CN108641052B - Halogenated polymer, polymer film, preparation method and application thereof - Google Patents

Halogenated polymer, polymer film, preparation method and application thereof Download PDF

Info

Publication number
CN108641052B
CN108641052B CN201810469017.XA CN201810469017A CN108641052B CN 108641052 B CN108641052 B CN 108641052B CN 201810469017 A CN201810469017 A CN 201810469017A CN 108641052 B CN108641052 B CN 108641052B
Authority
CN
China
Prior art keywords
halogenated
polymer
polymer film
metal salt
film
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
CN201810469017.XA
Other languages
Chinese (zh)
Other versions
CN108641052A (en
Inventor
谢海明
丛丽娜
孙立群
刘佳
刘军
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.)
Jilin Dongchi New Energy Technology Co.,Ltd.
Original Assignee
Northeast Normal 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 Northeast Normal University filed Critical Northeast Normal University
Priority to CN201810469017.XA priority Critical patent/CN108641052B/en
Publication of CN108641052A publication Critical patent/CN108641052A/en
Application granted granted Critical
Publication of CN108641052B publication Critical patent/CN108641052B/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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention provides a preparation method of a halogenated polymer, belonging to the technical field of high molecular materials and comprising the following preparation steps: alpha, omega-halogenated-2-propionate polyether or alpha-halogenated-2-methyl propionate-omega-methoxy polyether, organic solvent, alkali promoter, metal halide catalyst, nitrogen-containing initiator ligand and halogenated unsaturated hydrocarbon are mixed and then subjected to polymerization reaction to obtain the polymer. The invention obtains a high-voltage-resistant polymer film by a simple atom transfer radical polymerization method, and the high-voltage-resistant polymer film is applied to a high-voltage electrochemical device, shows good compatibility with a high-voltage anode material, and simultaneously shows excellent mechanical strength and room-temperature ionic conductivity.

