WO2013181967A1 - Matériau de membrane polymère ionique, procédé de préparation s'y rapportant et batterie secondaire au lithium - Google Patents

Matériau de membrane polymère ionique, procédé de préparation s'y rapportant et batterie secondaire au lithium Download PDF

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Publication number
WO2013181967A1
WO2013181967A1 PCT/CN2013/073856 CN2013073856W WO2013181967A1 WO 2013181967 A1 WO2013181967 A1 WO 2013181967A1 CN 2013073856 W CN2013073856 W CN 2013073856W WO 2013181967 A1 WO2013181967 A1 WO 2013181967A1
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Prior art keywords
sulfonate
membrane material
polymer
ionic polymer
ceramic filler
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PCT/CN2013/073856
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English (en)
Chinese (zh)
Inventor
潘中来
黄兴兰
马先果
邓佳闽
王璐
高建东
杜鸿昌
李仁贵
邓正华
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成都中科来方能源科技有限公司
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Priority claimed from CN201210181362.6A external-priority patent/CN102702657B/zh
Priority claimed from CN201210219590.8A external-priority patent/CN102719046B/zh
Application filed by 成都中科来方能源科技有限公司 filed Critical 成都中科来方能源科技有限公司
Publication of WO2013181967A1 publication Critical patent/WO2013181967A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • 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
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • 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
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2275—Heterogeneous membranes
    • 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
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a separator material for an energy storage device such as a lithium ion secondary battery and a method of producing the same, and relates to the field of lithium battery manufacturing.
  • a battery is composed of a positive electrode, a negative electrode, a separator, and an electrolyte.
  • the separator is one of the important components in the battery. Its function in the battery is to act as a separator between the positive and negative electrodes inside the battery. It prevents the direct contact between the positive and negative electrodes and causes internal short circuit. At the same time, it is necessary to isolate the electrons and ensure the electrolyte. The ions pass smoothly to support the electrochemical reaction of the battery.
  • the separator of a lithium ion battery since the lithium ion battery has a high operating voltage, the oxidation property of the positive electrode material and the reduction property of the negative electrode material are high, the lithium ion battery separator material and the highly electrochemically active positive and negative electrode materials should have an excellent phase. Capacitance, should also have excellent stability, solvent resistance, ionic conductivity, electronic insulation, good mechanical strength, high heat resistance and fuse isolation.
  • the physical and chemical properties of the membrane depend on the material of the membrane material. Different membranes have different physical and chemical properties and thus exhibit significantly different battery performance in the battery.
  • microporous membranes used in lithium-sulfur batteries, mainly polyolefin microporous membranes.
  • the role of the microporous membrane in the battery is to act as a separator between the positive and negative electrodes inside the battery, to prevent internal short circuit caused by direct contact between the positive and negative electrodes, and to isolate electrons while ensuring smooth passage of ions in the electrolyte to support the battery. Electrochemical reaction.
  • a polyolefin resin is melted, extruded, and blown into a film to form a crystalline polymer film, which is subjected to crystallization treatment and annealing to obtain a highly oriented multilayer structure, which is further stretched at a high temperature to form a crystal interface. Peeling is performed to form a porous structure, and the pore diameter of the film can be increased.
  • the dry method can be divided into dry uniaxial stretching and biaxial stretching according to different stretching directions.
  • the dry uniaxial stretching process is a method of producing a highly crystalline oriented film by using a method of hard elastic fibers to prepare a highly oriented PE or PP separator having a low crystallinity and then annealing at a high temperature.
  • the film is first stretched at a low temperature to form defects such as silver streaks, and then the defects are pulled apart at a high temperature to form micropores.
  • the United States Celgard company, Japan Ube company use this
  • the process produces a single layer of PE, PP and a 3-layer PP / PE / PP composite film.
  • the membrane produced by this process has a flat long microporous structure, and since the uniaxial stretching is performed only, the transverse strength of the separator is relatively poor, but there is almost no heat shrinkage in the transverse direction.
  • the dry biaxial stretching process is a preparation process developed by the Institute of Chemistry of the Chinese Academy of Sciences in the early 1990s.
  • a nucleation ⁇ crystal modifier in PP By adding a nucleation ⁇ crystal modifier in PP, the crystal form is transformed into micropores during the stretching process by utilizing the difference in density between different phases of ruthenium.
  • the strength in the transverse direction is improved, and the transverse and longitudinal stretching ratios can be appropriately changed according to the strength requirements of the separator to obtain desired properties.
  • the dry stretching process is simple and non-polluting, and is a common method for preparing lithium ion battery separators.
  • the pore size and porosity of the process are difficult to control, and the stretching is relatively small, only about 1 to 3, while stretching at low temperature. It is easy to cause perforation of the diaphragm, and the product cannot be made very thin.
  • the wet method is also called phase separation method or thermal phase separation method.
  • the liquid hydrocarbon or some small molecular substances are mixed with the polyolefin resin, heated and melted to form a uniform mixture, and then the temperature is separated for phase separation, and the membrane is pressed to be pressed.
  • the membrane is heated to near the melting point temperature, biaxially stretched to orient the molecular chain, and finally kept for a certain period of time, and the residual solvent is eluted with a volatile substance to prepare a microporous membrane material which is interpenetrated.
