CN103219544B - A kind of low-temperature electrolyte for ternary power lithium ion battery and preparation method - Google Patents
A kind of low-temperature electrolyte for ternary power lithium ion battery and preparation method Download PDFInfo
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- CN103219544B CN103219544B CN201310123054.2A CN201310123054A CN103219544B CN 103219544 B CN103219544 B CN 103219544B CN 201310123054 A CN201310123054 A CN 201310123054A CN 103219544 B CN103219544 B CN 103219544B
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Abstract
nullThe present invention relates to lithium ion power battery electrolyte technical field，It is specifically related to a kind of low-temperature electrolyte for ternary power lithium ion battery，By lithium salts、Organic solvent and additive composition，Wherein the percent by volume of organic solvent and additive is: organic solvent accounts for 85%、Additive accounts for 15%，The addition of lithium salts makes the concentration of electrolyte lithium salts be 0.6mol/L，Preparation method is: first under the protection of dry noble gas，It is proportionally added into water content to join in fluorination bottle less than the organic solvent of 10ppm and carry out molecular sieve dehydration process，Stir，Make its water content between 0 10ppm，In the organic solvent stirred, add the additive of setting ratio and lithium salts again and material stirs，Obtain required low-temperature electrolyte，Controlling temperature in operating process is 8 12 DEG C，Electrolyte of the present invention has relatively low fusing point and viscosity，Temperature window wide ranges，Higher electrical conductivity is had in the range of room temperature to 40 DEG C，Present invention can apply to the use of ternary power lithium ion battery under cryogenic conditions.
Description
Technical field
The present invention relates to electrokinetic cell technical field of electrolyte, specifically disclose a kind of ternary electrokinetic cell low-temperature electrolyte and preparation method.
Background technology
It is known that, lithium ion battery has the advantages such as voltage is high, specific energy is big, discharge and recharge life-span length, discharge performance are stable, use is safe, environmentally friendly, increasingly obtain the extensive application of people, wherein ternary material lithium battery energy density is higher by more than 30% than ferric phosphate lithium cell, and its cryogenic property, concordance etc. are the most even better, there is great room for promotion future.
Along with developing rapidly of lithium ion battery applications, the field such as military and aviation requires that the low temperature range of lithium ion battery is below-40 DEG C.Having document to report, at-40 DEG C, discharge capacity of the cell is extremely low even can not be put.In terms of the influence factor of lithium ion battery, significant portion is relevant with electrolyte.So, the low temperature performance of lithium ion battery, solvent as wide in selection operating temperature range can be improved by the structure optimizing electrolyte；Consider mixed solvent system, thus solve safety and the environmental suitability of electrolyte；Select suitable solute, improve the environmental suitability of battery；Add the appropriate additive to favors low temperature, improve filming performance, it is ensured that the interface stability of electrode/electrolyte and then the cryogenic property of raising battery.
Summary of the invention
The invention provides a kind of ternary low temperature electrolytes for Li-ion batteries, its reasonable mixture ratio of components, there is preferable low temperature performance, be effectively increased (-40 DEG C) under lithium ion battery low temperature and be little to a difficult problem for electric discharge.
The present invention mainly uses the little molecule ol ester of low melting point, efficiently solves the problem that current lithium ion battery low temperature discharging efficiency is low.
The present invention is reached by following measure:
A kind of low-temperature electrolyte for ternary power lithium ion battery, it is characterized in that being made up of 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 the addition of lithium salts makes the concentration of electrolyte lithium salts be 0.6-1.5mol/L.
One or more in following electrolyte lithium salt: LiPF taken from by lithium salts of the present invention6、LiBF4、LiBOB、LiDFOB、LiTFSI。
Organic solvent of the present invention takes from following one or more, ethylene carbonate EC, Allyl carbonate PC, Ethyl methyl 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 n-butyrate. EB, n-propyl acetate PA, machine aqueous solvent content is not more than 10ppm.
Additive of the present invention takes from one or more in 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.
