CN109980279A - A kind of Non-aqueous lithium battery electrolyte and serondary lithium battery - Google Patents
A kind of Non-aqueous lithium battery electrolyte and serondary lithium battery Download PDFInfo
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- CN109980279A CN109980279A CN201711458978.2A CN201711458978A CN109980279A CN 109980279 A CN109980279 A CN 109980279A CN 201711458978 A CN201711458978 A CN 201711458978A CN 109980279 A CN109980279 A CN 109980279A
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- lithium battery
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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
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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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- 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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Abstract
The present invention relates to a kind of Non-aqueous lithium battery electrolyte, including lithium salts, organic solvent and functional additive, the functional additive includes 2- sulfosalicylic acid acid anhydride derivative, and the general structure of the 2- sulfosalicylic acid acid anhydride derivative isWherein, R1、R2、R3、R4Independently selected from hydrogen, hydroxyl, halogen, alkyl, alkoxy, halogenated alkyl, halogenated alkoxy, alkylene, haloalkene alkyl, phenyl, halogenophenyl, xenyl, halogenated biphenyl base, phenylate base, triphenyl, halogeno-benzene ether, halogenated triphenyl, amino, ester group or cyano, the halogen is F, Cl or Br, it is described it is halogenated be that part replaces or all replaces.Electrolyte of the invention can be good at inhibiting the dissolution of the metal ion in positive electrode, and protection anode effectively reduces the thickness swelling of lithium battery, and improve the capacity retention ratio of serondary lithium battery.
Description
Technical field
The invention belongs to electrochemical technology fields, and in particular to a kind of Non-aqueous lithium battery electrolyte and serondary lithium battery.
Background technique
With the fast development of portable electronic device, hybrid electric vehicle, electric car and space technology etc., secondary electricity
Pond specific capacity, cycle life, in terms of more stringent requirements are proposed.Currently practical widely applied lithium ion battery
Positive electrode is cobalt acid lithium, LiMn2O4, LiFePO4 etc..And the gold with the progress that battery charging and discharging recycles, in positive electrode
Belong to Ion release into electrolyte, positive active material also accelerates therewith with reacting for electrolyte, causes battery in cyclic process
Inflatable is serious, and battery capacity decaying is obvious, and cycle performance reduces, and seriously constrains the performance of positive electrode performance.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of non-aqueous lithium electricity for inhibiting positive electrode digestion of metallic ion
Pond electrolyte.
Another technical problem to be solved by this invention is to provide a kind of serondary lithium battery using above-mentioned electrolyte.
In order to achieve the above objectives, the technical solution adopted by the present invention is that:
It is an object of the present invention to provide a kind of Non-aqueous lithium battery electrolyte, including lithium salts, organic solvent and functionality
Additive, the functional additive include 2- sulfosalicylic acid acid anhydride derivative,
The general structure of the 2- sulfosalicylic acid acid anhydride derivative is
Wherein, R1、R2、R3、R4Independently selected from hydrogen, hydroxyl, halogen, alkyl, alkoxy, halogenated alkyl, haloalkoxy
Base, alkylene, haloalkene alkyl, phenyl, halogenophenyl, xenyl, halogenated biphenyl base, phenylate base, triphenyl, halogenated phenylate
Base, halogenated triphenyl, amino, ester group or cyano, the halogen are F, Cl or Br, it is described it is halogenated be that part replaces or all
Replace.
Preferably, R1、R2、R3、R4Independently being alkyl, carbon atom number that hydrogen, hydroxyl, halogen, carbon atom number are 1~5 is
Halogenated alkoxy that halogenated alkyl that 1~5 alkoxy, carbon atom number are 1~5, carbon atom number are 1~5, carbon atom number 2
~5 alkylene, the haloalkene alkyl that carbon atom number is 2~5, phenyl, halogenophenyl, xenyl, halogenated biphenyl base, phenylate
Base, triphenyl, halogeno-benzene ether, halogenated triphenyl, amino, ester group or cyano.
