CN111293357A - Non-aqueous electrolyte and application thereof - Google Patents

Non-aqueous electrolyte and application thereof Download PDF

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Publication number
CN111293357A
CN111293357A CN201811500992.9A CN201811500992A CN111293357A CN 111293357 A CN111293357 A CN 111293357A CN 201811500992 A CN201811500992 A CN 201811500992A CN 111293357 A CN111293357 A CN 111293357A
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Prior art keywords
additive
lithium
electrolytic solution
nonaqueous electrolytic
carbonate
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陈晓琴
甘朝伦
张力
顾名遥
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Zhangjiagang Guotai Huarong New Chemical Materials Co Ltd
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Zhangjiagang Guotai Huarong New Chemical Materials Co Ltd
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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
    • 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
    • H01M10/0568—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
    • H01M10/056—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
    • 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
    • H01M2300/004—Three 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 relates to a nonaqueous electrolyte, which comprises lithium salt, an organic solvent and an additive, wherein the additive comprises an additive A and/or an additive B, and the structural general formula of the additive A is as follows:
Figure DDA0001898136590000011
the structural general formula of the additive B is as follows:
Figure DDA0001898136590000012
wherein R is1To R8Independently one or more of alkyl, alkoxy, alkenyl, keto, fluoroalkyl, fluoroalkoxy, fluoroalkenyl and fluoroketo. The invention passes throughThe improvement of the non-aqueous electrolyte improves the normal-temperature and high-temperature cycle performance of the battery while basically maintaining the first discharge efficiency and the capacity retention rate.