Description

Halogenated polymer, polymer film, preparation method and application thereof
Technical Field
The invention relates to the technical field of high molecular materials, in particular to a polymer, a polymer film, and preparation methods and applications thereof.
Background
High molecular polymer materials have been rapidly developed in the field of chemical power sources because of their unique properties, such as light weight, ease of film formation, good viscoelasticity and excellent safety characteristics. As early as 1978, ArmandThe research of applying polymer-salt complex system in chemical power source has stimulated the research interest of researchers in polymer and settled the solid foundation and scientific basis for developing all-solid-state electrochemical device system. After 30 years of development and research, numerous polymer systems have emerged, and among them, mature polymer systems have been successfully put into commercial use. For example, Quebec, France, initially used polyoxyethylene-based polymers as thin films applied to Li/LiFePO4In and authorizing Bollore, France, developed a polymer electrochemical system with an energy density of 200 Wh/kg. However, the energy density achieved at present can only maintain the longest 250km of electric taxis in the city. In order to further improve the energy density of the polymer electrochemical device, active research and development of a novel high-voltage-resistant polymer electrolyte thin film matched with a high-voltage positive electrode are key points.
Currently, most of the research on the application of polymer thin films is mainly focused on how to reduce crystallinity, increase room temperature ionic conductivity of the polymer or improve mechanical strength of the film. However, the polymer electrolyte used in most of the prior art undergoes a severe decomposition reaction at a voltage of 4V or more, which affects the performance of the electrochemical device with high specific energy and long cycle performance, mainly because the bond energy of the C-H bond in the high molecular organic polymer is relatively small, and the bond is easily broken and decomposed at a high voltage.
Halogen elements substitute H in the organic polymer to enable the physical and chemical properties of organic molecules to be changed correspondingly, for example, the strong electronegativity of halogen enables the electrochemical and chemical stability of carbon-halogen bonds to be improved, and the high-voltage operation of an electrochemical device is facilitated; the melting point is reduced, which is beneficial to the low-temperature operation of the electrochemical device; the flash point is increased, and the safety of the electrochemical system is further improved; the viscosity is reduced, and the ionic conductivity is improved to a certain extent. It is clear that halogen substitution is an effective modification to improve the electrochemical and chemical stability of polymers. However, if the halogen substitution is directly performed on a single polymer molecule by an organic chemical synthesis method, there are technical obstacles, and the technical difficulties are complex halogenation process, high experimental operation difficulty and strong toxicity.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing a halogenated polymer, and the method provides a high-voltage-resistant polymer thin film through a simple atom transfer radical polymerization method, and the high-voltage-resistant polymer thin film is applied to a high-voltage electrochemical device, and exhibits good compatibility with a high-voltage positive electrode material, and also exhibits excellent mechanical strength and room-temperature ionic conductivity.
A process for preparing a halogenated polymer comprising the steps of:
mixing an ether polymer, an organic solvent, an alkaline promoter, a metal halide catalyst, a nitrogen-containing initiator ligand and halogenated unsaturated hydrocarbon for polymerization reaction to obtain a halogenated polymer; the ether polymer is alpha, omega-halogenated-2-propionate polyether or alpha-halogenated-2-methyl propionate-omega-methoxy polyether;
the halogenated unsaturated hydrocarbon is one of halogenated vinyl monomers, halogenated propenyl monomers, halogenated cyclopentenyl ketone monomers, halogenated styrene monomers, halogenated naphthalene vinyl monomers, halogenated acrylate alkenyl monomers or copolymers prepared from the monomers.
Preferably, the α, ω -halo-2-propanoate polyether and the α -halo-2-propanoate methyl- ω -methoxy polyether have the structural formulae shown in formula I and formula II, respectively:
Figure BDA0001662616400000021
formula I or
Figure BDA0001662616400000022
Formula II
X is independently F, Cl or Br, R is independently C2～C12N is an integer of 2 to 10000.
Preferably, the organic solvent is dichloromethane, tetrahydrofuran, N-methylpyrrolidone, N-dimethylformamide, dimethyl sulfoxide, toluene, 1,1, 1-trichlorotrifluoroethane or 1,1,1,3, 3-pentafluorobutane.
Preferably, the basic promoter is triethylamine, KOH or NaOH.
Preferably, the metal halide catalyst is CuBr, CuCl, FeCl2、FeBr2、CoCl2Or CoBr2。
Preferably, the nitrogen-containing initiator ligand is azobisisobutyronitrile or 4, 4-azobis (4-cyanovaleric acid).
Preferably, the halogenated vinyl monomer is 1, 1-difluoroethylene, 1-dichloroethylene or 1, 1-dibromoethylene;
the halogenated propenyl monomer is 1, 1-difluoropropylene, 1-dichloropropene, 1-dibromopropylene or hexafluoropropylene;
the halogenated cyclopentenyl ketone monomer group monomer is 4-fluoro-1, 3-dioxol-2-one, 4, 5-difluoro-1, 3-dioxol-2-one, 4-fluoro-5-chloro-1, 3-dioxol-2-one, 4-chloro 5-methyl-1, 3-dioxol-2-one, 4-fluoromethyl-1, 3-dioxol-2-one, 4-difluoromethyl-1, 3-dioxol-2-one, 4-trifluoromethylmethyl-1, 3-dioxol-2-one or 4, 5-bis (trifluoromethyl) -1, 3-dioxolen-2-one;
the halogenated styrene monomer is 1,2, 2-trifluorostyrene, m-chlorostyrene, p-fluorostyrene, p-chlorostyrene or p-bromostyrene;
the halogenated naphthalene vinyl monomer is 6-fluoro-2-vinylnaphthalene;
the halogenated acrylate alkenyl monomer is perfluoroalkyl ethyl acrylate, dodecafluoroheptyl methacrylate, allyl chloroformate, trifluoroethyl methacrylate, hexafluorobutyl methacrylate, alpha-fluoro methyl acrylate, alpha-chloro methyl acrylate, alpha-bromo methyl acrylate, alpha-fluoro methyl methacrylate, alpha, beta-difluoro methyl methacrylate, alpha-chloro methyl methacrylate, alpha, beta-dichloro methyl methacrylate, alpha-bromo methyl methacrylate, alpha, beta-dibromo methyl methacrylate or perfluoropolyether dimethacrylate.