  • the method is applicable to a wide range of materials. .
  • the pore size range of the membrane produced by the wet biaxial stretching method is on the order of the size of the phase micro interface, which is relatively small and uniform, and the biaxial stretching ratio can reach 5 to 7, so that the membrane performance is isotropic and the transverse tensile strength is high.
  • the puncture strength is large, the normal process will not cause perforation, the product can be made thinner, and the battery energy density is higher.
  • the microporous membrane has poor liquid absorption and liquid retention ability. Tantalum or niobium is a non-polar material, which has poor affinity with strong polar electrolyte solution, electrolyte and The lower affinity of the polyolefin microporous membrane leads to the poor absorption and retention of the microporous membrane. The absorption and retention of the microporous membrane is closely related to the charge and discharge cycle life of the battery. Second, the microporous membrane is poor in thermal stability, because the polyolefin microporous membrane is a microporous membrane obtained by mechanical stretching, or mechanically stretching and then extracting the pores with an organic solvent, and being heat-set.
  • the preparation process causes residual stress in the microporous membrane, so that the microporous membrane has a shape memory effect.
  • the microporous membrane tends to restore the shape before stretching and produces a larger shape.
  • Shrinkage, microporous film heat shrinkage must accompany volume shrinkage, film area shrinkage occurs, so that the microporous membrane loses the barrier between positive and negative, thus causing a short circuit between the positive and negative electrodes inside the battery, causing battery burning, Security issues such as explosions.
  • a lithium ion battery separator having a thermal expansion fusion closing effect (Chinese Patent Application No. CN 102280605A) has been proposed, which comprises a microporous polyolefin membrane and a surface coated with a polymer colloidal particle coating having a particle size of 10 to 100 nm.
  • the polymer colloidal particle coating is a polymer colloidal emulsion formed by polymerizing acrylonitrile in an organic solvent of EVA, and is formed by drying on the surface of the microporous polyolefin separator.
  • the modified membrane has a thermal expansion and fusion closing effect, good thermal stability, low shrinkage after heating, and avoids burning and explosion of the battery. It improves the safety and reliability of the battery; in addition, it has good liquid absorption and liquid retention ability for the electrolyte melt, thereby giving the lithium ion battery excellent cycle life.
  • the inventors of the present invention believe that although the film has good battery performance and safety, it is obtained by modifying on the basis of the microporous polyolefin separator, which is bound to increase the cost of the battery separator and is practically affected by the separator.
  • the film needs to use a large amount of toluene as a solvent in the preparation process, which has a problem of environmental pollution and also increases the manufacturing cost of the polymer film.
  • An object of the present invention is to provide a non-porous dense film having an colloidal particle structure, an ionic polymer film material.
  • the ionic polymer film material provided by the present invention is composed of polymer colloidal particles having a sulfonate group on the surface. It is a non-porous dense membrane that does not cause significant heat shrinkage when the battery is overheated.
  • the polymer colloidal particles having a sulfonate group on the surface are acrylate-based polymer colloidal particles having a sulfonate group on the surface, which ensures that the ionic polymer membrane material and the electrolyte have Better compatibility.
  • the ionic polymer membrane material of the present invention is a polymer colloidal emulsion having a sulfonate group on its surface during the polymerization reaction using a reactive sulfonate surfactant as an emulsifier.
  • the reactive sulfonate surfactants are vinyl sulfonate, allyl sulfonate, methallyl sulfonate, allyloxy hydroxypropyl sulfonate, hydroxypropyl methacrylate
  • One or more of a sulfonate, 2-acrylamido-2-methylpropanesulfonate, and a styrenesulfonate are used in combination; wherein the cation is a lithium ion, a sodium ion or a potassium ion.
  • the polymer colloidal emulsion is cast into a film to form a polymer film that maintains a colloidal particle structure.
  • the diaphragm does not substantially shrink.
  • the polymer film absorbs the electrolyte, a colloidal ion conduction path is formed between the colloidal particles and the colloidal particles, and after absorbing the electrolyte solution or the solvent, the ionic polymer film material can still maintain the colloidal particle structure, and the colloidal particle spherical structure
  • the dense accumulation increases the tortuosity of the ion conduction path and improves the electronic insulation performance of the polyanion electrolyte membrane.
  • a second object of the present invention is to form an ionic polymer/ceramic composite film by adding a ceramic filler to the above ionic polymer film to increase the rigidity of the ionic polymer film and to reduce the deformation of the ionic polymer film. It is still a dense film with no 90 pores.
  • the polymer colloidal particles having a sulfonate group on the surface are acrylate-based polymer colloidal particles having a sulfonate group on the surface, which ensures that the ionic polymer membrane material and the electrolyte have Better compatibility.
  • the ionic polymer membrane material of the present invention is a polymer colloidal emulsion having a sulfonate group on its surface during the polymerization reaction using a reactive sulfonate surfactant as an emulsifier.
  • a ceramic filler 95 slurry is added to the above polymer colloidal emulsion, uniformly dispersed, and then cast into a film to form an ionic polymer/ceramic filler composite film.
  • the ionic polymer/ceramic filler composite film forms a penetrating ion conduction path between the colloidal particles and the colloidal particles after absorbing the electrolyte, and the composite film material can maintain the colloidal particle structure after absorbing the electrolyte solution or solvent.
