CN104900917A - Electrolyte for lithium titanate lithium ion battery - Google Patents
Electrolyte for lithium titanate lithium ion battery Download PDFInfo
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- CN104900917A CN104900917A CN201510401505.3A CN201510401505A CN104900917A CN 104900917 A CN104900917 A CN 104900917A CN 201510401505 A CN201510401505 A CN 201510401505A CN 104900917 A CN104900917 A CN 104900917A
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- lithium
- electrolyte
- ion battery
- titanate
- lithium ion
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Classifications
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
-
- 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 electrolyte for a lithium titanate lithium ion battery. The electrolyte for the lithium titanate lithium ion battery comprises main electrolyte lithium salts, auxiliary electrolyte lithium salts, non-aqueous solvent and additives, wherein main electrolyte lithium salts are lithium hexafluorophosphate, and the concentration of the lithium hexafluorophosphate in the electrolyte is 0.5 to 1.5mol/L; the concentration of the auxiliary electrolyte lithium salts in the electrolyte is 0.005 to 0.5mol/L and the auxiliary electrolyte lithium salts are selected from any one or two or more than two kinds of lithium tetrafluoroborate, lithium bisoxalatoborate, lithium bisfluoroxalatoborate, lithium bis(trifluoromethane sulfonimide) and lithium bis(fluorosulfonyl)imide. According to the electrolyte provided by the invention, the electrolyte lithium salts approximately count for 8 to 15 percent of the total mass percent and are formed by compounding the main electrolyte lithium salts and the auxiliary electrolyte lithium salts; the electrolyte additives are optimized. The lithium titanate lithium ion battery adopting the electrolyte disclosed by the invention has excellent cycle performance, rate performance and high-and-low temperature performance; in addition, an effective interfacial film is formed on a cathode lithium titanate interface, so that the gas expansion phenomenon of the lithium titanate lithium ion battery is greatly relieved.
Description
Technical field
The invention belongs to field of lithium ion battery, relate to a kind of electrolyte, more specifically, relate to a kind of electrolyte for lithium titanate lithium ion battery.
Background technology
From the nineties in last century lithium ion battery because of its high-energy-density, have extended cycle life, advantages of environment protection is widely used in electronic product, just because of this, people consider and apply it to the higher electric automobile of the requirement of energy density, circulation and security performance and energy-storage system.It is at present the requirement that its cycle performance of lithium ion battery of negative material and security performance also cannot meet electric automobile and energy-storage system with material with carbon element.
Spinel type lithium titanate (Li
4ti
5o
12, LTO) and the theoretical capacity 175mAh/g of material between 2.5 ~ 1.0V, and the volume with material in excellent invertibity and charge and discharge process changes hardly, LTO also has long circulating and high safety performance simultaneously.But LTO battery is in discharge and recharge and storage process, especially there will be in the case of a high temperature flatulence phenomenon, have a strong impact on the security performance of battery, also the use on a large scale of lithium titanate battery is constrained, but people are to the reason of flatulence, and opinions vary, there is no unified conclusion, mainly think and have caused by following reason: the impact of (1) moisture; (2) electrolyte is in the decomposition at LTO interface, and therefore the electrolyte of exploitation solution or alleviation LTO battery flatulence becomes the task of top priority.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of electrolyte for lithium titanate battery is provided, solve or alleviate the problem of LTO battery flatulence.
For achieving the above object, the invention provides a kind of electrolyte for lithium titanate battery, the electrolyte that this lithium titanate battery uses comprises main electrolyte lithium salt, assisted electrolysis matter lithium salts, nonaqueous solvents and additive; Wherein, described main electrolyte lithium salt is lithium hexafluoro phosphate, and its concentration is in the electrolytic solution 0.5 ~ 1.5mol/L; Described auxiliary electrolyte lithium salt concentration is in the electrolytic solution 0.005 ~ 0.5mol/L, this auxiliary electrolyte lithium salt select in LiBF4, di-oxalate lithium borate, two fluorine Lithium bis (oxalate) borate, two trifluoromethanesulfonimide lithium, two fluorine sulfimide lithium any one or two or more.From the view point of electrochemical stability, our preferred di-oxalate lithium borate and two fluorine Lithium bis (oxalate) borate.
The electrolyte of above-mentioned lithium titanate lithium ion battery, wherein, in described electrolyte, additive proportion is 0% ~ 20% by weight percentage.
