CN108341932B - Functional polymer, polymer electrolyte membrane, flame-retardant polymer electrolyte composite membrane, preparation method of flame-retardant polymer electrolyte composite membrane and lithium ion battery - Google Patents

Functional polymer, polymer electrolyte membrane, flame-retardant polymer electrolyte composite membrane, preparation method of flame-retardant polymer electrolyte composite membrane and lithium ion battery Download PDF

Info

Publication number
CN108341932B
CN108341932B CN201710051528.5A CN201710051528A CN108341932B CN 108341932 B CN108341932 B CN 108341932B CN 201710051528 A CN201710051528 A CN 201710051528A CN 108341932 B CN108341932 B CN 108341932B
Authority
CN
China
Prior art keywords
polymer electrolyte
flame
membrane
solution
retardant
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.)
Active
Application number
CN201710051528.5A
Other languages
Chinese (zh)
Other versions
CN108341932A (en
Inventor
侯红军
薛旭金
王永勤
杨华春
刘海霞
薛峰峰
李霞
郭贤慧
马广辉
杨明霞
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.)
Duofudo New Material Co.,Ltd.
Original Assignee
Duo Fluoride Chemicals Co Ltd
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 Duo Fluoride Chemicals Co Ltd filed Critical Duo Fluoride Chemicals Co Ltd
Priority to CN201710051528.5A priority Critical patent/CN108341932B/en
Publication of CN108341932A publication Critical patent/CN108341932A/en
Application granted granted Critical
Publication of CN108341932B publication Critical patent/CN108341932B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
    • C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
    • C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/12—Copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/142—Side-chains containing oxygen
    • C08G2261/1424—Side-chains containing oxygen containing ether groups, including alkoxy
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/142—Side-chains containing oxygen
    • C08G2261/1426—Side-chains containing oxygen containing carboxy groups (COOH) and/or -C(=O)O-moieties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/147—Side-chains with other heteroatoms in the side-chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
    • C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
    • C08G2261/3324—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms derived from norbornene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/40—Polymerisation processes
    • C08G2261/41—Organometallic coupling reactions
    • C08G2261/418—Ring opening metathesis polymerisation [ROMP]
    • 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
    • H01M2300/0088—Composites
    • H01M2300/0094—Composites in the form of layered products, e.g. coatings
    • 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

Landscapes

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

Abstract

The invention relates to a functional polymer, a polymer electrolyte membrane, a flame-retardant polymer electrolyte composite membrane, a preparation method of the flame-retardant polymer electrolyte composite membrane and a lithium ion battery, and belongs to the technical field of lithium ion batteries. The functional polymer comprises a polymer chain formed by structural units, wherein a 1-position or a 2-position of the structural units of the polymer chain is connected with a flame retardant group and a lithium ion conducting group, and the molar ratio of the flame retardant group to the lithium ion conducting group is 1 (2-4). The flame-retardant group in the invention ensures that the functional polymer has good flame-retardant function, and the lithium ion conducting group ensures that Li+Can be transferred in functional polymer at a high speed. The flame-retardant polymer electrolyte composite membrane has the advantages of high conductivity, strong flame retardant property and the like, and has potential application value in the field of lithium ion batteries.

