WO2018092676A1 - Mélange d'électrodes, procédé de production de mélange d'électrodes, corps de structure d'électrode, procédé de production de corps de structure d'électrode et batterie secondaire - Google Patents

Mélange d'électrodes, procédé de production de mélange d'électrodes, corps de structure d'électrode, procédé de production de corps de structure d'électrode et batterie secondaire Download PDF

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WO2018092676A1
WO2018092676A1 PCT/JP2017/040408 JP2017040408W WO2018092676A1 WO 2018092676 A1 WO2018092676 A1 WO 2018092676A1 JP 2017040408 W JP2017040408 W JP 2017040408W WO 2018092676 A1 WO2018092676 A1 WO 2018092676A1
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electrode mixture
electrode
formula
metal oxide
lithium metal
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PCT/JP2017/040408
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English (en)
Japanese (ja)
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哲広 小林
健太 青木
正太 小林
靖浩 多田
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株式会社クレハ
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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 an electrode mixture, and more particularly to an electrode mixture for a lithium ion secondary battery.
  • the electrode of a lithium ion secondary battery is prepared by, for example, mixing a binder (binder) with a powdered electrode material such as an electrode active material and a conductive auxiliary agent added as necessary, and dissolving or dispersing in a suitable solvent.
  • a binder binder
  • a powdered electrode material such as an electrode active material and a conductive auxiliary agent added as necessary
  • a suitable solvent dissolving or dispersing in a suitable solvent.
  • the obtained slurry-like electrode mixture (hereinafter, also referred to as electrode mixture slurry) is applied on a current collector, and the solvent is stripped to form a structure that is retained as an electrode mixture layer.
  • the conventional electrode mixture since the conventional electrode mixture has low binding strength between the current collector and the electrode active material, the electrode active material may fall off during use of the lithium ion secondary battery, or the electrode mixture layer may collect the current. Sometimes peeled from the body. When such a phenomenon is observed, when the lithium ion secondary battery is used for a long period of time, the discharge capacity may be greatly reduced. Further, when the binding strength of the electrode mixture is increased, there is a problem that the electrode mixture slurry is easily gelled.
  • an electrode mixture for the purpose of suppressing gelation of the electrode mixture slurry has been developed so far.
  • a negative electrode mixture for a non-aqueous electrolyte secondary battery containing a polar group-containing vinylidene fluoride polymer, a chlorine atom-containing vinylidene fluoride polymer, an electrode active material and an organic solvent.
  • Patent Document 1 a lithium-containing composite oxide with a specific composition containing nickel as the positive electrode active material, and a polyvinylidene fluoride and vinylidene fluoride-chlorotrifluoroethylene copolymer as the positive electrode binder.
  • Patent Document 2 a lithium-containing composite oxide with a specific composition containing nickel as the positive electrode active material, and a polyvinylidene fluoride and vinylidene fluoride-chlorotrifluoroethylene copolymer as the positive electrode binder.
  • the present invention has been made in view of the above problems, and an object of the present invention is an electrode mixture used in a lithium ion battery, which can suppress gelation of an electrode mixture slurry, and a current collector and an electrode
  • the object is to provide an electrode mixture capable of realizing high binding strength with an active material.
  • the present inventors can suppress gelation of the electrode mixture slurry by using an electrode mixture containing a specific copolymer and a binder composition containing a specific lithium metal oxide, and The present inventors have found that high adhesive strength between the electric body and the electrode active material can be realized, and have completed the present invention. That is, the present invention can be expressed as follows.
  • An electrode mixture according to the present invention contains an electrode active material provided on a current collector and a binder composition for binding the electrode active material to the current collector.
  • R 1 , R 2 and R 3 are each independently a hydrogen atom, a chlorine atom or an alkyl group having 1 to 5 carbon atoms, and X is a molecular weight having a main chain composed of 1 to 20 atoms. 500 or less atomic groups.
  • the electrode active material contains a lithium metal oxide, and the pH of the water when the lithium metal oxide is extracted with water is 10.5 or more. It is.
  • the manufacturing method of the electrode mixture according to the present invention includes vinylidene fluoride and the following formula (1) or the following formula (2).
