CN105576291A - Lithium ion battery and electrolyte for high-voltage lithium ion battery - Google Patents

Lithium ion battery and electrolyte for high-voltage lithium ion battery Download PDF

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Publication number
CN105576291A
CN105576291A CN201510956600.XA CN201510956600A CN105576291A CN 105576291 A CN105576291 A CN 105576291A CN 201510956600 A CN201510956600 A CN 201510956600A CN 105576291 A CN105576291 A CN 105576291A
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electrolyte
ion battery
lithium ion
ethylene carbonate
solvent
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CN201510956600.XA
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CN105576291B (en
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王小龙
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Suzhou Huayi New Energy Technology Co.,Ltd.
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SUZHOU HUAYI NEW ENERGY TECHNOLOGY 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
    • H01M10/0568—Liquid materials characterised by the solutes
    • 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
    • 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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • H01M2300/004—Three solvents
    • 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)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)

Abstract

The invention discloses an electrolyte for a high-voltage lithium ion battery. Total mass of the electrolyte is 100%. The electrolyte is composed of, by mass, 80-89% of solvent, 10-15% of lithium salt and 0.5-5% of additive, the solvent is formed by mixing ethylene carbonate, methyl ethyl carbonate and methyl fluorobutyl ether , and the additive is composed of vinyl ethylene carbonate, fluoroethylene carbonate and adiponitrile. Methyl fluorobutyl ether is added into the solvent, so that the electrolyte does not have flashing points and is high in safety; the lithium ion battery adopting the additive is stable in circulating performance at normal temperature, is free of inflation at high temperature, small in internal resistance change and high in safety and has good high-temperature performance and high-voltage performance.