  • the dense packing of the colloidal particle structure and the ceramic filler particles uniformly dispersed in the film increase the tortuosity of the ion conduction path and improve the electronic insulation properties of the polyelectrolytic film.
  • the presence of ceramic filler particles increases the rigidity of the ionic polymer film and reduces the deformation of the ion 100 polymer film.
  • the reactive sulfonate surfactants are vinyl sulfonate, allyl sulfonate, methallyl sulfonate, allyloxy hydroxypropyl sulfonate, hydroxypropyl methacrylate
  • One or more of a sulfonate, 2-acrylamido-2-methylpropanesulfonate, and a styrenesulfonate are used in combination; wherein the cation is a lithium ion, a sodium ion or a potassium ion.
  • the preferred particle size range of the ceramic filler particles is from 10 nm to 5.00; the preferred particle size of the ceramic filler particles is from 10 nm to 5.00; Yes, the average particle size of the colloidal particles ranges from 20 to 200 nm, and the average particle size of the ceramic filler particles ranges from 20 nn! ⁇ 0. 5 ; more preferably 20 nm to 200 nm.
  • the ceramic filler particles account for 10-60% by mass of the film. It is preferably 15-50%, more preferably 25-30%.
  • the ionic polymer/ceramic filler composite film has a thickness of 10 to 40 m. The following are the preparation methods:
  • the ionic polymer film of the present invention is prepared by the following method:
  • the polymerization monomer is methyl acrylate.
  • the reactive sulfonate surfactants of the above methods are vinyl sulfonate, allyl sulfonate, methallyl sulfonate, allyloxy hydroxypropyl sulfonate, hydroxy methacrylate
  • One or more of propyl sulfonate, 2-acrylamido-2-methylpropane sulfonate, and styrene sulfonate are used in combination; wherein the cation is a lithium ion, a sodium ion or a potassium ion.
  • a further preferred embodiment of the present invention is to add a second polymerization monomer CH to the polymerization reaction system.
  • ⁇ CRiR 2 is subjected to polymerization.
  • R 2 - C 6 H 5 , an OCOCH 3 , a CN, a C 4 H 6 ON, a C 2 H 3 C0 3 , -COO ( CH 2 ) n CH 3 , n is 0 ⁇ 14.
  • the second monomer is used in combination of any one or more of the above monomers in an amount of 2 to 125 50%, preferably 2 to 10% by weight based on the total mass of the polymerizable monomers.
  • the starting materials for the polymerization are added in one portion, dropwise or stepwise.
  • the polymerization monomer described herein is a combination of a methyl acrylate monomer or a methyl acrylate monomer and a second monomer.
  • the polymerization reaction time is preferably completed to complete the polymerization reaction. Usually 4-36 hours, preferably 8 to 24 hours.
  • the polymerization temperature is 50 to 90 ° C, preferably 55 to 70 ° C.
  • the ionic polymer/ceramic filler composite film of the present invention is prepared by the following method:
  • Synthesis of polymer colloidal emulsion Add colloidal protective agent and distilled water to the reaction flask, heat and stir until completely dissolved, add reactive sulfonate surfactant, polymerization monomer and crosslinker (in any order) Mixing uniformly, then adding initiator polymerization to obtain a polymer colloidal emulsion;
  • Ceramic filler and dispersant are added to distilled water. After dispersing evenly, it is further milled and dispersed by a ball mill. The sieve is passed through 200 mesh to remove the unmilled larger particles.
  • step 140 3 Add the polymer colloidal emulsion prepared in step 1 to the ceramic filler slurry prepared in step 2, disperse uniformly and then apply it on a plastic base tape, such as PET (polyethylene terephthalate) base tape, and bake. After drying the water, it is peeled off to obtain an ionic polymer/ceramic filler composite film.
  • a plastic base tape such as PET (polyethylene terephthalate) base tape
  • bake After drying the water, it is peeled off to obtain an ionic polymer/ceramic filler composite film.
  • the mass percentage of the ceramic filler in the ionic polymer/ceramic filler composite film is 10-60%. It is preferably 15-50%.
  • the reactive sulfonate surfactant of the above method is vinyl sulfonate, allyl sulfonate, methallyl sulfonate, allyloxy hydroxypropyl sulfonate. a mixture of one or more of an acid salt, a hydroxypropyl methacrylate sulfonate, a 2-acrylamido-2-methylpropane sulfonate, and a styrene sulfonate; wherein the cation is a lithium ion,
  • the sodium ion or potassium ion is used in an amount of 2 to 50%, preferably 2 to 10%, based on the total mass of the polymerization monomer.
  • the colloidal protective agent described in the step 1 is one of polyvinyl alcohol, polyethylene oxide, polyacrylate, and polyvinylpyrrolidone, and preferably polyvinyl alcohol.
  • the amount of the colloidal protective agent is 5 to 30%, preferably 10 to 25%, based on the total mass of the polymerization monomer.
  • the dispersing agent in the step 2 is one of polyvinyl alcohol, polyethylene oxide, polyacrylate, and polyvinylpyrrolidone, preferably polyvinyl alcohol.
  • the content of the ceramic filler is 80 to 95%
  • the content of the dispersant is 5 to 155 20%
  • the solid content of the slurry is 20 to 50%.
