CN105789611A - Electrolyte of considering high temperature cycle performance and low temperature cycle performance of battery and lithium-ion battery - Google Patents
Electrolyte of considering high temperature cycle performance and low temperature cycle performance of battery and lithium-ion battery Download PDFInfo
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- CN105789611A CN105789611A CN201610170292.2A CN201610170292A CN105789611A CN 105789611 A CN105789611 A CN 105789611A CN 201610170292 A CN201610170292 A CN 201610170292A CN 105789611 A CN105789611 A CN 105789611A
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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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- 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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- Condensed Matter Physics & Semiconductors (AREA)
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- Battery Electrode And Active Subsutance (AREA)
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Abstract
The invention discloses a nonaqueous electrolyte, for a lithium-ion battery, of considering the high temperature cycle performance and the low temperature cycle performance of the battery and the lithium-ion battery employing the electrolyte. The electrolyte comprises a nonaqueous solvent, an additive and a lithium salt as shown in a general formula shown in the specification, wherein R1 and R2 are one of halogen elements; and the additive is one or more of vinylene carbonate, propylene sulfite, methylene methanedisulfonate and vinylethylene carbonate. By changing the lithium salt in the electrolyte for the lithium-ion battery and adding a certain amount of film-forming additive, the impedance of the battery in the cyclic process is reduced; and the stability of the electrolyte in a high temperature cycle and a low temperature cycle is improved, so that the high temperature cycle performance and the low temperature cycle performance of the battery are improved.
Description
Technical field
The invention belongs to lithium-ion battery electrolytes technical field, be specifically related to a kind of non-aqueous electrolyte for lithium ion cell that can take into account battery high-temperature cycle performance and cold cycle performance, and use the lithium ion battery of this electrolyte.
Background technology
Compared with traditional secondary cell, lithium ion battery has that running voltage height, volume be little, light weight, energy density height, memory-less effect, pollution-free, and the advantage such as self discharge is little, have extended cycle life.Nineteen ninety, Sony corporation of Japan produces first piece of lithium ion battery, has started the commercialization tide of lithium ion battery.In recent years, lithium rechargeable battery, except being applied in consumer electronics product field, is also widely used on electric automobile, and is considered to solve automobile exhaust pollution, reduce the important means that fossil energy consumes.But temperature range that lithium ion battery is suitable for is narrow, be typically in being higher than 55 DEG C and during lower than-10 DEG C battery capacity decay fast, in some instances it may even be possible to there is burning or blast, seriously limit its extensive use.Research finds, during lithium cell charging, the solvent in electrolyte is in positive pole generation oxidation Decomposition, and catabolite hinders the electrochemical reaction desired by battery, therefore causes that battery performance declines.Additionally, during repeated charge, the solvent in electrolyte also can cause the decline of battery performance in the reduction decomposition of graphite cathode, and the electrolyte oxidation particularly with materials such as high voltage nickel manganese, ternarys decomposes more serious, and the potential safety hazard caused is bigger.In order to promote high/low temperature cycle performance and the security performance of lithium ion battery, except seeking novel positive and negative pole material, developing new electrolyte prescription is also a kind of important solution.
Non-aqueous electrolyte for lithium ion cell is mainly dissolved by electrolyte lithium salt and to be formed in organic solvent.Conventional lithium battery electrolytes, electrical conductivity, circulation and high-temperature behavior are general, and when the high temperature performance of battery product is proposed requirements at the higher level, conventional electrolysis liquid material can not make its battery material function optimization.In the constituent of electrolyte, electrolysis additive consumption is little, instant effect, by developing high/low temperature electrolysis additive, it is possible under the premise keeping lithium ion battery room temperature performance, improve high/low temperature stability, solve its high/low temperature safety issue, widen the range of application of lithium ion battery.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of nonaqueous electrolytic solution that can take into account high temperature cyclic performance and cold cycle performance, and the lithium ion battery containing this electrolyte, the addition of the change by middle lithium salts of this electrolyte and film for additive, high temperature cyclic performance and the cold cycle performance of battery can be taken into account, and nonflammable, security performance is good.