Description

Non-aqueous electrolyte and application thereof
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a non-aqueous electrolyte and application thereof.
Background
Lithium ion batteries are more and more widely inserted into the production and life of people, among all environmental factors, the temperature has the greatest influence on the charge and discharge performance of the batteries, the electrochemical reaction at the electrode/electrolyte interface is related to the environmental temperature, and the electrode/electrolyte interface is regarded as the heart of the batteries. If the temperature decreases, the reaction rate of the electrode also decreases. Assuming that the battery voltage remains constant, the discharge current decreases and the power output of the battery also decreases. If the temperature rises, the reverse is true, i.e., the output of the lithium polymer battery rises. The temperature also affects the transfer speed of the electrolyte, the temperature rise is accelerated, the transfer temperature is reduced, the transfer is slowed down, and the battery charge and discharge performance is also affected. However, the temperature is too high, exceeding 45 ℃, which may break the chemical equilibrium in the battery, resulting in side reactions. This makes its temperature environment a concern, and lithium batteries are relatively more likely to cause problems in high temperature environments.
Disclosure of Invention
The invention aims to solve the technical problem of providing a non-aqueous electrolyte capable of improving the high-temperature and normal-temperature cycle performance of a lithium ion battery and application thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention aims to provide a nonaqueous electrolyte which comprises a lithium salt, an organic solvent and an additive, wherein the additive comprises an additive A and/or an additive B, and the additive A has a structural general formula as follows:
Figure RE-GDA0001935724110000011
the structural general formula of the additive B is as follows:
Figure RE-GDA0001935724110000012
wherein R is1To R8Independently an alkyl, alkoxy, alkenyl, keto, fluoroalkyl, fluoroalkoxy,One or more of fluoro-alkenyl and fluoro-ketone.
Preferably, the additive A is
Figure RE-GDA0001935724110000013
(pentaerythritol sulfate); the additive B is
Figure RE-GDA0001935724110000021
(pentaerythritol sulfite).
Preferably, the feeding mass of the additive A and/or the additive B is 0.05-5% of the total mass of the nonaqueous electrolyte.
Preferably, the organic solvent is a mixture of cyclic ester and chain ester.
Further preferably, the cyclic ester is one or more selected from gamma-butyrolactone (GBL), Ethylene Carbonate (EC), Propylene Carbonate (PC) and fluoroethylene carbonate (FEC); the chain ester is one or more selected from dimethyl carbonate (DMC), Ethyl Methyl Carbonate (EMC), diethyl carbonate (DEC), Methyl Propyl Carbonate (MPC), Methyl Propionate (MP), Ethyl Propionate (EP), Propyl Propionate (PP), Methyl Acetate (MA), Ethyl Acetate (EA), Propyl Acetate (PA), Methyl Butyrate (MB), Ethyl Butyrate (EB), Propyl Butyrate (PB), methyl Fluoropropionate (FMP), propyl fluoropropionate and ethyl fluoropropionate.
More preferably, the organic solvent is a mixture of Propylene Carbonate (PC), Ethyl Methyl Carbonate (EMC) and dimethyl carbonate (DMC) in a volume ratio of 1: 0.8-1.2.
Preferably, the lithium salt is lithium hexafluorophosphate (LiPF)6) Lithium tetrafluoroborate (LiBF)4) Lithium hexafluoroarsenate (LiAsF)6) Anhydrous lithium perchlorate (LiClO)4) Lithium bis (trifluoromethanesulfonate imide) (LiN (SO)2CF3)2) Lithium difluorooxalate phosphate (LiPF)2(C2O4)2) Lithium difluorophosphate (LiPO)2F2) Lithium trifluoromethanesulfonate (LiSO)3CF3) Lithium bis (oxalato) borate (LiC)2O4BC2O4) Lithium monooxalyldifluoroborate (LiF)2BC2O4) Lithium bis (fluorosulfonylimide) (LiN (SO)2F)2) One or more of them.
Further preferably, the lithium salt is lithium hexafluorophosphate (LiPF)6)。
Preferably, the concentration of the lithium salt is 0.7-2 mol/L.
Preferably, the additive also comprises other additives, and the feeding mass of the other additives is 0.1-15% of the total mass of the nonaqueous electrolyte.
Further preferably, the other additive is one or more of 1, 3-Propane Sultone (PS), ethylene carbonate (VEC), Biphenyl (BP), Cyclohexylbenzene (CHB), propylene sulfate (TSA), trioctyl phosphate (TOP), vinyl sulfate, 4-methyl vinyl sulfate, vinyl sulfite and lithium difluorophosphate.
The invention also aims to provide a lithium ion battery, and the lithium ion battery adopts the nonaqueous electrolyte.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
the invention improves the non-aqueous electrolyte, basically maintains the first discharge efficiency and the capacity retention rate, and improves the normal temperature and high temperature cycle performance of the battery.
Drawings
FIG. 1 is a graph of the cycle performance at 25 ℃ for example 1, example 2 and comparative example 1;
FIG. 2 is a graph of the cycle performance at 45 ℃ for example 1, example 2 and comparative example 1;
