CN102790237A - Non-aqueous electrolyte solution of boron-containing compound - Google Patents
Non-aqueous electrolyte solution of boron-containing compound Download PDFInfo
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- CN102790237A CN102790237A CN2011101288192A CN201110128819A CN102790237A CN 102790237 A CN102790237 A CN 102790237A CN 2011101288192 A CN2011101288192 A CN 2011101288192A CN 201110128819 A CN201110128819 A CN 201110128819A CN 102790237 A CN102790237 A CN 102790237A
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- boron
- containing compound
- carbonate
- electrolyte solution
- electrolytic solution
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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
The invention discloses a non-aqueous electrolyte solution of a boron-containing compound. The non-aqueous electrolyte solution comprises a lithium salt, the boron-containing compound, a carbonate and/ether organic solvent, and an additive having other functions, wherein the molar concentration of the lithium salt in the electrolyte solution is 0.001-2mol/L, the mass percentage of the boron-containing compound in the electrolyte solution is 0.01-10%, the mass percentage of the carbonate and/ether organic solvent in the electrolyte solution is 50-95%, and the molar concentration of the an additive having other functions in the electrolyte solution is 0-0.5mol/L. The non-aqueous electrolyte solution can inhibit the decomposition of materials in a lithium battery, increase the cycle life and the service life of the lithium battery, inhibit the improvement of the resistance of the battery, improve the capacity retention rate of the battery, and improve the capacity retention rate and the cycle life of the battery in a high temperature environment
Description
Technical field
The present invention relates to a kind of non-aqueous electrolytic solution, belong to the chemical material technical field.
Background technology
At present, the commercialization lithium cell electrolyte is mainly by organic carbonate---like dimethyl carbonate (being called for short DMC), and diethyl carbonate (vehicle economy C), ethylene carbonates (being called for short EC) etc. and conducting salt (mainly are LiPF
6) form.The optimization of organic carbonate non-aqueous electrolytic solution and selection are to improve one of research direction of lithium ion battery combination property.Be applied to the non-aqueous electrolytic solution of lithium ion battery, generally should satisfy following requirement: (1) ionic conductivity is high, generally should reach 10～3S/cm; (2) lithium ion transference number is high, to obtain high lithium ion conductivity; (3) electrochemical window is wide, promptly satisfy lithium ion in the reversible embedding of positive and negative electrode with deviate from, and chemistry or electrochemical decomposition does not take place electrolyte; (4) thermal stability is high, and chemistry or electrochemical decomposition do not take place in the operating temperature range of broad; (5) chemical stability is high, and promptly the electrode material with battery system like positive pole, negative pole, collector, binding agent, conductive agent and barrier film etc. chemical reaction does not take place; (6) has lower interfacial migration resistance; (7) with at present the main positive and negative pole material compatibility of using is good; (8) nontoxic, pollution-free, safe in utilization, preferably can biodegradation; (9) preparation easily, cost is low.
Through research and the practice of decades, the non-aqueous electrolytic solution that is applied to the commercialization serondary lithium battery is at present generally selected lithium hexafluoro phosphate (LiPF
6) as conducting salt, the mixed solvent that the ethylene carbonate (be called for short EC), propene carbonate (being called for short PC) mostly solvent is high viscosity, high-k and dimethyl carbonate (being called for short DMC), diethyl carbonate (vehicle economy C) or the Methylethyl carbonic ester (being called for short EMC) of low viscosity, low-k constitute.This type of system finally can be used on a large scale, is not that its each item index has outstanding characteristic, and its overall target can satisfy the application in industry requirement of existing serondary lithium battery basically.
Negative pole has used the non-aqueous electrolyte lithium ion or the lithium secondary battery of material with carbon element, oxide, lithium alloy or lithium metal can realize high energy density, and therefore the power supply as portable phone, notebook computer, electric tool and the vehicles enjoys attracting attention of people.Known in this secondary cell, generate layer of surface film (SEI, solid electrolyte interface) in negative terminal surface.Known this interfacial film brings very big influence can for the efficiency for charge-discharge, cycle life, fail safe of battery etc., and therefore the control of film is indispensable in the high performance median surface of negative pole.For material with carbon element, oxide material, need to reduce its irreversible capacity, for lithium metal, alloy anode, need to solve the reduction of efficiency for charge-discharge and have dendrite to generate the safety issue that is caused.
