CN103219544A - Low-temperature electrolyte for ternary power lithium ion battery and preparation method - Google Patents
Low-temperature electrolyte for ternary power lithium ion battery and preparation method Download PDFInfo
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Abstract
The invention relates to the technical field of electrolyte for power lithium ion batteries, and in particular relates to low-temperature electrolyte for a ternary power lithium ion battery. The low-temperature electrolyte is characterized by consisting of lithium salt, an organic solvent and an additive, wherein the organic solvent accounts for 85% to 97% in mass percent while the additive accounts for 3% to 15% in mass percent; and the lithium salt is added to ensure that the concentration of the lithium salt of the electrolyte is 0.6 to 1.5 mol/L. The preparation method comprises the following steps of: adding the organic solvent with water content lower than 10ppm into a fluorinated bottle according to a proportion under the protection of dry inert gas for performing molecular sieve dehydration treatment, uniformly stirring the organic solvent until the water content of the organic solvent is 0 to 10ppm, adding the additive and the lithium salt according to set proportions into the uniformly stirred organic solvent, and uniformly stirring the three materials to obtain the required low-temperature electrolyte, wherein the temperature in an operation process is controlled to range from 8 to 12 DEG C. The electrolyte is low in melting point and viscosity and wide in temperature window range, has high electric conductivity at room temperature to -40 DEG C, and can be applied to the use of the ternary power lithium ion battery under a low-temperature condition.
Description
Technical field
The present invention relates to electrokinetic cell electrolyte technical field, specifically disclose a kind of ternary electrokinetic cell with low-temperature electrolyte and preparation method.
Background technology
As everyone knows, lithium ion battery have voltage height, specific energy big, discharge and recharge long, advantage such as discharge performance is stable, safe in utilization, environmentally friendly of life-span, more and more obtain people's extensive use, wherein ternary material lithium battery energy density is higher more than 30% than ferric phosphate lithium cell, and its cryogenic property, consistency etc. are all even better, and great room for promotion will be arranged future.
Along with developing rapidly of lithium ion battery applications, fields such as military and aviation require the low temperature scope of application of lithium ion battery below-40 ℃.Bibliographical information is arranged, and under-40 ℃, discharge capacity of the cell is extremely low even can not put.From the influencing factor of lithium ion battery, very most of relevant with electrolyte.So, can improve the low temperature performance of lithium ion battery by the structure of optimizing electrolyte, as selecting the wide solvent of operating temperature range; Consider mixed solvent system, thereby solve the fail safe and the environmental suitability of electrolyte; Select suitable solute, improve the environmental suitability of battery; Add an amount of additive favourable, improve filming performance, guarantee the interface stability of electrode/electrolyte and then the cryogenic property of raising battery low temperature.
Summary of the invention
The invention provides a kind of ternary lithium ion battery low-temperature electrolyte, its reasonable mixture ratio of components has the good low-temperature discharge performance, has effectively improved the difficult problem that (40 ℃) almost can not discharge under the lithium ion battery low temperature.
The present invention mainly adopts low-melting micromolecule ol ester, efficiently solves the inefficient problem of present lithium ion battery low temperature discharge.
The present invention reaches by following measure:
A kind of ternary power lithium-ion battery low-temperature electrolyte, it is characterized in that forming by lithium salts, organic solvent and additive, wherein the percent by volume of organic solvent and additive is: organic solvent accounts for 85%-97%, additive accounts for 3%-15%, and it is 0.6-1.5mol/L that the addition of lithium salts makes the concentration of electrolyte lithium salts.
Lithium salts of the present invention is taken from one or more in the following electrolyte lithium salt: LiPF
6, LiBF
4, LiBOB, LiDFOB, LiTFSI.
Organic solvent of the present invention is taken from following one or more, ethylene carbonate EC, propene carbonate PC, methyl ethyl carbonate EMC, dimethyl carbonate DMC, diethyl carbonate DEC, gamma-butyrolacton GBL, methyl acetate MA, ethyl acetate EA, methyl formate MF, methyl propionate MP, ethyl propionate EP, methyl butyrate MB, ethyl butyrate EB, n-propyl acetate PA, machine aqueous solvent content is not more than 10ppm.
Additive of the present invention is taken from one or more in the following additive: vinylene carbonate VC, 1,3-N-morpholinopropanesulfonic acid lactone PS, vinylethylene carbonate VEC, fluorinated ethylene carbonate FEC, biphenyl BP, cyclohexyl benzene CHB, ethylene sulfite ES, dimethyl sulfite DMS, sulfurous acid diethyl ester DES, N, N-dimethyl trifluoroacetamide DTA, 2-methyltetrahydrofuran MTHF.
