WO2013091413A1 - Électrolyte de batterie au lithium-ion et batterie au lithium-ion comprenant celui-ci - Google Patents

Électrolyte de batterie au lithium-ion et batterie au lithium-ion comprenant celui-ci Download PDF

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Publication number
WO2013091413A1
WO2013091413A1 PCT/CN2012/081676 CN2012081676W WO2013091413A1 WO 2013091413 A1 WO2013091413 A1 WO 2013091413A1 CN 2012081676 W CN2012081676 W CN 2012081676W WO 2013091413 A1 WO2013091413 A1 WO 2013091413A1
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WIPO (PCT)
Prior art keywords
lithium ion
ion battery
electrolyte
battery electrolyte
battery
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Application number
PCT/CN2012/081676
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English (en)
Chinese (zh)
Inventor
丁杰
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华为技术有限公司
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Publication of WO2013091413A1 publication Critical patent/WO2013091413A1/fr

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Classifications

    • 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
    • H01M10/0569—Liquid materials characterised by the 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

Definitions

  • Lithium-ion battery electrolyte and lithium ion battery containing the same The application is submitted to the Chinese Patent Office on February 21, 2011, and the application number is 2 0 1 1 1 3 3 3 1 2 9 The invention is entitled "Li-Ion Battery Electrolyte and Lithium Ion Battery Containing the Electrolyte", the entire disclosure of which is incorporated herein by reference.
  • the present invention relates to the field of batteries, and in particular to a lithium ion battery electrolyte and a lithium ion battery containing the same.
  • lithium-ion batteries have become a research hotspot with their high energy density and good cycle performance.
  • lithium-ion batteries may cause safety problems such as thermal runaway and internal pressure rise, which may eventually lead to battery explosion and fire. To a certain extent, it limits the wide application of lithium ion batteries. And the occurrence of these problems is closely related to the nature of the electrolyte.
  • the researchers have improved the safety performance of the battery through electrode modification technology, and most of them use the pole piece coating technology to reduce the influence of the heat of the battery on the material and the electrolyte, and further Improve the safety of the battery.
  • the pole coating technique blocks a part of the lithium ion channel, so that the electrolyte cannot be infiltrated into the electrode, which affects the deintercalation of lithium ion L i + , resulting in a decrease in the rate performance of the battery.
  • the separator which plays a safety role in the lithium ion battery has also attracted attention.
  • researchers started with a diaphragm to develop a heat-resistant diaphragm that greatly improved the safety of the battery.
  • the heat of the battery rises instantaneously to 100-00 ° C, while the heat-closed diaphragm pores have a thermal shutdown temperature of 1 30-150 ° C.
  • the heat of the battery is lower than that of the diaphragm.
  • the separator may still be thermally closed in the future but has caused its own shrinkage.
  • the positive and negative electrodes of the battery cause the thermal runaway phenomenon to be intensified, so that the purpose of protecting the battery and improving safety cannot be achieved.
  • Embodiments of the present invention provide a lithium ion battery electrolyte and a lithium ion battery containing the same, which can reduce the further generation of heat in the event of thermal runaway, thereby improving the safety performance of the battery.
  • a lithium ion battery electrolyte comprising:
  • Lithium salts non-aqueous organic solvents, film forming additives and thermosetting materials
  • thermosetting material When the lithium ion battery electrolyte reaches a prescribed temperature, the thermosetting material is converted into a solid state in the electrolytic solution.
  • a lithium ion battery comprising the lithium ion battery electrolyte described above.
  • the lithium ion battery electrolyte provided by the embodiment of the invention and the lithium ion battery containing the electrolyte contain a thermosetting material, which can be converted into a solid state when the electrolyte reaches a predetermined temperature.
  • a safety problem such as thermal runaway
  • the electrolyte reaches the specified temperature after the heat is out of control.
  • the thermosetting material turns into a solid state, blocks the lithium ion channel, increases the internal resistance of the battery, causes the battery to form an open circuit, and reduces the further generation of heat in time. , thereby improving the safety of the battery.
  • Example 1 is a schematic view showing the molecular structure of a phenol resin in Example 1;
  • Example 2 is a schematic view showing the molecular structure of an aminotriazine phenol resin in Example 2.
  • Embodiments of the present invention provide a lithium ion battery electrolyte, including: Lithium salts, non-aqueous organic solvents, film forming additives and thermosetting materials;
  • thermosetting material When the lithium ion battery electrolyte reaches a prescribed temperature, the thermosetting material is converted into a solid state in the electrolytic solution.
  • thermosetting material refers to a material which can be cured under heat and has insoluble and infusible properties.
  • the lithium ion battery maintains normal operation within the normal use and storage temperature range of the lithium ion battery, and the safety can be effectively ensured.
  • a lithium-ion battery has a thermal runaway problem such as a short circuit, a serious rise in heat and temperature may cause a safety problem such as a fire or explosion of the battery.
  • the lithium ion battery electrolyte provided by the embodiment of the present invention adds a thermosetting material to the electrolyte, and the thermosetting material can be converted into a solid state when the electrolyte reaches a predetermined temperature.
  • the specified temperature is a critical temperature at which the battery has a safety hazard. According to the difference between the performance and the safety level of the battery, the specified temperature corresponding to different batteries may be the same or different, and the lithium provided in the embodiment of the present invention.
  • thermosetting material When the temperature of the electrolyte of the ion battery is lower than the predetermined temperature, the thermosetting material is in a liquid state, and does not affect the cycle and charge and discharge performance of the lithium ion battery; and when the temperature is reached or higher than the specified temperature, the heat curing material will Curing changes to a solid state.
  • thermosetting material when the battery has a safety problem such as thermal runaway, the electrolyte reaches the specified temperature after the thermal runaway. At this time, the thermosetting material is turned into a solid state, and the solid thermosetting material will block the lithium ion channel, increase the internal resistance of the battery, and cause the battery to form an open circuit. Timely reduce the further generation of heat, thereby effectively avoiding the safety of the battery and improving the safety performance of the battery.