FIG. 3 is a graph of the cycle performance at 25 ℃ for example 3, example 4 and comparative example 2;
FIG. 4 is a graph of the cycle performance at 45 ℃ for example 3, example 4 and comparative example 2.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples. In this specification, "%" represents mass% unless otherwise specified.
Example 1:
in an argon-filled glove box (H)2O<10ppm), as PC: EMC DMC 1: 1: 1, and then 1.0mol/L of lithium hexafluorophosphate (LiPF) was dissolved6) Wherein, 0.5 percent of pentaerythritol sulfate by mass is added into the electrolyte.
The electrolyte is injected into an LCO soft package battery, the battery is formed by charging and discharging at 0.1C, the first charging and discharging efficiency is measured, the result is shown in table 1, the circulation at normal temperature of 25 ℃ and high temperature of 45 ℃ is carried out, the test result is shown in figures 1 and 2, the experiment is carried out after the battery is placed at 85 ℃ for 4 hours, and the test result is shown in table 2.
Example 2:
in an argon-filled glove box (H)2O<10ppm), as PC: EMC DMC 1: 1: 1, and then 1.0mol/L of lithium hexafluorophosphate (LiPF) was dissolved6) Wherein, 1 percent by mass of pentaerythritol sulfate is added into the electrolyte.
The electrolyte was chemically converted under the same conditions as in example 1, and then the cycle performance at 25 ℃ and 45 ℃ at normal temperature was measured under the same conditions as in example 1, and the results are shown in table 1, fig. 1, and fig. 2. The test was carried out at 85 ℃ for 4 hours with the test results shown in Table 2.
Comparative example 1:
in an argon-filled glove box (H)2O<10ppm), as PC: EMC DMC 1: 1: 1, and then 1.0mol/L of lithium hexafluorophosphate (LiPF) was dissolved6) Wherein the process is carried out.
The electrolyte solution was chemically converted under the same conditions as in example 1, and then cycle performance tests at normal temperature of 25 ℃ and at high temperature of 45 ℃ were performed under the same conditions as in example 1, and the results are shown in table 1, fig. 1, and fig. 2. The test was carried out at 85 ℃ for 4 hours with the test results shown in Table 2.
TABLE 1
Formation charge/mAh 0.1C discharge/mAh First discharge efficiency (%)
Example 1 2190.4 1926.5 87.95
Example 2 2192.9 1936.8 88.32
Comparative example 1 2195.1 1952.5 88.95
TABLE 2
Electrolyte numbering Charging capacity (mAh) Discharge capacity (mAh) Capacity retention (%)
Example 1 1948.6 1724.4 88.494
Example 2 1965.8 1794.4 91.281
Comparative example 1 1952 1827.6 93.627
Example 3:
in an argon-filled glove box (H)2O<10ppm), as PC: EMC DMC 1: 1: 1, and then 1.0mol/L of lithium hexafluorophosphate (LiPF) was dissolved6) Wherein the process is carried out. 1, 3-propane sultone with the mass percent of 1.5 percent and pentaerythritol sulfite with the mass percent of 1.5 percent are added into the electrolyte.
The electrolyte was chemically converted under the same conditions as in example 1, and then cycle performance tests at normal temperature of 25 ℃ and at high temperature of 45 ℃ were performed under the same conditions as in example 1, and the results are shown in table 3, fig. 3, and fig. 4. The test was carried out at 85 ℃ for 4 hours with the test results shown in Table 4.
Example 4:
in an argon-filled glove box (H)2O<10ppm), as PC: EMC DMC 1: 1: 1, and then 1.0mol/L of lithium hexafluorophosphate (LiPF) was dissolved6) Wherein the process is carried out. 1, 3-propane sultone with the mass percent of 1.5 percent and 1.5 percent of the electrolyte are addedPentaerythritol sulfate ester.
The electrolyte was chemically converted under the same conditions as in example 1, and then cycle performance tests at normal temperature of 25 ℃ and at high temperature of 45 ℃ were performed under the same conditions as in example 1, and the results are shown in table 3, fig. 3, and fig. 4. The test was carried out at 85 ℃ for 4 hours with the test results shown in Table 4.
Comparative example 2:
in an argon-filled glove box (H)2O<10ppm), as PC: EMC DMC 1: 1: 1, and then 1.0mol/L of lithium hexafluorophosphate (LiPF) was dissolved6) Wherein the process is carried out. 1, 3-propane sultone with the mass percent of 1.5 percent is added into the electrolyte.
The electrolyte was chemically converted under the same conditions as in example 1, and then cycle performance tests at normal temperature of 25 ℃ and at high temperature of 45 ℃ were performed under the same conditions as in example 1, and the results are shown in table 3, fig. 3, and fig. 4. The test was carried out at 85 ℃ for 4 hours with the test results shown in Table 4.
TABLE 3
Formation charge/mAh 0.1C discharge/mAh First discharge efficiency (%)
Example 3 2105.9 1813.6 86.12
Example 4 2108.2 1832.7 86.93
Comparative example 2 2101.5 1847.6 87.92
TABLE 4
Electrolyte numbering Charging capacity (mAh) Discharge capacity (mAh) Capacity retention (%)
Example 3 1842.8 1663.7 90.279
Example 4 1856.2 1694.4 91.281
Comparative example 2 1852.7 1740.3 93.935
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.

