CN104425840A - High-temperature electrolyte of power battery - Google Patents

High-temperature electrolyte of power battery Download PDF

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Publication number
CN104425840A
CN104425840A CN201310382696.4A CN201310382696A CN104425840A CN 104425840 A CN104425840 A CN 104425840A CN 201310382696 A CN201310382696 A CN 201310382696A CN 104425840 A CN104425840 A CN 104425840A
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CN
China
Prior art keywords
carbonate
electrolyte
power battery
high temperature
organic solvent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201310382696.4A
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Chinese (zh)
Inventor
肖兆亚
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ZHANGJIAGANG JUNBO NEW MATERIAL Co Ltd
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ZHANGJIAGANG JUNBO NEW MATERIAL Co Ltd
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Priority to CN201310382696.4A priority Critical patent/CN104425840A/en
Publication of CN104425840A publication Critical patent/CN104425840A/en
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/056Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564Accumulators 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
    • H01M10/0566Liquid materials
    • H01M10/0567Liquid materials characterised by the additives
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/056Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564Accumulators 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
    • H01M10/0566Liquid materials
    • H01M10/0569Liquid materials characterised by the solvents
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy 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 high-temperature electrolyte of a power battery. The high-temperature electrolyte is mainly prepared from an organic solvent, conductive lithium ion salt and an additive; conductive lithium ion salt is added into the organic solvent at -5 DEG C so as to form intermediate electrolyte, and finally, the additive with a certain ratio is added based on the weight of the intermediate electrolyte; the intermediate electrolyte comprises the following components in percentage by weight: 50-92% of the organic solvent and the balance being 0.5-1.8mol/L conductive lithium ion salt; the weight of the additive accounts for 1-10% of the weight of the intermediate electrolyte. The high-temperature electrolyte of the power battery is reasonable in component proportion, has good charge and discharge and high-temperature cycle stability performances, and is suitable for power lithium battery operating at high temperature.

Description

A kind of power battery at high temperature electrolyte
Technical field
The invention belongs to lithium-ion-power cell field, particularly relate to a kind of power battery at high temperature electrolyte that can improve lithium rechargeable battery high temperature cyclic performance.
 
Background technology
The electrokinetic cell more than 95% of China's electric bicycle adopts lead-acid battery, applies MH-Ni battery and Li-ion battery on a small quantity.Predict according to domestic authoritative institution, the output value to Chinese electric bicycle in 2015 will reach 1,000 hundred million yuan, wherein 16,000,000,000 yuan, supporting battery, and the replacement battery of secondary market reaches 48,000,000,000 yuan, and this is a huge Battery Market.From the trend of Development of Electric Vehicles, the demand of lithium battery of electric vehicle increases rapidly in several annual meetings in future, and electric motor car lithium ion battery producer is to the corresponding also rapid growth of the demand of battery electrolyte.In hot summer, electric motor car, bicycle and the electric automobile high-temperature behavior to battery has stricter requirement.
 
Summary of the invention
For solving the problems of the technologies described above, object provided by the invention is to provide a kind of lithium-ion-power cell high-temperature electrolyte with good properties at high temperature, cycle performance.
For achieving the above object, technical scheme of the present invention is as follows:
A kind of power battery at high temperature electrolyte, formulated primarily of organic solvent, lithium ion conducting salt and additive, electrolyte in the middle of lithium ion conducting salt joins in the organic solvent of five degrees below zero and formed, finally add a certain proportion of additive based on described middle electrolyte weight, part by weight in described middle electrolyte shared by each composition is: organic solvent 50 ~ 92%, lithium ion conducting salt 0.5 ~ 1.8 mol/L, and the weight of described additive is 1 ~ 10% of described middle electrolyte weight.
Preferably, described organic solvent is one or more in ethylene carbonate, propene carbonate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl propyl carbonate, ethyl acetate, methyl propionate.
Preferably, described additive is one or more in vinylene carbonate, fluorinated ethylene carbonate, vinylethylene carbonate, adiponitrile, succinonitrile methane-disulfonic acid methylene ester, 1-3 propane sultone.
Preferably, described lithium ion conducting salt is one or more in lithium hexafluoro phosphate, dioxalic acid lithium borate, LiBF4, hexafluoro conjunction arsenic (V) sour lithium, lithium perchlorate.
Preferably, described organic solvent is made up of ethylene carbonate, propene carbonate, diethyl carbonate and methyl ethyl carbonate, and its proportion is 35:10:20:35.
Preferably, described additive is made up of vinylene carbonate, fluorinated ethylene carbonate, 1-3 propane sultone, succinonitrile, and its proportion is 1:1:1:1.
Preferably, described lithium ion conducting salt is lithium hexafluoro phosphate, and its concentration is 1.2mol/L.
The invention has the beneficial effects as follows: 1, compared with traditional electrolyte, the solvent used in electrolyte of the present invention and additive circulate under being more suitable for high temperature 60 degree of environment; 2, the present invention adopt solvent and additive can ensure that electrolyte fully dissolves, and electrode surface surperficial SEI film is more stable under the high temperature conditions; 3, instant component reasonable mixture ratio, has good discharge and recharge and high temperature circulation stability, is applicable to the dynamic lithium battery worked under the high temperature conditions.
 