  • the lithium ion battery electrolyte provided by the embodiment of the present invention, the specified temperature is
  • the specific value of the specified temperature can be determined by those skilled in the art based on the actual operating temperature of the battery and the desired level of safety.
  • the thermosetting material is selected from one or more of a phenolic resin, an epoxy resin, an amino resin, an unsaturated polyester, and a silicone resin.
  • the total weight of the electrolyte is preferably from 0.1 to 50% by weight of the total weight of the electrolyte.
  • the specific types and content of the thermosetting material are not limited in the embodiment of the present invention, and those skilled in the art can specifically select according to common knowledge or common technical means.
  • the lithium ion battery electrolyte provided by the embodiment of the present invention further includes a curing agent.
  • a curing agent also known as a hardener, a curing agent or a modifier, is a substance or mixture capable of enhancing or controlling the curing reaction.
  • the curing agent can be combined with a thermosetting material to achieve a better curing effect.
  • the curing agent is selected from one or more of an amine curing agent, an acid anhydride curing agent, a polymeric curing agent containing an inorganic element, cyclohexanone peroxide, and dibenzoyl peroxide.
  • inorganic elements in the polymer curing agent containing an inorganic element include P, S i, B, F, Mg, and the like.
  • the specific types and content of the curing agent are not limited in the embodiment of the present invention, and those skilled in the art can specifically select according to common knowledge or common technical means.
  • the lithium ion battery electrolyte provided by the embodiment of the present invention, the lithium salt is selected from the group consisting of L iPF 6 , L iBF 4 , L iC 10 4 , L iPF 3 (CF 2 CF 3 ) 3 , L iCF 3 S0 One or more of 3 and L iBOB.
  • the embodiments of the present invention are not limited thereto, and those skilled in the art may specifically select according to common knowledge or common technical means.
  • the non-aqueous organic solvent is selected from one or more of a carbonate, a carbonate derivative, an ester, an ether and a ketone.
  • the content of the non-aqueous organic solvent is preferably from 40 to 80% by weight based on the total weight of the electrolyte.
  • non-aqueous organic solvent in the examples of the present invention are not limited, and those skilled in the art can specifically select according to common knowledge or common technical means.
  • the film forming additive is selected from the group consisting of vinylene carbonate, ethylene carbonate, 1,3-sulfonic acid propiolactone, and 1, 4-sulfonic acid.
  • the film forming additive is selected from the group consisting of vinylene carbonate, ethylene carbonate, 1,3-sulfonic acid propiolactone, and 1, 4-sulfonic acid.
  • the content of the film-forming additive is preferably from 0.1 to 1% by weight based on the total weight of the electrolytic solution.
  • Embodiments of the present invention also provide a lithium ion battery, wherein the lithium ion battery includes the above Lithium ion battery electrolyte.
  • the lithium ion battery provided by the embodiment of the present invention can be prepared by using the above-described lithium ion battery electrolyte by a well-known method for preparing a lithium ion battery. Since the present invention relates only to the improvement of the electrolyte of the lithium ion battery, there is no particular limitation on the other structure and composition of the lithium ion battery.
  • the electrolyte contains a thermosetting material, which can be converted into a solid state when the electrolyte reaches a predetermined temperature.
  • the electrolyte reaches the specified temperature after the heat is out of control.
  • the thermosetting material turns into a solid state, blocks the lithium ion channel, increases the internal resistance of the battery, causes the battery to form an open circuit, and reduces the further generation of heat in time. , thereby improving the safety of the battery.
  • the following detailed description will be given by way of specific examples.
  • a lithium ion battery which is designated as Bl, was prepared by a known method for preparing a lithium ion battery using the electrolytic solution A1 prepared above.
  • EC ethylene carbonate
  • EMC ethyl methyl carbonate
  • DMC dimethyl carbonate
  • A2 a mixed solvent of dimethyl carbonate
  • VC ethylene carbonate
  • aminotriazine phenol resin having a total weight of 3% of the electrolyte
  • a lithium ion battery was prepared by the same method as in Example 1 using the electrolytic solution A2 obtained above, which was B2.
  • a lithium ion battery was prepared by the same method as in Example 1 using the electrolytic solution A prepared above, and it was designated as B.
  • Example 1 Five of the lithium ion batteries in Example 1, Example 2 and Comparative Example were selected and subjected to a needle punch test.
  • the test method is as follows:
  • a high-temperature steel needle with a diameter of 3-8 mm is used to penetrate from the direction perpendicular to the battery plate at a speed of 10-40 mm/s, and the steel needle stays in the battery.
  • Example 1 Five lithium ion batteries in Example 1, Example 2 and Comparative Example were selected and subjected to a charge test.
  • the test method is as follows:
  • the battery terminal voltage reaches the rated voltage, it is changed to constant voltage charging until the charging current is less than or equal to 0.01C, and the charging is stopped.
  • thermocouple was used to monitor the battery temperature change. When the battery temperature dropped to about 10 ° C lower than the peak temperature, the test was terminated.
  • Example 1 Five of the lithium ion batteries in Example 1, Example 1 and Comparative Example were selected for short-circuit test.
  • the test method is as follows:
  • the battery with the thermocouple is placed in the fume hood, and the positive and negative electrodes are shorted by the line with the total resistance of not more than 50 ⁇ .
  • the temperature change of the battery is monitored by the thermocouple. When the temperature drops to about 10 ° C lower than the peak, the test is terminated.
  • the battery B1 made of the electrolyte A1 to which the phenol resin is added and the battery B2 made of the electrolyte A2 to which the aminotriazine phenol resin is added are subjected to acupuncture and overcharge. And the short-circuit test performed well, and no safety problems such as fire and explosion occurred.
  • the battery B made of the electrolyte A without the thermosetting material in the comparative example showed various safety problems such as fire or explosion after the test. Therefore, the lithium ion battery electrolyte and the lithium ion battery provided by the embodiments of the present invention effectively improve the safety performance of the battery.