There is kinds of schemes to propose to solve the method for these problems.For example, in JP-A-7-302617, disclosing cathode of lithium is exposed in the electrolyte that contains hydrofluoric acid, is the reaction of negative pole and hydrofluoric acid, thus in the technology of its surface coverage lithium fluoride film.In JP-A-5-275077, proposed at the film of the surface-coated lithium-ion-conducting solid electrolyte of material with carbon element and the negative pole that forms.In JP-A-7-122296, the secondary cell that contains the vinylene carbonate derivative in the nonaqueous electrolytic solution secondary battery kind is disclosed, can known electrolyte decomposition on the carbon negative pole, can improve the cycle characteristics of battery.But in above-mentioned technology, all can not obtain the sufficient tunicle effect that increases with respect to battery behavior, at first be skin covering of the surface deterioration when using repeatedly, and function reduces; Secondly decomposition in various degree such as 45～60 degree, all can take place in the effect of tunicle under high-temperature slightly, causes the composition of tunicle and character that irreversible variation takes place, thereby has a strong impact on battery performance.In a series of patents such as CN101154753A; Mention and in electrolyte, add 1; Compounds such as 3-dioxane can suppress the decomposition of solvent, improve the cycle life of battery, but 1; The decomposition meeting of compounds such as 3-dioxane significantly increases the interface impedance of side of the positive electrode, and battery performance is brought loss.
Summary of the invention
In view of the defective that above-mentioned prior art exists, the objective of the invention is to propose a kind ofly can to suppress material breakdown in the lithium battery, improve the non-aqueous electrolytic solution of the boron-containing compound in lithium battery useful life.。
The object of the invention will be achieved by the following technical programs:
The non-aqueous electrolytic solution of boron-containing compound, said non-aqueous electrolytic solution comprises: (A) lithium salts; (B) boron-containing compound; (C) carbonates and/or ether organic solvent; (D) other functional additives; Wherein the molar concentration scope of (A) lithium salts in this electrolyte solution is: 0.001～2 mol; (B) scope of the mass percent of boron-containing compound in this electrolyte solution is: 0.01%～10%; (C) scope of carbonates and/or the ether organic solvent mass percent in this electrolyte solution is: 50%～95%, and (D) the molar concentration scope of other functional additives in this electrolyte solution is: 0～0.5 mol.
Further, said (B) boron-containing compound is made up of in the compound with following structural formula one or more:
In the following formula, R
1Be selected from alkyl, haloalkyl, alkylene, haloalkene alkyl, phenyl, xenyl, halogenophenyl and the halogenated biphenyl base one or more; R
2Be selected from hydrogen, halogen, alkyl, alkoxyl, haloalkyl and the halogenated alkoxy one or more, said halogen is F, Cl or Br, said haloalkyl and halogenated alkoxy be singly replace, part replaces or full the replacement.
Further, said (A) lithium salts one or more compositions in the compound with following molecular formula: LiBF that serves as reasons
4, LiPF
6, LiAsF
6, LiClO
4, LiN (SO
2CF
3)
2, LiN (SO
2F)
2, LiN (SO
2C
2F
5)
2, LiSO
3CF
3, LiC
2O
4BC
2O
4, LiF
2BC
2O
4, LiFC
6F
5BC
2O
4, LiBF
a[(C
6F
x(C
nF
mH
(2n+1-m))
yH
(5-x-y))]
(4-a), a=0,1,2,3; X=0,1,2,3,4,5; Y=0,1,2,3,4,5; N, m are the integer more than or equal to zero, and LiPF
b[(C
6F
s(C
pF
qH
(2p+1-q))
tH
(5-s-t))]
(6-b), b=0,1,2,3,4,5; S=0,1,2,3,4,5; T=0,1,2,3,4,5; P, q are the integer more than or equal to zero.
Further, said (C) carbonates organic solvent is cyclic carbonates and/or linear carbonate compounds; Said ether organic solvent is selected from oxolane, 2-methyltetrahydrofuran, 1,3-dioxolanes, dimethoxymethane, 1, one or more compositions in 2-dimethoxy ethane and the diethylene glycol dimethyl ether.
Further, said cyclic carbonate compounds is selected from one or more compositions in ethylene carbonate, propene carbonate, gamma-butyrolacton and the butylene carbonate; Said linear carbonate compounds is selected from dimethyl carbonate, diethyl carbonate, dipropyl carbonate, carbonic acid Methylethyl ester and carbon number be the single alcohol of 3～8 straight or branched fat with the synthetic carbonic acid ester derivative of carbonic acid in one or more compositions.
Further, said (D) other functional additives are one or more compositions in the following compounds: biphenyl, vinylene carbonate, vinylethylene carbonate; Fluorinated ethylene carbonate, propylene sulfite, sulfurous acid butene esters, 1,3-propane sultone; 1,4-butyl sultone, 1,3-(1-propylene) sultone, ethylene sulfite, sulfuric acid vinyl ester; Cyclohexyl benzene, tert-butyl benzene, tert-amyl benzene and fourth dicyan.