  • the polymerizable monomer is methyl acrylate
  • the methyl acrylate content in the polymer colloid is 40 to 80%.
  • R 2 _C 6 H 5 , _OCOCH 3 , a CN, a C 4 H 6 ON, _C 2 H 3 C0 3 , — COO(CH 2 )nCH 3 , n is 0 ⁇ 14.
  • the second monomer is used in combination of any one or more of the above monomers in an amount of 2 to 50%, preferably 2 to 10% based on the total mass of the polymerizable monomers.
  • the crosslinking agent described in 165 is a polymerizable monomer having two or more double bonds, such as divinylbenzene, trimethylolpropane triacrylate, dipropylene adipate, methylene. 0 ⁇ 10. 0% ⁇
  • the bis acrylamide, the amount of the total weight of the polymerization monomer is 2. 0 ⁇ 10. 0%.
  • the initiator is 0. 2 ⁇ 1. 0% ⁇ The initiator is 0. 2 ⁇ 1. 0%.
  • the starting materials for the polymerization are added in one portion, dropwise or stepwise.
  • the polymerization monomer described herein is methyl acrylate A combination of a monomer or a methyl acrylate monomer and a second monomer.
  • the polymerization reaction time is preferably 92% or more of the conversion ratio of the monomer polymerization reaction. Usually 4-36 hours, preferably 8 ⁇ 24 hours.
  • the polymerization temperature is 50 to 90 ° C, preferably 55 to 70 ° C.
  • the ceramic filler is a metal oxide and a metal composite oxide, and has the general formula NzMxOy, wherein N is an alkali metal or alkaline earth metal element, M is a metal element, Z is 0 to 5, and X is 1 to 6, y is 1 to 15.
  • the average grain diameter (D50) of the ceramic filler is 10 nn! ⁇ 5.0, preferably 20 nn! ⁇ 0.5 , the preferred ceramic filler is A1 2 0 3 and the average particle diameter (D50) is 20 nm to 200 nm.
  • the present invention provides a lithium ion battery separator and an ionic polymer/ceramic filler composite membrane which are simple in production process, low in manufacturing cost, environmentally friendly, non-polluting, and environmentally friendly with water as a dispersion medium. .
  • the ionic polymer membrane material of the invention is composed of acrylate polymer colloidal particles
  • the ionic polymer/ceramic filler composite membrane material is composed of acrylate polymer colloid particles and inorganic filler
  • the solubility parameter of the acrylate polymer is The solubility parameters of the electrolyte organic solvent are similar, which ensures that the ionic polymer/ceramic filler composite membrane has good compatibility with the electrolyte, achieves good liquid absorption and liquid retention capacity, and can improve battery cycle life.
  • the invention is made by using a polymer colloidal emulsion casting film forming process, and the obtained product is a non-porous dense film, which should not be
  • the ionic polymer/ceramic filler composite film absorbs the electrolyte and forms a penetrating ion conduction path between the colloidal particles and the colloidal particles, and after absorbing the electrolyte solution or solvent, the composite film material can maintain the colloidal particle structure.
  • the dense packing of the colloidal particle structure and the ceramic filler particles uniformly dispersed in the film increase the tortuosity of the ion conduction path and improve the electronic insulation performance of the polyelectrolyte film.
  • the presence of ceramic filler particles increases the rigidity of the ionic polymer film and reduces
  • Figure 1 Schematic diagram of polymer colloidal particles containing a sulfonate group on a single surface, a for the sulfonate group and b for the polymer colloidal particles bearing the sulfonate group on the surface.
  • Figure 2 is a schematic illustration of a polymer colloidal emulsion containing a sulfonate group on the surface.
  • Figure 3 is a schematic representation of an ionic polymer film composed of polymer colloidal particles containing sulfonate groups on the surface. 4 is an SEM after immersion of the ionic polymer membrane electrolyte of the present invention.
  • Fig. 5 is a graph showing the charge and discharge characteristics of a lithium battery in which the ionic polymer film of the present invention is a separator, and the ordinate is the voltage (V) and the abscissa is the gram capacity (mAh/g).
  • Fig. 6 is a graph showing the capacity retention ratio of the ionic polymer film during the charge and discharge cycle of the lithium battery as a function of the number of cycles.
  • the vertical 205 coordinate is the capacity retention ratio (%), and the abscissa is the number of cycles (times).
  • Example 7 is a comparison of discharge curves of lithium batteries prepared by the ionic polymer film and the ionic polymer/A1 2 3 composite film prepared in Example 1 and Example 13, wherein the ordinate is voltage (V) and the abscissa is gram capacity (mAh/).
  • V voltage
  • mAh gram capacity
  • a is an ionic polymer/A1 2 0 3 composite membrane battery
  • b is an ionic polymer membrane battery.
  • Figure 8 is a diagram showing the fifth and 100th charge and discharge curves of a lithium battery of the ionic polymer/A1 2 3 composite film prepared in Example 13, with the ordinate on the voltage (V) and the abscissa as the gram capacity (mAh/). g), A is the 5th charge and discharge curve, and B is the 100th charge and discharge curve.
  • Figure 9 is a scanning electron micrograph of the ionic polymer/A1 2 3 composite film prepared in Example 13. The invention is further described in detail below by way of specific examples, but does not represent that the invention can be practiced in the following manner.
