CN102479977A - Non-aqueous electrolyte solution and application thereof - Google Patents
Non-aqueous electrolyte solution and application thereof Download PDFInfo
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- CN102479977A CN102479977A CN2010105628998A CN201010562899A CN102479977A CN 102479977 A CN102479977 A CN 102479977A CN 2010105628998 A CN2010105628998 A CN 2010105628998A CN 201010562899 A CN201010562899 A CN 201010562899A CN 102479977 A CN102479977 A CN 102479977A
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- carbonate
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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
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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 provides a non-aqueous electrolyte solution and an application thereof. The electrolyte solution comprises lithium salt, fluorine containing solvent, carbonic ester and/or ether organic solvent and function additives, wherein the mole concentration of the lithium salt in the electrolyte is 0.001-2 mol/L, the weight of the fluorine containing solvent accounts for 0.01-90 % of that of the electrolyte, the weight of the carbonic ester and/or ether organic solvent accounts for 0-90 % of that of the electrolyte, and the mole concentration of the function additives in the electrolyte is 0-0.5 mol/L. The non-aqueous electrolyte solution provided by the invention can inhibit the decomposition of the solvent, raise the working voltage of a lithium battery, prolong the cycle life and service life of the lithium battery, prevent the resistor of the battery from rising, increasing the capacity maintenance rate of the battery, and increase the capacity conservation rate and prolong the service life of the battery at high temperature.
Description
Technical field
The present invention relates to a kind of non-aqueous electrolytic solution and uses thereof, 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.
The present invention is the invention of making in view of the above fact, and the invention reside in provides a kind of non-aqueous electrolytic solution and the application in lithium battery thereof.This non-aqueous electrolytic solution can suppress the decomposition of solvent; Improve the operating voltage of 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.
Summary of the invention
The objective of the invention is to solve above-mentioned technical problem, a kind of non-aqueous electrolytic solution and uses thereof is provided.
The object of the invention is realized through following technical scheme:
A kind of non-aqueous electrolytic solution; Wherein this electrolyte solution is made up of four types of compositions: (A) lithium salts; (B) contain fluorous solvent; (C) carbonates and/or ether organic solvent and (D) functional additive, wherein the molar concentration scope of (A) lithium salts in this electrolyte is: 0.001～2 mol (B) contains fluorous solvent shared mass ratio range in this electrolyte and is: 0.01%～90%; (C) carbonates and/or ether organic solvent shared mass ratio range in this electrolyte is: 0%～90%, and the molar concentration scope of component (D) functional additive in this electrolyte is: 0～0.5 mol; Said (B) contains fluorous solvent and is selected from least a in the following molecular structure:
In above-mentioned S-1, S-2, S-3, S-4 and the S-5 structural formula, the Rf group is selected from a kind of in fluorine-based or the fluoro-alkyl, can a plurality of Rf groups coexistences in the same circulus, and wherein fluoro-alkyl carbon atom number is 1～5, fluoro comprises part fluoro and perfluoro; In above-mentioned S-6 and the S-7 structural formula, Rf
1, Rf
2And Rf
3Optional fluoro-alkyl from a carbon atom numerical digit 1～10, wherein fluoro comprises part fluoro and perfluoro.
Further, above-described a kind of non-aqueous electrolytic solution, wherein said (A) lithium salts are one or more compositions that have in the compound of following molecular formula: LiBF
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, above-described a kind of non-aqueous electrolytic solution, wherein said (C) carbonates organic solvent is cyclic carbonates and/or linear carbonate compounds; Said ether organic solvent is selected from oxolane (THF), 2-methyltetrahydrofuran, 1,3-dioxolanes (DOL), dimethoxymethane (DMM), 1, one or more compositions in 2-dimethoxy ethane (DME) and the diethylene glycol dimethyl ether.
Further, above-described a kind of non-aqueous electrolytic solution, wherein said cyclic carbonate compounds are selected from one or more compositions in ethylene carbonate (EC), propene carbonate (PC), gamma-butyrolacton (GBL) and the butylene carbonate (BC); Said linear carbonate compounds is selected from dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), carbonic acid Methylethyl ester (EMC) 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, above-described a kind of non-aqueous electrolytic solution, wherein said (B) contain fluorous solvent and are selected from least a in the following compound:
Further, above-described a kind of non-aqueous electrolytic solution, wherein said (D) other additives are one or more compositions in the following compounds: biphenyl (BP); Vinylene carbonate (VC), vinylethylene carbonate (VEC), fluorinated ethylene carbonate (FEC); Propylene sulfite, sulfurous acid butene esters, 1,4-butyl sultone (BS); 1,3-(1-propylene) sultone (PST), ethylene sulfite (ESI), sulfuric acid vinyl ester (ESA); Cyclohexyl benzene (CHB), tert-butyl benzene (TBB), tert-amyl benzene (TPB) and fourth dicyan (SN).
