WO2020107858A1 - 交联聚合物电解质制备方法、半固态聚合物电池及制备方法 - Google Patents

交联聚合物电解质制备方法、半固态聚合物电池及制备方法 Download PDF

Info

Publication number
WO2020107858A1
WO2020107858A1 PCT/CN2019/090625 CN2019090625W WO2020107858A1 WO 2020107858 A1 WO2020107858 A1 WO 2020107858A1 CN 2019090625 W CN2019090625 W CN 2019090625W WO 2020107858 A1 WO2020107858 A1 WO 2020107858A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymer
organic solvents
organics
electrolyte
acrylate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2019/090625
Other languages
English (en)
French (fr)
Inventor
韦伟峰
戴宽
冯昊宇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Central South University
Original Assignee
Central South University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Central South University filed Critical Central South University
Priority to DE112019005862.2T priority Critical patent/DE112019005862T5/de
Publication of WO2020107858A1 publication Critical patent/WO2020107858A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing boron
    • 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
    • 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
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • 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
    • H01M10/058—Construction or manufacture
    • 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
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the invention relates to a method for preparing an electrolyte for a secondary battery, a secondary battery and a method for preparing the same, in particular to a method for preparing a polymer electrolyte, a polymer battery and a method for preparing the same.
  • polymer electrolytes Compared with traditional electrolytes, polymer electrolytes have the advantages of good mechanical performance, wide electrochemical window, high safety performance, and easy matching with high-voltage electrodes. They are more suitable for next-generation high-performance secondary batteries, especially large secondary lithium batteries.
  • the development needs of high-density and high energy density have broad application prospects in electric vehicles, energy storage power stations and other fields.
  • the polymer matrix under study can be divided into linear polymer, cross-linked polymer, comb polymer and other categories.
  • the cross-linked polymer electrolyte usually has an interpenetrating network or semi-interpenetrating network structure, which has good mechanical strength and thermal stability while obtaining high ionic conductivity. In recent years, people continue to study the application of cross-linked polymer electrolytes in lithium batteries.
  • the present invention provides a method for preparing a polymer electrolyte containing a borate crosslinker, as well as a semi-solid polymer secondary battery using the polymer electrolyte and a method for preparing the same.
  • the solution of the present invention is as follows.
  • a method for preparing a polymer electrolyte includes the following steps:
  • R is the residue of one compound of hydroxyethyl acrylate, hydroxyethyl methacrylate, polyethylene glycol methacrylate, polyethylene glycol acrylate;
  • the polymer monomer is polyethylene
  • the modifiers are carbonate organic solvents, ether organic solvents, nitriles Organic solvents, fluorocarbonate organic solvents, fluoroether organic solvents, fluoronitrile organic solvents, organic acid esters with carbon atoms less than 6, substituted oxyalkane organics, propane sultone, ethylene sulfite
  • the metal salt is one or more of alkali metal, magnesium salt, zinc salt or aluminum salt.
  • step I Under the protective atmosphere of argon gas with both water and oxygen contents less than 1 ppm, the prepolymerized solution prepared in step I was polymerized at 25 to 150°C for 0.1 to 48 hours to obtain a polymer electrolyte.
  • the pre-polymerization solution is generally coated on the porous support material and then thermally polymerized to form a polymer electrolyte membrane.
  • the metal salt is generally the lithium salt in the electrolyte of the lithium ion secondary battery in the prior art, such as lithium perchlorate, lithium hexafluorophosphate, lithium dioxalate borate, lithium hexafluoroarsenate, lithium tetrafluoroborate, dioxalate
  • lithium fluoroborate lithium trifluoromethanesulfonate
  • lithium bistrifluoromethylsulfonimide lithium bisfluorosulfonimide.
  • the polymer electrolyte prepared under this condition is suitable for the electrolyte of the most widely used lithium secondary battery at present.
  • metal salts are corresponding metal salts in existing electrolytes such as sodium batteries, zinc batteries, and magnesium batteries, such as sodium hexafluorophosphate, sodium perchlorate, zinc sulfate, magnesium sulfate, potassium hydroxide, etc.
  • a semi-solid polymer battery includes a positive electrode, an electrolyte, a separator, and a negative electrode, wherein the electrolyte is a polymer electrolyte prepared by the above method.
  • a preparation method of a semi-solid polymer battery includes the following steps:
  • R is the residue of one compound of hydroxyethyl acrylate, hydroxyethyl methacrylate, polyethylene glycol methacrylate, polyethylene glycol acrylate;
  • the polymer monomer is polyethylene
  • the modifiers are carbonate organic solvents, ether organic solvents, nitriles Organic solvents, fluorocarbonate organic solvents, fluoroether organic solvents, fluoronitrile organic solvents, organic acid esters with carbon atoms less than 6, substituted oxyalkane organics, propane sultone, ethylene sulfite
  • the metal salt is one or more of alkali metal, magnesium salt or zinc salt.
  • the metal salt is generally the lithium salt in the electrolyte of the lithium ion secondary battery in the prior art, such as lithium perchlorate, lithium hexafluorophosphate, lithium dioxalate borate, lithium hexafluoroarsenate, lithium tetrafluoroborate, dioxalate
  • lithium fluoroborate lithium trifluoromethanesulfonate
  • lithium bistrifluoromethylsulfonimide lithium bisfluorosulfonimide.