Further, said (B) boron-containing compound is made up of in the compound with following structural formula one or more:
Compared with prior art; Beneficial effect of the present invention is: can suppress the decomposition of material in the lithium battery, increase the cycle life and the useful life of lithium battery, the resistance that suppresses battery raises; Improve the presented higher holdup of battery, improve capability retention and the cycle life of battery under hot environment.
Embodiment
Below in conjunction with embodiment technical scheme of the present invention is elaborated.
The present invention has enumerated the composition composition of 1 to 65 kind of non-aqueous electrolytic solution and the test data that adopts the capability retention of each electrolyte solution battery with the form of form, sees following table 1 for details.
The component of table 1 non-aqueous electrolytic solution and battery capacity percentage
Visible by the foregoing description, the non-aqueous electrolytic solution of employing boron-containing compound, the presented higher holdup of battery can effectively improve, and the cycle life of battery and useful life increase.Also can improve simultaneously capability retention and the cycle life of battery under hot environment.
The present invention still has multiple concrete execution mode, and all employings are equal to replacement or equivalent transformation and all technical schemes of forming all drop within the scope of requirement protection of the present invention.
Claims (7)
1. the non-aqueous electrolytic solution of boron-containing compound, it is characterized in that: said non-aqueous electrolytic solution comprises: (A) lithium salts; (B) boron-containing compound; (C) carbonates and/or ether organic solvent; (D) other functional additives; Wherein the molar concentration scope of (A) lithium salts in this electrolyte solution is: 0.001～2 mol; (B) scope of the mass percent of boron-containing compound in this electrolyte solution is: 0.01%～10%; (C) scope of carbonates and/or the ether organic solvent mass percent in this electrolyte solution is: 50%～95%, and (D) the molar concentration scope of other functional additives in this electrolyte solution is: 0～0.5 mol.
2. the non-aqueous electrolytic solution of boron-containing compound according to claim 1 is characterized in that: said (B) boron-containing compound is made up of in the compound with following structural formula one or more:
In the following formula, R
1Be selected from alkyl, haloalkyl, alkylene, haloalkene alkyl, phenyl, xenyl, halogenophenyl and the halogenated biphenyl base one or more; R
2Be selected from hydrogen, halogen, alkyl, alkoxyl, haloalkyl and the halogenated alkoxy one or more, said halogen is F, Cl or Br, said haloalkyl and halogenated alkoxy be singly replace, part replaces or full the replacement.
3. the non-aqueous electrolytic solution of boron-containing compound according to claim 2 is characterized in that: said (A) lithium salts one or more compositions in the compound with following molecular formula: LiBF that serves as reasons
4, LiPF
6, LiAsF
6, LiClO
4, LiN (SO
2CF
3)
2, LiN (SO
2F)
2, LiN (SO
2C
2F
5)
2, LiSO
3CF
3, LiC
2O
4BC
2O
4, LiF
2BC
2O
4, LiFC
6F
5BC
2O
4, LiBF
a[(CxF
x(C
nF
mH
(2n+1- M))
yH
(5-x-y))]
(4-a), a=0,1,2,3; X=0,1,2,3,4,5; Y=0,1,2,3,4,5; N, m are the integer more than or equal to zero, and LiPF
b[(C
6F
s(C
pF
qH
(2p+1-q))
tH
(5-s-t))]
(6-b), b=0,1,2,3,4,5; S=0,1,2,3,4,5; T=0,1,2,3,4,5; P, q are the integer more than or equal to zero.
4. the non-aqueous electrolytic solution of boron-containing compound according to claim 3, it is characterized in that: said (C) carbonates organic solvent is cyclic carbonates and/or linear carbonate compounds; Said ether organic solvent is selected from oxolane, 2-methyltetrahydrofuran, 1,3-dioxolanes, dimethoxymethane, 1, one or more compositions in 2-dimethoxy ethane and the diethylene glycol dimethyl ether.
5. the non-aqueous electrolytic solution of boron-containing compound according to claim 4, it is characterized in that: said cyclic carbonate compounds is selected from one or more compositions in ethylene carbonate, propene carbonate, gamma-butyrolacton and the butylene carbonate; Said linear carbonate compounds is selected from dimethyl carbonate, diethyl carbonate, dipropyl carbonate, carbonic acid Methylethyl ester and carbon number be the single alcohol of 3～8 straight or branched fat with the synthetic carbonic acid ester derivative of carbonic acid in one or more compositions.
6. the non-aqueous electrolytic solution of boron-containing compound according to claim 5, it is characterized in that: said (D) other functional additives are one or more compositions in the following compounds: biphenyl, vinylene carbonate; Vinylethylene carbonate, fluorinated ethylene carbonate, propylene sulfite; The sulfurous acid butene esters, 1,3-propane sultone, 1, the 4-butyl sultone; 1,3-(1-propylene) sultone, ethylene sulfite, sulfuric acid vinyl ester; Cyclohexyl benzene, tert-butyl benzene, tert-amyl benzene and fourth dicyan.