It is further preferred that the R1、R3、R4For hydrogen.
It is further preferable that the 2- sulfosalicylic acid acid anhydride derivative is
It is further preferred that the quality that feeds intake of the 2- sulfosalicylic acid acid anhydride derivative accounts for the Non-aqueous lithium battery electricity
Solve the 0.05%~10% of liquid gross mass.
It is highly preferred that the quality that feeds intake of the 2- sulfosalicylic acid acid anhydride derivative accounts for the Non-aqueous lithium battery electrolyte
The 0.5%~5% of gross mass.
Most preferably, the quality that feeds intake of the 2- sulfosalicylic acid acid anhydride derivative accounts for the Non-aqueous lithium battery electrolyte
The 0.5%~2% of gross mass.
Specifically, the lithium salts is selected from LiPF6、LiBF4、LiClO4、LiCH3SO3、LiSCN、LiNO3、
LiO3SCF2CF3、LiAsF6、LiAlCl4It is one or more.
Preferably, concentration of the lithium salts in the Non-aqueous lithium battery electrolyte is 0.7~1.5mol/L.
It is further preferred that concentration of the lithium salts in the Non-aqueous lithium battery electrolyte is 0.9~1.2mol/L.
It is further preferred that the lithium salts is LiPF6。
Specifically, the organic solvent is one of carbonic ester, carboxylate, ether, sulfone class or a variety of.
In the present invention, when the organic solvent is two or more mixing, the organic solvent can any weight
Ratio.
Preferably, the carbonic ester is cyclic carbonate and/or linear carbonate, when while using the cyclic carbonate
When with the linear carbonate, the cyclic carbonate and the linear carbonate can any weight ratio.
It is further preferred that the carbonic ester is ethylene carbonate, propene carbonate, butylene carbonate base ester, carbonic acid diformazan
One or more of ester, diethyl carbonate, methyl ethyl carbonate, propene carbonate.
It is further preferable that it is 2~6:5~11:1~2:1 ethylene carbonate, carbonic acid that the organic solvent, which is mass ratio,
Methyl ethyl ester, dimethyl carbonate, propene carbonate mixed solvent.
Most preferably, it is 2~3:5~7:1~1.5:1 ethylene carbonate, carbon that the organic solvent, which is mass ratio,
Sour methyl ethyl ester, dimethyl carbonate, propene carbonate mixed solvent.
Preferably, the carboxylate is cyclic carboxylic esters and/or chain carboxylate, when while using the cyclic carbonate
When with the linear carbonate, the mass ratio of the cyclic carboxylic esters and the carboxylate is 1:0.5~2.5.
It is further preferred that the carboxylate is methyl formate, Ethyl formate, methyl acetate, ethyl acetate, acetic acid third
One or more of ester, ethyl propionate, methyl butyrate, ethyl butyrate.
It is further preferred that the ether is dimethoxymethane, 1,2- dimethoxy-ethane, tetrahydrofuran, 1,3- bis-
One or more of butyl oxide link.
It is further preferred that the sulfone is one or more of dimethyl sulfoxide, sulfolane, dimethyl sulfone.
It is a further object to provide a kind of serondary lithium batteries, use the electrolyte.
Due to the above technical solutions, the present invention has the following advantages over the prior art:
Electrolyte of the invention can be good at inhibiting the dissolution of the metal ion in positive electrode, and protection is positive, effectively
The thickness swelling of lithium battery is reduced, and improves the capacity retention ratio of serondary lithium battery.
Specific embodiment
The application is described in detail below with reference to embodiment, but the application is not limited to these embodiments.If not special herein
Illustrate, " % " representation quality percentage.
Comparative example 1
By lithium salts LiPF6It is dissolved in ethylene carbonate/methyl ethyl carbonate/dimethyl carbonate/propene carbonate (mass ratio 25/
50/15/10) in the mixed solvent, wherein LiPF6Concentration is 1mol/L, obtains comparison electrolyte.