Preferably, the temperature of the polymerization reaction is 50-90 ℃, and the time of the polymerization reaction is 8-32 h.
Preferably, the mass ratio of the ether polymer to the organic solvent is 100: 200-1000, wherein the mass ratio of the halogen, the alkaline promoter, the metal halide catalyst and the initiator in the ether polymer is 1: 1-3: 0.5-2: 1.5 to 4, wherein the molar ratio of the halogen in the ether polymer to the number of double bonds in the halogenated unsaturated hydrocarbon is 1: 1 to 1.5. .
The invention also provides a halogenated polymer obtained by the preparation method, the halogenated polymer is an A-B-A type or A-B type polymer, A is an unsaturated halogenated hydrocarbon polymerization chain segment, B is an alpha-omega-halogenated-2-propionate polyether polymerization chain segment or an alpha-halogenated-2-methyl propionate-omega-methoxy polyether chain segment, and the structures of the A-B-A type or A-B type polymer are respectively as follows:
Figure BDA0001662616400000031
A-B-A type,
Figure BDA0001662616400000032
Type A-B;
r is C2～C12The straight-chain alkane of (1);
when A is a halogenated vinyl mono-polymeric segment, R1，R2，R3And R4One or more of them are independent halogen, others are H;
when A is a halogenated propenyl monomer polymerization segment, R1，R2，R3，R4One of them is an independent methyl group, and the others are halogenated hydrocarbon groups;
when A is a halogenated cyclopentenyl ketone monomer polymerization chain segment, R1And R3、R1And R4、R2And R3Or R2And R4Cyclopentenyl and other groups are halogenated hydrocarbon groups;
when A is halogenated styrene-based monomer or halogenated naphthalene-based monomer polymerization chain segment, R1，R2，R3And R4One or more of which are independently phenyl or naphthyl, the others being halogenated hydrocarbyl;
when A is halogenated acrylic ester alkenyl monomer polymerized chain segment, R1，R2，R3，R4One of which is methyl and the others are halogenated hydrocarbon groups.
M is an integer of 2-1000, and n is an integer of 2-10000.
Preferably, the halogenated polymer contains 10-50% by mass of A and 50-90% by mass of B.
The invention provides a polymer film, which comprises the halogenated polymer and metal salt, wherein the metal salt is alkali metal salt or alkaline earth metal salt.
Preferably, the metal salt comprises LiN (CF)3SO2)2，LiN(SO2C2F5)2，LiN(SO2C4F9)SO3CF3，LiN(SO2(CF2)3SO2)2，LiN(SO2CF3)(SO2C4F9)2，LiCF3SO3，LiC(SO2CF3)3，LiCH(SO2CF3)2，LiCH2(SO2CF3)2，LiC2F5SO3，LiCF3CO3,LiBF4，LiBOB，LiODFB，LiFOB，Li2B12F12，Li2DFB，LiPF6，LiPF3(C2F5)3，NaCF3SO3，NaBF4，NaPF6，KCF3SO3，KBF4，KPF6，Mg{N(CF3SO2)2}2And Mg (BF)4)2One or more of them.
Preferably, the molar ratio of the B block [ RO ] active coordination group in the halogenated polymer to the cation in the metal salt is 15-30.
Preferably, the thickness of the thin film is 10 to 200 μm.
The invention also provides a preparation method of the polymer film, which comprises the following preparation steps:
mixing the halogenated polymer and acetonitrile to obtain a mixed solution;
and pouring the mixed solution on a tetrafluoroethylene or polytetrafluoroethylene plate for casting film forming to obtain the polymer film.
Preferably, the mass ratio of the halogenated polymer to the acetonitrile is 100: 200 to 1000.
The invention also provides the application of the polymer film in an electrochemical device.
The beneficial technical effects are as follows: the invention provides a preparation method of a halogenated polymer, which comprises the steps of mixing alpha, omega-halogenated-2-propionate polyether or alpha-halogenated-2-methyl propionate-omega-methoxy polyether, an organic solvent, an alkaline promoter, a metal halide catalyst, a nitrogen-containing initiator ligand and halogenated unsaturated hydrocarbon, and then carrying out polymerization reaction to obtain the halogenated polymer. According to the invention, a halogenated polymer is obtained by a simple atom transfer radical polymerization method, and a film prepared from the halogenated polymer is applied to a high-voltage electrochemical device, shows good compatibility with a high-voltage positive electrode material, and simultaneously shows excellent mechanical strength and room-temperature ionic conductivity, and specific examples show that the room-temperature ionic conductivity can reach 10-4S/cm. The polymer electrolyte film is applied to a high-voltage anode LiNi0.5Co0.2Mn0.3O2Button cells assembled with metallic lithium cathodes exhibit excellent high voltage cycling stability. At room temperature, when the cut-off voltage is 4.5V, the capacity retention rate is up to 90% after 70 cycles; when the high temperature is 70 ℃ and the cut-off voltage is 4.7V, the capacity retention rate can still reach 92% after 28 times of circulation.
Description of the drawings:
FIG. 1 is an SEM photograph and an apparent photograph of a polymer thin film prepared in example 1;
FIG. 2 is a window for electrochemical stability of the polymer film of example 1;
FIG. 3 is a graph showing the relationship between the ionic conductivity and the temperature of the polymer film in example 1;
FIG. 4 is a graph of the cycling performance of the assembled cell of example 1 at room temperature from 2.8 to 4.5V;
fig. 5 is a graph showing the cycle performance of the battery assembled in example 1 at a high temperature of 70 c at 2.8-4.7V.
Detailed Description
The invention provides a preparation method of a halogenated polymer, which comprises the following steps:
mixing an ether polymer, an organic solvent, an alkaline promoter, a metal halide catalyst, a nitrogen-containing initiator ligand and halogenated unsaturated hydrocarbon for polymerization reaction to obtain a halogenated polymer; the ether polymer is alpha, omega-halogenated-2-propionate polyether or alpha-halogenated-2-methyl propionate-omega-methoxy polyether;
the halogenated unsaturated hydrocarbon is one of halogenated vinyl monomers, halogenated propenyl monomers, halogenated cyclopentenyl ketone monomers, halogenated styrene monomers, halogenated naphthalene vinyl monomers, halogenated acrylate alkenyl monomers or copolymers prepared from the monomers.
In the present invention, the structural formulas of the α, ω -halo-2-propionate polyether and the α -halo-2-methyl propionate- ω -methoxy polyether are represented by formula I and formula II, respectively:
Figure BDA0001662616400000061
formula I or