7. according to the non-aqueous electrolytic solution of any described boron-containing compound among the claim 1-6, it is characterized in that: said (B) boron-containing compound is made up of in the compound with following structural formula one or more:
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103384018A (en) * | 2013-07-19 | 2013-11-06 | 四川剑兴锂电池有限公司 | Electrolyte capable of reducing gas output of lithium titanate battery |
| CN106340673A (en) * | 2016-10-28 | 2017-01-18 | 张家港市国泰华荣化工新材料有限公司 | Lithium battery electrolyte and lithium battery |
| CN108475814A (en) * | 2015-09-23 | 2018-08-31 | 深圳新宙邦科技股份有限公司 | LTO type lithium-ion battery electrolytes |
| WO2023206427A1 (en) * | 2022-04-29 | 2023-11-02 | 宁德时代新能源科技股份有限公司 | Secondary battery, battery module comprising same, battery pack, and electric device |
| WO2023206360A1 (en) * | 2022-04-29 | 2023-11-02 | 宁德时代新能源科技股份有限公司 | Secondary battery and battery module comprising same, battery pack, and electrical device |
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| US6352798B1 (en) * | 1997-12-08 | 2002-03-05 | Brookhaven Science Associates, Llc | Phenyl boron-based compounds as anion receptors for non-aqueous battery electrolytes |
| JP2008004557A (en) * | 1997-04-17 | 2008-01-10 | Ube Ind Ltd | Nonaqueous electrolyte for lithium secondary battery |
| CN101662030A (en) * | 2008-08-25 | 2010-03-03 | 中国科学院物理研究所 | Electrolyte solution, preparation method thereof and use thereof |
| CN102036912A (en) * | 2008-12-02 | 2011-04-27 | 斯泰拉化工公司 | Method for producing difluorophosphate, nonaqueous electrolyte solution, and nonaqueous electrolyte secondary battery |
-
2011
- 2011-05-18 CN CN201110128819.2A patent/CN102790237B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008004557A (en) * | 1997-04-17 | 2008-01-10 | Ube Ind Ltd | Nonaqueous electrolyte for lithium secondary battery |
| US6352798B1 (en) * | 1997-12-08 | 2002-03-05 | Brookhaven Science Associates, Llc | Phenyl boron-based compounds as anion receptors for non-aqueous battery electrolytes |
| CN101662030A (en) * | 2008-08-25 | 2010-03-03 | 中国科学院物理研究所 | Electrolyte solution, preparation method thereof and use thereof |
| CN102036912A (en) * | 2008-12-02 | 2011-04-27 | 斯泰拉化工公司 | Method for producing difluorophosphate, nonaqueous electrolyte solution, and nonaqueous electrolyte secondary battery |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103384018A (en) * | 2013-07-19 | 2013-11-06 | 四川剑兴锂电池有限公司 | Electrolyte capable of reducing gas output of lithium titanate battery |
| CN103384018B (en) * | 2013-07-19 | 2015-11-04 | 四川剑兴锂电池有限公司 | A kind of electrolyte reducing lithium titanate battery gas production |
| CN108475814A (en) * | 2015-09-23 | 2018-08-31 | 深圳新宙邦科技股份有限公司 | LTO type lithium-ion battery electrolytes |
| CN106340673A (en) * | 2016-10-28 | 2017-01-18 | 张家港市国泰华荣化工新材料有限公司 | Lithium battery electrolyte and lithium battery |
| WO2023206427A1 (en) * | 2022-04-29 | 2023-11-02 | 宁德时代新能源科技股份有限公司 | Secondary battery, battery module comprising same, battery pack, and electric device |
| WO2023206360A1 (en) * | 2022-04-29 | 2023-11-02 | 宁德时代新能源科技股份有限公司 | Secondary battery and battery module comprising same, battery pack, and electrical device |
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| Publication number | Publication date |
|---|---|
| CN102790237B (en) | 2014-10-22 |
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Address after: 215600 No.35 Nanhai Road, Jiangsu Yangzijiang International Chemical Industrial Park, Zhangjiagang, Suzhou, Jiangsu Province Patentee after: Zhangjiagang Guotai-Huarong New Chemical Materials Co.,Ltd. Address before: 215633 No.9 Nanhai Road, Jiangsu Yangzijiang International Chemical Industry Park, Zhangjiagang City, Jiangsu Province Patentee before: Zhangjiagang Guotai-Huarong New Chemical Materials Co.,Ltd. |