  • R 1 , R 2 and R 3 are each independently a hydrogen atom, a chlorine atom or an alkyl group having 1 to 5 carbon atoms, and X is a molecular weight having a main chain composed of 1 to 20 atoms. 500 or less atomic groups.
  • R 1 , R 2 and R 3 are each independently a hydrogen atom, a chlorine atom or an alkyl group having 1 to 5 carbon atoms
  • An electrode structure according to the present invention is an electrode structure including a current collector and an electrode mixture layer provided on the current collector, and the electrode mixture layer includes at least a binder composition and an electrode. It is a layer containing an active material, and the binder composition comprises vinylidene fluoride and the following formula (1) or the following formula (2).
  • R 1 , R 2 and R 3 are each independently a hydrogen atom, a chlorine atom or an alkyl group having 1 to 5 carbon atoms, and X is a molecular weight having a main chain composed of 1 to 20 atoms. 500 or less atomic groups.
  • the electrode active material contains a lithium metal oxide, and the pH of the water when the lithium metal oxide is extracted with water is 10.5. That's it.
  • An electrode structure according to the present invention is an electrode structure including a current collector and an electrode mixture layer provided on the current collector, and the electrode mixture layer includes at least a binder composition and an electrode. It is a layer containing an active material, and the binder composition comprises vinylidene fluoride and the following formula (1) or the following formula (2).
  • R 1 , R 2 and R 3 are each independently a hydrogen atom, a chlorine atom or an alkyl group having 1 to 5 carbon atoms, and X is a molecular weight having a main chain composed of 1 to 20 atoms. 500 or less atomic groups.
  • R 1 , R 2 and R 3 are each independently a hydrogen atom, a chlorine atom or an alkyl group having 1 to 5 carbon atoms
  • the pH of the water when the electrode mixture layer is extracted with water is 10.5 or more.
  • the method for producing an electrode structure according to the present invention comprises applying an electrode mixture containing a copolymer, a lithium metal oxide, and a solvent to the surface of the current collector and drying the electrode mixture. And a step of heat-treating the coating film, wherein the copolymer is vinylidene fluoride and the following formula (1) or (2)
  • R 1 , R 2 and R 3 are each independently a hydrogen atom, a chlorine atom or an alkyl group having 1 to 5 carbon atoms, and X is a molecular weight having a main chain composed of 1 to 20 atoms. 500 or less atomic groups.
  • R 1 , R 2 and R 3 are each independently a hydrogen atom, a chlorine atom or an alkyl group having 1 to 5 carbon atoms
  • the pH of the water when the lithium metal oxide is extracted with water is 10.5 or more.
  • the electrode mixture of the present invention it is possible to provide an electrode mixture that can suppress gelation of the electrode mixture slurry and that can realize high binding strength between the current collector and the electrode active material. .
  • FIG. 1 is an exploded perspective view of a secondary battery according to an embodiment of the present invention. It is a figure based on the graph which shows the viscosity change rate (thickening rate) of the electrode mixture at the time of using NCM111 as an electrode active material. It is a figure based on the graph which shows the viscosity change rate (thickening rate) of the electrode mixture at the time of using NCM523 as an electrode active material.
  • the electrode mixture of the present invention contains an electrode active material provided on a current collector and a binder composition for binding the electrode active material to the current collector.
  • R 1 , R 2 and R 3 are each independently a hydrogen atom, a chlorine atom or an alkyl group having 1 to 5 carbon atoms, and X is a molecular weight having a main chain composed of 1 to 20 atoms. 500 or less atomic groups.
  • the electrode active material contains a lithium metal oxide, and the pH of the water when the lithium metal oxide is extracted with water is 10.5 or more. It is what is.
  • Binder composition The binder composition in the present invention is used as a binder for binding an electrode active material onto a current collector.
  • the binder composition used in the present invention contains a copolymer of vinylidene fluoride and at least one of the monomers represented by the above formula (1) or the above formula (2). It is.
  • R 1 , R 2 and R 3 are each independently a hydrogen atom, a chlorine atom or an alkyl group having 1 to 5 carbon atoms. From the viewpoint of the polymerization reaction, particularly R 1 , R 2 Is preferably a substituent having a small steric hindrance, preferably hydrogen or an alkyl group having 1 to 3 carbon atoms, and more preferably hydrogen or a methyl group.