Description

Functional polymer, polymer electrolyte membrane, flame-retardant polymer electrolyte composite membrane, preparation method of flame-retardant polymer electrolyte composite membrane and lithium ion battery
Technical Field
The invention relates to a functional polymer, a polymer electrolyte membrane, a flame-retardant polymer electrolyte composite membrane, a preparation method of the flame-retardant polymer electrolyte composite membrane and a lithium ion battery, and belongs to the technical field of lithium ion batteries.
Background
Compared with other secondary batteries, lithium ion batteries have the characteristics of high energy density, high output voltage, high output power, small self-discharge effect, environmental friendliness, wide working temperature, no memory and the like, are industrialized by the company sony japan since 1991, and are widely applied to portable electronic devices such as mobile phones and notebook computers. Moreover, the lithium ion battery has a good application prospect in hybrid electric vehicles, plug-in hybrid electric vehicles and pure electric vehicles as a power battery.
In the prior art, the electrolyte generally used is an organic electrolyte (LiPF)6Dissolved in organic carbonate), PP/PE (polypropylene/polyethylene) microporous membrane with poor flame retardance is adopted as a diaphragm, and the battery is very easy to catch fire under the conditions of abuse, micro short circuit or overheating inside the battery, thereby causing accidents. The existing solid lithium ion electrolyte generally has the problem of low conductivity, and the flame retardant effect is very common. Therefore, the existing electrolyte, whether in liquid or solid state, has certain defects.
Chinese patent application publication No. CN103199301A discloses a composite gel polymer electrolyte, which is composed of a composite electrolyte membrane and a liquid electrolyte, wherein the composite electrolyte membrane is composed of two or more layers, at least one layer is a solid polymer electrolyte, and at least one layer is a polymer material different from the solid polymer electrolyte.
Chinese patent application publication No. CN102117938A discloses a polymer electrolyte membrane, which comprises a polymer containing a long chain of silicon-oxygen bonds and silicon oxide, wherein the polymer containing a long chain of silicon-oxygen bonds and the silicon oxide are products of a reaction of a polymer matrix and silicate in an organic solution with a pH value of 6.5-8.0, and the polymer matrix is selected from polyvinylidene fluoride-hexafluoropropylene and the like. The polymer electrolyte membrane has the advantages of strong liquid absorption, strong ionic conductivity, small internal resistance and the like, but the polymer electrolyte membrane still needs to use a plasticizer which is easy to burn, so that the polymer electrolyte membrane has the risk of fire and explosion.
Disclosure of Invention
The invention aims to provide a functional polymer with good flame retardant property.
It is another object of the present invention to provide a polymer electrolyte membrane comprising the above functional polymer.
Another object of the present invention is to provide a flame retardant polymer electrolyte composite membrane.
Another object of the present invention is to provide a method for preparing the above flame retardant polymer electrolyte composite membrane.
Another object of the present invention is to provide a lithium ion battery using the above flame retardant polymer electrolyte composite membrane.
In order to achieve the above object, the functional polymer of the present invention has the following technical scheme:
a functional polymer comprises a polymer chain formed by structural units shown as a formula 1, wherein a 1-position or a 2-position of the structural units of the polymer chain is connected with a flame retardant group and a lithium ion conducting group, and the molar ratio of the flame retardant group to the lithium ion conducting group is 1 (2-4);
Figure BDA0001217928870000021
wherein X in the formula 1 is an integer of 30-600;
the flame-retardant group has a structure shown in a formula 2,
Figure BDA0001217928870000022
in formula 2, R ═ CaH2a+1Wherein the value of a is an integer of 1-3;
the lithium ion conducting group has a structure as shown in formula 3,
Figure BDA0001217928870000031
in the formula 3, m is an integer of 7-16.
The number average molecular weight of the functional polymer is 8000-500000 g/mol.
The two ends of the polymer chain are connected with end capping groups, and the end capping groups are CH2Or CHPh.
The technical scheme of the polymer electrolyte membrane is as follows:
a polymer electrolyte membrane comprises the functional polymer and lithium salt.
The molar ratio of lithium in the polymer electrolyte membrane to the ethylene oxide repeating units in the functional polymer is 1: (4-25).
The technical scheme of the flame-retardant polymer electrolyte composite membrane comprises the following steps:
the flame-retardant polymer electrolyte composite membrane comprises the polymer electrolyte membrane and a matrix membrane compounded on the surface of the polymer electrolyte membrane.
The technical scheme of the preparation method of the flame-retardant polymer electrolyte composite membrane comprises the following steps:
a preparation method of a flame-retardant polymer electrolyte composite membrane comprises the following steps:
1) performing ring-opening displacement polymerization reaction on norbornene phosphate and norbornene polyethylene glycol monomethyl ether to prepare a functional polymer;
the structure of the norbornene phosphate is shown as formula 4:
Figure BDA0001217928870000032
wherein R ═ CaH2a+1A is an integer of 1 to 3;
the structure of the norbornene polyethylene glycol monomethyl ether is shown as a formula 5:
Figure BDA0001217928870000041
wherein m is an integer of 7 to 16;
2) uniformly mixing the functional polymer obtained in the step 1) and lithium salt in an organic solvent, and then casting to form a film to obtain a polymer electrolyte film;
3) compounding the polymer electrolyte membrane prepared in the step 2) with a matrix membrane to obtain the composite membrane.
The functional polymer and the lithium salt obtained in the step 2) are uniformly mixed in the organic solvent by adopting an ultrasonic mode. The ultrasonic frequency is 50-200 MHz. The ultrasonic time is 0.5-2 h.
The casting film in the step 2) is cast in a mould and dried to form a film.
The die used for casting and forming the film in the step 2) is a polytetrafluoroethylene die.
The drying film forming is drying film forming under the condition of negative pressure. The drying temperature is 70-80 ℃. The drying time is 24-30 h. The vacuum degree is-0.09 MPa to-0.1 MPa.
The organic solvent in the step 2) is an organic solvent with relatively high polarity, such as nitrogen-nitrogen dimethylformamide or acetonitrile. The use amount of the solvent can be used for completely dissolving the functional polymer and the lithium salt.
The lithium salt in the step 2) is lithium tetrafluoroborate or lithium bistrifluoromethylsulfonyl imide.
The molar ratio of lithium in the polymer electrolyte membrane to the ethylene oxide repeating units in the functional polymer in the above step 2) is 1: (4-25).
The preparation method of the flame-retardant polymer electrolyte composite membrane in the step 3) comprises the following steps:
soaking the surface of the matrix membrane and/or the polymer electrolyte membrane with ethanol water solution, then attaching the matrix membrane and the polymer electrolyte membrane to obtain a wet membrane, clamping the wet membrane between two flat plates, applying pressure of 0.01 MPa-0.03 MPa, and drying.
The drying is carried out for 20-30 h at the temperature of 60-80 ℃.
The flat plate is a polytetrafluoroethylene plate.
The preparation method of the flame-retardant polymer electrolyte composite membrane in the step 3) is preferably:
the matrix membrane was laid flat on a clean teflon plate, the surface was wetted with an aqueous ethanol solution (1/1, V/V), the prepared polymer electrolyte membrane was laid flat on the matrix membrane, the surface was also wetted with an aqueous ethanol solution, and another layer of matrix membrane was laid thereon. And after the operation is finished, clamping the prepared wet membrane between two clean polytetrafluoroethylene plates, applying a pressure of 0.01-0.03 MPa, and drying at the temperature of 60-80 ℃ for 20-30 h to obtain the composite flame-retardant polymer electrolyte membrane. The thickness of the film is 60 to 80 μm.