A kind of ternary power lithium-ion battery preparation method of low-temperature electrolyte is characterized in that step is as follows:
The present invention adopts the electrolyte of above-mentioned compound method combination and mixes under the protection of the inert gas of drying; its reasonable mixture ratio; have the good low-temperature discharge performance, effectively improved the inefficient problem of lithium ion battery low temperature discharge, low temperature discharge efficient height.
Description of drawings
Fig. 1 is a low-temperature electrolyte The performance test results table of the present invention.
Fig. 2, Fig. 3 are the discharge curve of embodiment 1 electrolyte battery.
Fig. 4, Fig. 5 are the discharge curve of embodiment 2 electrolyte batteries.
Fig. 6, Fig. 7 are the discharge curve of embodiment 3 electrolyte batteries.
Embodiment
The present invention is further described below in conjunction with embodiment:
A kind of ternary power lithium-ion battery low-temperature electrolyte, it is characterized in that forming by lithium salts, organic solvent and additive, wherein, the concentration of lithium salts in electrolyte is 0.6-1.5mol/L, the percent by volume of organic solvent and additive is in the electrolyte: organic solvent accounts for 85%-97%, additive accounts for 3%-15%, and described lithium salts is taken from one or more in the following electrolyte lithium salt: LiPF
6, LiBF
4LiBOB, LiDFOB, LiTFSI, described machine aqueous solvent content is not more than 10ppm, organic solvent is taken from following one or more, ethylene carbonate EC, propene carbonate PC, methyl ethyl carbonate EMC, dimethyl carbonate DMC, diethyl carbonate DEC, gamma-butyrolacton GBL, methyl acetate MA, ethyl acetate EA, methyl formate MF, methyl propionate MP, ethyl propionate EP, methyl butyrate MB, ethyl butyrate EB, n-propyl acetate PA, described additive is taken from one or more in the following additive: vinylene carbonate VC, 1,3-N-morpholinopropanesulfonic acid lactone PS, vinylethylene carbonate VEC, fluorinated ethylene carbonate FEC, biphenyl BP, cyclohexyl benzene CHB, ethylene sulfite ES, dimethyl sulfite DMS, sulfurous acid diethyl ester DES, N, N-dimethyl trifluoroacetamide DTA, 2-methyltetrahydrofuran MTHF.
A kind of ternary power lithium-ion battery preparation process of low-temperature electrolyte: elder generation is under the protection of the inert gas of drying; organic solvent is carried out molecular sieve dehydration to be handled; make its water content between 0-10ppm; in proportion water content is joined less than the organic solvent of 10ppm and fluoridize in the bottle; the additive and the lithium salts that add preset proportion then in the organic solvent that stirs also expect to stir; obtain needed low-temperature electrolyte, the control temperature is about 8-12 ℃ in the operating process.
Embodiment 1: in being full of the glove box of nitrogen (moisture is lower than 0.9ppm), organic solvent ethylene carbonate EC, dimethyl carbonate DMC, methyl ethyl carbonate EMC and methyl acetate MA after the dehydration are fully mixed, the volume ratio of organic solvent ethylene carbonate EC, dimethyl carbonate DMC, methyl ethyl carbonate EMC, methyl acetate MA is that the 4:9:6:6(water content is less than 10ppm), slowly add LiPF then
6And magnetic agitation is fully dissolved until lithium salts, add vinylene carbonate VC and 1 at last, 3-N-morpholinopropanesulfonic acid lactone PS, continue stirring and mix, shelve 0.5h, promptly obtain embodiment 1 electrolyte of low temp lithium ion battery until all components, the concentration of above-mentioned lithium salts in electrolyte is 1.5 mol/L, and organic solvent accounts for 95%, additive accounts for 5%.
Embodiment 2:
In being full of the glove box of nitrogen (moisture is lower than 0.9ppm), organic solvent ethylene carbonate EC, dimethyl carbonate DMC, methyl ethyl carbonate EMC and methyl acetate MA after the dehydration are fully mixed, the volume ratio of organic solvent ethylene carbonate EC, dimethyl carbonate DMC, methyl ethyl carbonate EMC, methyl acetate MA is that the 4:9:6:8(water content is less than 10ppm), the back slowly adds LiPF
6And fully dissolve until lithium salts with magnetic stirrer, add vinylene carbonate VC and 1 at last, 3-N-morpholinopropanesulfonic acid lactone PS, and continue to stir and to mix until all components, shelve 0.5h, promptly obtain embodiment 2 electrolyte of low temp lithium ion battery, concentration 0.8 mol/L of above-mentioned lithium salts in electrolyte, organic solvent account for 90%, additive accounts for 10%.