  • X may be an atomic group having a main chain of 1 to 20 atoms and having a molecular weight of 500 or less, but is preferably 200 or less.
  • the lower limit of the molecular weight in the case of an atomic group is not particularly limited, but is usually 15. This range is preferable in that gelation of the electrode mixture slurry can be suitably suppressed.
  • X is preferably a structure represented by the following formula (3).
  • X ′ is an atomic group having a main chain of 1 to 18 and having a molecular weight of 456 or less.
  • the main chain has 1 to 13 atoms and the main chain has 1 atom. It is more preferable that the molecular weight is 156 or less.
  • X ′ is not particularly limited as the lower limit of the molecular weight of the atomic group, but is usually 14. This range is preferable from the viewpoint of polymerizability.
  • the number of hydrogen atoms is not included in the number of atoms in the main chain.
  • the number of atoms in the main chain is the smallest of the carboxyl group described on the right side of X and the group (R 1 R 2 C ⁇ CR 3 —) described on the left side of X in the formula (1). It means the number of atoms in the skeleton part of the chain connected by the number of atoms.
  • X may be branched by including a functional group as a side chain. One or more side chains may be included in X.
  • the monomer represented by the above formula (1) is preferably a polar group-containing compound.
  • a polar group containing compound the compound containing a carboxyl group, an epoxy group, a hydroxyl group, a sulfonic acid group etc. is mentioned, for example, It is preferable that it is a compound containing a carboxyl group especially.
  • the polar group-containing compound represented by the above formula (1) preferably contains a carboxyl group from the viewpoint of good binding properties between the electrode active material and the current collector.
  • polar group-containing compound represented by the formula (1) examples include acrylic acid (AA), 2-carboxyethyl acrylate, 2-carboxyethyl methacrylate, acryloyloxyethyl succinic acid (AES), Examples thereof include acryloyloxypropyl succinic acid (APS), among which 2-carboxyethyl acrylate, acryloyloxyethyl succinic acid and acryloyloxypropyl succinic acid are preferable.
  • 1 type (s) or 2 or more types may be contained as a polar group containing compound represented by Formula (1).
  • the copolymer used in the present invention contains 0.01 to 10 mol% of a structural unit derived from the monomer represented by the formula (1) or (2) (provided that the structural unit derived from vinylidene fluoride)
  • the total of the structural units derived from the monomer represented by the formula (1) or (2) is preferably 100 mol%, more preferably 0.20 to 7 mol%, It is particularly preferable to have 30 to 4 mol%.
  • the structural unit derived from vinylidene fluoride is preferably 90 to 99.99 mol%, more preferably 93 to 99.75 mol%, and particularly preferably 96 to 99.63 mol%.
  • the structural unit derived from the monomer represented by the formula (1) or (2) is 0.01 mol% or more, the proportion occupied in the electrode mixture slurry of the formula (1) or (2) is small. The effect which suppresses gelatinization of an electrode mixture slurry can be acquired without becoming too much. Moreover, when the structural unit derived from the monomer represented by the formula (1) or (2) is 10 mol% or less, the viscosity of the electrode mixture slurry does not become too high, and the electrode mixture slurry is applied. Can be difficult.
  • the amount of the vinylidene fluoride unit of the copolymer and the amount of the monomer unit represented by the above formula (1) or the above formula (2) are usually 1 H NMR spectrum of the copolymer, It can be determined by Japanese titration.
  • the copolymer used in the present invention may have a component of a monomer other than the vinylidene fluoride and the monomer represented by the above formula (1) or the above formula (2).
  • a monomer other than the vinylidene fluoride and the monomer represented by the above formula (1) or the above formula (2) examples thereof include fluorine monomers copolymerizable with vinylidene fluoride or hydrocarbon monomers such as ethylene and propylene, and monomers copolymerizable with the above formulas (1) and (2).
  • the fluorine-based monomer copolymerizable with vinylidene fluoride include perfluoroalkyl vinyl ethers typified by vinyl fluoride, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, and perfluoromethyl vinyl ether.
  • Examples of the monomer copolymerizable with the above formulas (1) and (2) include (meth) acrylic acid, (meth) acrylic acid alkyl compounds represented by methyl (meth) acrylate, and the like.
  • another monomer may be used individually by 1 type and may use 2 or more types.
