CN113234195A - Preparation method of flame-retardant lithium ion battery gel electrolyte - Google Patents

Preparation method of flame-retardant lithium ion battery gel electrolyte Download PDF

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Publication number
CN113234195A
CN113234195A CN202110505387.6A CN202110505387A CN113234195A CN 113234195 A CN113234195 A CN 113234195A CN 202110505387 A CN202110505387 A CN 202110505387A CN 113234195 A CN113234195 A CN 113234195A
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China
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lithium
electrolyte
gel electrolyte
mass percent
flame
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CN202110505387.6A
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Chinese (zh)
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牧小卫
李星军
阚咏春
宋磊
胡源
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University of Science and Technology of China USTC
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University of Science and Technology of China USTC
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    • 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
    • C08F230/02—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 phosphorus
    • 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
    • H01M10/0565—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
    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of 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 discloses a preparation method of a flame-retardant lithium ion battery gel electrolyte, aiming at the defect of poor safety performance of a traditional diaphragm/electrolyte system of a lithium ion battery, a phosphorus-containing monomer is introduced into a cross-linking network by a chemical cross-linking method to prepare the flame-retardant gel polymer electrolyte, and the safety performance of the lithium ion battery can be effectively improved.

Description

Preparation method of flame-retardant lithium ion battery gel electrolyte
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a preparation method of a flame-retardant lithium ion battery gel electrolyte.
Background
In 1990, the sony corporation produced lithium ion batteries for the first time. With the increasing demand of people for portable electronic products and the increasing awareness of environmental protection, lithium ion batteries are becoming an indispensable part of electronic and electrical equipment. Lithium ion batteries generally consist of three parts, an electrode, an electrolyte and a separator. The conventional separator/electrolyte systems have major safety issues: on one hand, the polyolefin thin film material can undergo rapid thermal shrinkage at high temperature, which means that when a battery is charged and discharged at a high rate, a diaphragm can rapidly shrink, so that positive and negative electrode materials are contacted, the internal short circuit of the battery is caused, and thermal runaway occurs; on the other hand, the polyolefin diaphragm has poor affinity to the electrolyte, so that a large amount of flowable electrolyte exists in the system, and the electrolyte leaks from the battery, and the electrolyte is usually combustible, so that the safety performance of the battery is greatly reduced. Therefore, it is imperative to develop new flame retardant polymer electrolytes to replace the traditional separator/electrolyte systems.
By adding some flame retardants into the organic electrolyte, the flame retardant property of the electrolyte can be effectively improved, but the ionic conductivity and the electrochemical stability of the electrolyte can be reduced, and the liquid electrolyte still has the risk of leakage. The all-solid-state electrolyte can solve the safety performance of the battery, but the all-solid-state lithium ion battery has large interface impedance and poor multiplying power and cycle performance, and cannot meet the requirements of the existing use. The gel electrolyte has both excellent ionic conductivity of the liquid electrolyte and safety performance of the all-solid electrolyte, and thus has attracted extensive attention. Among various gel electrolytes, the chemical crosslinking type gel electrolyte contains a chemical crosslinking structure, and has better stability and mechanical property. The phosphorus-containing monomer is introduced into the cross-linking structure, so that the flame retardant property of the battery is improved, and the problem of leakage of the battery is solved.