The substrate film used in the step 3) is a polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) film.
In the preparation method of the flame-retardant polymer electrolyte composite membrane, the ring-opening shift polymerization reaction in the step 1) comprises the following steps:
dissolving norbornene phosphate and norbornene polyethylene glycol monomethyl ether in an organic solvent to obtain a solution 1; dissolving Grubbs second generation initiator in organic solvent to obtain solution 2; and adding the solution 1 into the solution 2, reacting for 2-6 h, adding a terminator, stopping the reaction, and removing the organic solvent. And (4) continuing the reaction for 20-40 min after adding the terminator. Preferably 30 min.
All the operations in the above ring-opening metathesis polymerization are preferably carried out in a nitrogen or argon glove box.
The operating environment temperature in the ring-opening shift polymerization reaction is 20-30 ℃, and preferably 25 ℃.
The organic solvent in the ring-opening shift polymerization reaction is dichloromethane or toluene.
The molar ratio of the norbornene phosphate to the norbornene polyethylene glycol monomethyl ether in the ring-opening shift polymerization reaction is 1 (2-4).
In the ring-opening displacement polymerization reaction, the norbornene phosphate and the norbornene polyethylene glycol monomethyl ether are dissolved in an organic solvent, and the sum of the molar concentrations of the norbornene phosphate and the norbornene polyethylene glycol monomethyl ether is 0.001-0.1 mol/L. Preferably 0.04 mol/L.
And adding norbornene phosphate and norbornene polyethylene glycol monomethyl ether into an organic solvent in the ring-opening shift polymerization reaction, and stirring for 10-60 min to obtain a solution 1. The preferred stirring time is 15 min.
In the ring-opening displacement polymerization reaction, Grubbs second-generation initiator is dissolved in organic solvent, and the molar concentration of the Grubbs second-generation initiator is 0.0005 mol/L-0.01 mol/L. Preferably 0.005 mol/L.
In the ring-opening shift polymerization reaction, Grubbs second-generation initiator is dissolved in organic solvent and stirred for 10-60 min. Preferably for 15 min.
When the solution 1 is added to the solution 2 in the ring-opening metathesis polymerization reaction, the addition should be completed in as short a time as possible.
And (3) adding the solution 1 into the solution 2 in the ring-opening shift polymerization reaction, and stirring at room temperature for 2-6 h. Preferably for 2 hours.
After the terminating agent is added into the preparation method of the functional polymer in the ring-opening shift polymerization reaction, the continuous reaction time is 20-40 min. Preferably 30 min.
The terminator in the ring-opening displacement polymerization reaction is preferably vinyl ethyl ether, and the molar ratio of the vinyl ethyl ether to the Grubbs second generation initiator is 800: 1. the reaction was continued while stirring.
In the above method for producing a functional polymer in ring-opening metathesis polymerization, after the reaction is stopped, the organic solvent is removed under a negative pressure. The conditions for removing the organic solvent were: the temperature is 30-60 ℃, the time is 15-30 h, and the vacuum degree is-0.03 to-0.07 MPa.
In the preparation method of the flame-retardant polymer electrolyte composite membrane, the ring-opening shift polymerization reaction in the step 1) comprises the following steps:
dissolving norbornene phosphate in an organic solvent to obtain a solution A; dissolving norbornene polyethylene glycol monomethyl ether in an organic solvent to obtain a solution B; dissolving Grubbs second generation initiator in organic solvent to obtain solution C; adding the solution A into the solution C to react for 2-6 hours to obtain a mixed solution, then adding the solution B into the mixed solution to react for 2-6 hours, then adding a terminator, stopping the reaction, and removing the organic solvent.
All the operations in the above ring-opening metathesis polymerization are preferably carried out in a nitrogen or argon glove box. The operating environment temperature of the glove box is 20-30 ℃. Preferably 25 deg.c.
The organic solvent in the ring-opening shift polymerization reaction is dichloromethane or toluene.
The molar ratio of the norbornene phosphate to the norbornene polyethylene glycol monomethyl ether in the ring-opening shift polymerization reaction is 1 (2-4).
In the ring-opening displacement polymerization reaction, norbornene phosphate and norbornene polyethylene glycol monomethyl ether are respectively dissolved in an organic solvent by stirring to form a solution A, B, wherein the molar concentration of the solution A is 0.001-0.1 mol/L. The molar concentration of the solution B is 0.001-0.1 mol/L. The molar concentration of the solution A is preferably 0.1 mol/L. The molar concentration of the solution B is preferably 0.03 mol/L. The stirring time is 10-60 min. Preferably 30 min.
In the ring-opening shift polymerization reaction, the Grubbs second-generation initiator is dissolved in an organic solvent by stirring, and the molar concentration of the Grubbs second-generation initiator is 0.0005-0.05 mol/L. Preferably 0.01 mol/L. And the stirring time is 10-60 min when the initiator is dissolved in the organic solvent. Preferably 30 min.
And adding the solution A into the solution C in the ring-opening shift polymerization reaction, and stirring for reaction for 2-6 h. Preferably 3 hours.
And adding the solution B into the ring-opening shift polymerization reaction, and stirring for reaction for 2-6 h. Preferably 4 hours.
The terminator in the ring-opening displacement polymerization reaction is preferably vinyl ethyl ether, and the molar ratio of the vinyl ethyl ether to the Grubbs second generation initiator is 800: 1. the reaction was continued while stirring.
And after adding a terminator into the ring-opening shift polymerization reaction, continuously reacting for 20-40 min. Preferably 20 min.
In the ring-opening displacement polymerization reaction, the organic solvent is removed under a negative pressure after the reaction is stopped. The conditions for removing the organic solvent were: the temperature is 30-60 ℃, the time is 15-30 h, and the vacuum degree is-0.03 to-0.07 MPa.
The technical scheme of the lithium ion battery is as follows:
a lithium ion battery comprises an electrolyte membrane, wherein the electrolyte membrane is the flame-retardant polymer electrolyte composite membrane.
The invention has the beneficial effects that:
the invention provides a functional polymer, which comprises a polymer chain formed by structural units, wherein the No. 1 or No. 2 position of the structural units of the polymer chain is connected with a flame retardant group and a lithium ion conducting group, the flame retardant group ensures that the functional polymer has a good flame retardant function, and the lithium ion conducting group ensures that Li is contained in the functional polymer+Can be transferred in functional polymer at a high speed.
The flame-retardant polymer electrolyte composite membrane provided by the invention comprises a polymer electrolyte membrane and a matrix membrane compounded on the surface of the polymer electrolyte membrane, wherein the polymer electrolyte membrane comprises the functional polymer. The flame-retardant polymer electrolyte composite membrane consists of a matrix membrane polyvinylidene fluoride-hexafluoropropylene membrane (PVDF-HTP) and a polymer electrolyte membrane which can transmit lithium ions and has flame retardant property.
Matrix film PVDF-HFP used in the present invention: PVDF is a partially crystallized fluorine-containing functional material, and has high mechanical strength, good heat resistance, good mechanical properties, chemical corrosion resistance, ultraviolet resistance and aging resistance. While amorphous HFP can reduce the crystallinity of the polymer and increase the conductivity of the polymer. PVDF-HFP combines the properties of the two polymers, so that the prepared flame-retardant polymer electrolyte composite membrane has good conductivity and mechanical properties.