The preparation method of a kind of low-temperature electrolyte for ternary power lithium ion battery, it is characterised in that step is as follows:
Step one, under the protection of dry noble gas, add organic solvents into fluorination bottle in carry out molecular sieve dehydration process so that it is water content is between 0-10ppm.
Step 2, the additive adding setting ratio in the organic solvent stirred and lithium salts material stir, and obtain required low-temperature electrolyte, control temperature and be 8-12 DEG C in operating process.
The present invention uses electrolyte that above-mentioned compound method combines and mixes under the protection of dry noble gas, its reasonable mixture ratio, has preferable low temperature performance, is effectively increased the problem that lithium ion battery low temperature discharging efficiency is low, and low temperature discharging efficiency is high.
Accompanying drawing explanation
Fig. 1 is the 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 battery.
Fig. 6, Fig. 7 are the discharge curve of embodiment 3 electrolyte battery.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further described:
A kind of low-temperature electrolyte for ternary power lithium ion battery, it is characterized in that being made up of lithium salts, organic solvent and additive, wherein, lithium salts concentration in the electrolytic solution is 0.6-1.5mol/L, in electrolyte, the percent by volume of organic solvent and additive is: organic solvent accounts for 85%-97%, additive accounts for 3%-15%, and one or more in following electrolyte lithium salt: LiPF taken from by described lithium salts6、LiBF4null、LiBOB、LiDFOB、LiTFSI，Described machine aqueous solvent content is not more than 10ppm，Organic solvent takes from following one or more，Ethylene carbonate EC、Allyl carbonate PC、Ethyl methyl 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 n-butyrate. EB、N-propyl acetate PA，Described additive takes from one or more in 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.
The preparation process of a kind of low-temperature electrolyte for ternary power lithium ion battery: first under the protection of dry noble gas; organic solvent is carried out molecular sieve dehydration process; make its water content between 0-10ppm; the organic solvent that water content is less than 10ppm in proportion joins in fluorination bottle; then in the organic solvent stirred, add the additive of setting ratio and lithium salts and material stirs; obtain required low-temperature electrolyte, operating process controls temperature and is about 8-12 DEG C.
Embodiment 1:
In the glove box of full nitrogen (moisture is less than 0.9ppm), organic solvent ethylene carbonate EC, dimethyl carbonate DMC, Ethyl methyl carbonate EMC and methyl acetate MA after dehydration is sufficiently mixed uniformly, organic solvent ethylene carbonate EC, dimethyl carbonate DMC, Ethyl methyl carbonate EMC, the volume ratio of methyl acetate MA are that 4:9:6:6(water content is less than 10ppm), it is then slowly added into LiPF6And magnetic agitation is until lithium salts fully dissolves, it is eventually adding vinylene carbonate VC and 1,3-N-morpholinopropanesulfonic acid lactone PS, continue to stir until all components mix homogeneously, shelve 0.5h, i.e. obtain embodiment 1 electrolyte of low temp lithium ion battery, above-mentioned lithium salts concentration in the electrolytic solution is 1.5 mol/L, and organic solvent accounts for 95%, additive accounts for 5%.
Embodiment 2:
In the glove box of full nitrogen (moisture is less than 0.9ppm), organic solvent ethylene carbonate EC, dimethyl carbonate DMC, Ethyl methyl carbonate EMC and methyl acetate MA after dehydration is sufficiently mixed uniformly, organic solvent ethylene carbonate EC, dimethyl carbonate DMC, Ethyl methyl carbonate EMC, the volume ratio of methyl acetate MA are 4:9:6:8(water content less than 10ppm), after be slowly added to LiPF6And by magnetic stirrer until lithium salts fully dissolves, it is eventually adding vinylene carbonate VC and 1,3-N-morpholinopropanesulfonic acid lactone PS, and continue to stir until all components mix homogeneously, shelve 0.5h, i.e. obtain embodiment 2 electrolyte of low temp lithium ion battery, above-mentioned lithium salts concentration 0.8 mol/L in the electrolytic solution, organic solvent accounts for 90%, additive accounts for 10%.
