CN111082140A - Novel sodium ion battery electrolyte and sodium battery - Google Patents

Novel sodium ion battery electrolyte and sodium battery Download PDF

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Publication number
CN111082140A
CN111082140A CN201911316944.9A CN201911316944A CN111082140A CN 111082140 A CN111082140 A CN 111082140A CN 201911316944 A CN201911316944 A CN 201911316944A CN 111082140 A CN111082140 A CN 111082140A
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sodium
additive
electrolyte
ion battery
novel
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陈性保
许杰
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Dongguan Kunqian New Energy Technology Co ltd
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Dongguan Kunqian New Energy Technology 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
    • H01M10/056—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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or 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

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)

Abstract

The invention discloses a novel sodium ion battery electrolyte, which comprises a solvent, sodium salt and an additive, wherein the additive comprises a water removal additive, and the additive comprises one or two of maleic anhydride and fluoromaleic anhydride. The invention also discloses a battery using the electrolyte. The water removal additive in the electrolyte provided by the invention adopts maleic anhydride or/and fluoromaleic anhydride, and can remove water carried by the Prussian blue sodium salt material of the positive electrode, thereby improving the cycle performance and other electrical properties of the sodium battery and prolonging the cycle life of the sodium battery.

Description

Novel sodium ion battery electrolyte and sodium battery
Technical Field
The invention relates to an electrolyte, in particular to a sodium ion battery electrolyte. The invention also relates to a sodium battery using the electrolyte.
Background
With the gradual scarcity of traditional fossil energy and the increasingly serious environmental problems, the development of new renewable energy sources is becoming a necessary trend. At present, an energy storage system of an electric automobile and a smart grid is rapidly developed, and a secondary battery is used as an energy storage technology with the highest efficiency and has the characteristics of high response speed, high energy density and the like. The limited lithium resource will become a major bottleneck restricting the large-scale energy storage application of the lithium ion battery. Development of sodium ions with abundant resources and environmental friendlinessThe sub-battery has important strategic significance. The metal sodium and lithium being elements of the same main group, Na/Na+Potential of standard electrode of-2.71V, and Li/Li+The standard potential is approximate to-3.04V, the working principle of the sodium ion battery is the same as that of the lithium ion battery, and sodium ions are inserted and removed between the positive electrode and the negative electrode of the battery in the charging and discharging process. Sodium ions have a larger ion radius than lithium ions, and therefore require a larger ion channel, and conventional lithium storage electrode materials are not necessarily suitable for storage of sodium ions. In recent years, a great deal of research work is carried out by scientific and technical personnel at home and abroad in the development of new sodium storage materials, and good progress is made. Prussian blue sodium salt material NaxPR (CN)6P and R are Fe, Co, Ni, Mn, etc., have a special open frame structure, are suitable for rapid migration of alkali metal ions, and have recently attracted much attention as a highly potential sodium storage material. The Prussian blue anode material has industrial application prospect due to simple preparation, low cost and good electrochemical performance, but the consistency of the material, the water content control of the material, a separation technology and the like are difficult to achieve, and the influence of moisture needs to be overcome by the electrolyte and the additive together.
Disclosure of Invention
One of the purposes of the invention is to provide a novel sodium-ion battery electrolyte.
The other object of the present invention is to provide a sodium battery using the above electrolyte.