Embodiment 3:
In being full of the glove box of nitrogen (moisture is lower than 0.9ppm), organic solvent ethylene carbonate EC, dimethyl carbonate DMC, methyl ethyl carbonate EMC and methyl acetate MA after the dehydration are fully mixed, the volume ratio of organic solvent ethylene carbonate EC, dimethyl carbonate DMC, methyl ethyl carbonate EMC, methyl acetate MA is that the 4:9:6:8(water content is less than 10ppm), slowly add LiPF then
6And magnetic agitation is fully dissolved until lithium salts, add vinylene carbonate VC, 1 at last, 3-N-morpholinopropanesulfonic acid lactone PS and fluorinated ethylene carbonate each a little, continue stirring and mix, shelve 0.5h, promptly obtain embodiment 3 electrolyte of low temp lithium ion battery until all components, the concentration of above-mentioned lithium salts in electrolyte is 0.6 mol/L, and organic solvent accounts for 85%, additive accounts for 15%.
According to the production standard of power lithium-ion battery, the low-temperature electrolyte of preparation is prepared into 95222333 type Soft Roll lithium ion batteries, positive electrode is a ternary material, negative material is a Delanium, through changing into, carry out behind the partial volume cryogenic property test.
Claims (8)
1. ternary power lithium-ion battery low-temperature electrolyte, it is characterized in that forming by lithium salts, organic solvent and additive, wherein the percent by volume of organic solvent and additive is: organic solvent accounts for 85%-97%, additive accounts for 3%-15%, and it is 0.6-1.5mol/L that the addition of lithium salts makes the concentration of electrolyte lithium salts.
2. a kind of ternary power lithium-ion battery low-temperature electrolyte according to claim 1 is characterized in that lithium salts takes from one or more in the following electrolyte lithium salt: LiPF
6, LiBF
4, LiBOB, LiDFOB, LiTFSI.
3. a kind of ternary power lithium-ion battery low-temperature electrolyte according to claim 1 is characterized in that machine aqueous solvent content is not more than 10ppm.
4. a kind of ternary power lithium-ion battery low-temperature electrolyte according to claim 1, it is characterized in that organic solvent takes from following one or more, ethylene carbonate EC, propene carbonate PC, methyl ethyl carbonate EMC, dimethyl carbonate DMC, diethyl carbonate DEC, gamma-butyrolacton GBL, methyl acetate MA, ethyl acetate EA, methyl formate MF, methyl propionate MP, ethyl propionate EP, methyl butyrate MB, ethyl butyrate EB, n-propyl acetate PA.
5. a kind of ternary power lithium-ion battery low-temperature electrolyte according to claim 1, it is characterized in that additive takes from one or more in the following additive: vinylene carbonate VC, 1,3-N-morpholinopropanesulfonic acid lactone PS, vinylethylene carbonate VEC, fluorinated ethylene carbonate FEC, biphenyl BP, cyclohexyl benzene CHB, ethylene sulfite ES, dimethyl sulfite DMS, sulfurous acid diethyl ester DES, N, N-dimethyl trifluoroacetamide DTA, 2-methyltetrahydrofuran MTHF.
6. a ternary power lithium-ion battery is characterized in that step is as follows with low-temperature electrolyte and preparation method:
Step 1, under the protection of the inert gas of drying; organic solvent joined to fluoridize carry out molecular sieve dehydration in the bottle and handle; stir; make its water content between 0-10ppm; step 2, the additive that adds preset proportion in the organic solvent that stirs and lithium salts and material stir; obtain needed low-temperature electrolyte, the control temperature is 8-12 ℃ in the operating process.
7. a kind of ternary power lithium-ion battery according to claim 6 is characterized in that with low-temperature electrolyte and preparation method organic solvent, lithium salts and additive are to mix, and make the lithium ion battery low-temperature electrolyte in fluoridizing container.
8. a kind of ternary power lithium-ion battery according to claim 7 is with low-temperature electrolyte and preparation method, it is characterized in that pro rata organic solvent at first mixes in fluoridizing container, add lithium salts and additive again and mix and make the lithium ion battery low-temperature electrolyte.
