CN105633463A - Lithium-ion secondary battery electrolyte applicable to low-temperature environment discharging - Google Patents
Lithium-ion secondary battery electrolyte applicable to low-temperature environment discharging Download PDFInfo
- Publication number
- CN105633463A CN105633463A CN201610009280.1A CN201610009280A CN105633463A CN 105633463 A CN105633463 A CN 105633463A CN 201610009280 A CN201610009280 A CN 201610009280A CN 105633463 A CN105633463 A CN 105633463A
- Authority
- CN
- China
- Prior art keywords
- lithium
- electrolyte
- secondary battery
- ion secondary
- component
- 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.)
- Granted
Links
Classifications
-
- 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
- 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
- H01M2300/0042—Four or more 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
Abstract
The invention discloses a lithium-ion secondary battery electrolyte applicable to low-temperature environment discharging. The lithium-ion secondary battery electrolyte has the beneficial effects that the electrolyte is assembled into the lithium-ion secondary battery; over 80% of normal-temperature capacity can be discharged through 0.2C rate discharging at -40 DEG C; the performance is stable; the cycle lifetime through 0.5C rate charging and discharging can reach 1500 times; the capacity retention ratio can reach over 70%; meanwhile, a quaternary system is adopted by an electrolyte solvent; the lithium-ion secondary battery electrolyte can be applied to various positive material systems and can also be applied to various negative material systems; and the application range of the electrolyte is expanded.
Description
Technical field
The present invention relates to technical field of lithium batteries, it particularly relates to a kind of electrolyte of lithium-ion secondary battery suitable in low temperature environment electric discharge.
Background technology
Along with developing rapidly of lithium ion battery applications, lithium battery technology is being deep into the technical fields such as military, aviation further, these fields require that the low temperature of lithium ion battery uses scope below-40 DEG C, current commercial lithium ion battery has been difficult to meet requirement, one of the main reasons is exactly anolyte portion solvent solidification under low temperature environment, lithium spreads between electrode and electrolyte interface and electric charge moves slowly, causing that conductivity is low, electrolyte is poor to the penetrance of barrier film to wellability and the lithium ion of barrier film at low ambient temperatures simultaneously.
Its freezing point of electrolyte conventional at present is at-30 DEG C, performance is far from the actual requirement meeting the low temperature such as military project, aviation field, electrolyte each component ratio in actual production process does not optimize through series, there is the problem that the scope of application is little, wellability is poor, low temperature performance is poor, cycle performance is poor.
Summary of the invention
It is an object of the invention to provide a kind of electrolyte of lithium-ion secondary battery suitable in low temperature environment electric discharge, to overcome currently available technology above shortcomings.
For realizing above-mentioned technical purpose, the technical scheme is that and be achieved in that:
A kind of electrolyte of lithium-ion secondary battery suitable in low temperature environment electric discharge, including electrolyte, main solvent and additive, by the mixture called after component one of main solvent and additive, described main solvent includes the dimethyl carbonate (DMC) 10.0%��20.0% relative to component one percentage by weight, ethylene carbonate (EC) 10.0%��20.0%, ethyl acetate (EA) 25.0%��35.0% and 1-4-fourth diester (GBL) 25.0%��35.0%, described additive includes the ethylene sulfite (ES) 1%��3% relative to component one percentage by weight, vinylene carbonate (VC) 1%��3%, 1, 3-propane sultone (PS) 0.5%��2.0%, methyl phenyl ethers anisole 0.1%��0.5%, fluorinated ethylene carbonate (FEC) 0.5%��2.0%, N, N-dimethyl trifluoroacetyl (DTA) 1.0%��2.0%, 2, 2-diphenyl propane 0.4%��2.0% and adiponitrile 0.1%��0.5%, described electrolyte includes lithium hexafluoro phosphate (LiPF6) 0.6��1.0mol/L relative to component one molar concentration and dioxalic acid Lithium biborate (LiBOB) 0.3��0.7mol/L.