For solving above-mentioned technical problem, the present invention by the following technical solutions:
On the one hand, the present invention provides a kind of electrolyte taking into account battery high/low temperature cycle performance.This electrolyte comprises the lithium salts shown in nonaqueous solvent, additive and below formula:
,
In formula, R1And R2For the one in halogen.
Wherein, described additive is one or more in vinylene carbonate (VC), propylene sulfite (PS), methane-disulfonic acid methylene ester (MMDS), vinylethylene carbonate (VEC).The content of additive is generally the 0.1%～20% of electrolyte gross weight；Preferably, the 0.5%～10% of electrolyte gross weight is accounted for；Optimum, account for the 1%～5% of electrolyte gross weight.
The concentration of described lithium salts is 0.8～1.4mol/L, it is preferred that 0.9～1.2mol/L, and that optimum is 1.0～1.1mol/L.
On the other hand, present invention also offers a kind of lithium ion battery, including positive plate, negative plate and above-mentioned electrolyte.
Wherein, the described positive electrode used by positive plate comprises nickel manganese binary material, ternary material, lithium ferric manganese phosphate, LiFePO4 or rich lithium material.
The described negative material used by negative plate comprises the mixing of one or more in native graphite, Delanium, silicon-carbon, silicon, hard carbon, lithium titanate material.
The invention has the beneficial effects as follows: the electrolyte provided shows good cycle performance, high temperature cyclic performance and cold cycle performance in lithium ion battery and is all greatly improved, widened the use temperature range of battery, enhanced the competitiveness of product.
Accompanying drawing explanation
Fig. 1 is 55 DEG C of high temperature circulation figure of embodiment 1 and comparative example 1；
Fig. 2 is-10 DEG C of cold cycle figure of embodiment 1 and comparative example 1.
Detailed description of the invention
Below in conjunction with accompanying drawing, the present invention will be described, it will be appreciated that detailed description of the invention described herein is merely to illustrate and explains the present invention, is not intended to limit the present invention.
Embodiment 1
(1) electrolyte quota: according to EC(ethylene carbonate): PC(Allyl carbonate): DEC(diethyl carbonate): EMC(methyl ethyl ester): VC(vinylene carbonate): PS(propylene sulfite) volume ratio of=35:5:35:25:2:2.5, preparation lithium salt is the electrolyte of 1mol/L, wherein EC, PC, DEC and EMC are nonaqueous solvent, VC and PS is additive, and lithium salts is the composition of following structural formula:
。
(2) preparation of positive electrode: the LiFePO of mixed weight percentage composition 91%4(positive active material), the SP(superconduction carbon black of weight percentage 4%) and the PVDF(binding agent of weight percentage 5%), and add N-Methyl pyrrolidone to it and make slurry, slurry is coated on aluminium foil, dried roll-in, obtain positive electrode.
(3) preparation of negative material: the Delanium of mixed weight percentage composition 75%, the MCMB of weight percentage 20%, the sodium carboxymethyl cellulose of weight percentage 5%, and add deionized water to it, then slurry is coated on Copper Foil, dried roll-in, obtains negative material.
(4) above-mentioned positive and negative electrode material is prepared into the square battery (i.e. length respectively 140mm, 65mm and 18mm) of 1865140 models, and wherein, positive electrode compacted density is 2.17g/cm3, the thickness of positive plate is 162 μm (two-sided)；Negative material compacted density 1.46g/cm3, the thickness of negative plate is 104 μm.