Disclosure of Invention
The invention provides a preparation method of a flame-retardant lithium ion battery gel electrolyte aiming at the defect of poor safety performance of a traditional diaphragm/electrolyte system of a lithium ion battery.
The preparation method of the flame-retardant lithium ion battery gel electrolyte comprises the following steps:
step 1: adding lithium salt into an organic solvent at room temperature, and mechanically stirring until the lithium salt is completely dissolved;
step 2: mixing the lithium salt solution obtained in the step 1, a cross-linking agent, a polymerization monomer and an initiator into a polymerization reaction tube, vacuumizing, sealing, and fully shaking up;
and step 3: and (3) placing the polymerization reaction tube under a temperature control device, and initiating polymerization reaction at a certain temperature to obtain the chemical crosslinking type flame-retardant gel electrolyte.
In the step 1, the lithium salt is one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium trifluoromethanesulfonate, lithium dioxalate borate, lithium difluorooxalate borate and lithium bistrifluoromethanesulfonylimide.
In the step 1, the organic solvent is one or a mixture of more of propylene carbonate, ethylene carbonate, ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, acetonitrile or ether solution.
In the step 2, the cross-linking agent is one or more of triethylene glycol diacrylate, triethylene glycol dimethacrylate, polyethylene glycol diacrylate, trihydroxy methyl propane trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate and polyether polyacrylate.
In the step 2, the polymerization monomer is one or more of allyl diethyl phosphate, vinyl diethyl phosphonate, allyl dimethyl phosphate, triallyl phosphate, propylene diphosphate and trifluoromethyl alkenyl phosphonate.
In the step 2, the initiator is one of dibenzoyl peroxide, dilauroyl peroxide, tert-butyl peroxy-2-ethylhexanoate, azobisisobutyronitrile and azobisisoheptonitrile.
In the reaction system of the step 2, the mass percent of the organic solvent is 60-90%, the mass percent of the lithium salt is 5-20%, the mass percent of the cross-linking agent is 1-5%, the mass percent of the polymerization monomer is 2-40%, and the mass percent of the initiator is 0.1-1%.
In the step 3, the polymerization reaction temperature is 40-90 ℃, and the reaction time is 20-100 min.
The polymerized monomer is a phosphorus flame retardant with a flame retardant effect, the selected cross-linking agent has a lithium ion transmission characteristic, and the intrinsically nonflammable cross-linked gel electrolyte with high ionic conductivity can be prepared through free radical polymerization.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, the alkenyl phosphate micromolecules and the cross-linking agent are copolymerized to obtain the chemical cross-linking type gel electrolyte, so that the problem of reduction of ionic conductivity and electrochemical stability of the electrolyte caused by adding a flame retardant into the electrolyte is avoided;
2. the chemical gel electrolyte prepared by the in-situ copolymerization method has good electrolyte solution retention capacity, and can greatly avoid electrolyte solution leakage;
3. the polymer monomer used by the gel electrolyte prepared by the invention is an organic phosphate monomer, has good flame retardant effect, and greatly improves the flame retardant property and the use safety of the electrolyte.
Drawings
FIG. 1 is a thermogravimetric curve of basic electrolyte and gel electrolyte in example 1 under nitrogen, wherein (a) the test conditions are at a heating rate of 1.5 ℃/min at 25-150 ℃ and at 50 ℃/min at 700 ℃ at 150-; (b) the temperature rise rate in the graph was 50 ℃/min, and the temperature rise rate in the graph (c) was 1.5 ℃/min.
FIG. 2 is a photograph showing the burning of the gel electrolyte in example 1.
Detailed Description
The invention is described in further detail below with reference to the figures and examples.
Example 1:
