CN103594730B - For electrolyte and the silicium cathode lithium battery of silicium cathode lithium battery - Google Patents

For electrolyte and the silicium cathode lithium battery of silicium cathode lithium battery Download PDF

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Publication number
CN103594730B
CN103594730B CN201310628294.8A CN201310628294A CN103594730B CN 103594730 B CN103594730 B CN 103594730B CN 201310628294 A CN201310628294 A CN 201310628294A CN 103594730 B CN103594730 B CN 103594730B
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electrolyte
silicium cathode
lithium battery
additive
cathode lithium
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CN103594730A (en
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袁杰
沈蕾
袁祥云
甘朝伦
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Zhangjiagang Guotai Huarong New Chemical Materials Co Ltd
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Zhangjiagang Guotai Huarong New Chemical Materials Co Ltd
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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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Secondary Cells (AREA)

Abstract

The present invention relates to a kind of electrolyte for silicium cathode lithium battery, be made up of lithium salts, solvent and additive, additive comprises additive M, and wherein, the molar concentration of lithium salts is 0.001 ~ 2 mol/L, and the mass percent that additive M accounts for electrolyte is 0.1 ~ 10%; The structural formula of additive M is or wherein, R 1, R 2, R 3, R 4, R 5independent is alkoxyl or halogenated alkoxy, R 6for alkyl or haloalkyl, the halogen of halo is any one in F, Cl, Br, and halo replaces for part or entirely replaces; M, n are independently the integer of 1 ~ 10, and x is the integer of 1 ~ 10.Organosilicon isocyanic acid compound containing polyether chain effectively can improve the charge-discharge performance of silicium cathode lithium battery, reduces the generation of side reaction, thus reduces battery flatulence, improves the cycle life of battery.

Description

For electrolyte and the silicium cathode lithium battery of silicium cathode lithium battery
Technical field
The invention belongs to field of material technology, be specifically related to a kind of electrolyte for silicium cathode lithium battery and silicium cathode lithium battery.
Background technology
Lithium ion battery has that operating voltage is high, specific energy is large, pollution-free, the advantage such as memory-less effect and long-life, be widely used in the portable electric apparatuses such as mobile phone, digital camera and notebook computer, also will apply on a large scale in electric motor car and hybrid electric vehicle as the alternative energy source of oil 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 and decomposition are along with huge change in volume, efflorescence or the crack of alloy can be caused, cause peeling off of the avalanche of silicon materials and electrode material, and make electrode material lose electrical contact, cause the cycle performance of silicon cathode lithium ion battery sharply to decline.Simultaneously due to the generation of side reaction, a large amount of gas can be produced in charge and discharge process, easy inside battery flatulence.
At present 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, such as, can improve the content of amorphous silicon in electrode material or adopt the silicon materials of carbon film coated.
In order to address this problem, the scheme of the cyclic carbonate using unsaturated bond is proposed, as VC, VEC etc. from electrolyte angle.But although this compounds forms overlay film in negative terminal surface, merge abundant not between this structure of film and silicium cathode, charge-discharge performance reduces, and gas produces very remarkable, and cell expansion is larger simultaneously.
Summary of the invention
Technical problem to be solved by this invention is to provide the high electrolyte for silicium cathode lithium battery of a kind of efficiency for charge-discharge.
Another technical problem to be solved by this invention is to provide a kind of silicium cathode lithium battery adopting 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, be made up of lithium salts, solvent and additive, 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 replaces for part or entirely replaces; M, n are independently the integer of 1 ~ 10, and x is the integer of 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 carbonate based organic solvent, ether organic solvent.
More preferably, one or more in the carbonic acid ester derivative that described carbonate based organic solvent is ethylene carbonate (EC), propene carbonate (PC), gamma-butyrolacton (GBL), butylene carbonate (BC), dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methyl ethyl ester (EMC), carbon number are the straight or branched aliphatic monool of 3 ~ 8 and carbonic acid synthesizes.
More preferably, described ether organic solvent is oxolane (THF), 2-methyltetrahydrofuran (2-Methyl-THF), 1, one or more in 3-dioxolanes (DOL), dimethoxymethane (DMM), 1,2-dimethoxy (DME), diethylene glycol dimethyl ether (dimethylcarbitol).
Preferably, described m, n are independently the integer of 1 ~ 3, and x is the integer of 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).
Adopt a silicium cathode lithium battery for above-mentioned electrolyte, the material of the silicium cathode of described silicium cathode lithium battery is silicon nanowire material or carbon is coated puts into silicon nanowire material.
Because technique scheme is used, the present invention compared with prior art has following advantages:
In silicium cathode lithium battery, by adopting the organosilicon isocyanic acid compound containing polyether chain in electrolyte, alkoxysilane-functional group in this chemical constitution and hydroxy functional group are in electrode/electrolyte surface reaction, the SEI overlay film of Si-O-Si structure is formed on silicium cathode surface, this overlay film and matrix silicium cathode merge fully, effectively can 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 eliminate existing electrolyte system due to LiPF 6be hydrolyzed and the acidic materials of generation, thus improve the performance of battery.Therefore, the organosilicon isocyanic acid compound containing polyether chain effectively can improve the charge-discharge performance of silicium cathode lithium battery, reduces the generation of side reaction, thus reduces battery flatulence, improves 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 being used for silicium cathode lithium battery, the one-tenth of concrete electrolyte is grouped into see table 1.
The cobalt acid lithium this electrolyte being injected 1Ah is positive pole, silicon nanowires is the lithium battery of negative pole, and change into battery with 0.1C discharge and recharge, at 25 DEG C, 1C discharge and recharge 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 for illustrating technical conceive of the present invention and feature; its object is to person skilled in the art can be understood content of the present invention and implement according to this; can not limit the scope of the invention with this; all equivalences done according to Spirit Essence of the present invention change or modify, and all should be encompassed within protection scope of the present invention.