(5) above-mentioned battery is made to be melted into according to following technique: 1) 260mA constant-current charge, pressure limiting 3.65V, in limited time 240min；2) 2600mA constant-current constant-voltage charging, pressure limiting 3.65V, current limliting 200mA, in limited time 240min.Then according to 1C(13000mA) technique carry out room temperature cycle charge-discharge；According to 1C(13000mA) carry out high temperature (55 DEG C) cycle charge-discharge and 0.5C(6500mA) carry out low temperature (-10 DEG C) cycle charge-discharge.Result shows (referring to Fig. 1 and Fig. 2), and when the 80% of capacity attenuation to initial capacity, high temperature circulation number of times is 1600 weeks, and cold cycle number of times is 400 weeks, and high/low temperature cycle performance is obviously improved.
Comparative example 1
(1) electrolyte quota: according to the volume ratio of EC:PC:DEC:EMC:VC:PS=35:5:35:25:2:2.5, compound concentration is the LiPF of 1mol/L6Electrolyte.
(2) preparation of positive electrode: the LiFePO of mixed weight percentage composition 91%4(positive active material), the SP(superconduction carbon black of weight percentage 4%) and the PVDF(binding agent of weight percentage 5%), and add N-Methyl pyrrolidone to it and make slurry, slurry is coated on aluminium foil, dried roll-in, obtain positive electrode.
(3) preparation of negative material: the Delanium of mixed weight percentage composition 75%, the MCMB of weight percentage 20%, the sodium carboxymethyl cellulose of weight percentage 5%, and add deionized water to it, then slurry is coated on Copper Foil, dried roll-in, obtains negative material.
(4) above-mentioned positive and negative electrode material is prepared into the square battery (i.e. length respectively 140mm, 65mm and 18mm) of 1865140 models, and wherein, positive electrode compacted density is 2.17g/cm3, the thickness of positive plate is 162 μm (two-sided)；Negative material compacted density 1.46g/cm3, the thickness of negative plate is 104 μm.
(5) above-mentioned battery is made to be melted into according to following technique: 1) 260mA constant-current charge, pressure limiting 3.65V, in limited time 240min；2) 2600mA constant-current constant-voltage charging, pressure limiting 3.65V, current limliting 200mA, in limited time 240min.Then according to 1C(13000mA) technique carry out room temperature cycle charge-discharge；According to 1C(13000mA) carry out high temperature (55 DEG C) cycle charge-discharge and 0.5C(6500mA) carry out low temperature (-10 DEG C) cycle charge-discharge.Result shows (referring to Fig. 1 and Fig. 2), and when the 80% of capacity attenuation to initial capacity, high temperature circulation number of times is 700 weeks, and cold cycle number of times is 50 weeks.
Embodiment described above is only that the preferred embodiment of the present invention is described; not the scope of the present invention is defined; under the premise designing spirit without departing from the present invention; various deformation that technical scheme is made by those of ordinary skill in the art and improvement, all should fall in the protection domain that claims of the present invention is determined.
Claims (7)
1. take into account an electrolyte for battery high/low temperature cycle performance, comprise the lithium salts shown in nonaqueous solvent, additive and below formula:
,
In formula, R1And R2For the one in halogen.
2. electrolyte according to claim 1, it is characterised in that: described additive is one or more in vinylene carbonate (VC), propylene sulfite (PS), methane-disulfonic acid methylene ester (MMDS), vinylethylene carbonate (VEC).
3. electrolyte according to claim 1, it is characterised in that: the concentration of described lithium salts is 0.8～1.4mol/L.
4. electrolyte according to claim 2, it is characterised in that: the content of described additive is the 0.1%～20% of electrolyte gross weight.
5. a lithium ion battery, including the electrolyte according to any one of positive plate, negative plate and Claims 1 to 4.
6. lithium ion battery according to claim 5, it is characterised in that: the positive electrode used by positive plate comprises nickel manganese binary material, ternary material, lithium ferric manganese phosphate, LiFePO4 or rich lithium material.