Figure BDA0001662616400000062
Formula II
Wherein X is independently preferably F, Cl or Br, more preferably F or Br; r is independently preferably C2～C12More preferably C2-C5(ii) a n is preferably an integer of 2 to 10000, more preferably an integer of 500 to 8000, and most preferably an integer of 3000 to 5000.
In the present invention, the molecular weight of the ether polymer is preferably 1000 to 10000g/mol, and more preferably 6000 to 10000 g/mol.
The source of the ether polymer in the present invention is not particularly limited, and commercially available products known to those skilled in the art may be selected.
In the present invention, the organic solvent is preferably dichloromethane, tetrahydrofuran, N-methylpyrrolidone, N-dimethylformamide, dimethylsulfoxide, toluene, 1,1, 1-trichlorotrifluoroethane or 1,1,1,3, 3-pentafluorobutane, and more preferably dichloromethane, tetrahydrofuran, N-methylpyrrolidone, N-dimethylformamide or dimethylsulfoxide.
In the present invention, the basic accelerator is preferably triethylamine, KOH or NaOH, more preferably triethylamine or KOH.
In the present invention, the metal halide catalyst is preferably CuBr, CuCl or FeCl2、FeBr2、CoCl2Or CoBr2More preferably CuBr, CuCl or FeCl2。
In the present invention, the nitrogen-containing initiator ligand is preferably azobisisobutyronitrile or 4, 4-azobis (4-cyanovaleric acid), more preferably azobisisobutyronitrile.
In the present invention, the halogenated vinyl monomer is preferably 1, 1-difluoroethylene, 1-dichloroethylene or 1, 1-dibromoethylene, and more preferably 1, 1-difluoroethylene or 1, 1-dichloroethylene.
In the present invention, the halopropenyl monomer is preferably 1, 1-difluoropropene, 1-dichloropropene, 1-dibromoene or hexafluoropropene, and more preferably 1, 1-difluoropropene or 1, 1-dichloropropene.
In the present invention, the halogenated cyclopentenyl ketone monomer is preferably 4-fluoro-1, 3-dioxol-2-one, 4, 5-difluoro-1, 3-dioxol-2-one, 4-fluoro-5-chloro-1, 3-dioxol-2-one, 4-chloro 5-methyl-1, 3-dioxol-2-one, 4-fluoromethyl-1, 3-dioxol-2-one, 4-difluoromethyl-1, 3-dioxol-2-one, 4-trifluoromethyl-1, 3-dioxol-2-one or 4, 5-bis (trifluoromethyl) -1, 3-dioxolen-2-one, more preferably 4-fluoro-1, 3-dioxolen-2-one, 4, 5-difluoro-1, 3-dioxolen-2-one, 4-fluoro-5-chloro-1, 3-dioxolen-2-one, 4-chloro-5-methyl-1, 3-dioxolen-2-one or 4-fluoromethyl-1, 3-dioxolen-2-one.
In the present invention, the halogenated styrene-based monomer is preferably 1,2, 2-trifluorostyrene, m-chlorostyrene, p-fluorostyrene, p-chlorostyrene or p-bromostyrene, and more preferably 1,2, 2-trifluorostyrene, m-chlorostyrene or p-fluorostyrene.
In the present invention, the halogenated naphthalene vinyl monomer is preferably 6-fluoro-2-vinylnaphthalene.
In the present invention, the halogenated acrylate alkenyl monomer is preferably perfluoroalkyl ethyl acrylate, dodecafluoroheptyl methacrylate, allyl chloroformate, trifluoroethyl methacrylate, hexafluorobutyl methacrylate, α -fluoro methyl acrylate, α -chloro methyl acrylate, α -bromo methyl acrylate, α -fluoro methyl methacrylate, methyl α, β -difluoromethyl acrylate, methyl α -chloromethacrylate, methyl α, β -dichloromethacrylate, methyl α -bromomethacrylate, methyl α, β -dibromomethacrylate or perfluoropolyether dimethacrylate, more preferably perfluoroalkylethyl acrylate, trifluoroethyl methacrylate, methyl α -fluoroacrylate, methyl α, β -difluoromethacrylate or perfluoropolyether dimethacrylate.
In the present invention, the mass ratio to the organic solvent is 100: 200-1000, wherein the mass ratio of the halogen, the alkaline promoter, the metal halide catalyst and the initiator in the ether polymer is 1: 1-3: 0.5-2: 1.5 to 4, wherein the molar ratio of the halogen in the ether polymer to the number of double bonds in the halogenated unsaturated hydrocarbon is 1: 1 to 1.5.
In the present invention, the polymerization reaction is preferably carried out in an inert gas atmosphere, and the inert gas is preferably Ar or N2More preferably, Ar.
In the invention, the polymerization temperature is preferably 50-90 ℃, more preferably 60-80 ℃, and most preferably 70 ℃, and the polymerization time is preferably 8-32 hours, more preferably 10-20 hours, and most preferably 15-18 hours.
The method for mixing the ether polymer, the organic solvent, the alkaline accelerator, the metal halide catalyst, the nitrogen-containing initiator ligand and the halogenated unsaturated hydrocarbon is not particularly limited, and a mixing method well known to those skilled in the art can be selected, specifically, the ether polymer solvent is preferably dissolved in the organic solvent, vacuum pumping is performed, inert gas is supplemented, and then the alkaline accelerator, the metal halide catalyst, the nitrogen-containing initiator ligand and the halogenated unsaturated hydrocarbon are sequentially added.
After the polymerization reaction is completed, the invention preferably mixes the polymerization reaction solution with absolute ethyl alcohol, precipitates are separated out, and the precipitates are dried to obtain a polymerization product.
In the invention, the mass ratio of the absolute ethyl alcohol to the polymerization reaction liquid is 1.5-5: 1.
In the invention, the drying temperature is preferably 50-70 ℃, and more preferably 60 ℃.
The invention also provides a halogenated polymer obtained by the preparation method, the halogenated polymer is an A-B-A type or A-B type polymer, A is an unsaturated halogenated hydrocarbon polymerization chain segment, B is an alpha-omega-halogenated-2-propionate polymer ether polymerization chain segment or an alpha-halogenated-2-methyl propionate-omega-methoxy polyether chain segment, and the structures of the A-B-A type or A-B type polymer are respectively as follows:
Figure BDA0001662616400000081
A-B-A type,
Figure BDA0001662616400000082
Type A-B;
wherein R is preferably C2～C12More preferably C2～C5Linear alkanes of (1).
In the present invention, when A is a halogenated vinyl mono-polymer segment, R1，R2，R3And R4Preferably one or more of them are independently halogen and the others are H, more preferably one of them is halogen and the others are H.
In the present invention, when A is a halopropenyl monomer polymerization segment, R1，R2，R3，R4Preferably one is independently methyl and the other is halohydrocarbyl, more preferably one or two are independently methyl and the other is difluoro-or dichloro-substituted.