Embodiment 1
By lithium salts LiPF6It is dissolved in ethylene carbonate/methyl ethyl carbonate/dimethyl carbonate/propene carbonate (mass ratio 25/
50/15/10) in the mixed solvent, wherein LiPF6Concentration is 1mol/L, calculates addition by electrolyte gross mass in the solution
1%Obtain electrolyte of the present invention.
Embodiment 2
By lithium salts LiPF6It is dissolved in ethylene carbonate/methyl ethyl carbonate/dimethyl carbonate/propene carbonate (mass ratio 30/
55/10/5) in the mixed solvent, wherein LiPF6Concentration is 1mol/L, calculates addition by electrolyte gross mass in the solution
1%Obtain electrolyte of the present invention.
Experimental result
The electrolyte that comparative example 1 and embodiment 1-2 obtain is injected into same batch in the cobalt acid lithium soft-package battery of model,
Test the cycle performance test that battery normal temperature environment at 2.75-4.2V carries out 1C.All comparative examples and embodiment normal temperature circulation
Capacity retention ratio and circulation front and back thickness compare data, and concrete outcome is as follows:
Table 1
By the charge-discharge performance test of the cobalt acid lithium battery of embodiment and comparative example nonaqueous electrolytic solution each in table 1 preparation
Data explanation, the cobalt acid lithium battery prepared by nonaqueous electrolytic solution of the invention is in 2.75-4.2V, the circulation longevity of 1C rate charge-discharge
Life and cell thickness expansion rate are substantially better than the cobalt acid lithium battery prepared by comparative example nonaqueous electrolytic solution.Also, reality therein
It is even more with extremely apparent excellent that example 1, which is applied, in circulating battery conservation rate, cell expansion degree and in terms of inhibiting digestion of metallic ion
Gesture.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention, it is all according to the present invention
Equivalent change or modification made by Spirit Essence, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of Non-aqueous lithium battery electrolyte, including lithium salts, organic solvent and functional additive, it is characterised in that: described
Functional additive includes 2- sulfosalicylic acid acid anhydride derivative,
The general structure of the 2- sulfosalicylic acid acid anhydride derivative is
Wherein, R1、R2、R3、R4Independently selected from hydrogen, hydroxyl, halogen, alkyl, alkoxy, halogenated alkyl, halogenated alkoxy, alkene
Base, haloalkene alkyl, phenyl, halogenophenyl, xenyl, halogenated biphenyl base, phenylate base, triphenyl, halogeno-benzene ether, halogenated three
Phenyl, amino, ester group or cyano, the halogen are F, Cl or Br, it is described it is halogenated be that part replaces or all replaces.
2. Non-aqueous lithium battery electrolyte according to claim 1, it is characterised in that: R1、R2、R3、R4It independently is hydrogen, hydroxyl
Halogenated alkyl that alkoxy that alkyl that base, halogen, carbon atom number are 1~5, carbon atom number are 1~5, carbon atom number are 1~5,
Haloalkene alkyl that alkylene that halogenated alkoxy that carbon atom number is 1~5, carbon atom number are 2~5, carbon atom number are 2~5,
Phenyl, halogenophenyl, xenyl, halogenated biphenyl base, phenylate base, triphenyl, halogeno-benzene ether, halogenated triphenyl, amino, ester group
Or cyano.
3. Non-aqueous lithium battery electrolyte according to claim 2, it is characterised in that: the R1、R3、R4For hydrogen.
4. Non-aqueous lithium battery electrolyte according to claim 3, it is characterised in that: the 2- sulfosalicylic acid acid anhydride is derivative
Object is
5. Non-aqueous lithium battery electrolyte according to any one of claim 1 to 4, it is characterised in that: the 2- sulfo group
The quality that feeds intake of benzoyl oxide derivative accounts for the 0.05%~10% of the Non-aqueous lithium battery electrolyte gross mass.