  • the polymer electrolyte prepared under this condition is suitable for the electrolyte of the most widely used lithium secondary battery at present.
  • the other metal salts are the corresponding metal salts in the existing electrolytes such as sodium batteries, zinc batteries, and magnesium batteries, such as sodium hexafluorophosphate, sodium perchlorate, zinc sulfate, magnesium sulfate, potassium hydroxide, and the like.
  • the present invention has the following advantages:
  • boric acid ester is used as a cross-linking agent, and the in-situ polymerization preparation process not only has a simple process flow, is easy to be scaled, but also can make the interface resistance between the polymer electrolyte and the electrode small and have good compatibility.
  • the polymer electrolyte prepared by using the borate cross-linking agent in the present invention has good mechanical properties while ensuring high conductivity and migration number.
  • Borate cross-linked polymer electrolyte with high porosity PP film as the supporting film has a tensile strength of 50 to 60 MPa, an elongation at break of 60% to 70%, and a tensile strength of 40 to 50 MPa, an elongation at break The growth rate is 50% to 60%.
  • the polymer electrolyte prepared by using a borate cross-linking agent in the present invention has a high dissociation rate of the metal salt, thereby obtaining higher conductivity and migration number, and the battery assembled with the polymer electrolyte has good stability And rate performance.
  • the electrolyte membrane has a conductivity of 3.0 ⁇ 10 -3 S/cm at room temperature and an electrochemical window of 5.0V.
  • the polypropylene separator, the lithium iron phosphate positive electrode and the lithium metal negative electrode were assembled into the case, and the above prepolymerization solution was injected into the case and packaged.
  • polymerization for 1h to prepare a semi-solid secondary lithium battery.
  • the semi-solid polymer LiFePO 4 battery has a 0.5C charge-discharge specific capacity at room temperature of 147mAh/g, and the capacity remains basically unchanged after 100 cycles.
  • borate crosslinker It is prepared by reacting monoglyceride containing methacrylic acid with trimethyl borate according to the stoichiometric ratio of 1:1, and then adding polyvinyl alcohol acrylate for reaction, stirring and reacting for 18h; drying to remove the solvent, and column chromatography to obtain The structural formula of borate crosslinker is
  • polyethylene glycol diacrylate polymer monomer, lithium bistrifluoromethanesulfonimide, Propylene carbonate modifier and azobisisoheptanonitrile are mixed to obtain a prepolymerized solution, in which the mass ratio of the above substances is 20:10:20:49.5:0.5, at 60 °C, in a cellulose nonwoven membrane
  • Polymer electrolyte membrane can be obtained by in-situ polymerization of materials for 10h. After testing, the electrolyte membrane has a conductivity of 1.0 ⁇ 10 -3 S/cm at room temperature and an electrochemical window of 5.2V.
  • the cellulose nonwoven membrane, the lithium iron phosphate positive electrode, and the lithium metal negative electrode are assembled into the case, and the above prepolymerized solution is injected into the case and packaged.
  • the above prepolymerized solution is injected into the case and packaged.
  • polymerized for 10h to produce a semi-solid secondary lithium battery.
  • the semi-solid polymer LiFePO 4 battery has a 0.5C charge-discharge specific capacity at room temperature of 142mAh/g, and the capacity remains basically unchanged after 100 cycles.
  • ester crosslinking agent It is prepared by reacting monoglyceride containing methacrylic acid and trimethyl borate according to the stoichiometric ratio of 1:1, and then adding polyvinyl alcohol acrylate for reaction, stirring and reacting for 10h; drying to remove acetonitrile, boron obtained by column chromatography
  • the structural formula of ester crosslinking agent is
  • this semi-solid polymer LiFePO 4 battery has a 0.5C charge-discharge specific capacity of 143mAh/g at room temperature, and its capacity remains basically unchanged after 100 cycles.
  • borate crosslinker It is prepared by reacting monoglyceride containing methacrylic acid with trimethyl borate at a stoichiometric ratio of 1:1, and then adding polyvinyl alcohol methacrylate for reaction, stirring and reacting for 24h; drying to remove acetonitrile, and column chromatography,
  • the structural formula of the obtained borate crosslinker is
  • the above structure of borate crosslinking agent, ethyl methacrylate polymer monomer, sodium hexafluorophosphate, methyl butyrate modifier and The tertiary butyl hydrogen peroxide initiator is mixed to obtain a pre-polymerization solution, wherein the mass ratio of the above substances is 10:5:5:79.8:0.2, which can be obtained by in-situ polymerization on a cellulose acetate porous membrane for 5h at 90°C Polymer electrolyte membrane. After testing, the electrolyte membrane has a conductivity of 8.1 ⁇ 10 -4 S/cm at room temperature and an electrochemical window of 4.9V.
  • the electrolyte membrane has a conductivity of 7.5 ⁇ 10 -4 S/cm at room temperature and an electrochemical window of 4.85V.
  • polyethylene glycol dimethacrylate polymer monomer, potassium difluorosulfonimide, di Dimethyl ether and diisopropyl peroxydicarbonate initiator are mixed to obtain a prepolymerized solution, in which the mass ratio of the above substances is 15:10:5:69:1, which is polymerized in situ on a polypropylene membrane at 55°C 15h can get polymer electrolyte membrane.
  • the electrolyte membrane has a conductivity of 9.2 ⁇ 10 -4 S/cm at room temperature and an electrochemical window of 5.1V.
  • the polypropylene separator, the potassium vanadate positive electrode and the potassium-sodium alloy negative electrode were assembled into the case, and the pre-polymerization solution was injected into the case to encapsulate.
  • a semi-solid polymer potassium battery was prepared for 15 hours.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Secondary Cells (AREA)