The electrolyte of above-mentioned lithium titanate lithium ion battery, wherein, described additive be in vinylene carbonate, vinyl vinylene carbonate, fluorinated ethylene carbonate, sultones class, nitrile, titanate coupling agent any one or two or more.Specifiable additive is as follows:
Sultones class: 1,3-propane sultone, 1,3-propene sultone, Isosorbide-5-Nitrae-butane sultones, 1,8-naphthalene sulfonic acids lactone etc.
Nitrile: acetonitrile, glutaronitrile, adiponitrile, methoxyacetonitrile, 3-methoxypropionitrile, acrylonitrile, benzonitrile etc.
Titanate coupling agent: isopropyl two oleic acid acyloxy (dioctyl phosphoric acid acyloxy) titanate esters, isopropyl three (dioctyl phosphoric acid acyloxy) titanate esters, isopropyl three oleic acid acyloxy titanate esters, two (ethyl acetoacetate base) diisopropoxy titanate esters, two (ethyl acetoacetate base) two isobutoxy titanate esters etc.
The electrolyte of above-mentioned lithium titanate lithium ion battery, wherein, described nonaqueous solvents be in carboxylate, lactone, carbonic ester, ether solvent any one or two or more; From the view point of physical characteristic and the electrochemical properties of electrolyte, can following solvents be enumerated, also can be used together solvents two or more in these solvents.
Carboxylate: methyl formate, Ethyl formate, propyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate etc.
Lactone: gamma-butyrolacton, α-acetyl group-gamma-butyrolacton, beta-butyrolactone, gamma-valerolactone, δ-valerolactone etc.
Carbonic ester: ethylene carbonate, propene carbonate, butylene, vinylene carbonate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate etc.
Ether: chain ether [carbon number 2 ~ 6 (diethyl ether, methyl isopropyl ether, glycol dimethyl ether, diethylene glycol dimethyl ether etc.), carbon number 7 ~ 12 (diethyl carbitol, triglyme etc.)]; Cyclic ether [carbon number 2 ~ 4 (oxolane, 1,3-dioxolanes, Isosorbide-5-Nitrae-diox etc.), carbon number 5 ~ 18 (4-butyl dioxolanes, crown ether etc.)].
The electrolyte of above-mentioned lithium titanate lithium ion battery, wherein, in described electrolyte, nonaqueous solvents carboxylate proportion is 0% ~ 80% by weight percentage.
The electrolyte of above-mentioned lithium titanate lithium ion battery, wherein, in described electrolyte, nonaqueous solvents lactone proportion is 0% ~ 50% by weight percentage.
The electrolyte of above-mentioned lithium titanate lithium ion battery, wherein, in described electrolyte, nonaqueous solvents carbonic ester proportion is 0% ~ 50% by weight percentage.
The electrolyte of above-mentioned lithium titanate lithium ion battery, wherein, in described electrolyte, in nonaqueous solvents, ether solvent proportion is 0% ~ 50% by weight percentage.
From the view point of electrochemical stability, water content in electrolyte of the present invention, based on the capacity of electrolyte, is preferably below 300ppm, be more preferably below 100ppm, be particularly preferably below 50ppm (the low and slow electrolytic cell flatulence of water content has positive role).Water content in electrolyte can adopt Karl_Fischer method (Karl Fischer method) to measure.
Electrolyte of the present invention is formed by main electrolyte lithium salt, assisted electrolysis matter lithium salts, nonaqueous solvents and additive mixed preparing.Electrolyte lithium salt in electrolyte of the present invention accounts for the 8%-15% of gross mass mark, and generally by main electrolyte lithium salt with assisted electrolysis matter lithium salts is composite forms (having synergy).Adopt electrolyte of the present invention, lithium titanate lithium ion battery has excellent cycle performance, high rate performance and high temperature performance, can form effective interfacial film simultaneously, greatly alleviate the flatulence phenomenon of lithium titanate lithium ion battery at negative pole lithium titanate interface.
Accompanying drawing explanation
Fig. 1 have employed the cycle graph of the lithium titanate battery of the electrolyte of embodiments of the invention 1.
Fig. 2 have employed the high rate performance figure of the lithium titanate battery of the electrolyte of embodiments of the invention 1.
Fig. 3 have employed the high temperature performance figure of the lithium titanate battery of the electrolyte of embodiments of the invention 1.
Embodiment
Below in conjunction with accompanying drawing, by specific embodiment, the invention will be further described, but should not be construed as the scope that the present invention is only limitted to the following example.The number of reagent involved in following examples and comparative example is mass fraction, and be equivalent to mass ratio, unit can make milligram, gram, kilogram, ton etc., and unit is unified.