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

Abstract

L'invention concerne un électrolyte de batterie au lithium-ion et une batterie au lithium-ion comprenant celui-ci, qui se rapporte au domaine des batteries et qui est apte à améliorer la performance de sécurité de la batterie. L'électrolyte de batterie au lithium-ion contient un sel de lithium, un solvant organique non aqueux, un additif de formation de film et un matériau thermodurcissable. Lorsque l'électrolyte de batterie au lithium-ion atteint une température prédéfinie, le matériau thermodurcissable devient solide dans l'électrolyte.
PCT/CN2012/081676 2011-12-21 2012-09-20 Électrolyte de batterie au lithium-ion et batterie au lithium-ion comprenant celui-ci WO2013091413A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN2011104331298A CN102610856A (zh) 2011-12-21 2011-12-21 一种锂离子电池电解液及含有该电解液的锂离子电池
CN201110433129.8 2011-12-21

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WO2013091413A1 true WO2013091413A1 (fr) 2013-06-27

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Families Citing this family (4)

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Publication number Priority date Publication date Assignee Title
CN102610856A (zh) * 2011-12-21 2012-07-25 华为技术有限公司 一种锂离子电池电解液及含有该电解液的锂离子电池
TWI538281B (zh) * 2013-03-08 2016-06-11 台灣塑膠工業股份有限公司 鋰電池電解質之添加劑與使用其之鋰電池電解質
CN103337379B (zh) * 2013-06-07 2016-08-31 江苏大学 一种集储能-结构一体化的多功能储能装置及其制备方法
CN111933879A (zh) * 2020-07-21 2020-11-13 清华大学 一种锂离子电池

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CN1360357A (zh) * 2000-09-19 2002-07-24 日清纺织株式会社 离子导电组合物、凝胶电解质、非水电解质电池和电容器
US20040076887A1 (en) * 2001-03-08 2004-04-22 Jan-Christoph Panitz Electrolytes for lithium ion batteries
WO2009157261A1 (fr) * 2008-06-25 2009-12-30 シャープ株式会社 Batterie secondaire non aqueuse contenant un ignifugeant
CN102610856A (zh) * 2011-12-21 2012-07-25 华为技术有限公司 一种锂离子电池电解液及含有该电解液的锂离子电池

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JP2000123866A (ja) * 1998-10-12 2000-04-28 Shin Kobe Electric Mach Co Ltd 有機電解液二次電池
KR100330148B1 (ko) * 1999-05-03 2002-03-28 김순택 리튬 이차 전지용 전해액
CN101394007A (zh) * 2008-11-03 2009-03-25 广州天赐高新材料股份有限公司 一种锰酸锂电池的电解液

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1360357A (zh) * 2000-09-19 2002-07-24 日清纺织株式会社 离子导电组合物、凝胶电解质、非水电解质电池和电容器
US20040076887A1 (en) * 2001-03-08 2004-04-22 Jan-Christoph Panitz Electrolytes for lithium ion batteries
WO2009157261A1 (fr) * 2008-06-25 2009-12-30 シャープ株式会社 Batterie secondaire non aqueuse contenant un ignifugeant
CN102610856A (zh) * 2011-12-21 2012-07-25 华为技术有限公司 一种锂离子电池电解液及含有该电解液的锂离子电池

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