Abstract

交联聚合物电解质制备方法、半固态聚合物电池及制备方法，用两端基为烯基的环状硼酸酯为交联剂，使得聚合物单体等在支撑材料上发生原位聚合，得到交联型聚合物电解质。电解质的制备方法简单，聚合物电解质与电极之间界面电阻小、兼容性好，具有优良的机械性能，并且具有较高的电导率和迁移数，用聚合物电解质组装的聚合物电池具有良好的稳定性和倍率性能。

Description

交联聚合物电解质制备方法、半固态聚合物电池及制备方法 技术领域
本发明涉及一种二次电池用电解质制备方法及二次电池和制备方法，特别涉及一种聚合物电解质制备方法、聚合物电池及制备方法。
背景技术
聚合物电解质相比于传统电解液，具有机械性能好、电化学窗口宽、安全性能高、易于与高电压电极匹配的优点，更适于下一代高性能二次电池特别是二次锂电池大型化、高能量密度的发展需求，在电动汽车、储能电站等领域具有广阔的应用前景。现在研究的聚合物基体可以分为线性聚合物、交联聚合物、梳形聚合物等类别。交联型聚合物电解质通常具有互穿网络或半互穿网络结构，在获得高离子电导率的同时兼具良好的机械强度和热稳定性。近年来，人们不断研究交联型聚合物电解质在锂电池中的应用。郑哲楠等人在CN201610270636.7中提出将苯乙烯/异戊二烯/丙烯酸甲酯嵌段共聚物溶于易挥发有机溶剂中，烘干成膜，再将该薄膜浸泡在含有热引发剂的电解液中，得到可热交联的聚合物电解质膜。但其电解质的制作工艺需经过成膜、浸泡、交联的复杂流程。刘晋等在CN201310461486.4中公开了一种以交联聚氧乙烯醚的全固态电解质材料，组装的电池具有高温循环稳定性好、充放电比容量高、保持率好的特点。但其室温电导率低，需在高温条件下才能稳定循环。
发明内容
本发明提供了一种含硼酸酯交联剂的聚合物电解质的制备方法，同时提供了采用该聚合物电解质的半固态聚合物二次电池及制备方法，本发明的方案如 下。
一种聚合物电解质的制备方法，包括以下步骤：
(Ⅰ)在水和氧含量均小于1ppm的氩气保护气氛下，将具有式1所示结构的环状硼酸酯交联剂、聚合物单体、碱金属盐和改性剂混合后，向其中加入自由基引发剂化合物得到预聚合溶液；
Figure PCTCN2019090625-appb-000001
其中，R为丙烯酸羟乙酯、甲基丙烯酸羟乙酯、聚乙二醇甲基丙烯酸酯、聚乙二醇丙烯酸酯中的一种化合物的残基；所述聚合物单体为聚乙二醇丙烯酸酯类有机物、甲基丙烯酸酯类有机物、碳酸烯酯类有机物或丙烯酸酯类有机物中的一种或多种；所述改性剂为碳酸酯类有机溶剂、醚类有机溶剂、腈类有机溶剂、氟代碳酸酯类有机溶剂、氟代醚类有机溶剂、氟代腈类有机溶剂、碳原子数小于6的有机酸酯、取代氧基烷烃类有机物、丙烷磺内酯、乙烯亚硫酸酯、氟代苯、二甲基亚砜或环丁砜中的一种或多种；所述金属盐为碱金属、镁盐、锌盐或铝盐中的一种或多种。
(Ⅱ)在水和氧含量均小于1ppm的氩气保护气氛下，将第Ⅰ步制得的预聚合溶液于25～150℃条件下进行聚合反应0.1～48h得到聚合物电解质。为方便使用，一般将预聚合溶液覆于多孔支撑材料上再进行热聚合，形成聚合物电解质膜。
所述的金属盐一般为现有技术中锂离子二次电池中的电解质中的锂盐，如高氯酸锂、六氟磷酸锂、二草酸硼酸锂、六氟砷酸锂、四氟硼酸锂、草酸二氟硼酸锂、三氟甲基磺酸锂、双三氟甲基磺酰亚胺锂和双氟磺酰亚胺锂中的一种或多种。该条件下制得的聚合物电解质适用于目前最广泛使用的锂二次电池的 电解质。其他金属盐为现有如钠电池、锌电池、镁电池、中所使用电解质中的相应的金属盐，如六氟磷酸钠、高氯酸钠等、硫酸锌、硫酸镁、氢氧化钾等
实验发现，当环状硼酸酯交联剂、聚合物单体、金属盐、改性剂和自由基引发剂的质量比为(1～30):(1～30):(0.02～30):(10～90):(0.002～5)时，聚合物电解质性能更佳。
一种半固态聚合物电池，包括正极、电解质、隔膜和负极，其中电解质为采用上述方法制备得到的聚合物电解质。
一种半固态聚合物电池的制备方法，包括以下步骤：
(Ⅰ)在水和氧含量均小于1ppm的氩气保护气氛下，将具有式1所示结构的环状硼酸酯交联剂、聚合物单体、碱金属盐和改性剂混合后，向其中加入自由基引发剂化合物得到预聚合溶液；
