CN103594730A - Electrolyte for lithium battery with silicon cathode and lithium battery with silicon cathode - Google Patents
Electrolyte for lithium battery with silicon cathode and lithium battery with silicon cathode Download PDFInfo
- Publication number
- CN103594730A CN103594730A CN201310628294.8A CN201310628294A CN103594730A CN 103594730 A CN103594730 A CN 103594730A CN 201310628294 A CN201310628294 A CN 201310628294A CN 103594730 A CN103594730 A CN 103594730A
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- Prior art keywords
- electrolyte
- lithium battery
- silicium cathode
- additive
- battery according
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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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- 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
- H01M10/0569—Liquid materials characterised by the solvents
-
- 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
-
- 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 relates to an electrolyte for a lithium battery with a silicon cathode. The electrolyte comprises a lithium salt, a solvent and an additive, wherein the additive comprises an additive M, the molar concentration of the lithium salt is 0.001 to 2 mol/L, and the additive M accounts for 0.1 to 10% of the mass of the electrolyte. The structural formula of the additive M is described in the specification; and in the formula, R1, R2, R3, R4 and R5 are independently alkoxy groups or halogenated alkoxy groups, R6 is an alkyl group or a halogenated alkyl group, halogenated halogen is any one selected from the group consisting of F, Cl and Br, halogenation is partial substitution or full substitution, m and n are integers in a range of 1 to 10, independently, and x is an integer in a range of 1 to 10. An organosilicon isocyanate compound containing a polyether chain can effectively improve charge and discharge performance of the lithium battery with the silicon cathode and reduce side reactions, so gas generation of the battery is reduced, and the cycle life of the battery is prolonged.
Description
Technical field
The invention belongs to material technology field, be specifically related to a kind of electrolyte for silicium cathode lithium battery and silicium cathode lithium battery.
Background technology
The advantages such as lithium ion battery has that operating voltage is high, specific energy is large, pollution-free, memory-less effect and long-life, be widely used in the portable electric apparatuses such as mobile phone, digital camera and notebook computer, as the alternative energy source of oil, in electric motor car and hybrid electric vehicle, also will apply on a large scale simultaneously.Silicium cathode has larger lithium storage content, and enriches content in the earth, is the desirable negative material of lithium ion battery.
Adopt silicium cathode as the negative pole of lithium ion battery, in charge and discharge cycles process, the reversible generation of Li-Si alloy is accompanied by huge change in volume with decomposition, can cause efflorescence or the crack of alloy, cause the avalanche of silicon materials and peeling off of electrode material, and electrode material is lost, electrically contact, cause the cycle performance of silicon cathode lithium ion battery sharply to decline.Due to the generation of side reaction, in charge and discharge process, can produce a large amount of gas, easily inside battery flatulence simultaneously.
Current for promoting the efficiency for charge-discharge of silicium cathode material lithium ion battery, mainly to change the master that consists of of battery pole piece, for example, can improve the content of amorphous silicon in electrode material or the silicon materials of employing carbon film coated.
In order to address this problem, the scheme of the cyclic carbonate of use unsaturated bond is proposed, as VC, VEC etc. from electrolyte angle.Yet, although this compounds forms overlay film in negative terminal surface, between this structure of film and silicium cathode, merge fully not, charge-discharge performance reduces, and γ-ray emission is very remarkable simultaneously, and cell expansion is larger.
Summary of the invention
Technical problem to be solved by this invention is to provide the electrolyte for silicium cathode lithium battery that a kind of efficiency for charge-discharge is high.
Another technical problem to be solved by this invention is to provide a kind of silicium cathode lithium battery that adopts above-mentioned electrolyte.