In order to realize one of the purposes, the invention provides the following technical scheme: a novel sodium ion battery electrolyte comprises a solvent, a sodium salt and an additive, wherein the additive comprises a water removal additive which comprises one or two of maleic anhydride and fluoromaleic anhydride.
The content of the water removal additive in the electrolyte is 0.5-10%.
The additives also include film forming additives, preferably 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether (D2), which form CEI and SEI at the cathode and anode, respectively. The content of the film forming additive is 0.5-5%.
The solvent is in a conventional content of 15-85% in the electrolyte, and comprises one or a combination of more than two of Ethylene Carbonate (EC), fluoroethylene carbonate (FEC), Ethyl Methyl Carbonate (EMC), fluoroethylene carbonate (FEMC), diethyl carbonate (DEC), diethyl fluoro carbonate (FDEC), Propylene Carbonate (PC), propylene trifluoro carbonate (FPC), Ethyl Acetate (EA) and ethyl fluoro acetate (FEA).
The sodium salt has a conventional content of 5-20% in the electrolyte. Including sodium hexafluorophosphate (NaPF)6) Sodium bisoxalato (NaBOB), sodium bis (fluorosulfonyl) imide (NaFSI), sodium bis (trifluoromethanesulfonyl) imide (NaTFSI), and sodium difluorooxalato (NaDFOB).
The second purpose of the invention is realized by the following technical scheme: a sodium battery comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the electrolyte comprises a solvent, sodium salt and an additive; wherein the additive comprises a water removal additive comprising one or both of maleic anhydride and fluoromaleic anhydride.
The mass fraction of the water removal additive in the electrolyte is 0.5-10%.
The additives also include film forming additives, preferably 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether (D2), which form CEI and SEI at the cathode and anode, respectively. The mass fraction of the film forming additive is 0.5-5%.
The solvent comprises one or more of Ethylene Carbonate (EC), fluoroethylene carbonate (FEC), Ethyl Methyl Carbonate (EMC), fluoroethylene carbonate (FEMC), diethyl carbonate (DEC), diethyl fluoro carbonate (FDEC), Propylene Carbonate (PC), propylene carbonate trifluoro carbonate (FPC), Ethyl Acetate (EA) and fluoroethylene acetate (FEA).
The sodium salt comprises sodium hexafluorophosphate (NaPF)6) Sodium bisoxalato (NaBOB), sodium bis (fluorosulfonyl) imide (NaFSI), sodium bis (trifluoromethanesulfonyl) imide (NaTFSI), and sodium difluorooxalato (NaDFOB).
The positive active material includes Prussian blue sodium salt material-NaxPR (CN)6P and R are Fe, Co, Ni, Mn, etc. The negative active material includes hard carbon. The separator comprises PP or PE.
The sodium battery also comprises outer packaging materials such as an aluminum-plastic film, a steel shell, an aluminum shell, a plastic shell and the like.
The invention has the beneficial effects that:
the water-removing additive in the electrolyte provided by the invention adopts maleic anhydride or/and fluoromaleic anhydride, and can remove the Prussian blue sodium salt material-NaxPR (CN) of the positive electrode6And (P and R are Fe, Co, Ni, Mn and the like) materials carry moisture spontaneously, so that the cycle performance and other electrical properties of the sodium battery are improved, and the cycle life of the sodium battery is prolonged.
Detailed Description
The following claims are hereby incorporated into the detailed description of the invention, with the understanding that the present disclosure is to be considered as a full and non-limiting example, and any limited number of modifications that fall within the spirit and scope of the claims are intended to be included therein.
Examples 1 to 6
Na for positive electrode2MnFe (CN)6 is a positive electrode active material, and the content is 92 percent; PVDF is adhesive, the content is 4%; S-P is a conductive agent and the content is 4 percent. Hard carbon is a negative active material, and the content is 94%; S-P is a conductive agent, and the content is 3%; PVDF was used as a binder in an amount of 3%.
Examples 7 to 8
Na for positive electrode2FeFe(CN)6Is a positive electrode active material, and the content is 92 percent; PVDF is adhesive, the content is 4%; S-P is a conductive agent and the content is 4 percent. Hard carbon is a negative active material, and the content is 94%; S-P is a conductive agent, and the content is 3%; PVDF was used as a binder in an amount of 3%.
Comparative electrolyte schemes are shown in the table below.
Figure BDA0002326085610000031