6. Non-aqueous lithium battery electrolyte according to claim 1, it is characterised in that: the lithium salts is selected from LiPF6、
LiBF4、LiClO4、LiCH3SO3、LiSCN、LiNO3、LiO3SCF2CF3、LiAsF6、LiAlCl4One or more, the lithium
Concentration of the salt in the Non-aqueous lithium battery electrolyte is 0.7~1.5mol/L.
7. Non-aqueous lithium battery electrolyte according to claim 1, it is characterised in that: the organic solvent is selected from carbonic acid
One of ester, carboxylate, ether, sulfone class are a variety of.
8. Non-aqueous lithium battery electrolyte according to claim 7, it is characterised in that: the carbonic ester is cyclic carbonate
And/or linear carbonate.
9. Non-aqueous lithium battery electrolyte according to claim 7, it is characterised in that: the carboxylate is cyclic carboxylic esters
And/or chain carboxylate.
10. a kind of serondary lithium battery, it is characterised in that: it uses Non-aqueous lithium battery electricity of any of claims 1-9
Solve liquid.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711458978.2A CN109980279B (en) | 2017-12-28 | 2017-12-28 | Non-aqueous lithium battery electrolyte and secondary lithium battery |
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| CN201711458978.2A CN109980279B (en) | 2017-12-28 | 2017-12-28 | Non-aqueous lithium battery electrolyte and secondary lithium battery |
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| CN109980279B CN109980279B (en) | 2022-05-24 |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1770546A (en) * | 2004-11-05 | 2006-05-10 | 索尼株式会社 | Battery |
| JP2008147118A (en) * | 2006-12-13 | 2008-06-26 | Sony Corp | Battery |
| CN101540422A (en) * | 2008-03-17 | 2009-09-23 | 索尼株式会社 | Secondary battery |
| CN103367800A (en) * | 2012-04-09 | 2013-10-23 | 张家港市国泰华荣化工新材料有限公司 | Non-aqueous electrolyte used for layered manganese acid lithium battery |
| CN103811739A (en) * | 2012-11-08 | 2014-05-21 | 索尼公司 | Active material, electrode, secondary battery, battery pack and electric vehicle |
| CN103996871A (en) * | 2013-02-15 | 2014-08-20 | 索尼公司 | Electrolytic solution, non-aqueous secondary battery, battery pack, electric vehicle, electric power storage system |
| WO2015188932A1 (en) * | 2014-06-12 | 2015-12-17 | Karlsruher Institut für Technologie | Electrolyte, cell and battery comprising the electrolyte, and use of the electrolyte |
-
2017
- 2017-12-28 CN CN201711458978.2A patent/CN109980279B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1770546A (en) * | 2004-11-05 | 2006-05-10 | 索尼株式会社 | Battery |
| JP2008147118A (en) * | 2006-12-13 | 2008-06-26 | Sony Corp | Battery |
| CN101540422A (en) * | 2008-03-17 | 2009-09-23 | 索尼株式会社 | Secondary battery |
| CN103367800A (en) * | 2012-04-09 | 2013-10-23 | 张家港市国泰华荣化工新材料有限公司 | Non-aqueous electrolyte used for layered manganese acid lithium battery |
| CN103811739A (en) * | 2012-11-08 | 2014-05-21 | 索尼公司 | Active material, electrode, secondary battery, battery pack and electric vehicle |
| CN103996871A (en) * | 2013-02-15 | 2014-08-20 | 索尼公司 | Electrolytic solution, non-aqueous secondary battery, battery pack, electric vehicle, electric power storage system |
| WO2015188932A1 (en) * | 2014-06-12 | 2015-12-17 | Karlsruher Institut für Technologie | Electrolyte, cell and battery comprising the electrolyte, and use of the electrolyte |
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