Embodiment 1
The ethylene carbonate 20 parts of lithium hexafluoro phosphate 12 parts, dehydration, propene carbonate 5 parts, dimethyl carbonate 20 parts, diethyl carbonate 10 parts, methyl ethyl carbonate 30 parts, two fluorine Lithium bis (oxalate) borate 0.5 part and vinylene carbonate 2.5 parts are dissolved in 25 DEG C of Homogeneous phase mixing, obtains electrolyte of the present invention (1).The moisture of electrolyte (1) is 15ppm.Water content in electrolyte adopts Karl_Fischer method (Karl Fischer method) to measure.
Embodiment 2
Lithium hexafluoro phosphate 13 parts, the ethylene carbonate 10 parts of dehydration, propene carbonate 15 parts, dimethyl carbonate 30 parts, methyl ethyl carbonate 30 parts, fluorinated ethylene carbonate 2 parts are dissolved in 25 DEG C of Homogeneous phase mixing, obtains electrolyte of the present invention (2).The moisture of electrolyte (2) is 25ppm.
Embodiment 3
The propene carbonate 20 parts of lithium hexafluoro phosphate 14 parts, dehydration, dimethyl carbonate 30 parts, carbonic acid methyl ethyl carbonate 20 parts, gamma-butyrolacton 10 parts, di-oxalate lithium borate 2 parts and vinyl ethylene carbonate 4 parts are dissolved in 25 DEG C of Homogeneous phase mixing, obtains electrolyte of the present invention (3).The moisture of electrolyte (3) is 25ppm.
Embodiment 4
By ethylene carbonate 10 parts, propene carbonate 5 parts, gamma-butyrolacton 20 parts, dimethyl carbonate 10 parts, diethyl carbonate 10 parts, the methyl ethyl carbonate 30 parts, 1 of lithium hexafluoro phosphate 6 parts, two fluorine Lithium bis (oxalate) borate 5 parts, dehydration, 3-propane sultone 1.5 parts and vinylene carbonate 2.5 parts dissolve in 25 DEG C of Homogeneous phase mixing, obtain electrolyte of the present invention (4).The moisture of electrolyte (4) is 40ppm.
Embodiment 5
By lithium hexafluoro phosphate 6 parts, di-oxalate lithium borate 3 parts, propene carbonate 10 parts, gamma-butyrolacton 30 parts, diethyl carbonate 18 parts, methyl ethyl carbonate 30 parts, 1,3-propane sultone 1.5 parts and adiponitrile 1.5 parts dissolve in 25 DEG C of Homogeneous phase mixing, obtain electrolyte of the present invention (5).The moisture of electrolyte (5) is 30ppm.
Embodiment 6
The ethylene carbonate 10 parts of lithium hexafluoro phosphate 6 parts, LiBF4 6 parts, dehydration, 20 parts, ethyl acetate, dimethyl carbonate 20 parts, methyl ethyl carbonate 30 parts, two fluorine Lithium bis (oxalate) borate 1.5 parts, fluorinated ethylene carbonate 4 parts and adiponitrile 2.5 parts are dissolved in 25 DEG C of Homogeneous phase mixing, obtains electrolyte of the present invention (6).The moisture of electrolyte (6) is 23ppm.
Embodiment 7
By ethylene carbonate 20 parts, gamma-butyrolacton 20 parts, dimethyl carbonate 15 parts, the methyl ethyl carbonate 30 parts, 1 of lithium hexafluoro phosphate 4 parts, two fluorine Lithium bis (oxalate) borate 3 parts, two trifluoromethanesulfonimide lithium 3 parts, dehydration, 3-propane sultone 3 parts and fluorinated ethylene carbonate 2 parts dissolve in 25 DEG C of Homogeneous phase mixing, obtain electrolyte of the present invention (7).The moisture of electrolyte (7) is 30ppm.
Embodiment 8
The propene carbonate 20 parts of lithium hexafluoro phosphate 10 parts, two fluorine sulfimide lithium 3 parts, dehydration, triglyme 20 parts, dimethyl carbonate 12 parts, methyl ethyl carbonate 30 parts, vinylene carbonate 2 parts, fluorinated ethylene carbonate 2 parts and isopropyl two oleic acid acyloxy (dioctyl phosphoric acid acyloxy) titanate esters 1 part are dissolved in 25 DEG C of Homogeneous phase mixing, obtains electrolyte of the present invention (8).The moisture of electrolyte (8) is 20ppm.