Embodiment 3:
In the glove box of full nitrogen (moisture is less than 0.9ppm), organic solvent ethylene carbonate EC, dimethyl carbonate DMC, Ethyl methyl carbonate EMC and methyl acetate MA after dehydration is sufficiently mixed uniformly, organic solvent ethylene carbonate EC, dimethyl carbonate DMC, Ethyl methyl carbonate EMC, the volume ratio of methyl acetate MA are that 4:9:6:8(water content is less than 10ppm), it is then slowly added into LiPF6And magnetic agitation is until lithium salts fully dissolves, be eventually adding vinylene carbonate VC, 1,3-N-morpholinopropanesulfonic acid lactone PS and fluorinated ethylene carbonate are each a little, continue to stir until all components mix homogeneously, shelve 0.5h, i.e. obtain embodiment 3 electrolyte of low temp lithium ion battery, above-mentioned lithium salts concentration in the electrolytic solution is 0.6 mol/L, and organic solvent accounts for 85%, additive accounts for 15%.
According to the making standard of power lithium-ion battery, the low-temperature electrolyte of preparation being prepared as 95222333 type soft bag lithium ionic cells, positive electrode is ternary material, and negative material is Delanium, carries out cryogenic property test after chemical conversion, partial volume.
Claims (3)
1. a low-temperature electrolyte for ternary power lithium ion battery, it is characterised in that: by lithium salts, organic solvent and
Additive forms, and described organic solvent is by ethylene carbonate EC, dimethyl carbonate DMC, Ethyl methyl carbonate
EMC and methyl acetate MA is sufficiently mixed and uniformly forms, organic solvent ethylene carbonate EC, dimethyl carbonate
DMC, Ethyl methyl carbonate EMC, the volume ratio of methyl acetate MA are 4:9:6:8, and wherein water-organic solvent contains
Amount is not more than 10ppm；Described additive is by vinylene carbonate VC, 1,3-propane sultone PS and fluoro
Ethylene carbonate forms, and described lithium salts is LiPF6, and lithium salts concentration in the electrolytic solution is 0.6mol/L, has
The percent by volume of machine solvent and additive is: organic solvent accounts for 85%, additive accounts for 15%.
A kind of low-temperature electrolyte for ternary power lithium ion battery the most according to claim 1, it is characterised in that:
Preparation method step is as follows: step one, under the protection of dry noble gas, adds organic solvents into fluorine
Change in bottle and carry out molecular sieve dehydration process, stir so that it is water content between 0-10ppm, step 2,
In the organic solvent stirred, add the additive of setting ratio and lithium salts and material stirs, obtain required
The low-temperature electrolyte wanted, controls temperature and is 8-12 DEG C in operating process, wherein said organic solvent, lithium salts and add
Adding agent is to be uniformly mixed in fluorination container, prepares low temperature electrolytes for Li-ion batteries.
A kind of low-temperature electrolyte for ternary power lithium ion battery the most according to claim 2, it is characterised in that:
First pro rata organic solvent is uniformly mixed in fluorination container, adds lithium salts and additive mixing is equal
Even prepared low temperature electrolytes for Li-ion batteries.
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| 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 |
| US20170338515A1 (en) * | 2014-12-19 | 2017-11-23 | Nec Energy Devices, Ltd. | 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 |
| 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 |
| 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 |
| CN111640579B (en) * | 2020-05-26 | 2022-01-11 | 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 |
| CN112687951B (en) * | 2020-11-24 | 2022-06-21 | 风帆有限责任公司 | Low-temperature-resistant high-voltage type soft package lithium ion 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 |
| 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 |
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| CN101645521A (en) * | 2009-01-20 | 2010-02-10 | 万向电动汽车有限公司 | Low temperature functional electrolyte of lithium-ion secondary battery and preparation method 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 |
| CN102702243B (en) * | 2012-06-12 | 2014-08-27 | 中南大学 | Method for preparation and purifying lithium difluoroborate |
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