The flame-retardant polymer electrolyte composite membrane of the invention is introduced with Ethylene Oxide (EO) groups, the oxygen on the chain segment has lone pair electrons, and Li+There is a 2s empty orbital that can form a coordination structure with the oxygen on the PEO chain. Migrating Li+The process of 'complexation-decomplexing-recompounding' is continuously carried out with oxygen to realize Li+And (4) fast migration.
The flame-retardant polymer electrolyte composite membrane of the invention is introduced with phosphate groups, and the phosphorus groups have good flame-retardant property: (1) when the phosphorus-containing high polymer is heated or combusted, the phosphorus-containing flame retardant in the system can be decomposed to generate oxyacid of phosphorus, so that a stable polymer is formed, a diaphragm is formed on the surface of a base material, and the combustion-supporting gas is prevented from contacting with combustible materials; (2) the oxyacids of phosphorus are capable of undergoing an endothermic dehydration carbonization reaction with the hydroxyl compounds to produce a significant amount of coke that coats the polymer surface and prevents further combustion of the polymer. Moreover, the dehydration reaction requires the absorption of a large amount of heat, which can retard the combustion rate.
The flame-retardant polymer electrolyte composite membrane has the advantages that: 1. functional polymers with flame-retardant functional structures are introduced into the flame-retardant polymer electrolyte composite membrane, so that the flame-retardant performance of the flame-retardant polymer electrolyte composite membrane is improved; 2. ethylene oxide groups are introduced into the flame-retardant polymer electrolyte composite membrane, and the flame-retardant polymer electrolyte composite membrane has good conductivity by utilizing the complexation-decomplexing-recompplexing action of lithium and oxygen; 3. the PVDF-HTP is used as the matrix membrane of the flame-retardant polymer electrolyte composite membrane, so that the flame-retardant polymer electrolyte composite membrane has excellent mechanical properties.
Drawings
Fig. 1 is an SEM image of the surface of a flame retardant polymer electrolyte composite membrane obtained in example 1;
fig. 2 is an SEM image of a cross section of the flame retardant polymer electrolyte composite membrane obtained in example 1.
Detailed Description
The following is a detailed description of the present invention, but not limited to the following, illustrating the preparation of the flame retardant polymer electrolyte composite membrane according to the present invention and the results of the performance test of the flame retardant polymer electrolyte composite membrane.
Example 1
The functional polymer in the embodiment comprises a polymer chain formed by structural units shown as a formula 1, wherein the No. 1 position of the structural unit on one part of chain segment of the polymer chain is connected with a flame retardant group, the No. 2 position of the structural unit on the other part of chain segment is connected with a lithium ion conducting group, the No. 2 position of the structural unit on part of chain segment is connected with a flame retardant group, and the No. 1 position of the structural unit on one part of chain segment is connected with a lithium ion conducting group; wherein the molar ratio of the flame-retardant group to the lithium ion conducting group is 1:4, the flame-retardant group has a structure shown as a formula 2, and the chemical formula of R is CH3(ii) a The lithium ion conducting group has a structure as shown in formula 3, wherein m ═ 10. The two ends of the polymer chain are connected with end-capping groups, one end of which is CH2And the other end capping group is CHPh. The number average molecular weight of the functional polymer in this example was 45761 g/mol.
The polymer electrolyte membrane of the present example includes the above functional polymer and a lithium salt uniformly mixed together, the lithium salt is lithium bistrifluoromethylsulfonyl imide, and the molar ratio of lithium in the polymer electrolyte membrane to ethylene oxide repeat units in the functional polymer is 1: 4.
the flame-retardant polymer electrolyte composite membrane of the embodiment comprises a layer of the polymer electrolyte membrane and two layers of substrate membranes which are respectively compounded on the upper surface and the lower surface of the polymer electrolyte membrane. The substrate film is a polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) film.
The preparation method of the flame-retardant polymer electrolyte composite membrane of the embodiment comprises the following steps:
the norbornene phosphate of this example has the structure shown in formula 4, wherein a ═ 1; the norbornene polyethylene glycol monomethyl ether of this example has a structure as shown in formula 5, where m ═ 10.
1) Dissolving 0.002mol of norbornene phosphate and 0.008mol of norbornene polyethylene glycol monomethyl ether in 150ml of dichloromethane in a nitrogen glove box at the temperature of 25 ℃, stirring for 15min to form a solution 1, dissolving 0.067mmol of Grubbs second generation initiator in 13ml of dichloromethane, and stirring for 15min to obtain a solution 2; rapidly adding the solution 1 into the solution 2, stirring and reacting for 2 hours at room temperature, adding 0.0536mol of vinyl ether terminator, continuously stirring and reacting for 30 minutes, and stopping reaction; drying the obtained solution for 15h at the temperature of 30 ℃ and the pressure of-0.07 MPa, and removing the organic solvent to obtain a functional polymer;
2) dissolving the functional polymer obtained in the step 1) and lithium bis (trifluoromethyl) sulfimide in N-dimethyl formamide, completely dissolving, performing ultrasonic treatment at 200MHz for 1h, uniformly mixing, casting the solution in a polytetrafluoroethylene mold, drying at 80 ℃ under-0.095 MPa for 30h, and demolding to obtain a polymer electrolyte membrane; the molar ratio of lithium in the polymer electrolyte membrane to ethylene oxide repeat units in the functional polymer is 1: 4;
3) and paving a polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) film serving as a matrix film on a clean polytetrafluoroethylene plate, soaking the surface of the matrix film by using an ethanol water solution (1/1, V/V), paving the prepared polymer electrolyte film on the matrix film, wetting the surface of the matrix film by using the ethanol water solution, and covering the other layer of PVDF-HTP film on the matrix film to obtain the interlayer composite wet film. Then clamping the prepared composite wet membrane between two clean polytetrafluoroethylene plates, applying a pressure of 0.01MPa, and drying for 20 hours at the temperature of 80 ℃ to obtain the flame-retardant polymer electrolyte composite membrane; the thickness of the film was 80 μm.
The lithium ion battery in the embodiment comprises a positive plate, a negative plate and the flame-retardant polymer electrolyte composite membrane arranged between the positive plate and the negative plate.
As can be seen from the SEM images of fig. 1 and 2, the interior of the prepared flame retardant polymer electrolyte composite membrane is an ordered network structure, which not only provides a favorable channel for the transmission of lithium ions, but also ensures the mechanical strength of the membrane as a whole. Meanwhile, the lithium ion has small radius, so that the lithium ion can be transferred in the middle compact layer, and other active substances in the anode and cathode materials cannot pass through the middle layer due to large ion radius, so that the internal micro short circuit of the battery is avoided.
The performance test shows that the ionic conductivity of the flame-retardant polymer electrolyte composite membrane in example 1 can reach 1.24ms/cm, the mechanical strength can reach 13.7MPa, and the oxygen index is 34.
Example 2
The functional polymer in the embodiment comprises a polymer chain formed by structural units shown as a formula 1, wherein the No. 1 position of the structural unit on one part of chain segment of the polymer chain is connected with a flame retardant group, the No. 2 position of the structural unit on the other part of chain segment is connected with a lithium ion conducting group, the No. 2 position of the structural unit on part of chain segment is connected with a flame retardant group, and the No. 1 position of the structural unit on one part of chain segment is connected with a lithium ion conducting group; wherein the molar ratio of the flame-retardant group to the lithium ion conducting group is 1:2, the flame-retardant group has a structure shown as a formula 2, and the chemical formula of R is C2H5(ii) a The lithium ion conducting group has a structure as shown in formula 3, wherein m ═ 7. The two ends of the polymer chain are connected with end-capping groups, one end of which is CH2And the other end capping group is CHPh. The number average molecular weight of the functional polymer in this example was 134520 g/mol.