  • the copolymer has other monomers as described above, if the total monomer units constituting the copolymer are 100 mol%, the other monomer units have 0.01 to 10 mol%. It is preferable.
  • the copolymer used in the present invention usually has a weight average molecular weight measured by GPC (gel permeation chromatography) in the range of 50,000 to 1,500,000.
  • the copolymer used in the present invention can be obtained by polymerizing vinylidene fluoride and at least one of the monomers represented by the above formula (1) or the above formula (2) by a conventionally known method. it can.
  • a conventionally known method for example, methods, such as suspension polymerization, emulsion polymerization, and solution polymerization, can be mentioned.
  • the polymerization method is preferably aqueous suspension polymerization or emulsion polymerization in view of ease of post-treatment.
  • polymerization and the monomer represented by the said Formula (1) and the said Formula (2) are already well-known compounds, respectively, and a general commercial item may be used.
  • the copolymer used in the present invention is usually 90 to 99.9 parts by weight of vinylidene fluoride and 0.1 to 10 parts by weight of the monomer represented by the above formula (1) or (2), More preferably, it can be obtained by copolymerizing 95 to 99.9 parts by weight of vinylidene fluoride and 0.1 to 5 parts by weight of the monomer represented by the above formula (1) or (2). Preferred (however, the total of the vinylidene fluoride and the monomer represented by the above formula (1) or the above formula (2) is 100 parts by weight).
  • the inherent viscosity ⁇ i of the copolymer used in the present invention is preferably 0.5 dl / g to 5.0 dl / g, more preferably 1.0 dl / g to 4.0 dl / g, More preferably, it is 1.5 dl / g to 3.5 dl / g. If the inherent viscosity is in the above range, it is preferable in that the electrode can be easily produced without deteriorating the productivity due to a decrease in the slurry solid content and without causing unevenness of the electrode thickness when the electrode mixture is applied.
  • the inherent viscosity ⁇ i described above can be obtained from the following equation by dissolving 80 mg of the polymer in 20 ml of N, N-dimethylformamide and using an Ubbelohde viscometer in a thermostat at 30 ° C.
  • ⁇ i (1 / C) ⁇ ln ( ⁇ / ⁇ 0 )
  • ⁇ is the viscosity of the polymer solution
  • ⁇ 0 is the viscosity of N, N-dimethylformamide as a solvent
  • C is 0.4 g / dl.
  • the electrode can be easily produced without causing deterioration in productivity due to a decrease in the solid content of the slurry and without causing unevenness of the electrode thickness when the electrode mixture is applied.
  • the electrode active material used in the present invention contains a lithium metal oxide.
  • the electrode active material may contain, for example, impurities and additives in addition to the lithium metal oxide.
  • the types of impurities and additives contained in the electrode active material are not particularly limited.
  • 49 g of ultrapure water is added to 1 g of lithium metal oxide, and after stirring for 10 minutes, the pH of the water when the pH of the water is measured is 10.5 or more. .
  • the upper limit of the pH of the water is not particularly limited.
  • lithium metal oxide used in the present invention examples include the following formula (4): LiMO 2 (4) The lithium metal oxide represented by these is mentioned.
  • M is preferably at least one selected from the group consisting of Ni, Co, Al, Fe, Mn, Cr and V, and M is Ni, Co or Al. More preferably, in addition to Ni, M further preferably contains one or more selected from the group consisting of Co, Mn and Al. It is preferable that the lithium metal oxide contains Ni in that the capacity of the secondary battery can be increased by increasing the capacity density. Further, it is preferable that the lithium metal oxide further contains Co or the like in addition to Ni in that stable cycle characteristics are exhibited by suppressing changes in the crystal structure during the charge / discharge process.
  • lithium metal oxide examples include LiCoO 2 and LiNiO 2 .
  • lithium metal oxide used in the present invention for example, the following formula (5) LiNi x N1 y O 2 (5) (In the formula, N1 represents Co or Mn, and 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1) Or a binary lithium metal oxide represented by the following formula (6) LiNi x Co y N2 z O 2 ⁇ (6) (Wherein N2 represents Mn or Al, and 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 1) and a ternary lithium metal oxide and a spinel type LiMn 2 O 4 is mentioned.