Claims (10)

1. The novel sodium-ion battery electrolyte comprises a solvent, a sodium salt and an additive, wherein the additive comprises a water removal additive, and the novel sodium-ion battery electrolyte is characterized in that the water removal additive comprises one or two of maleic anhydride and fluoromaleic anhydride.
2. The novel sodium-ion battery electrolyte as claimed in claim 1, wherein the water-removing additive is contained in the electrolyte in an amount of 0.5 to 10%.
3. The novel sodium-ion battery electrolyte as claimed in claim 1, wherein the additive further comprises a film-forming additive, and the content of the film-forming additive is 0.5-5%.
4. The novel sodium ion battery electrolyte of claim 3 wherein the film forming additive is 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether.
5. The novel sodium ion battery electrolyte as claimed in any one of claims 1 to 4 wherein the solvent comprises one or a combination of two or more of ethylene carbonate, fluoroethylene carbonate, propylene carbonate trifluoride, diethyl carbonate, diethyl fluorocarbonate, ethyl methyl carbonate, ethyl fluoromethyl carbonate, ethyl acetate and ethyl fluoroacetate.
6. The novel sodium ion battery electrolyte as claimed in any one of claims 1 to 4 wherein the sodium salt comprises one or a combination of two or more of sodium hexafluorophosphate, sodium dioxalate, sodium bis (fluorosulfonyl) imide, sodium bis (trifluoromethanesulfonyl) imide and sodium difluorooxalate.
7. A sodium battery comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the electrolyte comprises a solvent, sodium salt and an additive; wherein, the water-removing additive comprises one or two of maleic anhydride and fluoromaleic anhydride.
8. The sodium battery of claim 7, wherein the water scavenging additive is present in the electrolyte in an amount of 0.5% to 10%.
9. The sodium battery of claim 8, wherein the additive further comprises a film forming additive, wherein the film forming additive is present in an amount of 0.5% to 5%.
10. The sodium cell of claim 9 wherein the film forming additive is 1,1,2, 2-tetrafluoroethyl-2, 2,3, 3-tetrafluoropropyl ether.
CN201911316944.9A 2019-12-19 2019-12-19 Novel sodium ion battery electrolyte and sodium battery Pending CN111082140A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112510198A (en) * 2020-12-16 2021-03-16 武汉大学 Positive electrode active material, aqueous solution sodium ion battery and electronic device
CN114069051A (en) * 2021-11-23 2022-02-18 天津中电新能源研究院有限公司 Fluoro-carboxylic acid ester based low-temperature electrolyte and sodium ion battery containing same
CN114243114A (en) * 2021-12-28 2022-03-25 大连中比动力电池有限公司 Additive and electrolyte for Prussian blue sodium ion battery
WO2024021019A1 (en) * 2022-07-29 2024-02-01 宁德时代新能源科技股份有限公司 Sodium-ion battery electrolyte, secondary battery, battery module, battery pack, and electric device
WO2024086987A1 (en) * 2022-10-24 2024-05-02 宁德时代新能源科技股份有限公司 Mixed additive, electrolyte solution for sodium secondary battery, sodium secondary battery, battery module, battery pack, and electric device
CN116995302B (en) * 2023-09-11 2024-05-31 四川易纳能新能源科技有限公司 Organic electrolyte, preparation method thereof and sodium ion battery

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107171021A (en) * 2017-06-13 2017-09-15 中国电子新能源（武汉）研究院有限责任公司 A kind of sodium-ion battery electrolyte and sodium-ion battery
CN109786840A (en) * 2018-10-29 2019-05-21 上海紫剑化工科技有限公司 High safety type organic electrolyte, secondary cell and preparation method and application
CN109830751A (en) * 2019-03-08 2019-05-31 上海氟帝新材料科技有限公司 A kind of electrolyte functional additive, battery electrolyte and the battery
CN110518287A (en) * 2019-07-03 2019-11-29 上海紫剑化工科技有限公司 Sodium ion electrolyte, secondary cell and preparation method and application

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107171021A (en) * 2017-06-13 2017-09-15 中国电子新能源（武汉）研究院有限责任公司 A kind of sodium-ion battery electrolyte and sodium-ion battery
CN109786840A (en) * 2018-10-29 2019-05-21 上海紫剑化工科技有限公司 High safety type organic electrolyte, secondary cell and preparation method and application
CN109830751A (en) * 2019-03-08 2019-05-31 上海氟帝新材料科技有限公司 A kind of electrolyte functional additive, battery electrolyte and the battery
CN110518287A (en) * 2019-07-03 2019-11-29 上海紫剑化工科技有限公司 Sodium ion electrolyte, secondary cell and preparation method and application

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112510198A (en) * 2020-12-16 2021-03-16 武汉大学 Positive electrode active material, aqueous solution sodium ion battery and electronic device
CN114069051A (en) * 2021-11-23 2022-02-18 天津中电新能源研究院有限公司 Fluoro-carboxylic acid ester based low-temperature electrolyte and sodium ion battery containing same
CN114243114A (en) * 2021-12-28 2022-03-25 大连中比动力电池有限公司 Additive and electrolyte for Prussian blue sodium ion battery
WO2024021019A1 (en) * 2022-07-29 2024-02-01 宁德时代新能源科技股份有限公司 Sodium-ion battery electrolyte, secondary battery, battery module, battery pack, and electric device
WO2024086987A1 (en) * 2022-10-24 2024-05-02 宁德时代新能源科技股份有限公司 Mixed additive, electrolyte solution for sodium secondary battery, sodium secondary battery, battery module, battery pack, and electric device
CN116995302B (en) * 2023-09-11 2024-05-31 四川易纳能新能源科技有限公司 Organic electrolyte, preparation method thereof and sodium ion battery

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