The polymer electrolyte membrane of the present example includes the above functional polymer and a lithium salt uniformly mixed together, the lithium salt is lithium bistrifluoromethylsulfonyl imide, and the molar ratio of lithium in the polymer electrolyte membrane to ethylene oxide repeat units in the functional polymer is 1: 25.
the flame-retardant polymer electrolyte composite membrane of the embodiment comprises a layer of the polymer electrolyte membrane and two layers of substrate membranes which are respectively compounded on the upper surface and the lower surface of the polymer electrolyte membrane. The substrate film is a polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) film.
The preparation method of the flame-retardant polymer electrolyte composite membrane of the embodiment comprises the following steps:
the norbornene phosphate of this example has the structure shown in formula 4, wherein a ═ 2; the norbornene polyethylene glycol monomethyl ether of this example has a structure as shown in formula 5, where m ═ 7.
1) Dissolving 0.002mol of norbornene phosphate and 0.004mol of norbornene polyethylene glycol monomethyl ether in 150ml of dichloromethane in an argon glove box at the temperature of 25 ℃, stirring for 60min to form a solution 1, dissolving 0.01mmol of Grubbs second generation initiator in 13ml of dichloromethane, and stirring for 60min to obtain a solution 2; and (3) quickly adding the solution 1 into the solution 2, stirring and reacting for 6 hours at room temperature, adding 0.008mol of vinyl ether terminator, continuously stirring and reacting for 40 minutes, and stopping the reaction. Drying the obtained solution for 30h at the temperature of 60 ℃ and the pressure of-0.03 MPa, and removing the organic solvent to obtain a functional polymer;
2) dissolving the functional polymer obtained in the step 1) and lithium bis (trifluoromethyl) sulfimide in N-dimethyl formamide, performing ultrasonic treatment at 50MHz for 2h to completely dissolve, uniformly mixing, casting the solution in a polytetrafluoroethylene mold, and drying at 80 ℃ and under the vacuum degree of-0.09 MPa for 30h to obtain a polymer electrolyte membrane; the molar ratio of lithium in the polymer electrolyte membrane to ethylene oxide repeat units in the functional polymer is 1: 25;
3) and flatly paving the PVDF-HTP as a matrix film on a clean polytetrafluoroethylene plate, soaking the surface of the PVDF-HTP as the matrix film by using an ethanol water solution (1/1, V/V), flatly paving the prepared polymer electrolyte film on the matrix film, also wetting the surface of the prepared polymer electrolyte film by using the ethanol water solution, and covering another layer of PVDF-HTP film on the prepared polymer electrolyte film to obtain the interlayer composite wet film. And after the operation is finished, clamping the prepared interlayer composite wet film between two clean polytetrafluoroethylene plates, applying a pressure of 0.02MPa, and drying at 80 ℃ for 23 hours to obtain the flame-retardant polymer electrolyte composite film. The thickness of the film was 60 μm.
The lithium ion battery in the embodiment comprises a positive plate, a negative plate and the flame-retardant polymer electrolyte composite membrane arranged between the positive plate and the negative plate.
Through the test, the ionic conductivity of the flame-retardant polymer electrolyte composite membrane in the embodiment 2 can reach 1.75ms/cm, the mechanical strength can reach 11.6MPa, and the oxygen index is 45.
Example 3
The functional polymer in the embodiment comprises a polymer chain formed by structural units shown as a formula 1, wherein the No. 1 position of the structural unit on one part of chain segment of the polymer chain is connected with a flame retardant group, the No. 2 position of the structural unit on the other part of chain segment is connected with a lithium ion conducting group, the No. 2 position of the structural unit on part of chain segment is connected with a flame retardant group, and the No. 1 position of the structural unit on one part of chain segment is connected with a lithium ion conducting group; wherein the molar ratio of the flame-retardant group to the lithium ion conducting group is 1:3.5, the flame-retardant group has a structure shown as a formula 2, and the chemical formula of R is C3H7(ii) a The lithium ion conducting group has a structure as shown in formula 3, wherein m ═ 16. The two ends of the polymer chain are connected with end-capping groups, one end of which is CH2And the other end capping group is CHPh. The number average molecular weight of the functional polymer in this example was 296307 g/mol.
The polymer electrolyte membrane of the present example includes the above functional polymer and a lithium salt uniformly mixed together, the lithium salt is lithium bistrifluoromethylsulfonyl imide, and the molar ratio of lithium in the polymer electrolyte membrane to ethylene oxide repeat units in the functional polymer is 1: 10.
the flame-retardant polymer electrolyte composite membrane of the embodiment comprises a layer of the polymer electrolyte membrane and two layers of substrate membranes which are respectively compounded on the upper surface and the lower surface of the polymer electrolyte membrane. The substrate film is a polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) film.
The preparation method of the flame-retardant polymer electrolyte composite membrane of the embodiment comprises the following steps:
the norbornene phosphate of this example has the structure shown in formula 4, wherein a ═ 3; the norbornene polyethylene glycol monomethyl ether of this example has a structure as shown in formula 5, where m ═ 16.
1) Dissolving 0.002mol of norbornene phosphate in 20ml of toluene at the temperature of 30 ℃ in a nitrogen glove box, stirring for 40min to obtain a solution A, dissolving 0.007mol of norbornene polyethylene glycol monomethyl ether in 200ml of toluene, stirring for 40min to form a solution B, dissolving 0.013mmol of Grubbs second generation initiator in 10ml of toluene, and stirring for 30min to obtain a solution C; and (3) quickly adding the solution A into the solution C, stirring and reacting for 2 hours to obtain a mixed solution, quickly adding the solution B into the mixed solution, stirring and reacting for 3 hours, adding 0.0104mol of vinyl ethyl ether terminator, continuously stirring and reacting for 20 minutes, and stopping the reaction. Drying the obtained solution for 25h at 50 ℃ and-0.05 MPa, and removing the organic solvent to obtain a functional polymer;
2) dissolving the functional polymer obtained in the step 1) and lithium tetrafluoroborate in N-dimethylformamide, performing ultrasonic treatment at 150MHz for 1h to completely dissolve the functional polymer and the lithium tetrafluoroborate, uniformly mixing the functional polymer and the lithium tetrafluoroborate, casting the solution in a polytetrafluoroethylene mold, and drying the solution for 28h at the temperature of 70 ℃ and under the pressure of-0.1 MPa to obtain a polymer electrolyte membrane; the molar ratio of lithium in the polymer electrolyte membrane to ethylene oxide repeat units in the functional polymer is 1: 10;
3) and flatly paving the PVDF-HTP as a matrix film on a clean polytetrafluoroethylene plate, soaking the surface of the PVDF-HTP as the matrix film by using an ethanol water solution (1/1, V/V), flatly paving the prepared polymer electrolyte film on the matrix film, also wetting the surface of the prepared polymer electrolyte film by using the ethanol water solution, and covering another layer of PVDF-HTP film on the prepared polymer electrolyte film to obtain the interlayer composite wet film. And after the operation is finished, clamping the prepared interlayer composite wet film between two clean polytetrafluoroethylene plates, applying a pressure of 0.01MPa, and drying at 60 ℃ for 28h to obtain the flame-retardant polymer electrolyte composite film. The thickness of the film was 73 μm.