Beneficial effects of the present invention: the electrolyte of the present invention is assembled into lithium rechargeable battery, more than the 80% of room temperature capacity can be released with 0.2C multiplying power discharging under-40 DEG C of environment, and stable performance, 0.5C rate charge-discharge cycle life can reach 1500 capability retentions up to more than 70%, electrolyte solvent adopts quaternary system simultaneously, can apply to multiple positive electrode system, as: cobalt acid lithium, nickle cobalt lithium manganate, LiFePO4, multiple negative material system can also be applied to, as: Delanium, native graphite, silicon-carbon cathode material, expand the use scope of electrolyte.
Detailed description of the invention
Technical scheme in the embodiment of the present invention will be clearly and completely described below, it is clear that described embodiment is only a part of embodiment of the present invention, rather than whole embodiments. Based on the embodiment in the present invention, the every other embodiment that those of ordinary skill in the art obtain, broadly fall into the scope of protection of the invention.
Embodiment 1:
A kind of electrolyte of lithium-ion secondary battery suitable in low temperature environment electric discharge, including electrolyte, main solvent and additive, by the mixture called after component one of main solvent and additive, described main solvent includes the dimethyl carbonate (DMC) 10.0% relative to component one percentage by weight, ethylene carbonate (EC) 20.0%, ethyl acetate (EA) 35.0% and 1-4-fourth diester (GBL) 25.0%, described additive includes the ethylene sulfite (ES) 3% relative to component one percentage by weight, vinylene carbonate (VC) 1%, 1, 3-propane sultone (PS) 2%, methyl phenyl ethers anisole 0.5%, fluorinated ethylene carbonate (FEC) 2.0%, N, N-dimethyl trifluoroacetyl (DTA) 1.0%, 2, 2-diphenyl propane 0.4% and adiponitrile 0.1%, described electrolyte includes lithium hexafluoro phosphate (LiPF6) 0.6/L relative to component one molar concentration and dioxalic acid Lithium biborate (LiBOB) 0.7/L.
Embodiment 2:
A kind of electrolyte of lithium-ion secondary battery suitable in low temperature environment electric discharge, including electrolyte, main solvent and additive, by the mixture called after component one of main solvent and additive, described main solvent includes the dimethyl carbonate (DMC) 13% relative to component one percentage by weight, ethylene carbonate (EC) 14%, ethyl acetate (EA) 32% and 1-4-fourth diester (GBL) 32%, described additive includes the ethylene sulfite (ES) 2% relative to component one percentage by weight, vinylene carbonate (VC) 2%, 1, 3-propane sultone (PS) 1.2%, methyl phenyl ethers anisole 0.3%, fluorinated ethylene carbonate (FEC) 1.0%, N, N-dimethyl trifluoroacetyl (DTA) 1.2%, 2, 2-diphenyl propane 1.0% and adiponitrile 0.3%, described electrolyte includes lithium hexafluoro phosphate (LiPF6) 0.8mol/L relative to component one molar concentration and dioxalic acid Lithium biborate (LiBOB) 0.5mol/L.
Embodiment 3:
A kind of electrolyte of lithium-ion secondary battery suitable in low temperature environment electric discharge, including electrolyte, main solvent and additive, by the mixture called after component one of main solvent and additive, described main solvent includes the dimethyl carbonate (DMC) 20.0% relative to component one percentage by weight, ethylene carbonate (EC) 10.0%, ethyl acetate (EA) 25.0% and 1-4-fourth diester (GBL) 35.0%, described additive includes the ethylene sulfite (ES) 1% relative to component one percentage by weight, vinylene carbonate (VC) 3%, 1, 3-propane sultone (PS) 0.5%, methyl phenyl ethers anisole 0.5%, fluorinated ethylene carbonate (FEC) 0.5%, N, N-dimethyl trifluoroacetyl (DTA) 2.0%, 2, 2-diphenyl propane 2.0% and adiponitrile 0.5%, described electrolyte includes lithium hexafluoro phosphate (LiPF6) 1.0mol/L relative to component one molar concentration and dioxalic acid Lithium biborate (LiBOB) 0.3mol/L.