In the invention, when A is a halogenated cyclopentenyl ketone monomer polymerization chain segment, R1，R2，R3，R4With R being preferred1And R3、R1And R4、R2And R3、R2And R4And cyclopentenyl, and the other groups are halogenated hydrocarbon groups.
In the present invention, when A is a halogenated styrene-based monomer or halogenated naphthalene-based monomer polymerization segment, R1，R2，R3And R4Preferably one or several are independently phenyl or naphthyl, the others are halogenated hydrocarbyl, more preferably one or two are independently phenyl or naphthyl, the others are F or Cl.
In the invention, when A is a halogenated acrylate alkenyl monomer polymerization chain segment, R1，R2，R3，R4Preferably one is methyl, the other is a halogenated hydrocarbon-containing group, more preferably methyl, the other is C1～C5Fluorinated or chlorinated alkanes.
In the invention, m is preferably an integer of 2-1000, more preferably an integer of 100-800, and most preferably an integer of 300-600; the n is preferably an integer of 2 to 10000, more preferably an integer of 500 to 8000, and most preferably an integer of 2000 to 5000.
In the present invention, the percentage by mass of a in the halogenated polymer is preferably 10% to 50%, more preferably 20% to 40%, and the percentage by mass of B is preferably 50% to 90%, more preferably 60% to 80%.
The invention provides a polymer film, which comprises the halogenated polymer and metal salt, wherein the metal salt is alkali metal salt or alkaline earth metal salt.
In the present invention, the metal salt preferably comprises LiN (CF)3SO2)2，LiN(SO2C2F5)2，LiN(SO2C4F9)SO3CF3，LiN(SO2(CF2)3SO2)2，LiN(SO2CF3)(SO2C4F9)2，LiCF3SO3，LiC(SO2CF3)3，LiCH(SO2CF3)2，LiCH2(SO2CF3)2，LiC2F5SO3，LiCF3CO3,LiBF4，LiBOB，LiODFB，LiFOB，Li2B12F12，Li2DFB，LiPF6，LiPF3(C2F5)3，NaCF3SO3，NaBF4，NaPF6，KCF3SO3，KBF4，KPF6，Mg{N(CF3SO2)2}2And Mg (BF)4)2More preferably LiN (CF)3SO2)2、LiN(SO2C4F9)SO3CF3、LiC2F5SO3、LiCF3CO3,LiBF4、NaBF4、Mg{N(CF3SO2)2}2And Mg (BF)4)2One or more of the above; when the metal salt is a mixture of two or more kinds, the amount of each metal salt used in the present invention is not particularly limited, and a mixing method known to those skilled in the art may be used.
The electrolyte film is formed by mixing metal salt and polymer, wherein the salt can provide free ion quantity, and the electrolyte has high ion conductivity.
In the invention, the molar ratio of the B block [ RO ] active coordination group in the halogenated polymer to the cation in the metal salt is preferably 15-30: 1, and more preferably 20-25: 1.
In the present invention, the thickness of the polymer film is preferably 10 to 200 μm, and more preferably 50 to 150 μm.
The invention also provides a preparation method of the polymer film, which comprises the following preparation steps:
mixing the halogenated polymer with acetonitrile to obtain a mixed solution;
and pouring the mixed solution on a tetrafluoroethylene or polytetrafluoroethylene plate for casting film forming to obtain the polymer film.
The halogenated polymer is mixed with acetonitrile to obtain a mixed solution. In the present invention, the mass ratio of the halogenated polymer to acetonitrile is preferably 1: 2-10, more preferably 1: 5 to 8.
The method of mixing the halogenated polymer and acetonitrile in the present invention is not particularly limited, and a mixing method known to those skilled in the art may be used.
After the mixed solution is obtained, the mixed solution is injected on a tetrafluoroethylene or polytetrafluoroethylene plate for casting film forming, and the polymer film is obtained.
In the present invention, the mixed solution is preferably cast on a tetrafluoroethylene or polytetrafluoroethylene sheet, knife-coated, and dried to obtain a polymer film. The thickness of the blade coating is preferably not particularly limited in the present invention, and a blade coating thickness well known to those skilled in the art may be selected.
The method of knife coating in the present invention is not particularly limited, and a knife coating method known to those skilled in the art may be selected.
The invention also provides the application of the polymer film in an electrochemical device. The electrochemical device is a lithium ion battery, a sodium ion battery, a potassium ion battery, a magnesium ion battery, a lithium sulfur battery, a sodium sulfur battery and a super capacitor.
In the present invention, the polymer thin film is preferably applied between a positive electrode and a negative electrode of an electrochemical device.
In the present invention, the positive electrode is preferably a stainless steel sheet, an Au electrode prepared by sputtering or an ion-embeddable compound requiring a high voltage test.
In the present invention, the negative electrode preferably includes one or more of metal Li, metal Na, metal K, metal Mg, Li-B alloy, and Li-In alloy, and more preferably one or more of metal Li, metal Na, Li-B alloy, and Li-In alloy. In the present invention, when the negative electrode is a mixture of two or more metals and/or alloys, the respective amounts of the metals and/or alloys are not particularly limited and may be mixed in any ratio.
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1
Synthesis of triblock cross-linked polymer of fluoroethylene carbonate-alpha, omega-fluoro (polyethylene glycol) propionate-polyfluoroethylene carbonate.
The whole polymerization was carried out in a glove box filled with argon, and the reagents were subjected to a water-removing and oxygen-removing process for 7 days before use. 10g of an α, ω -halo-2-propanoate (polyethylene glycol) (molecular weight 10000g/mol) were first dissolved in 50ml of dichloromethane, 1.4ml of triethylamine were added, and stirred well for 20 minutes at room temperature. 5.2g of 4-fluoro-1, 3-dioxol-2-one, 30mg of CuBr and 300mg of azobisisobutyronitrile were added to the above system to form a mixed solution. Heating the mixed solution in an oil bath under the atmosphere of argon to 80 ℃, reacting for 15h, pouring the polymer into absolute ethyl alcohol after the reaction is finished, and removing the supernatant after the viscous polymer is precipitated. And drying the polymer in a vacuum drying oven at 60 ℃ for 12h to obtain the polymer. The yield of the polymer prepared was 81% and the molecular weight was 23200g/mol as determined by GPC.
FIG. 1 is an apparent photograph and SEM photograph of the polymer film of example 1, as can be seen from FIG. 1: the film is light yellow transparent and has good flexibility. The surface of the material is uniformly wrinkled under an SEM high-resolution electron microscope, so that the material is favorable for rapid conduction of ions.