The lithium ion battery in the embodiment comprises a positive plate, a negative plate and the flame-retardant polymer electrolyte composite membrane arranged between the positive plate and the negative plate.
Through the test, the conductivity of the flame-retardant polymer electrolyte composite membrane in the example 3 is 2.43ms/cm, the mechanical strength can reach 13.0MPa, and the oxygen index is 37.
Example 4
The functional polymer in this embodiment includes a polymer chain composed of structural units represented by the following formula 1, and the 1-position of the structural unit in a part of the chain segment of the polymer chain is connected toThe flame retardant group is connected, the No. 2 position of the structural unit on the other part of chain segment is connected with a lithium ion conducting group, the No. 2 position of the structural unit on the other part of chain segment is connected with the flame retardant group, and the No. 1 position of the structural unit on the other part of chain segment is connected with the lithium ion conducting group; wherein the molar ratio of the flame-retardant group to the lithium ion conducting group is 1:3, the flame-retardant group has a structure shown as a formula 2, and the chemical formula of R is CH3Wherein a is 1; the lithium ion conducting group has a structure as shown in formula 3, wherein m ═ 15. The two ends of the polymer chain are connected with end-capping groups, one end of which is CH2And the other end capping group is CHPh. The number average molecular weight of the functional polymer in this example was 157380 g/mol.
The polymer electrolyte membrane of the present example includes the above functional polymer and a lithium salt uniformly mixed together, the lithium salt is lithium bistrifluoromethylsulfonyl imide, and the molar ratio of lithium in the polymer electrolyte membrane to ethylene oxide repeat units in the functional polymer is 1: 14.
the flame-retardant polymer electrolyte composite membrane of the embodiment comprises a layer of the polymer electrolyte membrane and two layers of substrate membranes which are respectively compounded on the upper surface and the lower surface of the polymer electrolyte membrane. The substrate film is a polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) film.
The preparation method of the flame-retardant polymer electrolyte composite membrane of the embodiment comprises the following steps:
the norbornene phosphate of this example has the structure shown in formula 4, wherein a ═ 1; the norbornene polyethylene glycol monomethyl ether of this example has a structure as shown in formula 5, where m ═ 15.
1) Dissolving 0.002mol of norbornene phosphate in 20ml of toluene in an argon glove box at the temperature of 20 ℃, stirring for 30min to form a solution A, dissolving 0.006mol of norbornene polyethylene glycol monomethyl ether in 200ml of toluene, stirring for 30min to form a solution B, dissolving 0.02mmol of Grubbs second generation initiator in 2ml of toluene, and stirring for 30min to obtain a solution C; and (3) quickly adding the solution A into the solution C, stirring and reacting for 3 hours to obtain a mixed solution, quickly adding the solution B into the mixed solution, stirring and reacting for 4 hours, adding 0.016mol of vinyl ethyl ether terminator, continuously stirring and reacting for 20 minutes, and stopping the reaction. Drying the obtained solution at 40 ℃ and-0.04 MPa for 20h, and removing the organic solvent to obtain a functional polymer;
2) dissolving the functional polymer obtained in the step 1) and lithium bis (trifluoromethyl) sulfimide in N-dimethyl formamide, performing ultrasonic treatment at 120MHz for 2h to completely dissolve the functional polymer and the lithium bis (trifluoromethyl) sulfimide, uniformly mixing the functional polymer and the lithium bis (trifluoromethyl) sulfimide, and then casting the solution in a polytetrafluoroethylene mold, and drying the solution for 26h at a vacuum degree of-0.09 MPa and a drying temperature of 75 ℃ to obtain a polymer electrolyte membrane; the molar ratio of lithium in the polymer electrolyte membrane to ethylene oxide repeat units in the functional polymer is 1: 14;
3) and spreading PVDF-HTP as a matrix film on a clean polytetrafluoroethylene plate, soaking the surface of the matrix film by using an ethanol aqueous solution (1/1, V/V), spreading the prepared polymer electrolyte film on the matrix film, wetting the surface of the matrix film by using the ethanol aqueous solution, and covering another layer of PVDF-HTP film on the matrix film to obtain the interlayer composite wet film. And after the operation is finished, clamping the prepared interlayer composite wet film between two clean polytetrafluoroethylene plates, applying pressure of 0.015Mpa, and drying for 25 hours at the temperature of 75 ℃ to obtain the flame-retardant polymer electrolyte composite film. The thickness of the film was 66 μm.
The lithium ion battery in the embodiment comprises a positive plate, a negative plate and the flame-retardant polymer electrolyte composite membrane arranged between the positive plate and the negative plate.
Through the test, the mechanical strength of the flame-retardant polymer electrolyte composite membrane in the embodiment 4 can reach 12.6MPa, the conductivity is 2.96ms/cm, and the oxygen index is 40.
Test examples
The performance test method of the flame-retardant polymer electrolyte composite membrane comprises the following steps:
(1) testing of conductivity: cutting the polymer electrolyte membrane into circular sheets in a glove box, assembling the circular sheets into a SS/polymer electrolyte membrane/SS symmetrical battery by taking a stainless Steel Sheet (SS) as a working electrode and a reference electrode, and carrying out alternating current impedance on the SS/polymer electrolyte membrane/SS symmetrical battery by adopting an electrochemical comprehensive tester (PARSTAT 2273, Princeton applied research, USA)Tests were performed to analyze the resistance of the electrolyte. The test frequency range is 0.01-106Hz, and the bias voltage is 10 mV. And analyzing the Nyquist map to obtain an electrolyte bulk resistance (Rb) value, and calculating according to a formula (1) to obtain a conductivity value of the electrolyte.
Figure BDA0001217928870000141
Wherein: l-thickness of the film (cm), σ -conductivity (S/cm), S-area of the stainless Steel electrode (cm)2)，Rb-body resistance (Ω).
(2) And (3) testing mechanical properties: and (3) testing the tensile property of the polymer electrolyte membrane by adopting Shimadzu AG-50kN under the following test conditions: the test temperature was 25 ℃, the test rate was 1N/min, the sample width was 8mm, and the sample length was 60 mm.
(3) And (3) testing the flame retardant property: according to the national standard GB 5454-85, an HC-1 type oxygen index tester is used for measuring the oxygen index of a sample, wherein the oxygen index is less than 22 and belongs to a combustible material, the oxygen index is between 22 and 27 and belongs to a combustible material, and the oxygen index is more than 27 and belongs to a flame-retardant material. Testing parameters: 70mm long, 6mm wide and 3.2mm thick.
(4) The charge and discharge performance is as follows: the polymer electrolyte membranes prepared in examples 1 to 4 were assembled into LiFePO4Li is charged, the charging and discharging performance is tested at 80 ℃, and the discharge multiplying power is tested to be 0.2C. And (3) testing the application value of the prepared polymer electrolyte membrane in a complete battery system.
The test data are listed in table 1.
TABLE 1
Figure BDA0001217928870000151
By analyzing the data in table 1, the following conclusions can be drawn:
(1) the flame-retardant polymer electrolyte composite membrane prepared by the scheme of the invention has very high mechanical strength (13.7MPa) and conductivity (2.96ms/cm), and the oxygen index is as high as 45, which shows that the flame-retardant polymer electrolyte composite membrane can solve the problems that the conductivity and the mechanical strength can not be considered at the same time, and the flame retardant property is poor.
(2) The flame-retardant polymer electrolyte composite membrane prepared by the scheme of the invention has high conductivity, good mechanical property and good flame retardant property, and is suitable for lithium ion batteries.