Further, above-described a kind of non-aqueous electrolytic solution wherein is characterized in that: said non-aqueous electrolytic solution is applied to make lithium primary battery, lithium secondary battery or lithium ion battery.
The invention has the beneficial effects as follows: this non-aqueous electrolytic solution can suppress the decomposition of solvent; Improve the operating voltage of lithium battery; Increase the cycle life and the useful life of lithium battery; The resistance that suppresses battery raises, and improves the presented higher holdup of battery, improves capability retention and the cycle life of battery under hot environment.
Embodiment
The present invention has enumerated the composition composition of 1 to 74 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, adopt the non-aqueous electrolytic solution that contains fluorous solvent, 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. non-aqueous electrolytic solution; It is characterized in that: this electrolyte solution is made up of four types of compositions: (A) lithium salts; (B) contain fluorous solvent; (C) carbonates and/or ether organic solvent and (D) functional additive, wherein the molar concentration scope of (A) lithium salts in this electrolyte is: 0.001～2 mol (B) contains fluorous solvent shared mass ratio range in this electrolyte and is: 0.01%～90%; (C) carbonates and/or ether organic solvent shared mass ratio range in this electrolyte is: 0%～90%, and the molar concentration scope of component (D) functional additive in this electrolyte is: 0～0.5 mol; Said (B) contains fluorous solvent and is selected from least a in the following molecular structure:
In above-mentioned S-1, S-2, S-3, S-4 and the S-5 structural formula, the Rf group is selected from a kind of in fluorine-based or the fluoro-alkyl, can a plurality of Rf groups coexistences in the same circulus, and wherein fluoro-alkyl carbon atom number is 1～5, fluoro comprises part fluoro and perfluoro; In above-mentioned S-6 and the S-7 structural formula, Rf
1, Rf
2And Rf
3Optional fluoro-alkyl from a carbon atom numerical digit 1～10, wherein fluoro comprises part fluoro and perfluoro.
2. a kind of non-aqueous electrolytic solution as claimed in claim 1 is characterized in that: said (A) lithium salts is one or more compositions that have in the compound of following molecular formula: LiBF
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.
3. a kind of non-aqueous electrolytic solution as claimed in claim 1 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.
4. a kind of non-aqueous electrolytic solution as claimed in claim 3 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.
5. like said any one non-aqueous electrolytic solution of claim 1 to 4, it is characterized in that: said (B) contains fluorous solvent and is selected from least a in the following compound:
6. a kind of non-aqueous electrolytic solution as claimed in claim 1 is characterized in that: said (D) other 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, 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. the purposes of the described a kind of non-aqueous electrolytic solution of claim 1 is characterized in that: said non-aqueous electrolytic solution is applied to make lithium primary battery, lithium secondary battery or lithium ion battery.
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| CN2010105628998A CN102479977A (en) | 2010-11-29 | 2010-11-29 | Non-aqueous electrolyte solution and application thereof |
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| CN2010105628998A CN102479977A (en) | 2010-11-29 | 2010-11-29 | Non-aqueous electrolyte solution and application thereof |
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ID=46092517
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103296306A (en) * | 2013-06-13 | 2013-09-11 | 苏州诺信创新能源有限公司 | Lithium-ion battery electrolyte |
| CN104934637A (en) * | 2014-03-21 | 2015-09-23 | 思伊纳化学科技（北京）有限公司 | High voltage lithium ion battery nonaqueous electrolytic solution |