Figure PCTCN2019090625-appb-000002
其中，R为丙烯酸羟乙酯、甲基丙烯酸羟乙酯、聚乙二醇甲基丙烯酸酯、聚乙二醇丙烯酸酯中的一种化合物的残基；所述聚合物单体为聚乙二醇丙烯酸酯类有机物、甲基丙烯酸酯类有机物、碳酸烯酯类有机物或丙烯酸酯类有机物中的一种或多种；所述改性剂为碳酸酯类有机溶剂、醚类有机溶剂、腈类有机溶剂、氟代碳酸酯类有机溶剂、氟代醚类有机溶剂、氟代腈类有机溶剂、碳原子数小于6的有机酸酯、取代氧基烷烃类有机物、丙烷磺内酯、乙烯亚硫酸酯、氟代苯、二甲基亚砜或环丁砜中的一种或多种；所述金属盐为碱金属、镁盐或锌盐中的一种或多种。
(Ⅱ)在水和氧含量均小于1ppm的氩气保护气氛下，将预聚合溶液、隔离膜、 正极和负极组装成电池，密封后，再于25～150℃条件下热处理0.1～48h得到半固聚合物二次电池。
当环状硼酸酯交联剂、聚合物单体、金属盐、改性剂和自由基引发剂的质量比为(1～30):(1～30):(0.02～30):(10～90):(0.002～5)时，由于电解质性能较佳，聚合物二次电池的性能也较优。
所述的金属盐一般为现有技术中锂离子二次电池中的电解质中的锂盐，如高氯酸锂、六氟磷酸锂、二草酸硼酸锂、六氟砷酸锂、四氟硼酸锂、草酸二氟硼酸锂、三氟甲基磺酸锂、双三氟甲基磺酰亚胺锂和双氟磺酰亚胺锂中的一种或多种。该条件下制得的聚合物电解质适用于目前最广泛使用的锂二次电池的电解质。其他金属盐为现有如钠电池、锌电池、镁电池、中所使用电解质中的相应的金属盐，如六氟磷酸钠、高氯酸钠等、硫酸锌、硫酸镁、氢氧化钾等。
与现有技术相比，本发明具有以下优点：
1、本发明中采用硼酸酯作交联剂，原位聚合制备工艺，不仅工艺流程简单，易于规模化，并且可使得聚合物电解质与电极之间界面电阻小、兼容性好。
2、本发明中采用硼酸酯交联剂制备的聚合物电解质，在保证电导率和迁移数高的同时具有较好的机械性能。以高孔隙率PP膜为支撑膜的硼酸酯交联聚合物电解质的拉伸强度为50～60MPa、断裂伸长率为60％～70％，而拉伸强度则为40～50MPa、断裂伸长率为50％～60％。
3、本发明中采用硼酸酯交联剂制备的聚合物电解质，金属盐的离解率高，从而能获得较高的电导率和迁移数，用该聚合物电解质组装的电池具有良好的稳定性和倍率性能。
具体实施方式
实施例1
由含甲基丙烯酸单甘油酯与硼酸三甲酯按照化学计量比1:1反应制得，然后加入两端为羟基的聚氧乙稀醇进行桥联，搅拌反应18h；干燥脱除溶剂，经柱层析，得到硼酸酯交联剂结构式为
Figure PCTCN2019090625-appb-000003
在水和氧含量均小于1ppm的氩气保护气氛下，采用上述结构的硼酸酯交联剂、聚乙二醇二丙烯酸酯的聚合物单体、六氟磷酸锂、碳酸乙烯酯改性剂和偶氮二异丁腈引发剂混合得到预聚合溶液，其中上述物质的质量之比为20:10:10:59:1，在70℃下，在聚丙烯隔膜材料原位聚合1h可得到聚合物电解质膜。经测试，该电解质膜室温下电导率为3.0×10 -3S/cm，电化学窗口为5.0V。
在水和氧含量均小于1ppm的氩气保护气氛下，将聚丙烯隔膜、磷酸铁锂正极和锂金属负极装配入壳体后，向其中注入上述预聚合溶液后封装。于70℃下，聚合1h制得半固态二次锂电池。经测试，该半固态聚合物LiFePO 4电池，室温下0.5C充放电比容量可以达到147mAh/g，循环100圈后容量基本保持不变。
实施例2
由含甲基丙烯酸单甘油酯与硼酸三甲酯按照化学计量比1:1反应制得，然后加入聚乙烯醇丙烯酸酯进行反应，搅拌反应18h；干燥脱除溶剂，经柱层析，得到的硼酸酯交联剂结构式为
Figure PCTCN2019090625-appb-000004
在水和氧含量均小于1ppm的氩气保护气氛下，采用上述结构的硼酸酯交联剂、聚乙二醇二丙烯酸酯的聚合物单体、双三氟甲基磺酰亚胺锂、碳酸丙烯酯 改性剂和偶氮二异庚腈引发剂混合得到预聚合溶液，其中上述物质的质量之比为20:10:20:49.5:0.5，在60℃下，在纤维素无纺膜材料原位聚合10h可得到聚合物电解质膜。经测试，该电解质膜室温下电导率为1.0×10 -3S/cm，电化学窗口为5.2V。