The configuration process of electrolyte is as follows:
Becoming mixed solution, record volume to be V1 according to quality hundred ratio according to recipe configuration according to recipe requirements, main solvent and additive, lithium salts is according to molal volume than adding, and the lithium salts that first will add by recipe requirements becomes quality by molar concentration with density conversion;
First by main solvent rectification, then purpose beats in measuring tank respectively through pipeline for removing impurity and purification, and measuring tank self has the function calculated the weight;
Successively dimethyl carbonate (DMC), ethylene carbonate (EC), ethyl acetate (EA), 1-4-fourth diester (GBL) are joined in reactor by measuring tank respectively according to weight ratio, stir at normal temperatures 0.5 to 1 hour after adding these three kinds of main solvents, this whipping process need argon (purity is more than 99.999%) protect in whole process, protection air pressure is 1.02 ~ 1.08MPa, monitoring water content, water content should lower than 10ppm;
By measuring tank, lithium hexafluoro phosphate is joined in reactor, stir 1 hour, add dioxalic acid Lithium biborate (LIBOB) and stir 1.5 ~ 2.5 hours, protecting air pressure in course of reaction is 1.02 ~ 1.08MPa, monitoring water and fluohydric acid content, water content is lower than 10ppm, and Fluohydric acid. (HF) content is lower than 20ppm;
By measuring tank according to weight ratio respectively successively by ethylene sulfite (ES), vinylene carbonate (VC), 1,3-propane sultone (PS), methyl phenyl ethers anisole, fluorinated ethylene carbonate (FEC), (N, N-dimethyl trifluoroacetyl) DTA, 2,2-diphenyl propane, adiponitrile join in reactor, stir 0.5-2 hour, protecting air pressure in course of reaction is 1.02 ~ 1.08MPa, monitoring water and fluohydric acid content, water content is lower than 10ppm, and Fluohydric acid. (HF) content is lower than 20ppm;
Finally the electrolyte being made into is injected battery core internal.
In sum, technique scheme by means of the present invention, the electrolyte of the present invention is assembled into lithium rechargeable battery, more than the 80% of room temperature capacity can be released with 0.2C multiplying power discharging under-40 DEG C of environment, and stable performance, 0.5C rate charge-discharge cycle life can reach 1500 capability retentions up to more than 70%, electrolyte solvent adopts quaternary system simultaneously, can apply to multiple positive electrode system, as: cobalt acid lithium, LiFePO4, multiple negative material system can also be applied to, as: Delanium and a small amount of native graphite, expand the use scope of electrolyte.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all within the spirit and principles in the present invention, any amendment of making, equivalent replacement, improvement etc., should be included within protection scope of the present invention.
Claims (1)
1. the electrolyte of lithium-ion secondary battery being applicable to low temperature environment electric discharge, it is characterized in that, including electrolyte, main solvent and additive, by the mixture called after component one of main solvent and additive, described main solvent includes the dimethyl carbonate (DMC) 10.0%��20.0% relative to component one percentage by weight, ethylene carbonate (EC) 10.0%��20.0%, ethyl acetate (EA) 25.0%��35.0% and 1-4-fourth diester (GBL) 25.0%��35.0%, described additive includes the ethylene sulfite (ES) 1%��3% relative to component one percentage by weight, vinylene carbonate (VC) 1%��3%, 1, 3-propane sultone (PS) 0.5%��2.0%, methyl phenyl ethers anisole 0.1%��0.5%, fluorinated ethylene carbonate (FEC) 0.5%��2.0%, N, N-dimethyl trifluoroacetyl (DTA) 1.0%��2.0%, 2, 2-diphenyl propane 0.4%��2.0% and adiponitrile 0.1%��0.5%, described electrolyte includes lithium hexafluoro phosphate (LiPF6) 