CN111640989A - Electrolyte for reducing gas generation of lithium titanate battery cell - Google Patents
Electrolyte for reducing gas generation of lithium titanate battery cell Download PDFInfo
- Publication number
- CN111640989A CN111640989A CN202010725769.5A CN202010725769A CN111640989A CN 111640989 A CN111640989 A CN 111640989A CN 202010725769 A CN202010725769 A CN 202010725769A CN 111640989 A CN111640989 A CN 111640989A
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- Prior art keywords
- lithium
- carbonate
- electrolyte
- lithium titanate
- reducing gas
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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
-
- 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
- H01M2300/0025—Organic electrolyte
-
- 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 provides an electrolyte for reducing gas generation of a lithium titanate battery cell, which comprises a lithium salt, an organic solvent and an additive, wherein the organic solvent is a carbonate substance, and the volume of the additive is 1.0-10% of the sum of the volumes of the lithium salt and the organic solvent. The electrolyte for reducing the gas generation of the lithium titanate battery cell can form a protective film on the surface of a negative electrode, effectively inhibits the decomposition of the electrolyte in the later cycle and use processes of the battery cell, and can well prevent the direct contact between a lithium ion battery electrode and an electrolyte solvent in the pre-charging process, thereby inhibiting the gas generation of the lithium titanate battery cell, solving the problems of battery bulging and influence on appearance and use caused by the gas generation of the lithium titanate battery cell, further improving the industrial productivity, increasing the safety in the production process of the lithium ion battery, and improving the cycle performance of the lithium ion battery.
Description
Technical Field
The invention belongs to the field of lithium ion batteries, and particularly relates to an electrolyte for reducing gas generation of a lithium titanate battery cell.
Background
Along with the shortage of non-renewable energy and the control of the whole society on environmental pollution, governments of various countries actively encourage the development of new energy, and the development and application of lithium ion batteries become a bright point of the new energy industry. More and more large-capacity lithium ion batteries are applied to the fields of electric automobiles and energy storage. In order to meet various requirements of electric automobiles and energy storage, higher and higher requirements are put forward on the performance and the appearance size of the lithium ion battery, and particularly, along with the increase of the large capacity of the battery, the appearance size of the battery is also increased correspondingly. At present, due to the advantages of the soft package lithium ion battery in size design and manufacture, the types of the large-capacity soft package lithium ion batteries are more and more.
Lithium titanate (Li)4Ti5O12) The spinel-type lithium-ion battery electrode material has a spinel structure, is a zero-strain electrode material, has stable discharge voltage, high lithium-embedding potential, is not easy to cause the precipitation of metal lithium, has wide material source, and is clean and environment-friendly. The battery using lithium titanate as the cathode has excellent cycle performance and is expected to be applied to electric vehicles and energy storage batteries. However, during the cycle, especially at high temperature, the battery may generate gas to some extent, causing the battery to swell, affecting the appearance and use.
In the prior art, the electrolyte is prepared by mixing lithium salt with proper concentration in an organic solvent, and the gas production of the battery cell cannot be reduced fundamentally. The lithium ion battery produces more gas in the pre-charging process, thereby seriously affecting the fluency of the industrial production of the lithium ion battery and greatly reducing the industrial productivity; the problem of more gas production in the pre-charging process of the lithium ion battery also influences the cycle performance and other performances of the battery.
Disclosure of Invention
In view of the above, the invention provides an electrolyte for reducing gas generation of a lithium titanate battery cell, which can form a protective film on the surface of a negative electrode, effectively inhibit the decomposition of the electrolyte in the later cycle and use processes of the battery cell, and well prevent the direct contact between the lithium ion battery electrode and the electrolyte solvent in the pre-charging process, thereby inhibiting the gas generation of the lithium titanate battery cell, solving the problems of battery swelling and influence on appearance and use caused by the gas generation of the lithium titanate battery cell, thereby improving the industrial capacity, increasing the safety in the production process of the lithium ion battery, and improving the cycle performance of the lithium ion battery.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
the electrolyte for reducing the gas generation of the lithium titanate battery cell comprises a lithium salt, an organic solvent and an additive, wherein the organic solvent is a carbonate substance, and the volume of the additive is 1.0-10% of the sum of the volumes of the lithium salt and the organic solvent.
Further, the lithium salt is one or a mixture of more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium carbonate and lithium perchlorate.
Further, the mass concentration of the lithium salt is 0.5-2.0 mol/L.
Further, the amount concentration of the substance of the lithium salt is preferably 1.0 to 1.5 mol/L.
Further, the organic solvent is one or a mixture of ethylene carbonate, ethyl methyl carbonate, dimethyl carbonate and diethyl carbonate.
Further, the organic solvent is preferably a mixture of ethylene carbonate, propylene carbonate, ethyl methyl carbonate and diethyl carbonate, wherein the volume ratio of the ethylene carbonate to the propylene carbonate to the ethyl methyl carbonate to the diethyl carbonate is 10:10:60: 20.