Embodiment 9
By ethylene carbonate 10 parts, propene carbonate 10 parts, gamma-butyrolacton 20 parts, 20 parts, ethyl acetate, methyl ethyl carbonate 15 parts, the crown ether 10 parts, 1 of di-oxalate lithium borate 6 parts, two fluorine Lithium bis (oxalate) borate 2 parts, two fluorine sulfimide lithium 3 parts, dehydration, 3-propane sultone 2 parts, adiponitrile 1 part and isopropyl two oleic acid acyloxy (dioctyl phosphoric acid acyloxy) titanate esters 1 part are dissolved in 25 DEG C of Homogeneous phase mixing, obtain electrolyte of the present invention (9).The moisture of electrolyte (9) is 35ppm.
Electrolyte of the present invention owing to can form good interfacial film on lithium titanate battery surface, thus ensure that the performance of the circulation of battery, as shown in Figure 1; And the conductivity of electrolyte of the present invention is high thus obtain good high rate performance (as shown in Figure 2) and good cryogenic property (as shown in Figure 3), so the electrolyte described in using can obtain the lithium titanate battery of circulation, multiplying power and high temperature performance excellence.Fig. 1-3 is test datas of its performance (cycle performance, high rate performance and cryogenic property) provided for the electrolyte of embodiment 1.Other embodiment 2-9 have also been obtained result as similar in Fig. 1-3, and because length limit, this specification does not just show one by one.
Electrolyte of the present invention contains main electrolyte lithium salt, assisted electrolysis matter lithium salts, nonaqueous solvents and additive.Electrolyte of the present invention is due to by main electrolyte lithium salt with assisted electrolysis matter lithium salts is composite forms, and the preferred electrolysis additive that can form effective interfacial film at LTO interface, alleviate the flatulence phenomenon of lithium titanate lithium ion battery.
Although content of the present invention has done detailed introduction by above preferred embodiment, will be appreciated that above-mentioned description should not be considered to limitation of the present invention.After those skilled in the art have read foregoing, for multiple amendment of the present invention and substitute will be all apparent.Therefore, protection scope of the present invention should be limited to the appended claims.
Claims (10)
1. for an electrolyte for lithium titanate battery, it is characterized in that, the electrolyte that described lithium titanate lithium ion battery uses comprises main electrolyte lithium salt, assisted electrolysis matter lithium salts, nonaqueous solvents and additive; Wherein, described main electrolyte lithium salt is lithium hexafluoro phosphate, and its concentration is in the electrolytic solution 0.5 ~ 1.5mol/L; Described auxiliary electrolyte lithium salt concentration is in the electrolytic solution 0.005 ~ 0.5mol/L, this auxiliary electrolyte lithium salt select in LiBF4, di-oxalate lithium borate, two fluorine Lithium bis (oxalate) borate, two trifluoromethanesulfonimide lithium, two fluorine sulfimide lithium any one or two or more.
2. the electrolyte of lithium titanate lithium ion battery as claimed in claim 1, is characterized in that, described auxiliary electrolyte lithium salt selects di-oxalate lithium borate or two fluorine Lithium bis (oxalate) borate.
3. the electrolyte of lithium titanate lithium ion battery as claimed in claim 1, it is characterized in that, in described electrolyte, additive proportion is 0% ~ 20% by weight percentage.
4. the electrolyte of lithium titanate lithium ion battery as claimed in claim 3, it is characterized in that, described additive be in vinylene carbonate, vinyl vinylene carbonate, fluorinated ethylene carbonate, sultones class, nitrile, titanate coupling agent any one or two or more.
5. the electrolyte of lithium titanate lithium ion battery as claimed in claim 1, is characterized in that, described nonaqueous solvents be in carboxylate, lactone, carbonic ester, ether solvent any one or two or more.
6. the electrolyte of lithium titanate lithium ion battery as claimed in claim 5, it is characterized in that, in described electrolyte, nonaqueous solvents carboxylate proportion is 0% ~ 80% by weight percentage.
7. the electrolyte of lithium titanate lithium ion battery as claimed in claim 5, it is characterized in that, in described electrolyte, nonaqueous solvents lactone proportion is 0% ~ 50% by weight percentage.
8. the electrolyte of lithium titanate lithium ion battery as claimed in claim 5, it is characterized in that, in described electrolyte, nonaqueous solvents carbonic ester proportion is 0% ~ 50% by weight percentage.
9. the electrolyte of lithium titanate lithium ion battery as claimed in claim 5, it is characterized in that, in described electrolyte, in nonaqueous solvents, ether solvent proportion is 0% ~ 50% by weight percentage.