Description

A kind of high-voltage lithium ion battery electrolyte and lithium ion battery
Technical field
The present invention relates to a kind of high-voltage lithium ion battery electrolyte and lithium ion battery.
Background technology
Lithium ion battery because of its there is high-energy-density, operating voltage is high, specific capacity is large, the advantage such as low, the wide operating temperature range of long circulation life, self-discharge rate and environmental protection, makes it become the main energy sources of the portable sets such as current mobile electronic device, video camera, notebook computer.But the develop rapidly of mobile electronic device particularly smart mobile phone (gentlier, thinner), also proposed higher demand to the energy density of lithium ion battery in recent years.And LiNiMnO 4, LiNiCoMnO 2, LiCoPO 4the deintercalation reaction of lithium ion can occur at higher voltages, and the energy density therefore for improving lithium ion battery brings new hope.But the electrolyte of lithium ion battery easily decomposes under high voltages, cause the efficiency for charge-discharge of lithium ion battery low, cycle performance is poor, constrains further developing of high-voltage lithium ion batteries, therefore exploitation is applicable to the high-voltage electrolyte that high-voltage anode material uses, and will have great importance.
Summary of the invention
An object of the present invention is to overcome the deficiencies in the prior art, a kind of high-voltage lithium ion battery electrolyte is provided.
For achieving the above object, the technical solution used in the present invention is: a kind of high-voltage lithium ion battery electrolyte, 100% is counted with the gross mass of electrolyte, described electrolyte is grouped into by the one-tenth of following mass percent: solvent 80 ~ 89%, lithium salts 10 ~ 15%, additive 0.5 ~ 5%, described solvent is mixed for butyl ether by ethylene carbonate, methyl ethyl carbonate and fluoromethane, and described additive is made up of vinyl ethylene carbonate, fluorinated ethylene carbonate, adiponitrile.
Preferably, count 100% with the gross mass of described electrolyte, described solvent is grouped into by the one-tenth of following mass percent: ethylene carbonate 35 ~ 40%, methyl ethyl carbonate 7 ~ 10%, fluoromethane are for butyl ether 35 ~ 45%.
Preferably, count 100% with the gross mass of described electrolyte, wherein, described additive is grouped into by the one-tenth of following mass percent: vinyl ethylene carbonate 0.2 ~ 3%, fluorinated ethylene carbonate 0.2 ~ 3%, adiponitrile 0.1 ~ 2%.
Preferably, described lithium salts is LiPF 6, LiBOB, LiODFB, LiN (CF 3sO 2) 2in one or more combination.
Further preferably, the feed concentrations of described lithium salts is 0.1 ~ 1mol/L.
Another object of the present invention is to provide a kind of lithium ion battery, and this lithium ion battery comprises positive plate, negative plate, lithium-ion membrane and above-mentioned electrolyte.
Due to the utilization of technique scheme, the present invention compared with prior art has following advantages: high-voltage lithium ion batteries electrolyte of the present invention, have employed the solvent mixed for butyl ether by ethylene carbonate, methyl ethyl carbonate and fluoromethane, this solvent joins the electrolyte that obtains in lithium salts without flash-point, security performance is high, meanwhile, the charge/discharge capacity of electrolyte to positive pole that have employed this solvent has no adverse effects, and has good cycle performance; And add vinyl ethylene carbonate, fluorinated ethylene carbonate in the electrolytic solution, contribute to the chemical property improving lithium battery, also improve positive electrode cycle performance at high temperature simultaneously; And add adiponitrile in the electrolytic solution, there is higher oxidation Decomposition current potential, the oxidation Decomposition of electrolyte under high potential can be suppressed, solve the battery problem that inflatable is serious under high voltage condition, cycle performance is poor, and by its synergy mixed for butyl ether with fluoromethane, the high-voltage lithium-ion battery electrolyte of preparation is made to have good resistance to elevated temperatures and high voltage performance, make high-voltage lithium ion batteries of the present invention stable cycle performance at normal temperatures, not inflatable under the high temperature conditions, internal resistance change is little, has good market prospects.
Embodiment
Below in conjunction with specific embodiment, technical scheme of the present invention is further elaborated.
Below as nothing specializes, the content in embodiment is mass percentage.Wherein, the gross mass of mass percentage=100% × each constituent mass/electrolyte of each component.