For achieving the above object, the technical solution used in the present invention is:
A kind of electrolyte for silicium cathode lithium battery, lithium salts, solvent and additive, consist of, described additive comprises additive M, wherein, the molar concentration of lithium salts is 0.001～2 mol/L, and the mass percent that additive M accounts for described electrolyte is 0.1～10%; The structural formula of described additive M is
Wherein, R
1, R
2, R
3, R
4, R
5independent is alkoxyl or halogenated alkoxy, R
6for alkyl or haloalkyl, the halogen of described halo is any one in F, Cl, Br, and described halo is that part replaces or entirely replaces; M, n are independently 1～10 integer, the integer that x is 1～10.
Preferably, described additive also comprises other additives, and other described additives are one or more in biphenyl (BP), cyclohexyl benzene (CHB), tert-butyl benzene (TBB), tert-amyl benzene (TPB), fourth dicyan (SN).
More preferably, the molar concentration of other described additives is 0.001～0.5 mol/L.
Preferably, described lithium salts is selected from LiClO
4, LiPF
6, LiAsF
6, LiSO
3f, LiCF
3sO
3in one or more.
Preferably, described solvent is the mixture of any one or two kinds in carbonates organic solvent, ether organic solvent.
More preferably, described carbonates organic solvent is that ethylene carbonate (EC), propene carbonate (PC), gamma-butyrolacton (GBL), butylene carbonate (BC), dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), carbonic acid Methylethyl ester (EMC), carbon number are one or more in the synthetic carbonic acid ester derivative of the straight or branched fat single methanol of 3～8 and carbonic acid.
More preferably, described ether organic solvent is oxolane (THF), 2-methyltetrahydrofuran (2-Methyl-THF), 1,3-dioxolanes (DOL), dimethoxymethane (DMM), 1, one or more in 2-dimethoxy ethane (DME), diethylene glycol dimethyl ether (dimethyl carbitol).
Preferably, described m, n are independently 1～3 integer, the integer that x is 2～3.
Preferably, described additive M is
(triethoxy methyl trimethoxy oxygen base silicon isocyanic acid)
Or
(fluoro triethoxy methyl dimethoxy oxygen base silicon propyl group isocyanic acid).
A silicium cathode lithium battery for above-mentioned electrolyte, the material of the silicium cathode of described silicium cathode lithium battery is the coated silicon nanowire material of putting into of silicon nanowire material or carbon.
Because technique scheme is used, the present invention compared with prior art has following advantages:
In silicium cathode lithium battery, in electrolyte, by employing, contain the organosilicon isocyanic acid compound of polyether chain, alkoxysilane-functional group in this chemical constitution and hydroxy functional group are in electrode/electrolyte surface reaction, on silicium cathode surface, form the SEI overlay film of Si-O-Si structure, this overlay film and matrix silicium cathode merge fully, can effectively suppress a large amount of depositions of the irreversible reduction of electrolyte on silicon electrode, improve the cycle life of electrode; Polyether chain in this chemical constitution provides and lithium ion hapto, carries out ion transfer; Isocyanic acid in this chemical constitution can be eliminated existing electrolyte system due to LiPF
6the acidic materials that are hydrolyzed and produce, thereby the performance of raising battery.Therefore, containing the organosilicon isocyanic acid compound of polyether chain, can effectively improve the charge-discharge performance of silicium cathode lithium battery, reduce the generation of side reaction, thereby reduce battery flatulence, improve the cycle life of battery.
Embodiment
Below in conjunction with specific embodiment, the present invention is elaborated:
Embodiment 1 to 11:
(H in the glove box of applying argon gas
2o<10ppm) make the electrolyte for silicium cathode lithium battery, the one-tenth of concrete electrolyte is grouped into referring to table 1.
The cobalt acid lithium that this electrolyte is injected to 1Ah, for the lithium battery that anodal, silicon nanowires are negative pole, discharges and recharges with 0.1C battery is changed into, and at 25 ℃, 1C discharges and recharges 100 weeks, tests its battery capacity percentage and cell expansion rate.Its result is as shown in table 1.