0.6��1.0mol/L relative to component one molar concentration and dioxalic acid Lithium biborate (LiBOB) 0.3��0.7mol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610009280.1A CN105633463B (en) | 2016-01-08 | 2016-01-08 | A kind of electrolyte of lithium-ion secondary battery suitable for low temperature environment electric discharge |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610009280.1A CN105633463B (en) | 2016-01-08 | 2016-01-08 | A kind of electrolyte of lithium-ion secondary battery suitable for low temperature environment electric discharge |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105633463A true CN105633463A (en) | 2016-06-01 |
| CN105633463B CN105633463B (en) | 2018-03-02 |
Family
ID=56048164
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610009280.1A Expired - Fee Related CN105633463B (en) | 2016-01-08 | 2016-01-08 | A kind of electrolyte of lithium-ion secondary battery suitable for low temperature environment electric discharge |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105633463B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109560324A (en) * | 2018-12-05 | 2019-04-02 | 江西赛特新能源科技有限公司 | A kind of resistance to super-low-temperature lithium-ion cell electrolyte |
| 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 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20230238581A1 (en) * | 2022-01-25 | 2023-07-27 | Sila Nanotechnologies, Inc. | Electrolytes for lithium-ion battery cells with nitrile additives |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101916878A (en) * | 2010-08-27 | 2010-12-15 | 上海奥威科技开发有限公司 | Low-temperature organic electrolyte taking gamma-butyrolactone as base solvent and application thereof |
| CN101931096A (en) * | 2010-08-27 | 2010-12-29 | 上海奥威科技开发有限公司 | Propylene carbonate based low-temperature organic electrolyte and application thereof |
| CN102306833A (en) * | 2011-08-17 | 2012-01-04 | 深圳新宙邦科技股份有限公司 | Flame retardant type non-aqueous electrolyte solution and battery thereof |
| CN102361097A (en) * | 2011-11-14 | 2012-02-22 | 中国海洋石油总公司 | Preparation method of low-temperature electrolyte for lithium iron phosphate power battery |
| CN102496739A (en) * | 2011-11-14 | 2012-06-13 | 中国海洋石油总公司 | Non-aqueous electrolyte manufacturing method for high-magnification charge-discharge lithium power battery |
| CN102709588A (en) * | 2012-01-12 | 2012-10-03 | 宁德新能源科技有限公司 | Lithium ion battery and electrolyte thereof |
| CN103078141A (en) * | 2013-01-25 | 2013-05-01 | 宁德新能源科技有限公司 | Lithium-ion secondary battery and electrolyte thereof |
| CN103641751A (en) * | 2011-05-20 | 2014-03-19 | 华中科技大学 | Alkali metal salts of binary or ternary fluorine-containing sulfimide and ionic liquid and applications thereof |
| CN103700884A (en) * | 2013-08-14 | 2014-04-02 | 江西世纪长河新电源有限公司 | Electrolyte of power lithium ion secondary battery |
| CN104321923A (en) * | 2012-03-06 | 2015-01-28 | 吉坤日矿日石能源株式会社 | Electrolyte for Li storage battery, and Li storage battery |
| CN105186034A (en) * | 2015-07-28 | 2015-12-23 | 珠海市赛纬电子材料有限公司 | Electrolyte employing propylene carbonate as main solvent and lithium-ion battery |
-
2016
- 2016-01-08 CN CN201610009280.1A patent/CN105633463B/en not_active Expired - Fee Related
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101916878A (en) * | 2010-08-27 | 2010-12-15 | 上海奥威科技开发有限公司 | Low-temperature organic electrolyte taking gamma-butyrolactone as base solvent and application thereof |
| CN101931096A (en) * | 2010-08-27 | 2010-12-29 | 上海奥威科技开发有限公司 | Propylene carbonate based low-temperature organic electrolyte and application thereof |
| CN103641751A (en) * | 2011-05-20 | 2014-03-19 | 华中科技大学 | Alkali metal salts of binary or ternary fluorine-containing sulfimide and ionic liquid and applications thereof |
| CN102306833A (en) * | 2011-08-17 | 2012-01-04 | 深圳新宙邦科技股份有限公司 | Flame retardant type non-aqueous electrolyte solution and battery thereof |