  • the ratio of Ni is 30 mol% or more. Preferably there is.
  • the ternary lithium metal oxide is particularly preferably used as the electrode active material of the present invention because it has a high charging potential and excellent cycle characteristics.
  • the composition of the binary lithium metal oxide used in the present invention is not particularly limited.
  • As the composition Li 1.0 Ni 0.8 Co 0.2 O 2 , Li 1.0 Ni 0.5 Mn 0.5 O 2 can be mentioned.
  • composition of the ternary lithium metal oxide used in the present invention is not particularly limited, and for example, Li 1.00 Ni 0.35 Co 0.34 Mn 0.34 O 2 (NCM111 ), Li 1.00 Ni 0.52 Co 0.20 Mn 0.30 O 2 (NCM523), Li 1.00 Ni 0.50 Co 0.30 Mn 0.20 O 2 (NCM532), Li 1.00 Ni 0.6 Co 0.2 Mn 0.2 O 2 (NCM 622), Li 1.00 Ni 0.83 Co 0.12 Mn 0.05 O 2 (NCM 811), Li 1.00 Ni 0.85 Co 0 .15 Al 0.05 O 2 (NCA811).
  • NCM111 Li 1.00 Ni 0.35 Co 0.34 Mn 0.34 O 2
  • NCM523 Li 1.00 Ni 0.52 Co 0.20 Mn 0.30 O 2
  • NCM532 Li 1.00 Ni 0.50 Co 0.30 Mn 0.20 O 2
  • NCM 622 Li 1.00 Ni 0.6 Co 0.2 Mn 0.2 O 2
  • NCM 811 Li 1.00 Ni 0.83 Co 0.12 Mn 0.05 O 2
  • the electrode active material used in the present invention may contain a plurality of different types of lithium metal oxides, for example, may contain a plurality of LiNi x Co y Mn Z O 2 having different compositions, x Co y Mn Z O 2 and LiNi x Co y Al z O 2 and may contain.
  • the binder composition used in the present invention may contain a solvent.
  • the solvent may be water or a non-aqueous solvent.
  • the non-aqueous solvent include N-methyl-2-pyrrolidone (NMP), dimethylformamide, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, N, N-dimethyl sulfoxide, hexamethylphosphoamide, Examples include dioxane, tetrahydrofuran, tetramethylurea, triethyl phosphate, trimethyl phosphate, acetone, cyclohexane, methyl ethyl ketone, and tetrahydrofuran.
  • NMP N-methyl-2-pyrrolidone
  • dimethylformamide N-dimethylformamide
  • N, N-dimethylacetamide dimethyl sulfoxide
  • N N-dimethyl sulfoxide
  • hexamethylphosphoamide examples include dio
  • the solvent content in the binder composition is preferably 400 to 10,000 parts by weight, more preferably 600 to 5000 parts by weight. Within the above range, an appropriate solution viscosity is obtained and the handling property is excellent, which is preferable.
  • the binder composition of the present invention may contain other components as necessary.
  • other components include a conductive aid and a pigment dispersant.
  • a conductive support agent is added for the purpose of improving the electroconductivity of the electrode mixture layer mentioned later.
  • the conductive assistant used in the present invention include natural graphite (eg, scaly graphite), artificial graphite, graphite such as fine graphite powder and graphite fiber, acetylene black, ketjen black, channel black, and furnace black. Examples thereof include carbon materials such as carbon blacks, carbon fibers, and carbon nano-nanotubes.
  • conductive fibers such as metal fibers such as Ni and Al, metal powders, conductive metal oxides, organic conductive materials, and the like are also included.
  • Pigment dispersant examples include polyvinyl pyrrolidone.
  • the other components described above are usually 0 to 10 parts by weight, preferably 0 to 5 parts by weight with respect to 100 parts by weight of the electrode mixture of the present invention.
  • the method for producing an electrode mixture of the present invention is a copolymer obtained by copolymerizing vinylidene fluoride and at least one of the monomers represented by the formula (1) or the formula (2) described above. And a step of kneading the above-described lithium metal oxide.
  • a solvent and other components may be kneaded as necessary, and the method is not particularly limited.
  • the order of addition of various components at the time of kneading is not particularly limited.
  • the electrode active material and the solvent may be first stirred and mixed, and then the copolymer may be added.