Table 1
Above-described embodiment is only explanation technical conceive of the present invention and feature; its object is to allow person skilled in the art can understand content of the present invention and implement according to this; can not limit the scope of the invention with this; all equivalences that Spirit Essence is done according to the present invention change or modify, within all should being encompassed in protection scope of the present invention.
Claims (10)
1. the electrolyte for silicium cathode lithium battery, by lithium salts, solvent and additive, formed, it is characterized in that: described additive comprises additive M, wherein, the molar concentration of lithium salts is 0.001～2 mol/L, and the mass percent that additive M accounts for described electrolyte is 0.1～10%; The structural formula of described additive M is
Wherein, R
1, R
2, R
3, R
4, R
5independent is alkoxyl or halogenated alkoxy, R
6for alkyl or haloalkyl, the halogen of described halo is any one in F, Cl, Br, and described halo is that part replaces or entirely replaces; M, n are independently 1～10 integer, the integer that x is 1～10.
2. the electrolyte for silicium cathode lithium battery according to claim 1, it is characterized in that: described additive also comprises other additives, other described additives are one or more in biphenyl, cyclohexyl benzene, tert-butyl benzene, tert-amyl benzene, fourth dicyan.
3. the electrolyte for silicium cathode lithium battery according to claim 2, is characterized in that: the molar concentration of other described additives is 0.001～0.5 mol/L.
4. the electrolyte for silicium cathode lithium battery according to claim 1, is characterized in that: described lithium salts is selected from LiClO
4, LiPF
6, LiAsF
6, LiSO
3f, LiCF
3sO
3in one or more.
5. the electrolyte for silicium cathode lithium battery according to claim 1, is characterized in that: described solvent is the mixture of any one or two kinds in carbonates organic solvent, ether organic solvent.
6. the electrolyte for silicium cathode lithium battery according to claim 5, is characterized in that: described carbonates organic solvent is that ethylene carbonate, propene carbonate, gamma-butyrolacton, butylene carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, carbonic acid Methylethyl ester, carbon number are one or more in the synthetic carbonic acid ester derivative of the straight or branched fat single methanol of 3～8 and carbonic acid.
7. the electrolyte for silicium cathode lithium battery according to claim 5, it is characterized in that: described ether organic solvent is oxolane, 2-methyltetrahydrofuran, 1,3-dioxolanes, dimethoxymethane, 1, one or more in 2-dimethoxy ethane, diethylene glycol dimethyl ether.
8. the electrolyte for silicium cathode lithium battery according to claim 1, is characterized in that: described m, n are independently 1～3 integer, the integer that x is 2～3.
9. the electrolyte for silicium cathode lithium battery according to claim 8, is characterized in that: described additive M is
10. a silicium cathode lithium battery that adopts the electrolyte described in any one in claim 1 to 9, is characterized in that: the material of the silicium cathode of described silicium cathode lithium battery is the coated silicon nanowire material of putting into of silicon nanowire material or carbon.