Accompanying drawing explanation
In order to be illustrated more clearly in the technical scheme in the embodiment of the present invention, below the accompanying drawing used required in describing embodiment is briefly described.
Fig. 1 is the comparing result of embodiment of the present invention the disclosed embodiments 3 and embodiment 2.
 
Embodiment
Below by specific embodiment, the present invention is described in further detail, but the present invention is not limited to these embodiments.
A kind of power battery at high temperature electrolyte, formulated primarily of organic solvent, lithium ion conducting salt and additive, electrolyte in the middle of lithium ion conducting salt joins in the organic solvent of five degrees below zero and formed, finally add a certain proportion of additive based on described middle electrolyte weight, part by weight in middle electrolyte shared by each composition is: organic solvent 50 ~ 92%, lithium ion conducting salt 0.5 ~ 1.8 mol/L, the weight of described additive is 1 ~ 10% of described middle electrolyte weight.
Organic solvent is one or more in ethylene carbonate, propene carbonate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl propyl carbonate, ethyl acetate, methyl propionate.
Additive is one or more in vinylene carbonate, fluorinated ethylene carbonate, vinylethylene carbonate, adiponitrile, succinonitrile methane-disulfonic acid methylene ester, 1-3 propane sultone.
Lithium ion conducting salt is lithium hexafluoro phosphate, dioxalic acid lithium borate, LiBF4, hexafluoro close arsenic (V) sour lithium, one or more in lithium perchlorate.
Embodiment 1
Get the ethylene carbonate after refining, propene carbonate, diethyl carbonate, methyl ethyl carbonate, carries out preparation mixing by weight 30:10:20:40, is then chilled to negative 5 degree in glove box, start slowly evenly to add lithium hexafluoro phosphate, be configured to the solution of 1mol/L, finally add 1% vinylene carbonate based on electrolyte weight, 1% 1-3 propane sultone.Analytical sampling is analyzed moisture content, hydrofluoric acid, density, conductivity etc., carries out battery testing after qualified.
After tested, in obtained high-temperature electrolyte, battery high-temperature high temperature 60 circulates 1000 weeks capability retentions 80%.
Embodiment 2
Get the ethylene carbonate after refining, diethyl carbonate, methyl ethyl carbonate, in glove box, preparation mixing is carried out by weight 1:1:1, then negative 5 degree are chilled to, start slowly evenly to add anhydrous lithium hexafluoro phosphate, be configured to the solution of 1mol/L, finally add 1% vinylene carbonate based on electrolyte weight.
After tested, make battery at the electrolyte of gained, high temperature is decayed quickly, high temperature 60 degree of circulations 60 weeks capability retentions 70%.
Embodiment 3
Get the ethylene carbonate after refining, propene carbonate, diethyl carbonate, methyl ethyl carbonate, by weight 35:10:20:35, carries out preparation mixing in glove box, then negative 5 degree are chilled to, start slowly evenly to add anhydrous lithium hexafluoro phosphate, be configured to the solution of 1.2 mol/L, finally add 1% vinylene carbonate, 1% fluorinated ethylene carbonate, 1% 1-3 propane sultone, 1% succinonitrile based on electrolyte weight.Analytical sampling is to moisture content, and hydrofluoric acid density conductivity etc. is analyzed, and carries out battery testing after qualified.
After tested, in obtained high-temperature electrolyte, battery high-temperature 60 circulates 1091 weeks capability retentions 84%.
Example 3 comparative example 2 the results are shown in Figure 1, wherein laterally represents electrolyte charge and discharge cycles number of times, longitudinally represents electrolyte volume.
In sum, the invention has the beneficial effects as follows:
1, compared with traditional electrolyte, the solvent used in electrolyte of the present invention and additive circulate under being more suitable for high temperature 60 degree of environment;
2, the present invention adopt solvent and additive can ensure that electrolyte fully dissolves, and electrode surface surperficial SEI film is more stable under the high temperature conditions;
3, instant component reasonable mixture ratio, has good discharge and recharge and high temperature circulation stability, is applicable to the dynamic lithium battery worked under the high temperature conditions.