adding fluoroethylene carbonate with the volume content of 5% into ethylene carbonate and dimethyl carbonate according to the volume ratio of 1:1, then adding 1mol/L lithium hexafluorophosphate, and uniformly mixing to obtain the basic electrolyte. Triethylene glycol diacrylate with the mass content of 5% and allyl dimethyl phosphate with the mass content of 15% are added into the basic electrolyte, then azobisisobutyronitrile with the mass content of 1% of the triethylene glycol diacrylate and the allyl dimethyl phosphate is added, the mixture is stirred evenly, and the temperature is controlled at 40 ℃ to react for 30min, so that the gel electrolyte is obtained.
FIG. 1 is a thermogravimetric curve of the basic electrolyte and the gel electrolyte under different temperature-rise rates and nitrogen conditions in example 1, wherein (a) the test conditions of the graph are that the temperature-rise rate is 1.5 ℃/min at 25-150 ℃ and 50 ℃/min at 150-; (b) the temperature rise rate in the graph was 50 ℃/min, and the temperature rise rate in the graph (c) was 1.5 ℃/min. As can be seen from the graph (a), the base electrolyte had a mass loss (T) of 5 wt%5wt％) The temperature at (B) was 55.2 ℃ and the mass loss (T) at 50 wt.% was50wt％) The temperature was 244.4 ℃. T of gel electrolyte compared with base electrolyte5wt％、T50wt％The temperature was increased by 12.1 ℃ and 126 ℃ respectively. The process simulates the temperature rise rate of the battery in thermal runaway, the temperature rise rate is 1.5 ℃/min and 50 ℃/min, and the T of the gel electrolyte50wt％Is greatly increased compared with the electrolyte. When the temperature rise rate is 1.5 ℃/min, the residual carbon content of the basic electrolyte is 3.8%, compared with the residual carbon content of the gel electrolyte, the residual carbon content of the gel electrolyte is increased by 19.6%, and the residual carbon content is consistent with 80% of the mass of the electrolyte in the reaction ratio. As can be seen from FIG. 2, the prepared gel electrolyte still does not burn after encountering open fire, which shows that the gel electrolyte has remarkable flame retardant effect.
Example 2:
adding fluoroethylene carbonate with the volume content of 5% into ethylene carbonate and dimethyl carbonate according to the volume ratio of 1:1, then adding 1mol/L lithium hexafluorophosphate, and uniformly mixing to obtain the basic electrolyte. Triethylene glycol diacrylate with the mass content of 4% and allyl dimethyl phosphate with the mass content of 8% are added into the basic electrolyte, and then azobisisobutyronitrile with the mass content of 1% of the triethylene glycol diacrylate and the allyl dimethyl phosphate is added and stirred uniformly. Controlling the temperature to react for 30min at 40 ℃ to obtain the gel electrolyte.
Example 3:
adding fluoroethylene carbonate with the volume content of 5% into ethylene carbonate and dimethyl carbonate according to the volume ratio of 1:1, then adding 1mol/L lithium hexafluorophosphate, and uniformly mixing to obtain the basic electrolyte. Adding 5 mass percent of polyethylene glycol diacrylate and 15 mass percent of allyl dimethyl phosphate into the basic electrolyte, then adding 1 mass percent of azobisisobutyronitrile into the basic electrolyte, and stirring the mixture evenly. Controlling the temperature to react for 30min at 40 ℃ to obtain the gel electrolyte.
Example 4:
adding fluoroethylene carbonate with the volume content of 5% into ethylene carbonate and dimethyl carbonate according to the volume ratio of 1:1, then adding 1mol/L lithium hexafluorophosphate, and uniformly mixing to obtain the basic electrolyte. Triethylene glycol diacrylate with the mass content of 5% and trifluoromethyl alkenyl phosphonate with the mass content of 15% are added into the basic electrolyte, and then azodiisobutyronitrile with the mass content of 1% of the triethylene glycol diacrylate and the trifluoromethyl alkenyl phosphonate is added and stirred uniformly. Controlling the temperature to react for 30min at 40 ℃ to obtain the gel electrolyte.
Example 5:
adding fluoroethylene carbonate with the volume content of 5% into ethylene carbonate and dimethyl carbonate according to the volume ratio of 1:1, then adding 1mol/L lithium hexafluorophosphate, and uniformly mixing to obtain the basic electrolyte. Adding polyether polyacrylate with the mass content of 4% and allyl dimethyl phosphate with the mass content of 8% into the basic electrolyte, then adding azodiisobutyronitrile with the mass content of 1% of triethylene glycol diacrylate and allyl dimethyl phosphate, and stirring uniformly. Controlling the temperature to react for 30min at 40 ℃ to obtain the gel electrolyte.