The prepared polymer film is used as an electrolyte diaphragm, metal lithium is used as a negative electrode, a stainless steel sheet is used as a positive electrode, and the 2025 button cell is assembled in a glove box. And (3) placing the battery in a constant-temperature oven with the high temperature of 70 ℃ for heat preservation for 12 h. And performing linear sweep voltammetry test through an electrochemical workstation, wherein the test voltage range is 2.0-6.0V, and the sweep rate is 0.1 mV/s. The electrochemical stability window of the obtained polymer film is more than 5V. Fig. 2 shows the electrochemical stability window of the polymer film prepared in example 1, and as can be seen from fig. 2, the electrochemical stability window of the polymer film obtained in example 2 is greater than 5V.
Sandwiching a polymer film between two sheetsAnd (5) placing the stainless steel sheet in a constant-temperature oven with the high temperature of 70 ℃ for heat preservation for 12 hours. Performing electrochemical impedance test at 10 deg.C via electrochemical workstation2-107Hz, amplitude 20 mV. The test temperature range is room temperature-100 ℃. FIG. 3 is a graph of ionic conductivity versus temperature for the polymer film of example 1. As can be seen from FIG. 3, the change rule of the ionic conductivity of the polymer film with temperature conforms to the Arrhenius formula, and the ionic conductivity at room temperature is 10-4S/cm, high-temperature 90 ℃ ion conductivity can reach 10-3Above S/cm, the ionic conductivity of the electrolyte is basically equal to that of the current liquid electrolyte.
Selecting LiNi0.5Co0.2Mn0.3O2The positive electrode material, the metal lithium as the negative electrode, and the polymer film with the thickness of 41um as the electrolyte are assembled into the CR2025 button cell. The tested battery needs to be kept in a constant temperature oven at the high temperature of 70 ℃ for 12 hours. The test voltage ranges are 2.8-4.5V and 2.8-4.7V, the multiplying power is 0.1C, and the test voltage respectively shows excellent cycling stability at room temperature and high temperature of 70 ℃ after multiple cycles.
Fig. 4 is a graph of the cycle performance of the assembled battery in example 1 at room temperature of 2.8-4.5V, and it can be seen from fig. 4 that the capacity retention of the polymer electrolyte membrane reaches 90% after 70 cycles at room temperature and the cut-off voltage of 4.5V.
Fig. 5 is a cycle performance curve diagram of the battery assembled in example 1 at a high temperature of 70 ℃ under 2.8-4.7V, and fig. 5 shows that the capacity retention rate of the polymer electrolyte film can still reach 92% after 28 cycles under the high temperature of 70 ℃ and the cut-off voltage of 4.7V.
Example 2
Synthesis of tri-block polymer of trifluoro-styrene-alpha, omega-bromo (polyethylene glycol) propionate-trifluoro-styrene.
The synthesis reaction device is the same as the above. 10g of alpha, omega-chloro-2-propanoate (polyethylene glycol) (g) (molecular weight 10000g/mol) were first dissolved in 75ml of toluene, 1.8ml of triethylamine were added and stirred well for 30 minutes at room temperature. 10.1g of 1,2, 2-trifluorostyrene, 30mg of FeBr2And 300mg of azobisisobutyronitrile were added to the above system to form a mixed solution. Heating the mixed solution in an oil bath under the argon atmosphere to 80 ℃, reacting for 15h, and reactingAfter completion, the polymer was poured into absolute ethanol, and after the viscous polymer precipitated, the supernatant was removed. The polymer was dried in a vacuum oven at 60 ℃ for 12 h. The yield of the polymer prepared was 78% and the molecular weight was 20110g/mol as determined by GPC.
Example 3
Synthesizing an alpha, beta-dibromo methyl methacrylate-alpha-bromo-2-methyl propionate-omega-methoxy polyether diblock copolymer.
The synthesis reaction device is the same as the above. 10g of methyl α -bromo-2-propionate- ω -methoxypolyether (molecular weight 10000g/mol) are initially dissolved in 50ml of dichloromethane, 0.005g of NaOH are added and stirring is carried out thoroughly for 30 minutes at room temperature. 6.3g of methyl α, β -dibromomethacrylate, 20mg of CuBr and 200mg of azobisisobutyronitrile were added to the above system to form a mixed solution. Heating the mixed solution in an oil bath under the atmosphere of argon to 80 ℃, reacting for 15h, pouring the polymer into absolute ethyl alcohol after the reaction is finished, and removing the supernatant after the viscous polymer is precipitated. The polymer was dried in a vacuum oven at 60 ℃ for 12 h. The yield of the polymer prepared was 75% and the molecular weight was 17800g/mol by GPC.
Example 4
Synthesis of perfluoro polyether dimethacrylate-alpha-fluoro-2-methyl propionate-omega-methoxy polyether diblock copolymer.
The synthesis reaction device is the same as the above. 10g of methyl α -fluoro-2-propionate ω -methoxy polyether (molecular weight 10000g/mol) were first dissolved in 50ml of 1,1,1,3, 3-pentafluorobutane, 1.4ml of triethylamine were added and stirred well for 20 minutes at room temperature. 8g of perfluoropolyether dimethacrylate (molecular weight: 1100g/mol), 60mg of CuBr and 600mg of azobisisobutyronitrile were added to the above system to form a mixed solution. Heating the mixed solution in an oil bath under the atmosphere of argon to 50 ℃, reacting for 24h, pouring the polymer into absolute ethyl alcohol after the reaction is finished, and removing the supernatant after the viscous polymer is precipitated. The polymer was dried in a vacuum oven at 60 ℃ for 12 h. The yield of the polymer prepared was 85% and the molecular weight was 16600g/mol as determined by GPC.
Example 5
The preparation process of the block polymer film, electrochemical stability window, ionic conductivity and charge and discharge test.
2g of one of the synthesized examples 1 to 4 was dissolved in 2ml of anhydrous acetonitrile, 0.65g of LiTFSI was added thereto, and the mixture was stirred at 60 ℃ for 10 hours. Pouring the solvent onto a polytetrafluoroethylene plate after the solvent is evaporated to be viscous, uniformly coating the solvent by using a scraper, standing for 30 minutes until no bubbles exist, and putting the solvent into a vacuum oven for drying. The film thickness was measured by a micrometer screw to be 41 um.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.

