonaqueous electrolytic solution DC2 and battery DS2 are prepared using method same as Example 1, except that preparing non-water power
When solving liquid, additive of the present invention is not added, and adds the propylene sulfite (PS) of 2wt.%.
The test of cycle performance of battery
Battery S1-S13 and DS1-DS2 is taken to be melted into, the chemical conversion condition of battery are as follows: extremely with the electric current constant-current charge of 0.05C
4.35V, then constant pressure, until electric current is less than 50mA.Above-mentioned battery is tested as follows:
At 25 DEG C, charge and discharge cycles test is carried out to battery with 0.5C to battery S1-S13 and DS1-DS2, voltage range is
3-4.35V；
At 45 DEG C, charge and discharge cycles test, voltage range 3- are carried out to battery with 0.5C to battery S1-S13 and DS1-DS2
4.35V；
At 25 DEG C, charge and discharge cycles test is carried out to battery with 0.5C to battery S1-S13 and DS1-DS2, voltage range is
3-4.4V。
First charge discharge efficiency=(for the first time discharge capacity/for the first time discharge capacity) × 100%；
Capacity retention ratio=(discharge capacity/discharge capacity for the first time after circulation 300 times) × 100% after circulation 300 times.
Specific test result is shown in Table 1.
Table 1
。
Table as above, S1-S7 are the battery for having used our additives and DS1(without additive), DS2(is containing PS) comparison
As can be seen that no matter from room temperature (25 DEG C) normal pressure (4.35V), room temperature (25 DEG C) high pressure (4.4V) or high temperature (45 DEG C) normal pressure
Under the conditions of (4.35V), the cycle performance of battery is promoted, and illustrates that our additive is able to ascend battery in high temperature, height
The cycle performance of pressure.
Wherein S1, S3, S6 are containing NH2The cycle performance of the additive of group, corresponding battery is better than S2, S4, S5, S7,
S8, S9 are that C atomicity is more than 5, and cycle performance is substantially reduced；S10-S13 is the research to different content additive, can be seen
Out, preferably additive level is 0.2wt.%-10wt.%, is more than this range, and cycle performance decreases.
Claims (14)
1. a kind of nonaqueous electrolytic solution, which contains lithium salts, organic solvent and additive, which is characterized in that described to add
Add agent that there is structural formula shown in formula (1):
Formula (1)
In formula, R is selected from alkyl, aminoalkyl, amino, alkoxy, phenyl, dimethoxy alkyl, hydroxyl, amide groups, acyloxy
One of with carboxymethyl group.
2. nonaqueous electrolytic solution according to claim 1, which is characterized in that it is the alkyl of 1-5, carbon original that R, which is selected from carbon atom number,
In the dimethoxy alkyl and phenyl that alkoxy that aminoalkyl that son is 1-5, carbon atom number are 1-5, carbon atom number are 1-5
It is a kind of.
3. nonaqueous electrolytic solution according to claim 1 or 2, which is characterized in that the phenyl is selected from、WithOne of, wherein X is hydrogen atom, alkyl, alkoxy, aminoalkyl, ammonia
It is a kind of in base, dimethoxy alkyl, hydroxyl, amide groups, acyloxy or carboxymethyl group.
4. nonaqueous electrolytic solution according to claim 3, which is characterized in that the X is selected from hydrogen atom, carbon atom number 1-5
Alkyl, carbon atom be 1-5 alkoxy, carbon atom number be 1-5 aminoalkyl and carbon atom number be 1-5 dimethoxy alkane
One of base or amino.
5. nonaqueous electrolytic solution according to claim 1, which is characterized in that R is selected from aminoalkyl, amino, amide groups, amino
One of phenyl, aminoalkyl phenyl, amidophenyl.
6. nonaqueous electrolytic solution according to claim 1, which is characterized in that the additive includes 5- amino -1,3, and 2,4-
Two dislike thiazole -2- oxide, 5- phenyl -1,3,2,4- two dislikes thiazole -2- oxide, 5- aminophenyl -1,3,2,4- two dislikes thiophene
Azoles -2- oxide, 5- p-methoxyphenyl -1,3,2,4- two dislike thiazole -2- oxide, 5- methyl-1, and 3,2,4- bis- dislikes thiazole -
2- oxide and 5- amino-ethyl -1,3,2,4- two dislike one of thiazole -2- oxide or a variety of.
7. nonaqueous electrolytic solution according to claim 1, which is characterized in that on the basis of the gross mass of the nonaqueous electrolytic solution,
The content of the additive is 0.05%-20%.
8. nonaqueous electrolytic solution according to claim 7, which is characterized in that on the basis of the gross mass of the nonaqueous electrolytic solution,
The content of the additive is 0.2%-10%.
9. nonaqueous electrolytic solution according to claim 1, which is characterized in that the nonaqueous electrolytic solution also contains auxiliary addition
Agent, the auxiliary additive include 1,3 propane sultones, Isosorbide-5-Nitrae butane sultone, propenyl-1,3-sulfonic acid lactone, sulfuric acid ethylene
In ester, sulfuric acid acrylic ester, butylene sulfite, vinylene carbonate, fluorinated ethylene carbonate, double oxalic acid boric acid and double fluorine sulphonyl
One or more of imine lithium.
10. nonaqueous electrolytic solution according to claim 9, which is characterized in that using the gross mass of the nonaqueous electrolytic solution as base
Standard, the content of the auxiliary additive are 0.05%-20%.
11. nonaqueous electrolytic solution according to claim 1, which is characterized in that the organic solvent is selected from dimethyl carbonate, carbon
Diethyl phthalate, methyl ethyl carbonate, methyl propyl carbonate, dipropyl carbonate, ethylene carbonate, propene carbonate, vinylene carbonate,
Gamma-butyrolacton, sultone, ethylene sulfite, propylene sulfite, methyl sulfide, diethyl sulfite, methyl formate, third
One or more of e pioic acid methyl ester, methyl butyrate and ethyl acetate.
12. nonaqueous electrolytic solution according to claim 1, which is characterized in that the lithium salts is selected from LiBOB, LiPF6、LiBF4、
LiSbF6、LiClO4、LiCF3SO3、Li(CF3SO2)2N、LiC4F9SO3、LiAlO4、LiAsF6、LiAlCl4, LiCl, LiI and low
One or more of fatty acid lithium carbonate, the concentration of the lithium salts are 0.3-3 mol/L.
13. a kind of battery, the battery includes battery case and is sealed in the intracorporal battery core of battery case and nonaqueous electrolytic solution, institute
Stating battery core includes anode, cathode and diaphragm, which is characterized in that the nonaqueous electrolytic solution is described in claim 1-12 any one
Nonaqueous electrolytic solution.
14. a kind of electric vehicle, which contains battery described in claim 13.
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| WO2021259202A1 (en) * | 2020-06-23 | 2021-12-30 | 比亚迪股份有限公司 | Lithium ion battery and electrolyte for use therein |
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