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Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103500850A (en) * | 2013-10-23 | 2014-01-08 | 山东大学 | Low-temperature electrolyte of lithium iron phosphate battery |
| CN103779605A (en) * | 2013-12-20 | 2014-05-07 | 宁波维科电池股份有限公司 | Low-temperature lithium iron phosphate ion battery electrolyte and preparation method thereof |
| CN104810554A (en) * | 2014-07-15 | 2015-07-29 | 万向A一二三系统有限公司 | Low temperature electrolyte for lithium-ion power battery and preparation method thereof |
| CN105390748A (en) * | 2015-12-14 | 2016-03-09 | 苏州华一新能源科技有限公司 | Lithium ion battery electrolyte and lithium ion battery |
| CN106099193A (en) * | 2016-07-29 | 2016-11-09 | 华蓥友达精密模具制造有限公司 | A kind of low temperature electrolyte for lithium ion battery |
| CN106531984A (en) * | 2016-09-30 | 2017-03-22 | 罗仕雄 | Low-temperature lithium-ion battery |
| CN107004896A (en) * | 2014-12-19 | 2017-08-01 | Nec 能源元器件株式会社 | Lithium rechargeable battery |
| CN107221707A (en) * | 2017-06-12 | 2017-09-29 | 百川化工(如皋)有限公司 | A kind of ferromanganese lithium low-temperature electrolyte and preparation method thereof |
| CN107681198A (en) * | 2017-08-08 | 2018-02-09 | 广州鹏辉能源科技股份有限公司 | A kind of lithium-ion battery electrolytes and its lithium ion battery |
| CN107689462A (en) * | 2017-07-22 | 2018-02-13 | 深圳卓朗新能源科技有限公司 | A kind of low-temperature electrolyte of ferric phosphate lithium ion battery |
| CN108878980A (en) * | 2018-08-03 | 2018-11-23 | 浙江长兴中俄新能源材料技术研究院有限公司 | Long-life lithium-ion-power cell function type eletrolysis solution and preparation method thereof |
| CN111293359A (en) * | 2018-12-07 | 2020-06-16 | 金华晨阳科技有限公司 | Additive for low-temperature lithium ion battery, electrolyte using additive and lithium ion battery |
| CN111640579A (en) * | 2020-05-26 | 2020-09-08 | 广州金立电子有限公司 | Ultralow temperature electrolyte |
| CN112086685A (en) * | 2020-10-26 | 2020-12-15 | 长兴中俄新能源材料技术研究院 | Three-lithium salt-quaternary solvent system performance complementary type 5V lithium ion battery electrolyte |
| CN112687951A (en) * | 2020-11-24 | 2021-04-20 | 风帆有限责任公司 | Low-temperature-resistant high-voltage type soft package lithium ion battery and preparation method thereof |
| CN113594544A (en) * | 2021-07-02 | 2021-11-02 | 安徽天时新能源科技有限公司 | Electrolyte for low-temperature lithium battery and preparation method thereof |
| CN113594549A (en) * | 2021-08-31 | 2021-11-02 | 迈奇化学股份有限公司 | Low-temperature lithium ion battery electrolyte and preparation method and application thereof |
| CN114824487A (en) * | 2022-04-27 | 2022-07-29 | 上海兰钧新能源科技有限公司 | Electrolyte preparation method, battery manufacturing method, electrolyte and battery |
| CN117613390A (en) * | 2024-01-28 | 2024-02-27 | 烯晶碳能电子科技无锡有限公司 | Preparation method of wide-temperature-range electrolyte of lithium ion battery |
| CN118156587A (en) * | 2024-03-28 | 2024-06-07 | 哈尔滨理工大学 | Preparation method and application of low-temperature electrolyte for lithium metal battery |
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| 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 |
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Cited By (28)
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| CN103500850A (en) * | 2013-10-23 | 2014-01-08 | 山东大学 | Low-temperature electrolyte of lithium iron phosphate battery |
| CN103500850B (en) * | 2013-10-23 | 2016-01-20 | 山东大学 | A kind of low-temperature electrolyte of ferric phosphate lithium cell |
| CN103779605A (en) * | 2013-12-20 | 2014-05-07 | 宁波维科电池股份有限公司 | Low-temperature lithium iron phosphate ion battery electrolyte and preparation method thereof |