Claims (8)

1. A polymer film comprising a halogenated polymer and a metal salt, wherein the metal salt is an alkali metal salt or an alkaline earth metal salt;
the halogenated polymer is an A-B-A type or A-B type polymer, A is an unsaturated halogenated hydrocarbon polymerization chain segment, B is an ether polymer chain segment, and the structures of the A-B-A type or A-B type polymer are respectively as follows:
Figure FDA0002650897980000011
r is C2～C12The straight-chain alkane of (1);
when A is a halogenated vinyl mono-polymeric segment, R1，R2，R3And R4One or more of them are independent halogen, others are H;
when A is a halogenated propenyl monomer polymerization segment, R1，R2，R3，R4One of them is an independent methyl group, and the others are halogenated hydrocarbon groups;
when A is a halogenated cyclopentenyl ketone monomer polymerization chain segment, R1And R3、R1And R4、R2And R3Or R2And R4Cyclopentenyl and other groups are halogenated hydrocarbon groups;
when A is halogenated styrene-based monomer or halogenated naphthalene-based monomer polymerization chain segment, R1，R2，R3And R4One of which is independently phenyl or naphthyl, the others being halogenated hydrocarbon groups;
when A is halogenated acrylic ester alkenyl monomer polymerized chain segment, R1，R2，R3，R4One is methyl and the others are halogenated hydrocarbon groups;
m is an integer of 2-1000, and n is an integer of 2-10000;
the polymer comprises 10-50% of A and 50-90% of B by mass.
2. The polymer film of claim 1, wherein the metal salt comprises LiN (CF)3SO2)2，LiN(SO2C2F5)2，LiN(SO2C4F9)SO3CF3，LiN(SO2(CF2)3SO2)2，LiN(SO2CF3)(SO2C4F9)2，LiCF3SO3，LiC(SO2CF3)3，LiCH(SO2CF3)2，LiCH2(SO2CF3)2，LiC2F5SO3，LiCF3CO3,LiBF4，LiBOB，LiODFB，LiFOB，Li2B12F12，Li2DFB，LiPF6，LiPF3(C2F5)3，NaCF3SO3，NaBF4，NaPF6，KCF3SO3，KBF4，KPF6，Mg{N(CF3SO2)2}2And Mg (BF)4)2One or more of them.
3. The polymer film according to claim 1 or 2, wherein the molar ratio of the B block [ RO ] active coordination group in the halogenated polymer to the cation in the metal salt is 15 to 30: 1.
4. the polymer film according to claim 1, wherein the film has a thickness of 10 to 200 μm.
5. The method for producing a polymer film according to any one of claims 1 to 4, comprising the following production steps:
mixing halogenated polymer with acetonitrile and metal salt to obtain a mixed solution;
and pouring the mixed solution on a polytetrafluoroethylene or polytetrafluoroethylene plate for casting to form a film, thus obtaining the polymer film.
6. The method according to claim 5, wherein the mass ratio of the halogenated polymer to the acetonitrile is 100: 200 to 1000.
7. Use of the polymer thin film according to any one of claims 1 to 4 as a separator for an electrochemical device.
8. Use according to claim 7, wherein the polymer film is applied intermediate a positive electrode and a negative electrode of the electrochemical device;
the positive electrode is a stainless steel sheet, an Au electrode or a lithium-containing compound capable of releasing lithium;
the negative electrode material is one or more of metal Li, metal Na, metal K, metal Mg, Li-B alloy and Li-In alloy.
CN201810469017.XA 2018-05-16 2018-05-16 Halogenated polymer, polymer film, preparation method and application thereof Active CN108641052B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810469017.XA CN108641052B (en) 2018-05-16 2018-05-16 Halogenated polymer, polymer film, preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810469017.XA CN108641052B (en) 2018-05-16 2018-05-16 Halogenated polymer, polymer film, preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN108641052A CN108641052A (en) 2018-10-12
CN108641052B true CN108641052B (en) 2020-12-11