7. lithium ion battery according to claim 5, it is characterised in that: the negative material used by negative plate comprises the mixing of one or more in native graphite, Delanium, silicon-carbon, silicon, hard carbon, lithium titanate material.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106252715A (en) * | 2016-09-30 | 2016-12-21 | 合肥国轩高科动力能源有限公司 | A kind of high-temperature electrolyte of lithium ion battery |
| CN107195967A (en) * | 2017-05-25 | 2017-09-22 | 东莞锂威能源科技有限公司 | A kind of low-temperature lithium ion battery |
| CN108336406A (en) * | 2018-01-16 | 2018-07-27 | 河南师范大学 | A kind of lithium ion battery Low ESR high voltage additive and nonaqueous electrolytic solution |
| WO2018232979A1 (en) * | 2017-06-23 | 2018-12-27 | 宁德时代新能源科技股份有限公司 | Lithium iron phosphate battery |
| EP3796437A4 (en) * | 2019-05-31 | 2021-11-03 | Contemporary Amperex Technology Co., Limited | Lithium-ion secondary battery |
| CN114006041A (en) * | 2021-10-12 | 2022-02-01 | 合肥国轩高科动力能源有限公司 | Low-temperature electrolyte for improving low-temperature performance of lithium iron phosphate-graphite battery |
| CN114267877A (en) * | 2021-11-30 | 2022-04-01 | 合肥国轩高科动力能源有限公司 | Lithium ion battery electrolyte and lithium ion battery |
| US11611081B2 (en) | 2019-05-31 | 2023-03-21 | Contemporary Amperex Technology Co., Limited | Lithium ion secondary battery, battery core, negative electrode plate, and apparatus |
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| EP2503633A2 (en) * | 2011-03-23 | 2012-09-26 | SB LiMotive Co., Ltd. | Electrolyte for rechargeable lithium battery and rechargeable lithium battery including the same |
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| CN101139352A (en) * | 2007-09-29 | 2008-03-12 | 张家港市国泰华荣化工新材料有限公司 | Method for preparing difluorine oxalic acid boracic acid lithium |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106252715A (en) * | 2016-09-30 | 2016-12-21 | 合肥国轩高科动力能源有限公司 | A kind of high-temperature electrolyte of lithium ion battery |
| CN107195967A (en) * | 2017-05-25 | 2017-09-22 | 东莞锂威能源科技有限公司 | A kind of low-temperature lithium ion battery |
| CN107195967B (en) * | 2017-05-25 | 2019-04-19 | 东莞锂威能源科技有限公司 | A kind of low-temperature lithium ion battery |
| WO2018232979A1 (en) * | 2017-06-23 | 2018-12-27 | 宁德时代新能源科技股份有限公司 | Lithium iron phosphate battery |
| EP3447838A4 (en) * | 2017-06-23 | 2019-04-10 | Contemporary Amperex Technology Co., Limited | Lithium iron phosphate battery |
| US20200020980A1 (en) * | 2017-06-23 | 2020-01-16 | Contemporary Amperex Technology Co., Limited | Lithium iron phosphate battery |
| CN108336406A (en) * | 2018-01-16 | 2018-07-27 | 河南师范大学 | A kind of lithium ion battery Low ESR high voltage additive and nonaqueous electrolytic solution |
| EP3796437A4 (en) * | 2019-05-31 | 2021-11-03 | Contemporary Amperex Technology Co., Limited | Lithium-ion secondary battery |
| US11611081B2 (en) | 2019-05-31 | 2023-03-21 | Contemporary Amperex Technology Co., Limited | Lithium ion secondary battery, battery core, negative electrode plate, and apparatus |
| US11646424B2 (en) | 2019-05-31 | 2023-05-09 | Contemporary Amperex Technology Co., Limited | Lithium-ion secondary battery |
| CN114006041A (en) * | 2021-10-12 | 2022-02-01 | 合肥国轩高科动力能源有限公司 | Low-temperature electrolyte for improving low-temperature performance of lithium iron phosphate-graphite battery |
| CN114267877A (en) * | 2021-11-30 | 2022-04-01 | 合肥国轩高科动力能源有限公司 | Lithium ion battery electrolyte and lithium ion battery |
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Application publication date: 20160720 |