| JP2017520100A (en) * | 2014-05-23 | 2017-07-20 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーＥ．Ｉ．Ｄｕ Ｐｏｎｔ Ｄｅ Ｎｅｍｏｕｒｓ Ａｎｄ Ｃｏｍｐａｎｙ | Non-aqueous electrolyte composition containing cyclic sulfate and lithium borate |
| CN107293793A (en) * | 2017-07-06 | 2017-10-24 | 清华大学 | Electrolyte and electrochemical cell |
| CN107408733A (en) * | 2015-02-27 | 2017-11-28 | 索尼公司 | Electrolyte, battery, battery pack, electronic equipment, electric vehicle, electric power storing device and power system |
| CN108270035A (en) * | 2016-12-30 | 2018-07-10 | 浙江省化工研究院有限公司 | A kind of battery electrolyte containing high concentration lithium salts |
| US10756384B2 (en) * | 2015-10-22 | 2020-08-25 | Daikin Industries, Ltd. | Electrolytic solution, electrochemical device, lithium-ion secondary cell, and module |
| WO2021069923A1 (en) * | 2019-10-10 | 2021-04-15 | Mexichem Fluor S.A. De C.V. | Composition |
| WO2023134262A1 (en) * | 2022-01-14 | 2023-07-20 | 南方科技大学 | Non-aqueous electrolyte and secondary battery |
| WO2024077544A1 (en) * | 2022-10-13 | 2024-04-18 | 宁德时代新能源科技股份有限公司 | Electrolyte solution, battery cell comprising same, battery and electric device |
| WO2024113210A1 (en) * | 2022-11-30 | 2024-06-06 | 宁德时代新能源科技股份有限公司 | Fluoroacetal compound, electrolyte, secondary battery, and electric device |
| WO2024145811A1 (en) * | 2023-01-04 | 2024-07-11 | 宁德时代新能源科技股份有限公司 | Electrolyte solution, secondary battery comprising same, and electric device |
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| CN101874326A (en) * | 2008-01-29 | 2010-10-27 | 大金工业株式会社 | Solvent for dissolving electrolyte salt of lithium secondary battery |
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103296306A (en) * | 2013-06-13 | 2013-09-11 | 苏州诺信创新能源有限公司 | Lithium-ion battery electrolyte |
| CN104934637A (en) * | 2014-03-21 | 2015-09-23 | 思伊纳化学科技（北京）有限公司 | High voltage lithium ion battery nonaqueous electrolytic solution |
| JP2017520100A (en) * | 2014-05-23 | 2017-07-20 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーＥ．Ｉ．Ｄｕ Ｐｏｎｔ Ｄｅ Ｎｅｍｏｕｒｓ Ａｎｄ Ｃｏｍｐａｎｙ | Non-aqueous electrolyte composition containing cyclic sulfate and lithium borate |
| CN107408733B (en) * | 2015-02-27 | 2020-12-04 | 株式会社村田制作所 | Electrolyte solution, battery pack, electronic device, electric vehicle, power storage device, and power system |
| CN107408733A (en) * | 2015-02-27 | 2017-11-28 | 索尼公司 | Electrolyte, battery, battery pack, electronic equipment, electric vehicle, electric power storing device and power system |
| US10756384B2 (en) * | 2015-10-22 | 2020-08-25 | Daikin Industries, Ltd. | Electrolytic solution, electrochemical device, lithium-ion secondary cell, and module |
| CN108270035B (en) * | 2016-12-30 | 2020-07-07 | 浙江省化工研究院有限公司 | Battery electrolyte containing high-concentration lithium salt |
| CN108270035A (en) * | 2016-12-30 | 2018-07-10 | 浙江省化工研究院有限公司 | A kind of battery electrolyte containing high concentration lithium salts |
| CN107293793B (en) * | 2017-07-06 | 2020-03-31 | 清华大学 | Electrolyte and electrochemical cell |
| CN107293793A (en) * | 2017-07-06 | 2017-10-24 | 清华大学 | Electrolyte and electrochemical cell |
| WO2021069923A1 (en) * | 2019-10-10 | 2021-04-15 | Mexichem Fluor S.A. De C.V. | Composition |
| CN114555575A (en) * | 2019-10-10 | 2022-05-27 | 墨西哥氟石股份公司 | Composition comprising a metal oxide and a metal oxide |
| CN114555575B (en) * | 2019-10-10 | 2024-08-20 | 墨西哥氟石股份公司 | Composition and method for producing the same |
| WO2023134262A1 (en) * | 2022-01-14 | 2023-07-20 | 南方科技大学 | Non-aqueous electrolyte and secondary battery |
| WO2024077544A1 (en) * | 2022-10-13 | 2024-04-18 | 宁德时代新能源科技股份有限公司 | Electrolyte solution, battery cell comprising same, battery and electric device |
| WO2024113210A1 (en) * | 2022-11-30 | 2024-06-06 | 宁德时代新能源科技股份有限公司 | Fluoroacetal compound, electrolyte, secondary battery, and electric device |
| WO2024145811A1 (en) * | 2023-01-04 | 2024-07-11 | 宁德时代新能源科技股份有限公司 | Electrolyte solution, secondary battery comprising same, and electric device |
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Application publication date: 20120530 |