| CN104810554A (en) * | 2014-07-15 | 2015-07-29 | 万向A一二三系统有限公司 | Low temperature electrolyte for lithium-ion power battery and preparation method thereof |
| CN107004896B (en) * | 2014-12-19 | 2019-05-14 | Nec 能源元器件株式会社 | Lithium ion secondary battery |
| CN107004896A (en) * | 2014-12-19 | 2017-08-01 | Nec 能源元器件株式会社 | Lithium rechargeable battery |
| CN110048090A (en) * | 2014-12-19 | 2019-07-23 | 远景Aesc能源元器件有限公司 | Lithium ion secondary battery |
| CN105390748A (en) * | 2015-12-14 | 2016-03-09 | 苏州华一新能源科技有限公司 | Lithium ion battery electrolyte and lithium ion battery |
| CN106099193A (en) * | 2016-07-29 | 2016-11-09 | 华蓥友达精密模具制造有限公司 | A kind of low temperature electrolyte for lithium ion battery |
| CN106099193B (en) * | 2016-07-29 | 2019-01-25 | 华蓥友达精密模具制造有限公司 | A kind of low temperature electrolyte for lithium ion battery |
| CN106531984B (en) * | 2016-09-30 | 2019-04-02 | 罗仕雄 | A kind of low-temperature lithium ion battery |
| CN106531984A (en) * | 2016-09-30 | 2017-03-22 | 罗仕雄 | Low-temperature lithium-ion battery |
| CN107221707A (en) * | 2017-06-12 | 2017-09-29 | 百川化工(如皋)有限公司 | A kind of ferromanganese lithium low-temperature electrolyte and preparation method thereof |
| CN107689462A (en) * | 2017-07-22 | 2018-02-13 | 深圳卓朗新能源科技有限公司 | A kind of low-temperature electrolyte of ferric phosphate lithium ion battery |
| CN107681198A (en) * | 2017-08-08 | 2018-02-09 | 广州鹏辉能源科技股份有限公司 | A kind of lithium-ion battery electrolytes and its lithium ion battery |
| CN108878980A (en) * | 2018-08-03 | 2018-11-23 | 浙江长兴中俄新能源材料技术研究院有限公司 | Long-life lithium-ion-power cell function type eletrolysis solution and preparation method thereof |
| CN111293359A (en) * | 2018-12-07 | 2020-06-16 | 金华晨阳科技有限公司 | Additive for low-temperature lithium ion battery, electrolyte using additive and lithium ion battery |
| CN111640579A (en) * | 2020-05-26 | 2020-09-08 | 广州金立电子有限公司 | Ultralow temperature electrolyte |
| CN112086685B (en) * | 2020-10-26 | 2024-03-08 | 长兴中俄新能源材料技术研究院 | Trilithium salt-quaternary solvent system performance complementary type 5V lithium ion battery electrolyte |
| CN112086685A (en) * | 2020-10-26 | 2020-12-15 | 长兴中俄新能源材料技术研究院 | Three-lithium salt-quaternary solvent system performance complementary type 5V lithium ion battery electrolyte |
| CN112687951A (en) * | 2020-11-24 | 2021-04-20 | 风帆有限责任公司 | Low-temperature-resistant high-voltage type soft package lithium ion battery and preparation method thereof |
| CN113594544A (en) * | 2021-07-02 | 2021-11-02 | 安徽天时新能源科技有限公司 | Electrolyte for low-temperature lithium battery and preparation method thereof |
| CN113594544B (en) * | 2021-07-02 | 2024-04-12 | 重庆毅达智能装备有限公司 | Electrolyte for low-temperature lithium battery and preparation method thereof |
| CN113594549B (en) * | 2021-08-31 | 2023-02-28 | 迈奇化学股份有限公司 | Low-temperature lithium ion battery electrolyte and preparation method and application thereof |
| CN113594549A (en) * | 2021-08-31 | 2021-11-02 | 迈奇化学股份有限公司 | Low-temperature lithium ion battery electrolyte and preparation method and application thereof |
| CN114824487A (en) * | 2022-04-27 | 2022-07-29 | 上海兰钧新能源科技有限公司 | Electrolyte preparation method, battery manufacturing method, electrolyte and battery |
| CN117613390A (en) * | 2024-01-28 | 2024-02-27 | 烯晶碳能电子科技无锡有限公司 | Preparation method of wide-temperature-range electrolyte of lithium ion battery |
| CN118156587A (en) * | 2024-03-28 | 2024-06-07 | 哈尔滨理工大学 | Preparation method and application of low-temperature electrolyte for lithium metal battery |
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