Further, the additive is one or a mixture of more of lithium difluoro oxalate borate, ethylene carbonate, succinic anhydride, propylene sulfite, vinylene sulfate, biphenyl and lithium tetrafluoro oxalate phosphate.
Further, the additive is preferably a mixture of vinylene carbonate, propylene sulfite and biphenyl, wherein the weight percentage of the vinylene carbonate, the propylene sulfite and the biphenyl is 0.7:0.7: 2.
Further, the additive is a mixture of succinic anhydride, propylene sulfite and lithium tetrafluoro oxalate phosphate, wherein the mass percentage of the succinic anhydride, the propylene sulfite and the lithium tetrafluoro oxalate phosphate is 0.8:0.8: 2.
Compared with the prior art, the electrolyte for reducing the gas generation of the lithium titanate battery cell has the following advantages: the protective film can be formed on the surface of the negative electrode, the decomposition of the electrolyte in the later cycle and use process of the battery cell is effectively inhibited, and the direct contact between the lithium ion battery electrode and the electrolyte solvent can be well prevented in the pre-charging process, so that the gas generation of the lithium titanate battery cell is inhibited, the problems of battery bulging and influence on appearance and use caused by the gas generation of the lithium titanate battery cell are solved, the industrial productivity is improved, the safety in the production process of the lithium ion battery is improved, and the cycle performance of the lithium ion battery is improved.
Detailed Description
It should be noted that the embodiments and features of the embodiments of the present invention may be combined with each other without conflict.
The invention will be described in detail with reference to the following examples.
Example 1
Firstly, preparing a battery cell according to the following steps:
(1) preparing anode slurry and cathode slurry: respectively adding 90 mass percent of nickel cobalt lithium manganate material, 6 mass percent of conductive carbon black and 4 mass percent of PVDF into NMP, and uniformly mixing the materials after high-speed stirring to obtain anode slurry; adding 88 mass percent of lithium titanate material, 5 mass percent of conductive carbon black and 7 mass percent of PVDF into NMP, and uniformly mixing the materials after high-speed stirring to obtain negative electrode slurry.
(2) Preparing a positive pole piece: uniformly coating the prepared anode slurry on two surfaces of an aluminum foil through a coating machine, and drying and rolling to obtain an anode piece; and uniformly coating the prepared negative electrode slurry on two sides of an aluminum foil through a coating machine, drying and rolling to obtain a negative electrode plate.
(3) Preparing an electric core: stacking or winding the prepared positive and negative pole pieces into a battery cell in a positive and negative alternative mode, wherein the positive and negative poles are separated by a diaphragm, and the size of the negative pole in the material attachment area is ensured to be larger than or equal to that of the positive pole; the positive electrode lug and the negative electrode lug are fixed by welding;
(4) the battery core is placed into a battery shell with a larger air bag for packaging, and a liquid injection port is reserved on one side of the battery shell; after the packaging is finished, the battery core is baked for 24 hours at the temperature of 80 ℃ to remove moisture.
(5) And injecting the baked core cladding with the electrolyte, and packaging with an aluminum-plastic film, wherein the capacity of the core cladding is 30-70 Ah. The rate capability of the lithium ion battery and the gas production rate after the lithium ion battery is stored for 112 days at 60 ℃ are detected, and the experimental results are shown in table 1.
The electrolyte comprises lithium salt, organic solvent and additive; the lithium salt is lithium hexafluorophosphate, the concentration of the lithium salt in the electrolyte is 0.5mol/L, the organic solvent is a mixture of ethylene carbonate, propylene carbonate, ethyl methyl carbonate and diethyl carbonate, and the volume ratio of the ethylene carbonate, the propylene carbonate, the ethyl methyl carbonate and the diethyl carbonate is 10:10:60: 20.
Example 2
Steps (1) to (4) described in example 1 were repeated, and then the procedure was continued in accordance with the following step (5).
(5) And injecting the baked core cladding with the electrolyte, and packaging with an aluminum-plastic film, wherein the capacity of the core cladding is 30-70 Ah. The rate capability of the lithium ion battery and the gas production rate after the lithium ion battery is stored for 112 days at 60 ℃ are detected, and the experimental results are shown in table 1.
The electrolyte comprises lithium salt, organic solvent and additive; the lithium salt is lithium hexafluorophosphate, the concentration of the lithium salt in the electrolyte is 0.5mol/L, the organic solvent is a mixture of ethylene carbonate, propylene carbonate, ethyl methyl carbonate and diethyl carbonate, and the volume ratio of the ethylene carbonate, the propylene carbonate, the ethyl methyl carbonate and the diethyl carbonate is 10:10:60: 20. The additive is a mixture of vinylene carbonate, propylene sulfite and biphenyl, wherein the weight percentage of the vinylene carbonate, the propylene sulfite and the biphenyl is 0.7:0.7: 2.
Example 3
Steps (1) to (4) described in example 1 were repeated, and then the procedure was continued in accordance with the following step (5).
(5) And injecting the baked core cladding with the electrolyte, and packaging with an aluminum-plastic film, wherein the capacity of the core cladding is 30-70 Ah. The rate capability of the lithium ion battery and the gas production rate after the lithium ion battery is stored for 112 days at 60 ℃ are detected, and the experimental results are shown in table 1.