  • the ionic polymer film material is composed of acrylate-based polymer colloidal particles having a sulfonate group on the surface.
  • the polymer is preferably an acrylate-based polymer having a solvent solubility parameter similar to that used in the electrolyte, and the strong polar group on the surface of the ionic polymer film forms a chemical association with the super solvent of the non-aqueous electrolyte, thereby ensuring the present invention.
  • the ionic polymer membrane material has good compatibility with the electrolyte, and achieves good liquid absorption and liquid retention capabilities.
  • the ionic polymer film material of the present invention is an acrylate polymer colloidal emulsion having a sulfonate group on the surface thereof during the polymerization reaction using a reactive sulfonate surfactant as an emulsifier.
  • the emulsion is cast into a film to form a polymer film that maintains the structure of the colloidal particles.
  • a through ion conduction path can be formed between the colloidal particles, and after the electrolyte solution or the solvent is absorbed, the ionic polymer film material can maintain the colloidal particle structure, colloid. Dense packing of particle sphere structure, increasing ion conduction path
  • the tortuosity of 225 improves the electrical insulation properties of the polyanion electrolyte membrane.
  • the average particle diameter of the colloidal particles is observed by a scanning electron microscope to be in the range of 10 nm to 1.0 m, preferably 20 to 200 nm.
  • the ionic polymer film has a thickness of 10 to 40 m.
  • the reactive sulfonate surfactants are vinyl sulfonate, allyl sulfonate, methallyl sulfonate, 230 allyloxy hydroxypropyl sulfonate, hydroxypropyl methacrylate
  • One or more of a sulfonate, a 2-acrylamido-2-methylpropanesulfonate, and a styrenesulfonate are used in combination; wherein the cation is a lithium ion, a sodium ion or a potassium ion.
  • the ionic polymer film is prepared by the following method:
  • the polymerizable monomer is methyl acrylate.
  • a further preferred embodiment of the present invention is to add a second polymerization monomer CHfCR ⁇ to the polymerization reaction system.
  • R 2 is subjected to a polymerization 240 reaction.
  • R 2 - C 6 H 5 , an OCOCH 3 , a CN, a C 4 H 6 ON, a C 2 H 3 C0 3 , -COO ( CH 2 ) n CH 3 , n is 0 ⁇ 14.
  • the second monomer is used in combination of any one or more of the above monomers in an amount of 2 to 50%, preferably 2 to 10% based on the total mass of the polymerizable monomers.
  • the starting materials for the polymerization are added in one portion, dropwise or stepwise.
  • the polymerization monomer described herein is a combination of a methyl acrylate monomer or a methyl acrylate monomer and a second monomer.
  • the polymerization time is preferably completed to complete the polymerization. Usually 4-36 hours, preferably 8 to 24 hours.
  • the polymerization temperature is 50 to 90 ° C, preferably 55 to 70 ° C.
  • distilled water and polyvinyl alcohol are added to the reaction apparatus, and the temperature is raised to 85 to 95 ° C. After the polyvinyl alcohol is completely dissolved, it is cooled to 55 to 70 ° C, and then the polymerization raw material is further added to carry out polymerization.
  • the colloidal protective agent of the present invention is one of polyvinyl alcohol, polyethylene oxide, polyacrylate, and polyvinylpyrrolidone 255, and is preferably polyvinyl alcohol.
  • the amount of the colloidal protective agent is 5 to 30%, preferably 10 to 25%, based on the total mass of the polymerization monomer.
  • the crosslinking agent is a polymerizable monomer having two or more double bonds, such as divinylbenzene or trimethylol. 0%, 0%, preferably 0. 0 ⁇ 7. 0%, 0%, 0%, 0%, 0%, 0%, 0%, 0%, 0%, 0%, 0%, 0%, 0%, 0%, 0%, 0%. 0%, 0%, 0%, 0%, 0%, 0%.
  • the total weight of the polymerized monomer is 0.1% by weight of the total weight of the polymerized monomer.
  • the initiator is a commonly used initiator for the polymerization, such as ammonium persulfate, potassium persulfate, hydrogen peroxide, azobisisobutyl hydrazine and the like. ⁇ 0. 0%, preferably 0. 5 ⁇ 1. 0%.
  • the ionic polymer/ceramic filler composite film material is composed of acrylate-based polymer colloidal particles having a sulfonate group on the surface and a ceramic filler.
  • the polymer is preferably an acrylate-based polymer having a solvent solubility parameter similar to that used in the electrolyte, and the strong polar group on the surface of the ionic polymer/ceramic filler composite membrane colloidal particles and the non-aqueous electrolyte of the super-265 electrolyte form chemistry.
  • the cooperation ensures that the ionic polymer membrane material of the invention has good compatibility with the electrolyte, and achieves good liquid absorption and liquid retention ability.
  • the polymer colloidal particles having a sulfonate group on the surface have an average particle diameter ranging from 10 nm to 1.0.
  • the colloidal particles have an average particle size ranging from 20 to 200 nm, and the ceramic filler particles have an average particle size range of 20 nn! ⁇ 0. 5 ; more preferably 20 nm to 200 nm.