Comparative example 1
The preparation of electrolyte: this electrolyte comprises solvent, the lithium salts of 13.5%, the additive of 6% of 80.5%, wherein, this solvent is mixed by the diethyl carbonate of 48.3%, the ethylene carbonate of 24.1%, the propene carbonate of 8.1%, here the lithium salts adopted is lithium hexafluoro phosphate, and this additive is mixed by the vinylene carbonate of 1.0%, the adiponitrile of 5.0%.
Embodiment 1
A kind of lithium ion battery, this lithium ion battery comprises positive plate, negative plate, lithium-ion membrane and electrolyte.This example provides a kind of preparation method of electrolyte, specific as follows: this electrolyte comprises solvent, the lithium salts of 15%, the additive of 5% of 80%, wherein, solvent is mixed for butyl ether by the ethylene carbonate of 35%, the methyl ethyl carbonate of 10%, the fluoromethane of 35%, additive is mixed by the vinyl ethylene carbonate of 2%, the fluorinated ethylene carbonate of 2.5%, the adiponitrile of 0.5%, and the lithium salts adopted here is LiPF 6, lithium salts here can adopt LiPF certainly 6, LiBOB, LiODFB, LiN (CF 3sO 2) 2in one or more combination, and the feed concentrations of this lithium salts controls at 0.1 ~ 1mol/L.
Embodiment 2
The preparation of electrolyte: this electrolyte comprises solvent, the lithium salts of 12%, the additive of 3% of 85%, wherein, solvent is mixed for butyl ether by the ethylene carbonate of 35%, the methyl ethyl carbonate of 10%, the fluoromethane of 40%, additive is mixed by the vinyl ethylene carbonate of 1%, the fluorinated ethylene carbonate of 1.3%, the adiponitrile of 0.7%, and the lithium salts adopted here is LiN (CF 3sO 2) 2.
Embodiment 3
The preparation of electrolyte: this electrolyte comprises solvent, the lithium salts of 10%, the additive of 1% of 89%, wherein, solvent is mixed for butyl ether by the ethylene carbonate of 40%, the methyl ethyl carbonate of 9%, the fluoromethane of 40%, additive is mixed by the vinyl ethylene carbonate of 0.4%, the fluorinated ethylene carbonate of 0.4%, the adiponitrile of 0.2%, and the lithium salts adopted here is LiN (CF 3sO 2) 2.
Embodiment 4
The preparation of electrolyte: this electrolyte comprises solvent, the lithium salts of 10%, the additive of 1% of 89%, wherein, solvent is mixed for butyl ether by the ethylene carbonate of 37%, the methyl ethyl carbonate of 9%, the fluoromethane of 43%, additive is mixed by the vinyl ethylene carbonate of 0.4%, the fluorinated ethylene carbonate of 0.4%, the adiponitrile of 0.2%, and the lithium salts adopted here is LiN (CF 3sO 2) 2.
Lithium-ion battery electrolytes prepared by the lithium-ion battery electrolytes prepare above-described embodiment 1 ~ 4 and comparative example 1 injects through fully dry graphite/LiNi 0.5mn 0.3co 0.2o 2battery, battery leaves standstill through an envelope, preliminary filling changes into, carry out 3.4V ~ 4.95V1C cycle charge-discharge normal temperature loop test after two envelope partial volumes and the full electric state 60 DEG C/6H of 4.95V stores test.
Normal temperature loop test:
Under 25 DEG C ± 3 DEG C conditions, in the mode of 1C multiplying power constant current-constant voltage, battery is charged to 4.95V, cut-off current is 0.05C; Then with 1C constant-current discharge to 3.4V, complete a 1C charge and discharge cycles; Repeat above-mentioned charge and discharge process, with the discharge capacity of the 200th time divided by primary discharge capacity, obtain the capability retention of circulation 200 times.
60 DEG C of high-temperature storage tests:
By battery with 0.5C multiplying power constant-current constant-voltage charging to 4.95V, test battery thickness, internal resistance, then put into 60 DEG C of baking ovens, take out battery after 7 days, while hot test battery thickness by battery, be down to after room temperature test internal resistance until battery;
Cell thickness before cell thickness bulging rate=(cell thickness before the cell thickness-storage after storage)/storage.
The battery produced according to above-mentioned comparative example and embodiment is carried out normal temperature 1C circulation, 60 degree of high-temperature storage tests, the results are shown in following table:
Table 1
From table 1, can find out, have employed ethylene carbonate, methyl ethyl carbonate and the fluoromethane mixed solution for butyl ether as solvent, adopt the mixing of vinyl ethylene carbonate, fluorinated ethylene carbonate and adiponitrile as additive, effectively improve the capability retention under lithium battery normal temperature, and its thickness increment rate and internal resistance increase rate are far superior to comparative example.
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 be implemented; 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 in protection scope of the present invention.