在水和氧含量均小于1ppm的氩气保护气氛下，将纤维素无纺膜、磷酸铁锂正极和锂金属负极装配入壳体后，向其中注入上述预聚合溶液后封装。于60℃下，聚合10h制得半固态二次锂电池。经测试，该半固态聚合物LiFePO 4电池，室温下0.5C充放电比容量可以达到142mAh/g，循环100圈后容量基本保持不变。
实施例3
由含甲基丙烯酸单甘油酯与硼酸三甲酯按照化学计量比1:1反应制得，然后加入聚乙烯醇丙烯酸酯进行反应，搅拌反应10h；干燥脱除乙腈，经柱层析得到的硼酸酯交联剂结构式为
Figure PCTCN2019090625-appb-000005
在水和氧含量均小于1ppm的氩气保护气氛下，采用上述结构的硼酸酯交联剂、甲基丙烯酸异辛酯的聚合物单体、草酸二氟硼酸锂、四乙二醇二甲醚改性剂和异过氧化环己酮引发剂混合得到预聚合溶液，其中上述物质的质量之比为10:5:5:79.5:0.5，在50℃下，在玻璃纤维上原位聚合15h可得到聚合物电解质膜。经测试，该电解质膜室温下电导率为2.8×10 -3S/cm，电化学窗口为4.9V。
在水和氧含量均小于1ppm的氩气保护气氛下，将玻璃纤维、磷酸铁锂正极和锂金属负极装配入壳体后，向其中注入上述预聚合溶液后封装。于50℃下，聚合15h制得半固态二次锂电池。经测试，该半固态聚合物LiFePO 4电池，室温 下0.5C充放电比容量可以达到143mAh/g，循环100圈后容量基本保持不变。
实施例4
由含甲基丙烯酸单甘油酯与硼酸三甲酯按照化学计量比1:1反应制得，然后加入聚乙烯醇甲基丙烯酸酯进行反应，搅拌反应24h；干燥脱除乙腈，经柱层析，得到的硼酸酯交联剂结构式为
Figure PCTCN2019090625-appb-000006
在水和氧含量均小于1ppm的氩气保护气氛下，采用上述结构的硼酸酯交联剂、甲基丙烯酸乙酯的聚合物单体、六氟磷酸钠、丁酸甲酯改性剂和叔丁基过氧化氢引发剂混合得到预聚合溶液，其中上述物质的质量之比为10:5:5:79.8:0.2，在90℃下，在醋酸纤维素多孔膜上原位聚合5h可得到聚合物电解质膜。经测试，该电解质膜室温下电导率为8.1×10 -4S/cm，电化学窗口为4.9V。
在水和氧含量均小于1ppm的氩气保护气氛下，将醋酸纤维素多孔膜、磷酸钒钠正极和钠金属负极装配入壳体后，向其中注入上述预聚合溶液后封装。于90℃下，聚合5h制得半固态聚合物钠电池。
实施例5
由含甲基丙烯酸单甘油酯与硼酸三甲酯按照化学计量比1:1反应制得，然后加入甲基丙烯酸羟乙酯进行反应，搅拌反应8h；干燥脱除溶液，经柱层析，得到的硼酸酯交联剂结构式为
Figure PCTCN2019090625-appb-000007
在水和氧含量均小于1ppm的氩气保护气氛下，采用上述结构的硼酸酯交联剂、丙烯酸羟乙酯的聚合物单体、硫酸锌、丙烷磺内酯改性剂和过氧化二苯甲酰引发剂混合得到预聚合溶液，其中上述物质的质量之比为10:5:5:78:2，在110℃下，在聚丙烯隔膜上原位聚合0.5h可得到聚合物电解质膜。经测试，该电解质膜室温下电导率为7.5×10 -4S/cm，电化学窗口为4.85V。
在水和氧含量均小于1ppm的氩气保护气氛下，将聚丙烯隔膜、锰酸钠、钠金属负极装配入壳体后，向其中注入上述预聚合溶液后封装。于110℃下，聚0.5h制得半固态聚合物钠电池。
实施例6
由含甲基丙烯酸单甘油酯与硼酸三甲酯按照化学计量比1:1反应制得，然后加入甲基丙烯酸羟丙酯进行反应，搅拌反应12h；干燥脱除乙腈，经柱层析，得到的硼酸酯交联剂结构式为
Figure PCTCN2019090625-appb-000008
在水和氧含量均小于1ppm的氩气保护气氛下，采用上述结构的硼酸酯交联剂、聚乙二醇二甲基丙烯酸酯的聚合物单体、双氟磺酰亚胺钾、二甲醚和过氧化二碳酸二异丙酯引发剂混合得到预聚合溶液，其中上述物质的质量之比为15:10:5:69:1，在55℃下，在聚丙烯隔膜上原位聚合15h可得到聚合物电解质膜。经测试，该电解质膜室温下电导率为9.2×10 -4S/cm，电化学窗口为5.1V。
在水和氧含量均小于1ppm的氩气保护气氛下，将聚丙烯隔膜、钒酸钾正极和钾钠合金的负极装配入壳体后，向其中注入上述预聚合溶液后封装。于55℃下，聚15h制得半固态聚合物钾电池。