Claims (10)

1. A functional polymer is characterized by comprising a polymer chain, a flame-retardant group, a lithium ion conducting group and a blocking group, wherein the polymer chain is composed of structural units shown as a formula 1, the 1 st position or the 2 nd position of the structural units of the polymer chain is connected with the flame-retardant group and the lithium ion conducting group, and the molar ratio of the flame-retardant group to the lithium ion conducting group is 1 (2-4);
Figure FDA0002388149720000011
wherein X in the formula 1 is an integer of 30-600;
the flame-retardant group has a structure shown in a formula 2,
Figure FDA0002388149720000012
in formula 2, R ═ CaH2a+1Wherein the value of a is an integer of 1-3;
the lithium ion conducting group has a structure as shown in formula 3,
Figure FDA0002388149720000013
in the formula 3, the value of m is an integer of 7-16;
the two ends of the polymer chain are connected with end capping groups, and the end capping groups are CH2Or CHPh.
2. A polymer electrolyte membrane comprising the functional polymer according to claim 1 and a lithium salt.
3. A flame retardant polymer electrolyte composite membrane comprising the polymer electrolyte membrane according to claim 2 and a substrate membrane compounded on a surface of the polymer electrolyte membrane.
4. A method for preparing a flame retardant polymer electrolyte composite membrane according to claim 3, comprising the steps of:
1) performing ring-opening displacement polymerization reaction on norbornene phosphate and norbornene polyethylene glycol monomethyl ether to prepare a functional polymer;
the structure of the norbornene phosphate is shown as a formula 4:
Figure FDA0002388149720000021
in formula 4, R ═ CaH2a+1A is an integer of 1-3;
the structure of the norbornene polyethylene glycol monomethyl ether is shown as a formula 5:
Figure FDA0002388149720000022
wherein m is an integer of 7-16;
2) uniformly mixing the functional polymer obtained in the step 1) and lithium salt in an organic solvent, and then casting to form a film to obtain a polymer electrolyte film;
3) compounding the polymer electrolyte membrane prepared in the step 2) with a matrix membrane to obtain the composite membrane.
5. The method of preparing a flame retardant polymer electrolyte composite membrane according to claim 4, wherein the ring-opening shift polymerization reaction in step 1) comprises the steps of:
dissolving norbornene phosphate and norbornene polyethylene glycol monomethyl ether in an organic solvent to obtain a solution 1; dissolving Grubbs second generation initiator in organic solvent to obtain solution 2; and adding the solution 1 into the solution 2, reacting for 2-6 h, adding a terminator, stopping the reaction, and removing the organic solvent.
6. The method of preparing a flame retardant polymer electrolyte composite membrane according to claim 4, wherein the ring-opening shift polymerization reaction in step 1) comprises the steps of:
dissolving norbornene phosphate in an organic solvent to obtain a solution A; dissolving norbornene polyethylene glycol monomethyl ether in an organic solvent to obtain a solution B; dissolving Grubbs second generation initiator in organic solvent to obtain solution C; adding the solution A into the solution C to react for 2-6 hours to obtain a mixed solution, then adding the solution B into the mixed solution to react for 2-6 hours, then adding a terminator, stopping the reaction, and removing the organic solvent.
7. The method of preparing a flame retardant polymer electrolyte composite membrane according to any one of claims 4 to 6, wherein the molar ratio of lithium in the polymer electrolyte membrane to ethylene oxide repeating units in the functional polymer in the step 2) is 1: (4-25).
8. The method of preparing a flame retardant polymer electrolyte composite membrane according to claim 4, wherein the lithium salt is lithium tetrafluoroborate or lithium bistrifluoromethylsulfonyl imide.
9. The method of preparing a flame retardant polymer electrolyte composite membrane according to claim 4, wherein the compounding in the step 3) comprises the steps of:
soaking the surface of the matrix membrane and/or the polymer electrolyte membrane with ethanol water solution, then attaching the matrix membrane and the polymer electrolyte membrane to obtain a wet membrane, clamping the wet membrane between two flat plates, applying pressure of 0.01 MPa-0.03 MPa, and drying.
10. A lithium ion battery comprising an electrolyte membrane, wherein the electrolyte membrane is the flame retardant polymer electrolyte composite membrane according to claim 3.
CN201710051528.5A 2017-01-23 2017-01-23 Functional polymer, polymer electrolyte membrane, flame-retardant polymer electrolyte composite membrane, preparation method of flame-retardant polymer electrolyte composite membrane and lithium ion battery Active CN108341932B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710051528.5A CN108341932B (en) 2017-01-23 2017-01-23 Functional polymer, polymer electrolyte membrane, flame-retardant polymer electrolyte composite membrane, preparation method of flame-retardant polymer electrolyte composite membrane and lithium ion battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710051528.5A CN108341932B (en) 2017-01-23 2017-01-23 Functional polymer, polymer electrolyte membrane, flame-retardant polymer electrolyte composite membrane, preparation method of flame-retardant polymer electrolyte composite membrane and lithium ion battery