The electrolyte comprises lithium salt, organic solvent and additive; the lithium salt is lithium hexafluorophosphate, the concentration of the lithium salt in the electrolyte is 0.5mol/L, the organic solvent is a mixture of ethylene carbonate, propylene carbonate, ethyl methyl carbonate and diethyl carbonate, the volume ratio of the ethylene carbonate to the propylene carbonate to the ethyl methyl carbonate to the diethyl carbonate is 10:10:60:20, the additive is a mixture of vinylene carbonate, propylene sulfite and biphenyl, and the mass percentage of the vinylene carbonate to the propylene sulfite to the biphenyl is 0.7:0.7: 2.
Example 4
Steps (1) to (4) described in example 1 were repeated, and then the procedure was continued in accordance with the following step (5).
(5) And injecting the baked core cladding with the electrolyte, and packaging with an aluminum-plastic film, wherein the capacity of the core cladding is 30-70 Ah. The rate capability of the lithium ion battery and the gas production rate after the lithium ion battery is stored for 112 days at 60 ℃ are detected, and the experimental results are shown in table 1.
The electrolyte comprises lithium salt, organic solvent and additive; the lithium salt is lithium hexafluorophosphate, the concentration of the lithium salt in the electrolyte is 0.5mol/L, the organic solvent is a mixture of ethylene carbonate, propylene carbonate, ethyl methyl carbonate and diethyl carbonate, the volume ratio of the ethylene carbonate, the propylene carbonate, the ethyl methyl carbonate and the diethyl carbonate is 15:15:60:10, the additive is a mixture of succinic anhydride, propylene sulfite and lithium tetrafluoro oxalate phosphate, and the mass percentages of the succinic anhydride, the propylene sulfite and the lithium tetrafluoro oxalate phosphate are 0.8:0.8: 2.
Table 160 deg.c gas production and multiplying power performance comparison indication table in different storage time
As can be seen from the above table, the electrolyte in the use embodiments 1 to 4 can well prevent the direct contact between the lithium ion battery electrode and the electrolyte solvent in the pre-charging process, thereby inhibiting the gas generation of the lithium titanate battery cell, solving the problems of battery swelling and appearance and use influence caused by the gas generation of the lithium titanate battery cell, and significantly improving the cycle performance of the lithium ion battery.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the invention, so that any modifications, equivalents, improvements and the like, which are within the spirit and principle of the present invention, should be included in the scope of the present invention.
Claims (9)
1. The utility model provides an electrolyte that reduces aerogenesis of lithium titanate electricity core which characterized in that: the lithium salt, the organic solvent and the additive are included, the organic solvent is carbonate, and the volume of the additive is 1.0-10% of the sum of the volumes of the lithium salt and the organic solvent.
2. The electrolyte solution for reducing gas evolution of a lithium titanate cell according to claim 1, wherein: the lithium salt is one or a mixture of more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium carbonate and lithium perchlorate.
3. The electrolyte solution for reducing gas evolution of a lithium titanate cell according to claim 1, wherein: the mass concentration of the lithium salt is 0.5-2.0 mol/L.
4. The electrolyte solution for reducing gas evolution of a lithium titanate cell according to claim 1, wherein: the mass concentration of the lithium salt is 1.0-1.5 mol/L.
5. The electrolyte solution for reducing gas evolution of a lithium titanate cell according to claim 1, wherein: the organic solvent is one or a mixture of ethylene carbonate, ethyl methyl carbonate, dimethyl carbonate and diethyl carbonate.
6. The electrolyte solution of claim 5 for reducing gas evolution from lithium titanate cells, wherein: the organic solvent is a mixture of ethylene carbonate, propylene carbonate, ethyl methyl carbonate and diethyl carbonate, wherein the volume ratio of the ethylene carbonate to the propylene carbonate to the ethyl methyl carbonate to the diethyl carbonate is 10:10:60: 20.
7. The electrolyte solution for reducing gas evolution of a lithium titanate cell according to claim 1, wherein: the additive is one or a mixture of more of lithium difluoro oxalate borate, ethylene carbonate, succinic anhydride, propylene sulfite, vinylene sulfate, biphenyl and lithium tetrafluoro oxalate phosphate.
8. The electrolyte solution of claim 7, wherein the electrolyte solution is capable of reducing gas evolution from a lithium titanate cell, and comprises: the additive is a mixture of vinylene carbonate, propylene sulfite and biphenyl, wherein the weight percentage of the vinylene carbonate, the propylene sulfite and the biphenyl is 0.7:0.7: 2.
9. The electrolyte solution of claim 7, wherein the electrolyte solution is capable of reducing gas evolution from a lithium titanate cell, and comprises: the additive is a mixture of succinic anhydride, propylene sulfite and lithium tetrafluoro oxalate phosphate, wherein the mass percentage of the succinic anhydride, the propylene sulfite and the lithium tetrafluoro oxalate phosphate is 0.8:0.8: 2.
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2020
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Application publication date: 20200908 |