Claims (5)

  1. 一种聚合物电解质的制备方法，其特征在于：包括以下步骤，
    (Ⅰ)在水和氧含量均小于1ppm的氩气保护气氛下，将具有式1所示结构的环状硼酸酯交联剂、聚合物单体、金属盐和改性剂混合后，向其中加入自由基引发剂化合物得到预聚合溶液；
    Figure PCTCN2019090625-appb-100001
    其中，R为丙烯酸羟乙酯、甲基丙烯酸羟乙酯、聚乙二醇甲基丙烯酸酯、聚乙二醇丙烯酸酯中的一种化合物的残基；所述聚合物单体为聚乙二醇丙烯酸酯类有机物、甲基丙烯酸酯类有机物、碳酸烯酯类有机物或丙烯酸酯类有机物中的一种或多种；所述改性剂为碳酸酯类有机溶剂、醚类有机溶剂、腈类有机溶剂、氟代碳酸酯类有机溶剂、氟代醚类有机溶剂、氟代腈类有机溶剂、碳原子数小于6的有机酸酯、取代氧基烷烃类有机物、丙烷磺内酯、乙烯亚硫酸酯、氟代苯、二甲基亚砜或环丁砜中的一种或多种；所述金属盐为碱金属、镁盐或锌盐中的一种或多种。
    (Ⅱ)在水和氧含量均小于1ppm的氩气保护气氛下，将第Ⅰ步制得的预聚合溶液于25～150℃条件下进行聚合反应0.1～48h得到聚合物电解质。
  2. 如权利要求1所述的聚合物电解质的制备方法，其特征在于：环状硼酸酯交联剂、聚合物单体、金属盐、改性剂和自由基引发剂的质量比为(1～30):(1～30):(0.02～30):(10～90):(0.002～5)。
  3. 一种聚合物电池，包括正极、电解质、隔膜和负极，其特征在于：所述电解质为权利要求1或2所述的方法制备得到的聚合物电解质。
  4. 一种聚合物电池的制备方法，其特征在于：包括以下步骤，
    (Ⅰ)在水和氧含量均小于1ppm的氩气保护气氛下，将具有式1所示结构的环状硼酸酯交联剂、聚合物单体、碱金属盐和改性剂混合后，向其中加入自由基引发剂化合物得到预聚合溶液；
    Figure PCTCN2019090625-appb-100002
    其中，R为丙烯酸羟乙酯、甲基丙烯酸羟乙酯、聚乙二醇甲基丙烯酸酯、聚乙二醇丙烯酸酯中的一种化合物的残基；所述聚合物单体为聚乙二醇丙烯酸酯类有机物、甲基丙烯酸酯类有机物、碳酸烯酯类有机物或丙烯酸酯类有机物中的一种或多种；所述改性剂为碳酸酯类有机溶剂、醚类有机溶剂、腈类有机溶剂、氟代碳酸酯类有机溶剂、氟代醚类有机溶剂、氟代腈类有机溶剂、碳原子数小于6的有机酸酯、取代氧基烷烃类有机物、丙烷磺内酯、乙烯亚硫酸酯、氟代苯、二甲基亚砜或环丁砜中的一种或多种；所述金属盐为碱金属、镁盐或锌盐中的一种或多种。
    (Ⅱ)在水和氧含量均小于1ppm的氩气保护气氛下，将预聚合溶液、隔离膜、正极和负极组装成电池，密封后，再于25～150℃条件下热处理0.1～48h得到聚合物二次电池。
  5. 如权利要求4所述的聚合物电池的制备方法，其特征在于：环状硼酸酯交联剂、聚合物单体、金属盐、改性剂和自由基引发剂的质量比为(1～30):(1～30):(0.02～30):(10～90):(0.002～5)。
PCT/CN2019/090625 2018-11-26 2019-06-11 交联聚合物电解质制备方法、半固态聚合物电池及制备方法 Ceased WO2020107858A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE112019005862.2T DE112019005862T5 (de) 2018-11-26 2019-06-11 Ein Herstellungsverfahren für einen vernetzten Polymerelektrolyten, eine halbfeste Polymerbatterie und deren Herstellungsverfahren