Claims (7)

1. a power battery at high temperature electrolyte, formulated primarily of organic solvent, lithium ion conducting salt and additive, it is characterized in that, electrolyte in the middle of lithium ion conducting salt joins in the organic solvent of five degrees below zero and formed, finally add a certain proportion of additive based on described middle electrolyte weight, part by weight in described middle electrolyte shared by each composition is: organic solvent 50 ~ 92%, lithium ion conducting salt 0.5 ~ 1.8 mol/L, and the weight of described additive is 1 ~ 10% of described middle electrolyte weight.
2. a kind of power battery at high temperature electrolyte according to claim 1, it is characterized in that, described organic solvent is one or more in ethylene carbonate, propene carbonate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl propyl carbonate, ethyl acetate, methyl propionate.
3. a kind of power battery at high temperature electrolyte according to claim 1, it is characterized in that, described additive is one or more in vinylene carbonate, fluorinated ethylene carbonate, vinylethylene carbonate, adiponitrile, succinonitrile methane-disulfonic acid methylene ester, 1-3 propane sultone.
4. a kind of power battery at high temperature electrolyte according to claim 1, it is characterized in that, described lithium ion conducting salt is lithium hexafluoro phosphate, dioxalic acid lithium borate, LiBF4, hexafluoro close arsenic (V) sour lithium, one or more in lithium perchlorate.
5. a kind of power battery at high temperature electrolyte according to claim 2, it is characterized in that, described organic solvent is made up of ethylene carbonate, propene carbonate, diethyl carbonate and methyl ethyl carbonate, and its proportion is 35:10:20:35.
6. a kind of power battery at high temperature electrolyte according to claim 3, is characterized in that, described additive is made up of vinylene carbonate, fluorinated ethylene carbonate, 1-3 propane sultone, succinonitrile, and its proportion is 1:1:1:1.
7. a kind of power battery at high temperature electrolyte according to claim 4, is characterized in that, described lithium ion conducting salt is lithium hexafluoro phosphate, and its concentration is 1.2mol/L.
CN201310382696.4A 2013-08-28 2013-08-28 High-temperature electrolyte of power battery Pending CN104425840A (en)

Priority Applications (1)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105336987A (en) * 2015-11-17 2016-02-17 深圳新宙邦科技股份有限公司 Non-aqueous electrolyte of lithium ion battery and lithium ion battery
CN105576291A (en) * 2015-12-18 2016-05-11 苏州华一新能源科技有限公司 Lithium ion battery and electrolyte for high-voltage lithium ion battery
CN106328996A (en) * 2015-06-30 2017-01-11 汽车能源供应公司 Lithium ion secondary battery
CN106785037A (en) * 2016-12-26 2017-05-31 河南华瑞高新材料科技股份有限公司 A kind of lithium-ion battery electrolytes for ternary material battery
CN107579279A (en) * 2017-08-20 2018-01-12 长沙小新新能源科技有限公司 A kind of lithium-ion electrolyte for improving lithium ion pole piece interface

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106328996A (en) * 2015-06-30 2017-01-11 汽车能源供应公司 Lithium ion secondary battery
CN106328996B (en) * 2015-06-30 2019-09-24 远景Aesc日本有限公司 Lithium ion secondary battery
CN105336987A (en) * 2015-11-17 2016-02-17 深圳新宙邦科技股份有限公司 Non-aqueous electrolyte of lithium ion battery and lithium ion battery
CN105576291A (en) * 2015-12-18 2016-05-11 苏州华一新能源科技有限公司 Lithium ion battery and electrolyte for high-voltage lithium ion battery
CN106785037A (en) * 2016-12-26 2017-05-31 河南华瑞高新材料科技股份有限公司 A kind of lithium-ion battery electrolytes for ternary material battery
CN106785037B (en) * 2016-12-26 2019-07-26 河南华瑞高新材料有限公司 A kind of lithium-ion battery electrolytes for ternary material battery
CN107579279A (en) * 2017-08-20 2018-01-12 长沙小新新能源科技有限公司 A kind of lithium-ion electrolyte for improving lithium ion pole piece interface

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Application publication date: 20150318