  • the ionic polymer/ceramic filler composite film is prepared by the following method:
  • reaction type sulfonate surfactant is added with methyl acrylate and the second monomer and the crosslinking agent at a time of 60 to 70 ° C, and then the initiator is added to initiate polymerization, or 1/5 to 1 may be added first.
  • reactive sulfonate surfactant with methyl acrylate is added with methyl acrylate
  • the remaining reactive sulfonate surfactant is added dropwise or stepwise to the methyl acrylate and the second monomer and the crosslinking agent, and the polymerization is carried out for 4 to 36 hours, preferably 8 to 24 hours.
  • pre-dispersed ceramic filler slurry Preparation of pre-dispersed ceramic filler slurry, adding ceramic filler and dispersant in distilled water, stirring and dispersing uniformly, then further grinding and dispersing by using agitating ball mill, grinding and dispersing time plume for 2 ⁇ 10 hours, preferably 3 ⁇ 5 The milled slurry was then filtered through a ⁇ 200 mesh screen to remove unmilled larger particles.
  • the reactive sulfonate surfactant is a vinyl sulfonate, an allyl sulfonate, a methallyl sulfonate,
  • ethylene sulfonates are used in combination; wherein the cation is lithium ion, sodium ion or potassium ion, and the amount is 2 to 50%, preferably 2 to 10%, based on the total weight of the polymerization monomer.
  • the colloidal protective agent according to step 1 is one of polyvinyl alcohol, polyethylene oxide, polyacrylate, and polyvinylpyrrolidone, and preferably polyvinyl alcohol.
  • the amount of the colloidal protective agent is 5 to 30% by weight based on the total weight of the polymerization monomer, preferably 10 to 25% by 290.
  • the ceramic filler dispersant of the step 2 is one of polyvinyl alcohol, polyethylene oxide, polyacrylate, and polyvinylpyrrolidone, preferably polyvinyl alcohol.
  • the content of the ceramic filler is 80 to 95%
  • the content of the dispersant is 5 to 20%
  • the solid content of the slurry is 20 to 50%.
  • the polymer colloid which is a preferred embodiment of the present invention has a methyl acrylate content of 40 to 80%.
  • the second monomer is used in combination of any one or more of the above monomers in an amount of 2 to 50%, preferably 2 to 10% based on the total mass of the polymerization monomer.
  • the crosslinking agent is a polymerizable monomer having two or more double bonds, such as divinylbenzene, trimethylol 300 propane triacrylate, dipropylene adipate, methylene Bisacrylamide or the like is used in an amount of from 2.0 to 10.0% by weight based on the weight of the monomer.
  • the initiator is a water-soluble initiator such as ammonium persulfate, potassium persulfate, hydrogen peroxide or azobisisobutylphosphonate, and is used in an amount of 0.2 to 1.0% by weight based on the weight of the monomer.
  • the starting materials for the polymerization are added in one portion, dropwise or stepwise.
  • the polymerization monomer described herein is a combination of a methyl acrylate 305 monomer or a methyl acrylate monomer and a second monomer.
  • the ceramic filler is a metal oxide and a metal composite oxide, and has the general formula NzMxOy, wherein N is an alkali metal or alkaline earth metal element, M is a metal element, Z is 0 to 5, and X is 1 to 6, y is 1 to 15.
  • N is an alkali metal or alkaline earth metal element
  • M is a metal element
  • Z is 0 to 5
  • X is 1 to 6
  • y is 1 to 15.
  • the average particle size of the ceramic filler (D50) is preferably 10 nn! ⁇ 5.0, better for 20 nn! ⁇ 0.5 ,
  • the preferred ceramic filler is A1 2 0 3 and the average particle diameter (D50) is 20 nm to 200 nm.
  • Methyl ester (MA) monomer 10 g of sodium allyloxyhydroxypropyl sulfonate (AHPS) and 10 g of cross-linking agent methylene bis acrylamide were stirred for 1 h, and polymerization was initiated by adding 2 g of ammonium persulfate. After the reaction was carried out for 6 hours, Further, 100 g (MA) and 5 g of AHPS were added, and 1.5 g of ammonium persulfate was further added for further polymerization for 10 hours to obtain a white polymer colloidal emulsion having a solid content of 23.9%, and the monomer conversion rate was 96%.
  • AHPS sodium allyloxyhydroxypropyl sulfonate
  • the synthesized polymer colloidal emulsion had a gel particle average particle diameter (D50) of 1.62 as measured by a laser particle size analyzer.
  • the prepared polymer colloidal emulsion was coated on a PET base tape, and after drying the moisture, an ionic polymer film having a thickness of 20 to 25 m was obtained, and the particle size of the colloidal particles was observed by scanning electron microscopy to be in the range of 80 to 100 nm.
  • Figure 1 is a schematic representation of polymer colloidal particles containing a sulfonate group on a single surface, a for the sulfonate group and b for the polymer colloidal particles bearing a sulfonate group on the surface.
  • Figure 2 is a schematic representation of a polymer colloidal emulsion containing a sulfonate group on the surface.
  • Figure 3 is a schematic representation of an ionic polymer film composed of polymer colloidal particles having a sulfonate group on the surface.