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201811419047.6A CN109575187B (zh) 2018-11-26 2018-11-26 交联聚合物电解质制备方法、半固态聚合物电池及制备方法
CN201811419047.6 2018-11-26

Publications (1)

Publication Number Publication Date
WO2020107858A1 true WO2020107858A1 (zh) 2020-06-04

Family

ID=65924691

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/090625 Ceased WO2020107858A1 (zh) 2018-11-26 2019-06-11 交联聚合物电解质制备方法、半固态聚合物电池及制备方法

Country Status (3)

Country Link
CN (1) CN109575187B (zh)
DE (1) DE112019005862T5 (zh)
WO (1) WO2020107858A1 (zh)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114920918A (zh) * 2022-05-26 2022-08-19 华中科技大学 一种嵌段共聚物电解质、其原位制备方法和应用
CN115692874A (zh) * 2022-10-24 2023-02-03 山东农业大学 一种通过可控聚合机制快速制备凝胶电解质的方法
JP2023125582A (ja) * 2022-02-28 2023-09-07 株式会社カネカ 硬化性組成物、自己修復材料および硬化物

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109575187B (zh) * 2018-11-26 2021-07-16 中南大学 交联聚合物电解质制备方法、半固态聚合物电池及制备方法
CN109950614B (zh) * 2019-04-12 2023-09-29 中南大学 聚合物固体电解质的制备方法、聚合物固体电解质二次锂电池及制备方法
CN111146496B (zh) * 2019-12-23 2021-07-13 珠海冠宇电池股份有限公司 一种聚合物电解质及含该聚合物电解质的锂离子电池
CN111138596B (zh) * 2019-12-23 2022-09-30 珠海冠宇电池股份有限公司 聚合物电解质及包括该聚合物电解质的锂离子电池
CN111162312B (zh) 2019-12-23 2022-04-01 珠海冠宇电池股份有限公司 一种含硼氟结构的固态聚合物电解质及其制备方法和应用
CN114614083B (zh) * 2020-12-03 2024-02-20 珠海冠宇电池股份有限公司 一种凝胶型聚合物及含该凝胶型聚合物的锂离子电池
US12570773B2 (en) 2020-09-15 2026-03-10 Zhuhai Cosmx Battery Co., Ltd. Polymer, solid-state electrolyte, gel electrolyte, and battery
CN113394376B (zh) * 2021-06-16 2022-07-01 哈尔滨工业大学 一种耐高压固态电池复合正极及其制备方法
CN117013084A (zh) * 2022-04-29 2023-11-07 中国科学院苏州纳米技术与纳米仿生研究所 一种单离子导体准固态电解质及其制备方法和锂离子电池
CN114865097B (zh) * 2022-05-25 2023-07-25 华中科技大学 一种基于硼酸酯交换反应的聚合物电解质、其制备方法及应用
CN114843599B (zh) * 2022-05-30 2025-12-05 南昌航空大学 一种硼酸酯交联自修复聚合物电解质及其制备方法和应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106432608A (zh) * 2016-09-20 2017-02-22 复旦大学 一种含硼凝胶聚合物电解质及其制备方法和应用
KR20170137279A (ko) * 2016-06-03 2017-12-13 서울대학교산학협력단 이차전지용 전해질 및 이를 포함하는 이차전지
CN109575187A (zh) * 2018-11-26 2019-04-05 中南大学 交联聚合物电解质制备方法、半固态聚合物电池及制备方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103772607B (zh) * 2014-01-26 2016-01-13 郑州大学 含磷交联凝胶聚合物电解质及其现场热聚合制备方法、应用
JP2015172128A (ja) * 2014-03-11 2015-10-01 トヨタ自動車株式会社 感温性ポリマー及びその製造方法
CN104479112B (zh) * 2014-12-25 2017-03-01 北京当代经典科技有限公司 一种自交联型梳状聚合物及锂离子固体聚合物电解质
CN104600358B (zh) * 2015-01-21 2017-04-26 中南大学 表面化学接枝无机粒子的全固态聚合物电解质及制备方法
CN108767252A (zh) * 2018-02-28 2018-11-06 中南大学 一种锂离子电池
CN108808082B (zh) * 2018-08-15 2022-06-07 中南大学 一种用于锂离子电池的聚合物固态电解质及制备方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20170137279A (ko) * 2016-06-03 2017-12-13 서울대학교산학협력단 이차전지용 전해질 및 이를 포함하는 이차전지
CN106432608A (zh) * 2016-09-20 2017-02-22 复旦大学 一种含硼凝胶聚合物电解质及其制备方法和应用
CN109575187A (zh) * 2018-11-26 2019-04-05 中南大学 交联聚合物电解质制备方法、半固态聚合物电池及制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ZHANG, JINFANG ET AL.: "A Star-Shaped Solid Composite Electrolyte Containing Multifunctional Moieties with Enhanced Electrochemical Properties for All Solid-State Lithium Batteries", JOURNAL OF MEMBRANE SCIENCE, vol. 552, 31 January 2018 (2018-01-31), XP085358710, ISSN: 0376-7388, DOI: 20190805143559A *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2023125582A (ja) * 2022-02-28 2023-09-07 株式会社カネカ 硬化性組成物、自己修復材料および硬化物
CN114920918A (zh) * 2022-05-26 2022-08-19 华中科技大学 一种嵌段共聚物电解质、其原位制备方法和应用
CN114920918B (zh) * 2022-05-26 2023-01-17 华中科技大学 一种嵌段共聚物电解质、其原位制备方法和应用
CN115692874A (zh) * 2022-10-24 2023-02-03 山东农业大学 一种通过可控聚合机制快速制备凝胶电解质的方法
CN115692874B (zh) * 2022-10-24 2025-12-02 山东农业大学 一种通过可控聚合机制快速制备凝胶电解质的方法