Family

ID=63756356

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810469017.XA Active CN108641052B (en) 2018-05-16 2018-05-16 Halogenated polymer, polymer film, preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN108641052B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118039804B (en) * 2024-04-11 2024-07-19 蜂巢能源科技股份有限公司 Lithium metal negative electrode, preparation method thereof and lithium metal battery

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1412236A (en) * 2001-10-17 2003-04-23 三星Sdi株式会社 Fluorine-containing copolymer, polymer electrolyte containing the same and lithium cell using said electrolyte
CN102099382A (en) * 2008-06-18 2011-06-15 汉高公司 Apparatus and methods for controlled radical polymerization
CN102199261A (en) * 2011-04-13 2011-09-28 山东交通学院 Polyethylene glycol (PEG)-b-polystyrene (PSt)-b-perfluorohexylethyl acrylate (PFHEA) and preparation method thereof
CN103931032A (en) * 2011-10-20 2014-07-16 阿克伦大学 Stretchable, solvent free, completely amorphous solid electrolyte films
CN104151501A (en) * 2014-08-04 2014-11-19 华中科技大学 Polymer containing polyethylene oxide as well as preparation method and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1412236A (en) * 2001-10-17 2003-04-23 三星Sdi株式会社 Fluorine-containing copolymer, polymer electrolyte containing the same and lithium cell using said electrolyte
CN102099382A (en) * 2008-06-18 2011-06-15 汉高公司 Apparatus and methods for controlled radical polymerization
CN102199261A (en) * 2011-04-13 2011-09-28 山东交通学院 Polyethylene glycol (PEG)-b-polystyrene (PSt)-b-perfluorohexylethyl acrylate (PFHEA) and preparation method thereof
CN103931032A (en) * 2011-10-20 2014-07-16 阿克伦大学 Stretchable, solvent free, completely amorphous solid electrolyte films
CN104151501A (en) * 2014-08-04 2014-11-19 华中科技大学 Polymer containing polyethylene oxide as well as preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Preparation and properties of gel-filled PVDF separators for lithium ion cells;Hao Li et al;《J. APPL. POLYM. SCI.》;20171231;第134卷(第7期);第44473(1-6)页 *
Synthesis and Surface-Active Behavior of New Fluorinated Hyperbranched Polymer;Yue Zhang et al;《J.Surfact.Deterg.》;20140507;第17卷;第967-975页 *

Also Published As

Publication number Publication date
CN108641052A (en) 2018-10-12

Similar Documents

Publication Publication Date Title
Li et al. Molecular brush with dense PEG side chains: design of a well-defined polymer electrolyte for lithium-ion batteries
Wang et al. In-situ generation of fluorinated polycarbonate copolymer solid electrolytes for high-voltage Li-metal batteries
Porcarelli et al. Single-ion block copoly (ionic liquid) s as electrolytes for all-solid state lithium batteries
Liu et al. Nonflammable and high-voltage-tolerated polymer electrolyte achieving high stability and safety in 4.9 V-class lithium metal battery
Khan et al. Synthesis and properties of poly-ether/ethylene carbonate electrolytes with high oxidative stability
Chen et al. A solid polymer electrolyte based on star-like hyperbranched β-cyclodextrin for all-solid-state sodium batteries
Lingua et al. Unique carbonate-based single ion conducting block copolymers enabling high-voltage, all-solid-state lithium metal batteries
CN111533851A (en) Preparation method of polymer electrolyte and application of polymer electrolyte in all-solid-state battery
Pelz et al. Self-assembled block copolymer electrolytes: enabling superior ambient cationic conductivity and electrochemical stability
US20070218371A1 (en) Nanoporous polymer electrolyte
Sun et al. Fluorine-containing triblock copolymers as solid-state polymer electrolytes for lithium metal batteries
Vijayakumar et al. Dioxolanone-anchored poly (allyl ether)-based cross-linked dual-salt polymer electrolytes for high-voltage lithium metal batteries
JP2009531820A (en) Solid polymer electrolytes based on triblock copolymers, especially polystyrene-poly (oxyethylene) polystyrene
JP2896361B2 (en) Polymer solid electrolyte, method for producing the same, and lithium secondary battery employing the polymer solid electrolyte
Sun et al. Scalable fabrication of solid-state batteries through high-energy electronic beam
JPH10237143A (en) Block-graft copolymer and polymer solid electrolyte produced from the same
Shaji et al. Multisalt chemistry in ion transport and interface of lithium metal polymer batteries
Chen et al. Lithium-Ion Transport in Poly (ionic liquid) Diblock Copolymer Electrolytes: Impact of Salt Concentration and Cation and Anion Chemistry
CN113270638A (en) Solid polymer electrolytes based on comb polymers
CN113265055A (en) Comb polymers
Hamrahjoo et al. Poly (poly (ethylene glycol) methyl ether methacrylate-co-acrylonitrile) gel polymer electrolytes for high performance lithium ion batteries: Comparing controlled and conventional radical polymerization
JP5000109B2 (en) Binder for electrode preparation, electrode and polymer battery
CN108641052B (en) Halogenated polymer, polymer film, preparation method and application thereof
Zeng et al. New UV-initiated lithiated-interpenetrating network gel-polymer electrolytes for lithium-metal batteries
Naboulsi et al. Correlation between Ionic Conductivity and Mechanical Properties of Solid-like PEO-based Polymer Electrolyte

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
TR01 Transfer of patent right

Effective date of registration: 20210916

Address after: Room 1002, financial building, No. 1577, Jinhui Road, China South Korea (Changchun) International Cooperation Demonstration Zone, Changchun, Jilin 130102

Patentee after: Jilin Dongchi New Energy Technology Co.,Ltd.

Address before: 130000 no.5268 Renmin Street, Changchun, Jilin Province

Patentee before: Northeast Normal University

TR01 Transfer of patent right