Claims (10)

1. A nonaqueous electrolytic solution comprising a lithium salt, an organic solvent and an additive, characterized in that: the additive comprises an additive A and/or an additive B, and the structural general formula of the additive A is as follows:
Figure FDA0001898136560000011
the structural general formula of the additive B is as follows:
Figure FDA0001898136560000012
wherein R is1To R8Independently one or more of alkyl, alkoxy, alkenyl, keto, fluoroalkyl, fluoroalkoxy, fluoroalkenyl and fluoroketo.
2. The nonaqueous electrolytic solution of claim 1, wherein: the additive A is
Figure FDA0001898136560000013
The additive B is
Figure FDA0001898136560000014
3. The nonaqueous electrolytic solution of claim 1 or 2, wherein: the feeding mass of the additive A and/or the additive B is 0.05-5% of the total mass of the nonaqueous electrolyte.
4. The nonaqueous electrolytic solution of claim 1, wherein: the organic solvent is a mixture of cyclic ester and chain ester.
5. The nonaqueous electrolytic solution of claim 4, wherein: the cyclic ester is one or more of gamma-butyrolactone, ethylene carbonate, propylene carbonate and fluoroethylene carbonate; the chain ester is one or more selected from dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl propyl carbonate, methyl propionate, ethyl propionate, propyl propionate, methyl acetate, ethyl acetate, propyl acetate, methyl butyrate, ethyl butyrate, propyl butyrate, methyl fluoropropionate, propyl fluoropropionate and ethyl fluoropropionate.
6. The nonaqueous electrolytic solution of claim 5, wherein: the organic solvent is a mixture of propylene carbonate, ethyl methyl carbonate and dimethyl carbonate in a volume ratio of 1: 0.8-1.2.
7. The nonaqueous electrolytic solution of claim 1, wherein: the lithium salt is one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium hexafluoroarsenate, anhydrous lithium perchlorate, lithium bis (trifluoromethylsulfonyl) imide, lithium difluorobis (oxalato) phosphate, lithium difluorophosphate, lithium trifluoromethylsulfonate, lithium dioxalate borate, lithium monooxalato bis (fluoroborate) and lithium bis (fluorosulfonyl) imide.
8. The nonaqueous electrolytic solution of claim 1 or 7, wherein: the concentration of the lithium salt is 0.7-2 mol/L.
9. The nonaqueous electrolytic solution of claim 1, wherein: the additive also comprises other additives, and the feeding mass of the other additives is 0.1-15% of the total mass of the nonaqueous electrolyte.
10. A lithium ion battery, characterized by: the lithium ion battery uses the nonaqueous electrolytic solution of any one of claims 1 to 9.
CN201811500992.9A 2018-12-10 2018-12-10 Non-aqueous electrolyte and application thereof Pending CN111293357A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023004821A1 (en) * 2021-07-30 2023-02-02 宁德时代新能源科技股份有限公司 Electrolyte, secondary battery, battery module, battery pack, and electric device
CN115911544A (en) * 2021-08-16 2023-04-04 张家港市国泰华荣化工新材料有限公司 Non-aqueous electrolyte and lithium battery
EP4187669A4 (en) * 2021-09-27 2023-09-20 Contemporary Amperex Technology Co., Limited Secondary battery, battery module, battery pack, and power-consuming apparatus

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CN1819324A (en) * 2006-03-03 2006-08-16 浙江阻燃锂电材料有限公司 Cell liquor and lithium ion battery therefor
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Publication number Priority date Publication date Assignee Title
WO2023004821A1 (en) * 2021-07-30 2023-02-02 宁德时代新能源科技股份有限公司 Electrolyte, secondary battery, battery module, battery pack, and electric device
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EP4187669A4 (en) * 2021-09-27 2023-09-20 Contemporary Amperex Technology Co., Limited Secondary battery, battery module, battery pack, and power-consuming apparatus

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