Claims (6)

1. a high-voltage lithium ion battery electrolyte, it is characterized in that, 100% is counted with the gross mass of electrolyte, described electrolyte is grouped into by the one-tenth of following mass percent: solvent 80 ~ 89%, lithium salts 10 ~ 15%, additive 0.5 ~ 5%, described solvent is mixed for butyl ether by ethylene carbonate, methyl ethyl carbonate and fluoromethane, and described additive is made up of vinyl ethylene carbonate, fluorinated ethylene carbonate, adiponitrile.
2. high-voltage lithium ion battery electrolyte according to claim 1, it is characterized in that, count 100% with the gross mass of described electrolyte, described solvent is grouped into by the one-tenth of following mass percent: ethylene carbonate 35 ~ 40%, methyl ethyl carbonate 7 ~ 10%, fluoromethane are for butyl ether 35 ~ 45%.
3. high-voltage lithium ion battery electrolyte according to claim 1, it is characterized in that, 100% is counted with the gross mass of described electrolyte, wherein, described additive is grouped into by the one-tenth of following mass percent: vinyl ethylene carbonate 0.2 ~ 3%, fluorinated ethylene carbonate 0.2 ~ 3%, adiponitrile 0.1 ~ 2%.
4. high-voltage lithium ion battery electrolyte according to claim 1, is characterized in that, described lithium salts is LiPF 6, LiBOB, LiODFB, LiN (CF 3sO 2) 2in one or more combination.
5. high-voltage lithium ion battery electrolyte according to claim 4, is characterized in that, the feed concentrations of described lithium salts is 0.1 ~ 1mol/L.
6. a lithium ion battery, comprises positive plate, negative plate, lithium-ion membrane and electrolyte, it is characterized in that, described electrolyte is the high-voltage lithium ion battery electrolyte described in claim 1 ~ 5 any one claim.
CN201510956600.XA 2015-12-18 2015-12-18 A kind of high-voltage lithium ion battery electrolyte and lithium ion battery Active CN105576291B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106207258A (en) * 2016-08-30 2016-12-07 中盐安徽红四方锂电有限公司 A kind of electrolyte of low temperature lithium battery
CN111082141A (en) * 2019-12-20 2020-04-28 中国电子科技集团公司第十八研究所 High-voltage lithium ion battery electrolyte and preparation method thereof
CN111656596A (en) * 2018-03-08 2020-09-11 阿莫绿色技术有限公司 Electrolyte for secondary battery, battery comprising same, and flexible battery

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Publication number Priority date Publication date Assignee Title
CN101673855A (en) * 2009-09-25 2010-03-17 深圳世纪新能源电池有限公司 Electrolyte flame-retardant additive of lithium ion battery and lithium ion battery using same
CN103384017A (en) * 2013-07-04 2013-11-06 珠海市赛纬电子材料有限公司 Non-aqueous electrolyte of high-voltage lithium ion batteries
CN104425840A (en) * 2013-08-28 2015-03-18 张家港骏博新材料有限公司 High-temperature electrolyte of power battery
CN104752770A (en) * 2013-12-30 2015-07-01 天津金牛电源材料有限责任公司 Preparation method of high voltage electrolyte used for lithium ion battery

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101673855A (en) * 2009-09-25 2010-03-17 深圳世纪新能源电池有限公司 Electrolyte flame-retardant additive of lithium ion battery and lithium ion battery using same
CN103384017A (en) * 2013-07-04 2013-11-06 珠海市赛纬电子材料有限公司 Non-aqueous electrolyte of high-voltage lithium ion batteries
CN104425840A (en) * 2013-08-28 2015-03-18 张家港骏博新材料有限公司 High-temperature electrolyte of power battery
CN104752770A (en) * 2013-12-30 2015-07-01 天津金牛电源材料有限责任公司 Preparation method of high voltage electrolyte used for lithium ion battery

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106207258A (en) * 2016-08-30 2016-12-07 中盐安徽红四方锂电有限公司 A kind of electrolyte of low temperature lithium battery
CN106207258B (en) * 2016-08-30 2019-06-25 中盐安徽红四方锂电有限公司 A kind of electrolyte of low temperature lithium battery
CN111656596A (en) * 2018-03-08 2020-09-11 阿莫绿色技术有限公司 Electrolyte for secondary battery, battery comprising same, and flexible battery
US11984557B2 (en) 2018-03-08 2024-05-14 Amogreentech Co., Ltd. Electrolyte solution for secondary battery, and battery and flexible battery comprising same
CN111082141A (en) * 2019-12-20 2020-04-28 中国电子科技集团公司第十八研究所 High-voltage lithium ion battery electrolyte and preparation method thereof

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Address after: 215433 GCL Middle Road, petrochemical District, taicanggang port, Suzhou City, Jiangsu Province

Patentee after: Suzhou Huayi New Energy Technology Co.,Ltd.

Address before: 215433 No.8, middle Xiexin Road, petrochemical District, taicanggang port area, Suzhou City, Jiangsu Province

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