Publications (2)

Publication Number Publication Date
CN108341932A CN108341932A (en) 2018-07-31
CN108341932B true CN108341932B (en) 2020-10-02

Family

ID=62974429

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710051528.5A Active CN108341932B (en) 2017-01-23 2017-01-23 Functional polymer, polymer electrolyte membrane, flame-retardant polymer electrolyte composite membrane, preparation method of flame-retardant polymer electrolyte composite membrane and lithium ion battery

Country Status (1)

Country Link
CN (1) CN108341932B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111063930B (en) * 2018-10-16 2020-12-29 多氟多化工股份有限公司 Solid polymer electrolyte for lithium ion battery and application thereof
CN111057028B (en) * 2018-10-17 2021-12-10 北京师范大学 Fluorine-containing cationic polymerization monomer and synthesis and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101728575A (en) * 2008-10-29 2010-06-09 三星电子株式会社 Electrolyte composition and catalyst ink used to form solid electrolyte membrane
CN102110851A (en) * 2009-12-24 2011-06-29 上海空间电源研究所 Lithium ion secondary battery

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101728575A (en) * 2008-10-29 2010-06-09 三星电子株式会社 Electrolyte composition and catalyst ink used to form solid electrolyte membrane
CN102110851A (en) * 2009-12-24 2011-06-29 上海空间电源研究所 Lithium ion secondary battery

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
Design and synthesis of a single ion conducting block copolymer electrolyte with multifunctionality for lithium ion batteries;Zhang Y, Lim C, Cai W, Rohan R, Xu G;《RSC Adv》;20140902(第4期);43857–43864 *
Multifunctional macromolecular design as self-standingelectrolyte for high-temperature single-ion lithium batteries;WANG Y;《J Appl Electrochem》;20161219;第47卷(第2期);237-248 *
Single-ion block copoly(ionic liquid)s as electrolytes for all-solid state lithium batteries;Porcarelli L, Shaplov AS, Salsamendi M, Nair JR, Vygodskii YS;《ACS Appl Mater Interfaces》;20160404(第8期);10350–10359 *
WANG Y.Multifunctional macromolecular design as self-standingelectrolyte for high-temperature single-ion lithium batteries.《J Appl Electrochem》.2016,第47卷(第2期), *

Also Published As

Publication number Publication date
CN108341932A (en) 2018-07-31

Similar Documents

Publication Publication Date Title
Xiang et al. A flame-retardant polymer electrolyte for high performance lithium metal batteries with an expanded operation temperature
Li et al. A PEO-based gel polymer electrolyte for lithium ion batteries
CN111224156B (en) Semi-interpenetrating network flame-retardant gel electrolyte, lithium ion battery and preparation method
Ren et al. An in situ formed copolymer electrolyte with high ionic conductivity and high lithium-ion transference number for dendrite-free solid-state lithium metal batteries
CN111732724B (en) Polyaryletherketone single-ion polymer and single-ion gel polymer electrolyte
CN111786018B (en) High-voltage polymer electrolyte, high-voltage polymer lithium metal battery and preparation method of battery
CN111548490B (en) Polyimide single-ion polymer, preparation method thereof and solid polymer electrolyte membrane
Qin et al. Polymer dispersed ionic liquid electrolytes with high ionic conductivity for ultrastable solid‐state lithium batteries
Jia et al. Multifunctional polymer bottlebrush-based gel polymer electrolytes for lithium metal batteries
Hu et al. Flexible, high-temperature-resistant, highly conductive, and porous siloxane-based single-ion conducting electrolyte membranes for safe and dendrite-free lithium-metal batteries
CN111029515A (en) Sulfonated graphene oxide-based single-ion polymer electrolyte membrane and preparation method and application thereof
CN108341932B (en) Functional polymer, polymer electrolyte membrane, flame-retardant polymer electrolyte composite membrane, preparation method of flame-retardant polymer electrolyte composite membrane and lithium ion battery
CN110224173B (en) Self-healing solid polymer electrolyte for lithium battery and preparation method thereof
CN108341964B (en) Functional polymer, polymer electrolyte for lithium battery, preparation method of polymer electrolyte, polymer electrolyte membrane and lithium ion battery
CN108341933B (en) Single-ion polymer electrolyte, single-ion polymer electrolyte composite membrane, preparation method of single-ion polymer electrolyte composite membrane and lithium ion battery
CN109326821A (en) A kind of nanometer-material-modified rubber-gel electrolyte film and Preparation method and use
Fang et al. A high-safety electrolyte based on functionalized ionic liquid and polyurethane for lithium batteries
CN103515654B (en) The manufacture method of a kind of copolymer solid electrolyte
CN116259833A (en) Crosslinked polymer solid electrolyte, preparation method and application thereof
CN110994016A (en) Polymer solid electrolyte and preparation method and application thereof
CN116231089A (en) Local high-concentration ionic liquid modified electrolyte and preparation method and application thereof
CN113185695B (en) Polyether sulfone single-ion polymer and single-ion gel polymer electrolyte
CN113363575B (en) Sulfonic polymer eutectic solid electrolyte and preparation method thereof
CN116053576A (en) All-solid-state battery with no interface, low impedance and high safety and preparation method thereof
CN109286040A (en) Four arm branched polymeric ionic liquid gel electrolyte membrances and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CP03 Change of name, title or address

Address after: 454191 Henan Province, Jiaozuo City Station area coke Rd

Patentee after: Duofudo New Material Co.,Ltd.

Address before: 454191, Feng County, Henan Province, Jiaozuo Feng Feng Chemical Industry Zone

Patentee before: DO-FLUORIDE CHEMICALS Co.,Ltd.

CP03 Change of name, title or address