Also Published As

Publication number Publication date
DE112019005862T5 (de) 2021-08-26
CN109575187B (zh) 2021-07-16
CN109575187A (zh) 2019-04-05

Similar Documents

Publication Publication Date Title
WO2020107858A1 (zh) 交联聚合物电解质制备方法、半固态聚合物电池及制备方法
CN109608592B (zh) 一种聚离子液体固态电解质的交联聚合制备的方法
CN105826603B (zh) 一种聚碳酸亚乙烯酯基锂离子电池聚合物电解质及其制备方法和应用
CN113429504B (zh) 一种锂电池用半固态聚离子液体电解质的制备方法
CN116315061B (zh) 锂电池用乙烯基咪唑聚离子液体基固态聚合物电解质膜及其制备方法
CN110071324B (zh) 一种多功能有机凝胶在锂离子电池中的应用
CN110336080A (zh) 一种复合单离子固态电解质的制备及应用方法
CN115986205A (zh) 一种功能性准固态聚合物电解质及其制备方法和应用
CN115395093A (zh) 用于高电压聚合物锂电池的电解质、锂电池及制备方法
CN112159507B (zh) 基于四臂聚氧化乙烯-聚合离子液体嵌段共聚物的固态电解质及其制备方法
CN117567771A (zh) 一种锌离子电池用双网络凝胶电解质及其制备方法与应用
CN116259833A (zh) 交联聚合物固态电解质及其制备方法和应用
CN115954550B (zh) 一种全天候锂离子电池电解液、电池、充放电方法
CN111525186B (zh) 基于两性离子液体修饰聚乙烯醇的全固态聚合物电解质及其制备方法
CN103474698B (zh) 金属锂高沉积高溶出效率的可充锂电池电解液及其制备
CN116014238A (zh) 一种半固态电解质及其合成方法和应用、一种半固态锂电池
CN115347230A (zh) 一种原位生成镁盐的镁二次电池非亲核电解液及其制备方法与应用
CN107565167A (zh) 一种电解液及双离子电池
CN119275357A (zh) 一种钠金属电池高压快充电解液及制备方法和应用
CN114069050B (zh) 一种高稳定性的钾离子电池酰胺类电解液及其应用
CN104393340A (zh) 含酯基功能化离子液体的凝胶聚合物电解质及其制备方法与应用
CN117374383A (zh) 一种锂金属电池共晶固态电解质及其制备方法和应用
CN116936924A (zh) 一种利用乙酰乙酸烯丙酯原位聚合制备锂金属电池聚合物电解质的方法
CN116646599A (zh) 一种含有机胺添加剂的可充镁电池电解液及其制备方法
CN115863774A (zh) 一种改善电化学性能的钠离子固态电池制作方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19890427

Country of ref document: EP

Kind code of ref document: A1

122 Ep: pct application non-entry in european phase

Ref document number: 19890427

Country of ref document: EP

Kind code of ref document: A1

122 Ep: pct application non-entry in european phase

Ref document number: 19890427

Country of ref document: EP

Kind code of ref document: A1

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 24/01/2022).

122 Ep: pct application non-entry in european phase

Ref document number: 19890427

Country of ref document: EP

Kind code of ref document: A1