10. the electrolyte of lithium titanate lithium ion battery as claimed in claim 1, it is characterized in that, the water content in this electrolyte is below 300ppm.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105655633A (en) * | 2016-03-30 | 2016-06-08 | 龙能科技（苏州）有限责任公司 | Lithium ion battery electrolyte suitable for lithium titanate battery |
| CN106159329A (en) * | 2016-08-31 | 2016-11-23 | 东莞市航盛新能源材料有限公司 | A kind of lithium titanate battery electrolyte and lithium titanate battery |
| CN106450463A (en) * | 2016-09-06 | 2017-02-22 | 东莞市航盛新能源材料有限公司 | Lithium titanate battery electrolyte and battery product thereof |
| CN107666011A (en) * | 2016-07-28 | 2018-02-06 | 微宏动力系统（湖州）有限公司 | A kind of nonaqueous electrolytic solution and nonaqueous electrolytic solution secondary battery |
| WO2018232863A1 (en) * | 2017-06-21 | 2018-12-27 | 苏州大学 | Lithium-sulfur battery electrolyte and preparation method therefor |
| CN109119699A (en) * | 2018-08-30 | 2019-01-01 | 成都市银隆新能源产业技术研究有限公司 | Low temperature improved lithium titanate battery and preparation method thereof |
| CN110429334A (en) * | 2019-07-16 | 2019-11-08 | 中国电子新能源（武汉）研究院有限责任公司 | Electrolyte and preparation method thereof and battery |
| CN110556582A (en) * | 2019-09-16 | 2019-12-10 | 营口路航新能源科技有限公司 | Lithium iron phosphate battery, electrolyte and preparation method of lithium iron phosphate battery |
| CN111512489A (en) * | 2017-12-26 | 2020-08-07 | 日本汽车能源株式会社 | Electrolyte for lithium ion secondary battery |
| CN111540951A (en) * | 2020-05-12 | 2020-08-14 | 上海纳米技术及应用国家工程研究中心有限公司 | Lithium ion battery high-voltage electrolyte for lithium titanate negative electrode material |
| CN113921914A (en) * | 2021-09-30 | 2022-01-11 | 宁德新能源科技有限公司 | Electrolyte solution, and electrochemical device and electronic device using same |
| CN117154233A (en) * | 2023-11-01 | 2023-12-01 | 英德市科恒新能源科技有限公司 | Lithium ion battery multiplying power type electrolyte, preparation method and lithium ion battery |
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| CN107666011A (en) * | 2016-07-28 | 2018-02-06 | 微宏动力系统（湖州）有限公司 | A kind of nonaqueous electrolytic solution and nonaqueous electrolytic solution secondary battery |
| CN106159329B (en) * | 2016-08-31 | 2019-07-30 | 湖南航盛新能源材料有限公司 | A kind of lithium titanate battery electrolyte and lithium titanate battery |
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| CN109119699A (en) * | 2018-08-30 | 2019-01-01 | 成都市银隆新能源产业技术研究有限公司 | Low temperature improved lithium titanate battery and preparation method thereof |
| CN110429334A (en) * | 2019-07-16 | 2019-11-08 | 中国电子新能源（武汉）研究院有限责任公司 | Electrolyte and preparation method thereof and battery |
| CN110429334B (en) * | 2019-07-16 | 2021-06-08 | 中国电子新能源（武汉）研究院有限责任公司 | Electrolyte, preparation method thereof and battery |
| CN110556582A (en) * | 2019-09-16 | 2019-12-10 | 营口路航新能源科技有限公司 | Lithium iron phosphate battery, electrolyte and preparation method of lithium iron phosphate battery |
| CN111540951A (en) * | 2020-05-12 | 2020-08-14 | 上海纳米技术及应用国家工程研究中心有限公司 | Lithium ion battery high-voltage electrolyte for lithium titanate negative electrode material |
| CN113921914A (en) * | 2021-09-30 | 2022-01-11 | 宁德新能源科技有限公司 | Electrolyte solution, and electrochemical device and electronic device using same |
| CN117154233A (en) * | 2023-11-01 | 2023-12-01 | 英德市科恒新能源科技有限公司 | Lithium ion battery multiplying power type electrolyte, preparation method and lithium ion battery |
| CN117154233B (en) * | 2023-11-01 | 2024-02-02 | 英德市科恒新能源科技有限公司 | Lithium ion battery multiplying power type electrolyte, preparation method and lithium ion battery |
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