Claims (8)

1. the electrolyte for silicium cathode lithium battery, be made up of lithium salts, solvent and additive, 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 .
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 carbonate based organic solvent, ether organic solvent.
6. the electrolyte for silicium cathode lithium battery according to claim 5, is characterized in that: one or more in the carbonic acid ester derivative that described carbonate based organic solvent is ethylene carbonate, propene carbonate, gamma-butyrolacton, butylene carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl ethyl ester, carbon number are the straight or branched aliphatic monool of 3 ~ 8 and carbonic acid synthesizes.
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, one or more in 3-dioxolanes, dimethoxymethane, 1,2-dimethoxy, diethylene glycol dimethyl ether.
8. adopt a silicium cathode lithium battery for the electrolyte according to any one of claim 1 to 7, it is characterized in that: the material of the silicium cathode of described silicium cathode lithium battery is the coated silicon nanowire material of silicon nanowire material or carbon.
CN201310628294.8A 2013-11-29 2013-11-29 For electrolyte and the silicium cathode lithium battery of silicium cathode lithium battery Active CN103594730B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109638351A (en) * 2018-11-02 2019-04-16 珠海市赛纬电子材料股份有限公司 A kind of high-voltage electrolyte that taking into account high temperature performance and its lithium ion battery

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107732304B (en) * 2015-12-30 2020-07-24 中国科学院广州能源研究所 Method for cooperatively using organic silicon electrolyte and silicon-based electrode material
CN106531963B (en) * 2016-09-21 2019-12-17 珠海光宇电池有限公司 Lithium ion battery cathode slurry and lithium ion battery
CN107293789B (en) * 2017-07-25 2019-09-13 合肥国轩高科动力能源有限公司 Lithium ion battery with good circulation effect and electrolyte thereof
CN111293364B (en) * 2018-12-10 2021-03-30 张家港市国泰华荣化工新材料有限公司 Non-aqueous electrolyte and lithium ion battery
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
CN111477964B (en) * 2020-04-14 2021-06-25 宁德新能源科技有限公司 Electrolyte and electrochemical device
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
CN114976010B (en) * 2022-06-16 2023-06-30 深圳市研一新材料有限责任公司 Negative electrode additive and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101425575A (en) * 2007-10-31 2009-05-06 索尼株式会社 Negative electrode and battery
CN102479973A (en) * 2010-11-24 2012-05-30 比亚迪股份有限公司 Silicon cathode lithium ion battery
CN102790236A (en) * 2011-05-18 2012-11-21 张家港市国泰华荣化工新材料有限公司 Non-aqueous electrolyte solution of fluorine-containing compound

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5222555B2 (en) * 2005-06-23 2013-06-26 三洋電機株式会社 Non-aqueous electrolyte secondary battery and non-aqueous electrolyte

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101425575A (en) * 2007-10-31 2009-05-06 索尼株式会社 Negative electrode and battery
CN102479973A (en) * 2010-11-24 2012-05-30 比亚迪股份有限公司 Silicon cathode lithium ion battery
CN102790236A (en) * 2011-05-18 2012-11-21 张家港市国泰华荣化工新材料有限公司 Non-aqueous electrolyte solution of fluorine-containing compound

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109638351A (en) * 2018-11-02 2019-04-16 珠海市赛纬电子材料股份有限公司 A kind of high-voltage electrolyte that taking into account high temperature performance and its lithium ion battery
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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