Claims (8)

1. A preparation method of a flame-retardant lithium ion battery gel electrolyte is characterized by comprising the following steps:
step 1: adding lithium salt into an organic solvent at room temperature, and mechanically stirring until the lithium salt is completely dissolved;
step 2: mixing the lithium salt solution obtained in the step 1, a cross-linking agent, a polymerization monomer and an initiator into a polymerization reaction tube, vacuumizing, sealing, and fully shaking up;
and step 3: and (3) placing the polymerization reaction tube under a temperature control device, and initiating polymerization reaction at a certain temperature to obtain the chemical crosslinking type flame-retardant gel electrolyte.
2. The method of claim 1, wherein:
in the step 1, the lithium salt is one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium trifluoromethanesulfonate, lithium dioxalate borate, lithium difluorooxalate borate and lithium bistrifluoromethanesulfonylimide.
3. The method of claim 1, wherein:
in the step 1, the organic solvent is one or a mixture of more of propylene carbonate, ethylene carbonate, ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, acetonitrile or ether solution.
4. The method of claim 1, wherein:
in the step 2, the cross-linking agent is one or more of triethylene glycol diacrylate, triethylene glycol dimethacrylate, polyethylene glycol diacrylate, trihydroxy methyl propane trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, ethoxylated trimethylolpropane triacrylate and polyether polyacrylate.
5. The method of claim 1, wherein:
in the step 2, the polymerization monomer is one or more of allyl diethyl phosphate, vinyl diethyl phosphonate, allyl dimethyl phosphate, triallyl phosphate, propylene diphosphate and trifluoromethyl alkenyl phosphonate.
6. The method of claim 1, wherein:
in the step 2, the initiator is one of dibenzoyl peroxide, dilauroyl peroxide, tert-butyl peroxy-2-ethylhexanoate, azobisisobutyronitrile and azobisisoheptonitrile.
7. The production method according to any one of claims 1 to 6, characterized in that:
in the reaction system of the step 2, the mass percent of the organic solvent is 60-90%, the mass percent of the lithium salt is 5-20%, the mass percent of the cross-linking agent is 1-5%, the mass percent of the polymerization monomer is 2-40%, and the mass percent of the initiator is 0.1-1%.
8. The method of claim 1, wherein:
in the step 3, the polymerization reaction temperature is 40-90 ℃, and the reaction time is 20-100 min.
CN202110505387.6A 2021-05-10 2021-05-10 Preparation method of flame-retardant lithium ion battery gel electrolyte Pending CN113234195A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113717328A (en) * 2021-08-31 2021-11-30 蜂巢能源科技有限公司 Gel electrolyte composition and preparation method thereof, gel electrolyte and preparation method and application thereof
CN113851707A (en) * 2021-09-30 2021-12-28 蜂巢能源科技有限公司 Gel electrolyte, preparation method thereof and battery
WO2023028514A1 (en) * 2021-08-24 2023-03-02 Global Graphene Group, Inc. Flame-resistant hybrid inorganic-polymeric solid-state electrolytes and lithium batteries containing same

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103772607A (en) * 2014-01-26 2014-05-07 郑州大学 Phosphorus-containing crosslinked gel polymer electrolyte and on-site thermal-polymerization preparation method and application thereof
CN111253523A (en) * 2020-01-19 2020-06-09 四川大学 Non-combustible gel polymer electrolyte and preparation method and application thereof
CN112582670A (en) * 2020-12-01 2021-03-30 中国科学院化学研究所 Flame-retardant gel electrolyte membrane, preparation method thereof and application thereof in secondary battery

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103772607A (en) * 2014-01-26 2014-05-07 郑州大学 Phosphorus-containing crosslinked gel polymer electrolyte and on-site thermal-polymerization preparation method and application thereof
CN111253523A (en) * 2020-01-19 2020-06-09 四川大学 Non-combustible gel polymer electrolyte and preparation method and application thereof
CN112582670A (en) * 2020-12-01 2021-03-30 中国科学院化学研究所 Flame-retardant gel electrolyte membrane, preparation method thereof and application thereof in secondary battery

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023028514A1 (en) * 2021-08-24 2023-03-02 Global Graphene Group, Inc. Flame-resistant hybrid inorganic-polymeric solid-state electrolytes and lithium batteries containing same
CN113717328A (en) * 2021-08-31 2021-11-30 蜂巢能源科技有限公司 Gel electrolyte composition and preparation method thereof, gel electrolyte and preparation method and application thereof
CN113851707A (en) * 2021-09-30 2021-12-28 蜂巢能源科技有限公司 Gel electrolyte, preparation method thereof and battery

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