  • Example 2 In a four-port reaction vessel with condensed water, 1000 g of distilled water and 51 g of polyvinyl alcohol were added, and then the temperature was raised to 92 ° C, and the mixture was stirred and dissolved. After the polyvinyl alcohol was completely dissolved, it was cooled to 60 ° C, and 156 g of acrylic acid was added. Methyl ester (MA) monomer, 10 g of 2-acrylamido-2-methylpropane sulfonate (AMPS) and 10 g of crosslinker methylene bis acrylamide were stirred for 1 h, and 2 g of ammonium persulfate was added to initiate polymerization. After the hour, 100 g (MA) and 5 g of AMPS were further added, and 1.5 g of ammonium persulfate was further added for further polymerization for 10 hours to obtain a white polymer colloidal emulsion.
  • MA 2-acrylamido-2-methylpropane sulfonate
  • the prepared polymer colloidal emulsion was coated on a PET base tape, and after drying the moisture, an ionic polymer film having a thickness of 20 to 25 m thick was obtained, and the particle size of the colloidal particles was observed by scanning electron microscopy to be in the range of 80 to 100 nm.
  • Example 3 In a four-port reaction vessel with condensed water, 1000 g of distilled water and 51 g of polyvinyl alcohol were added, and then the temperature was raised to 92 ° C, stirred and dissolved. After the polyvinyl alcohol was completely dissolved, it was cooled to 60 ° C, and 156 g of acrylic acid was added. The ester (MA) monomer, 8 g of allyl sulfonate (SAS) and 10 g of crosslinker methylene bis acrylamide were stirred for 1 h, and 2 g of ammonium persulfate was added to initiate polymerization. After 340 reaction for 6 hours, 100 g ( MA) and 4 g of SAS were simultaneously added with 1.5 g of ammonium persulfate to continue polymerization for 10 hours to obtain a white polymer colloidal emulsion.
  • MA allyl sulfonate
  • SAS crosslinker methylene bis acrylamide
  • the prepared polymer colloidal emulsion was coated on a PET base tape, and after drying the moisture, an ionic polymer film having a thickness of 20 to 25 ⁇ m was obtained, and the particle diameter of the colloidal particles was observed by a scanning electron microscope to be in the range of 40 to 60 nm.
  • Example 4
  • the polymer colloidal emulsion and the ionic polymer membrane of this example were prepared in the same manner as in Example 4 except that 25 g of the second monomer acrylamide (CH 2 CHCONH 2 ) was added.
  • the polymer colloidal emulsion and ionic polymer film of this example were prepared in the same manner as in Example 4 except that 25 g of the second monomer acrylonitrile (CH 2 CHCN) was added.
  • the polymer colloidal emulsion and the ionic polymer membrane of this example were prepared in the same manner as in Example 4, except that the addition of 25 g of the second monomer butyl acrylate (CH 2 CHCOOCH 2 CH 2 CH 2 CH 3 ) was increased by 360. .
  • the polymer colloidal emulsion and the ionic polymer film of this example were prepared in the same manner as in Example 4 except that 25 g of the second monomer vinyl vinyl carbonate (CH 2 CHC 2 H 3 C0 3 ) was added.
  • the ceramic filler slurry used in the following examples was prepared by the following method:
  • Example 10 Preparation of Ionic Polymer/Ceramic Filler Composite Film
  • the ionic polymer/ ⁇ 1 2 3 composite film of this embodiment was prepared in the same manner as in Example 9, except that the ⁇ 1 2 0 3 slurry plus 380 was 19.6 g, wherein A1 2 0 3 was in the film.
  • the mass percentage is 15%, and the ionic polymer/A1 2 0 3 composite film has a thickness of 20 to 25 ⁇ m.
  • the ionic polymer/ ⁇ 1 2 3 3 composite film of this embodiment is prepared in the same manner as in the embodiment 9, except that the ⁇ 1 2 0 3 slurry is added.
  • the 400-in is 111.2 g, wherein A1 2 0 3 accounts for 50% by mass in the film, and the ionic polymer/A1 2 0 3 composite film has a thickness of 20 to 25 ⁇ m.
  • the ionic polymer film prepared in Examples 1 to 8 was immersed in an electrolyte solution composed of ethylene carbonate/diethyl carbonate/dimethyl carbonate and LiPF 6 to be used after the ionic polymer film sufficiently absorbed the electrolyte solution.
  • the chemical conductivity meter was used to measure the ionic conductivity and the absorption of the electrolyte solution.
  • the ionic conductivity and the absorption of the electrolyte solution were also measured under the same conditions of commercial polypropylene and polypropylene microporous membranes. Listed in Table 1.
  • the ionic polymer films obtained in Examples 1 to 8 and commercial polypropylene and polypropylene microporous films were heated to 130 ° C and 415 150 ° C, and the heat shrinkage ratio thereof was measured. The test results are shown in Table 1.
  • the comparative data from Table 1 shows that the ionic polymer film of the present invention has a small heat shrinkage rate, and the polyethylene and polypropylene microporous films have undergone severe shrinkage or melting at the same temperature, for example, 150 °C.
  • Test Example 3
  • Example 5 The ionic polymer film prepared in Example 5 was assembled into a button cell preparation process familiar to those skilled in the art.