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|---|---|---|---|
| CN201310628294.8A CN103594730B (en) | 2013-11-29 | 2013-11-29 | For electrolyte and the silicium cathode lithium battery of silicium cathode lithium battery |
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|---|---|---|---|
| CN201310628294.8A CN103594730B (en) | 2013-11-29 | 2013-11-29 | For electrolyte and the silicium cathode lithium battery of silicium cathode lithium battery |
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| CN103594730A true CN103594730A (en) | 2014-02-19 |
| CN103594730B CN103594730B (en) | 2016-04-06 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106531963A (en) * | 2016-09-21 | 2017-03-22 | 珠海光宇电池有限公司 | Negative electrode paste of lithium ion battery and lithium ion battery |
| WO2017113473A1 (en) * | 2015-12-30 | 2017-07-06 | 中国科学院广州能源研究所 | Method for using organic silicon electrolyte in cooperation with silicon-based electrode material |
| CN107293789A (en) * | 2017-07-25 | 2017-10-24 | 合肥国轩高科动力能源有限公司 | A kind of circulating effect good lithium ion battery and its electrolyte |
| CN110224175A (en) * | 2019-04-23 | 2019-09-10 | 珠海市赛纬电子材料股份有限公司 | A kind of non-aqueous electrolyte for lithium ion cell and the lithium ion battery comprising the electrolyte |
| CN111293364A (en) * | 2018-12-10 | 2020-06-16 | 张家港市国泰华荣化工新材料有限公司 | Non-aqueous electrolyte and lithium ion battery |
| CN111477964A (en) * | 2020-04-14 | 2020-07-31 | 宁德新能源科技有限公司 | Electrolyte and electrochemical device |
| CN112271336A (en) * | 2020-11-25 | 2021-01-26 | 广州天赐高新材料股份有限公司 | Electrolyte and lithium secondary battery |
| CN114976010A (en) * | 2022-06-16 | 2022-08-30 | 深圳市研一新材料有限责任公司 | Negative electrode additive and preparation method and application thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109638351B (en) * | 2018-11-02 | 2021-08-24 | 珠海市赛纬电子材料股份有限公司 | High-voltage electrolyte with high and low temperature performance and lithium ion battery thereof |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107732304A (en) * | 2015-12-30 | 2018-02-23 | 中国科学院广州能源研究所 | The method that a kind of organosilicon electrolyte and silicon based electrode material fit use |
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| CN106531963A (en) * | 2016-09-21 | 2017-03-22 | 珠海光宇电池有限公司 | Negative electrode paste of lithium ion battery and lithium ion battery |
| CN107293789A (en) * | 2017-07-25 | 2017-10-24 | 合肥国轩高科动力能源有限公司 | A kind of circulating effect good lithium ion battery and its electrolyte |
| CN107293789B (en) * | 2017-07-25 | 2019-09-13 | 合肥国轩高科动力能源有限公司 | A kind of lithium ion battery and its electrolyte that circulating effect is good |
| CN111293364A (en) * | 2018-12-10 | 2020-06-16 | 张家港市国泰华荣化工新材料有限公司 | Non-aqueous electrolyte and lithium ion battery |
| CN110224175A (en) * | 2019-04-23 | 2019-09-10 | 珠海市赛纬电子材料股份有限公司 | A kind of non-aqueous electrolyte for lithium ion cell and the lithium ion battery comprising the electrolyte |
| CN110224175B (en) * | 2019-04-23 | 2021-05-25 | 珠海市赛纬电子材料股份有限公司 | Non-aqueous electrolyte of lithium ion battery and lithium ion battery comprising same |
| CN111477964A (en) * | 2020-04-14 | 2020-07-31 | 宁德新能源科技有限公司 | Electrolyte and electrochemical device |
| CN112271336A (en) * | 2020-11-25 | 2021-01-26 | 广州天赐高新材料股份有限公司 | Electrolyte and lithium secondary battery |
| CN112271336B (en) * | 2020-11-25 | 2021-08-27 | 广州天赐高新材料股份有限公司 | Electrolyte and lithium secondary battery |
| CN114976010A (en) * | 2022-06-16 | 2022-08-30 | 深圳市研一新材料有限责任公司 | Negative electrode additive and preparation method and application thereof |
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|---|---|
| CN103594730B (en) | 2016-04-06 |
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Address after: No.35 Nanhai Road, Jiangsu Yangzijiang International Chemical Industrial Park, Zhangjiagang, Suzhou, Jiangsu, 215634 (Cathay Huarong) Patentee after: Zhangjiagang Guotai-Huarong New Chemical Materials Co.,Ltd. Address before: 215634 No.9 Nanhai Road, Yangzijiang International Chemical Industrial Park, Zhangjiagang City, Suzhou City, Jiangsu Province Patentee before: Zhangjiagang Guotai-Huarong New Chemical Materials Co.,Ltd. |