| CN102361097A (en) * | 2011-11-14 | 2012-02-22 | 中国海洋石油总公司 | Preparation method of low-temperature electrolyte for lithium iron phosphate power battery |
| CN102496739A (en) * | 2011-11-14 | 2012-06-13 | 中国海洋石油总公司 | Non-aqueous electrolyte manufacturing method for high-magnification charge-discharge lithium power battery |
| CN102709588A (en) * | 2012-01-12 | 2012-10-03 | 宁德新能源科技有限公司 | Lithium ion battery and electrolyte thereof |
| CN104321923A (en) * | 2012-03-06 | 2015-01-28 | 吉坤日矿日石能源株式会社 | Electrolyte for Li storage battery, and Li storage battery |
| CN103078141A (en) * | 2013-01-25 | 2013-05-01 | 宁德新能源科技有限公司 | Lithium-ion secondary battery and electrolyte thereof |
| CN103700884A (en) * | 2013-08-14 | 2014-04-02 | 江西世纪长河新电源有限公司 | Electrolyte of power lithium ion secondary battery |
| CN105186034A (en) * | 2015-07-28 | 2015-12-23 | 珠海市赛纬电子材料有限公司 | Electrolyte employing propylene carbonate as main solvent and lithium-ion battery |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109560324A (en) * | 2018-12-05 | 2019-04-02 | 江西赛特新能源科技有限公司 | A kind of resistance to super-low-temperature lithium-ion cell electrolyte |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105633463B (en) | 2018-03-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2021110165A1 (en) | Lithium secondary battery electrolyte with low internal resistance and lithium secondary battery | |
| CN107195966B (en) | A kind of high voltage tertiary cathode material system lithium-ion battery electrolytes that high/low temperature performance is taken into account | |
| CN114937814A (en) | Lithium secondary battery electrolyte capable of reducing internal resistance of battery and lithium secondary battery | |
| US20140295288A1 (en) | Non-aqueous organic electrolyte, lithium ion secondary battery containing non-aqueous organic electrolyte, preparation method of lithium ion secondary battery and terminal communication device | |
| WO2022042373A1 (en) | Lithium ion battery | |
| CN103779607A (en) | Electrolyte solution and lithium-ion secondary battery | |
| CN105720304A (en) | Nonaqueous electrolyte and lithium-ion battery | |
| CN107017433B (en) | Nonaqueous electrolytic solution and lithium ion battery | |
| CN105470571B (en) | Lithium ion secondary battery and electrolyte thereof | |
| CN103456970B (en) | A kind of electrolytic solution and the lithium-ferrous disulfide battery containing this electrolytic solution | |
| CN108258312B (en) | Non-aqueous electrolyte of high-voltage lithium ion battery | |
| CN106229549B (en) | A kind of nonaqueous electrolytic solution of high-voltage lithium ion battery | |
| CN104752768A (en) | Electrolyte solution for lithium titanate battery and lithium titanate battery thereof | |
| CN110943251A (en) | Low-temperature lithium ion electrolyte and lithium ion battery prepared from same | |
| CN110148776A (en) | A kind of lithium secondary cell electrolyte and lithium secondary battery reducing battery impedance | |
| CN109687026B (en) | High-voltage ternary lithium ion battery electrolyte and lithium ion battery containing same | |
| WO2018094818A1 (en) | Non-aqueous electrolyte of lithium-ion battery and lithium-ion battery | |
| CN111029656A (en) | Lithium ion battery non-aqueous electrolyte and lithium ion battery thereof | |
| CN113659203A (en) | Electrolyte containing composite additive and application thereof | |
| CN110838595B (en) | Lithium ion battery electrolyte and application thereof | |
| CN103700884A (en) | Electrolyte of power lithium ion secondary battery | |
| CN108987810B (en) | Electrolyte and secondary lithium battery suitable for high-temperature environment | |
| CN105789685A (en) | Lithium ion battery and electrolyte thereof | |
| CN112234252A (en) | Wide-temperature-range lithium ion battery non-aqueous electrolyte for high voltage and lithium ion battery | |
| US20200136183A1 (en) | Electrolyte and lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180302 Termination date: 20210108 |