  • 2032 button battery which uses LiMn 2 0 4 as the positive electrode material, lithium metal as the negative electrode material and electrolyte solution composed of ethylene carbonate / diethyl carbonate / dimethyl carbonate / LiPF 6 , 2032 button lithium battery in The charge and discharge performance test was carried out under the condition of 0.2 C rate.
  • Figure 5 is a graph of the charge and discharge of a lithium battery of an ionic polymer film, which shows that the ionic polymer film is used as a battery separator, and the 425 battery has good charge and discharge performance.
  • Fig. 6 is a graph showing the capacity retention ratio as a function of the number of cycles during the charge and discharge cycle of the lithium battery of the ionic polymer film, which confirmed that the battery of the ionic polymer film has good charge and discharge cycle performance.
  • the ionic polymer/A1 2 3 composite film prepared in Examples 9 to 16 was immersed in an electrolyte solution composed of ethylene carbonate/diethyl carbonate/dicarbonate 430 methyl ester and LiPF 6 until the composite film sufficiently absorbed the electrolyte. After the solution, the amount of absorption of the electrolyte solution was measured, and the ionic conductivity was measured using an electrochemical impedance meter. The test results are shown in Table 2.
  • the ionic polymer/A1 2 3 composite film obtained in Examples 9 to 16 was heated to 130 ° C, and the heat shrinkage ratio thereof was measured. The test results are shown in Table 2.
  • the data in Table 2 shows that the ionic polymer/A1 2 3 composite film of the present invention gradually decreases in thermal shrinkage rate with the increase of A1 2 0 3 , and the electrical conductivity exhibits an optimum value at about 30% of the ceramic filler. After more than 50%, the conductivity decreases. Therefore, from the above data, the content of the ceramic filler should not exceed 60%. Preferably, it is 15-50%, more preferably 440 is 25-30%.
  • Example 1 and Example 13 were assembled into a 2032 button battery according to a button cell preparation process familiar to those skilled in the art, and the battery was LiMn 2 0 . 4 is a positive electrode material, metal lithium is composed of an anode material and an electrolyte solution composed of ethylene carbonate/diethyl carbonate/dimethyl carbonate/LiPF6,
  • the 445 2032 button lithium battery was tested for charge and discharge performance at 0.2C rate.
  • Figure 7 is a lithium battery discharge curve of the ionic polymer film and the ionic polymer/A1 2 3 composite film prepared in Example 1 and Example 13, which shows that the ionic polymer/A1 2 0 3 composite film is more than the ionic polymer film. has better charge-discharge characteristics, under the same conditions, the battery capacity g g manganese lithium ion polymer film material only 107mAh / g, and the ionic polymer / A1 2 battery lithium manganate material 03 of the composite film The capacity reaches 115 mAh/g. The increase in the gram capacity of lithium manganate material is supported by
  • the presence of a heterophase interface between the 450 A1 2 0 3 and the polymer colloid helps to increase the ionic conductivity of the ionic polymer/A1 2 3 composite film.
  • Example 8 is a fifth and 100th charge-discharge curve of a lithium battery of the ionic polymer/A1 2 3 composite film prepared in Example 13, and after 100 charge-discharge cycles, the capacity retention rate is 98 of the initial capacity. %, exhibits excellent charge and discharge cycle performance.
  • Figure 9 is a scanning electron micrograph of the ionic polymer/A1 2 3 composite film prepared in Example 13, which shows that the composite film is still composed of colloidal particles and ceramic filler particles after the electrolyte solution is impregnated.

Abstract

L'invention porte sur un matériau de membrane polymère ionique et sur un matériau de membrane composite de matériau de membrane polymère ionique/céramique et elle concerne le domaine de la fabrication de batteries au lithium. Le matériau de membrane polymère ionique est composé de particules colloïdales de polymère portant des groupes sulfonate sur leur surface. Le matériau de membrane polymère ionique est obtenu par l'utilisation d'un tensioactif sulfonate réactif utilisé comme agent émulsifiant pour synthétiser une émulsion de colloïde de polymère acrylique portant des groupes sulfonate sur sa surface et par l'opération consistant à soumettre l'émulsion à un procédé de coulage et de formation de film pour former une membrane. Le matériau de membrane composite de polymère ionique/charge de céramique est composé des particules colloïdales de polymère portant des groupes sulfonate sur leur surface et d'une charge céramique. Le matériau de membrane composite de polymère ionique/charge céramique est obtenu par l'utilisation d'un tensioactif sulfonate réactif utilisé en tant qu'agent émulsifiant pour synthétiser une émulsion de colloïde de polymère acrylique portant des groupes sulfonates sur sa surface, par l'ajout d'une suspension épaisse de charge céramique à l'émulsion de colloïde de polymère acrylique et, après dispersion totale jusqu'à l'homogénéité, par l'opération consistant à soumettre l'émulsion à un procédé de coulage et de formation de film pour former une membrane composite de polymère ionique/charge céramique conservant la structure des particules du colloïde.
PCT/CN2013/073856 2012-06-04 2013-04-08 Matériau de membrane polymère ionique, procédé de préparation s'y rapportant et batterie secondaire au lithium WO2013181967A1 (fr)

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CN201210181362.6 2012-06-04
CN201210219590.8A CN102719046B (zh) 2012-06-28 2012-06-28 离子聚合物/陶瓷复合膜材料及其制备方法和锂二次电池
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