  • FIG. 1 is a cross-sectional view of an electrode structure according to an embodiment of the present invention.
  • the electrode structure 10 includes a current collector 11 and electrode mixture layers 12a and 12b.
  • the current collector 11 is a base material for the electrode structure 10 and is a terminal for taking out electricity.
  • Examples of the material of the current collector 11 include iron, stainless steel, steel, aluminum, nickel, and titanium.
  • the shape of the current collector 11 is preferably a foil or a net. In the present invention, the current collector 11 is preferably an aluminum foil.
  • the thickness of the current collector 11 is preferably 5 to 100 ⁇ m, and more preferably 5 to 20 ⁇ m.
  • the electrode mixture layers 12a and 12b are layers made of the electrode mixture of the present invention.
  • the thickness of the electrode mixture layers 12a and 12b is 10 ⁇ m to 1000 ⁇ m, more preferably 20 to 250 ⁇ m, and still more preferably 20 to 150 ⁇ m.
  • the pH of the water is 10.5 or more. Specifically, the measurement was performed by the same method as the above-described method for measuring the pH of the lithium metal oxide except that the electrode mixture layer was peeled off from the current collector foil and used as a sample.
  • the electrode structure 10 has electrode mixture layers 12a and 12b formed on the upper and lower surfaces of the current collector 11.
  • the present invention is not limited to this. What has the electrode mixture layer formed in any one surface, ie, the electrode structure in which any one of the electrode mixture layers 12a and 12b was formed may be sufficient.
  • the electrode structure 10 of the present invention can be used, for example, as a positive electrode of a lithium secondary battery described later.
  • the method for producing an electrode structure of the present invention uses the electrode mixture of the present invention, and specifically, a slurry-like book containing at least a copolymer, a lithium metal oxide, and a solvent.
  • the electrode mixture of the invention (hereinafter also referred to as electrode mixture slurry) is applied to the surface of the current collector 11 and dried to form a coating film on the surface of the current collector 11, and the coating film is subjected to heat treatment.
  • the electrode structure 10 in which the electrode mixture layers 12a and 12b are formed on the upper and lower surfaces of the current collector 11 is obtained.
  • a known method can be used as a method for applying the electrode mixture slurry, and examples thereof include a bar coater, a die coater, and a comma coater.
  • the drying temperature for drying the electrode mixture slurry applied to the upper and lower surfaces of the current collector 11 can be 50 to 170 ° C., preferably 50 to 150 ° C.
  • the method of forming the electrode mixture layer by applying the electrode mixture slurry to the upper and lower surfaces of the current collector 11 has been described.
  • the electrode manufacturing method of the present invention is not limited to this.
  • the electrode mixture of the present invention may be applied to at least one surface of the current collector.
  • the peel strength refers to a single-side coated electrode having a basis weight of 200 g / m 2 according to the electrode structure of the present invention, cut into a length of 50 mm and a width of 20 mm, according to JIS K-6854. It means the peel strength obtained by performing a 90 degree peel test at a head speed of 10 mm / min using a tensile tester ("STA-1150 UNIVERSAL TESTING MACHINE" manufactured by ORIENTEC).
  • the peel strength represents the binding property between the binder composition and the current collector, and the higher the peel strength, the higher the binding property between the electrode active material and the current collector by the binder composition. Is shown.
  • the secondary battery of the present invention is a nonaqueous electrolyte secondary battery including the electrode structure of the present invention.
  • One embodiment of the secondary battery of the present invention will be described with reference to FIG.
  • FIG. 2 is an exploded perspective view of the secondary battery according to the present embodiment.
  • the secondary battery 100 has a structure in which a power generating element in which a separator 3 is disposed and laminated between a positive electrode 1 and a negative electrode 2 and wound in a spiral shape is housed in a metal casing 5.
  • the positive electrode 1 corresponds to the electrode structure 10 in FIG.
  • a known material such as a porous film of a polymer material such as polypropylene or polyethylene may be used.
  • a known material such as a porous film of a polymer material such as polypropylene or polyethylene may be used.
  • the members used in the secondary battery 100 those normally used in this field can be appropriately used.
  • the secondary battery 100 is a cylindrical battery, but of course, the secondary battery 100 in the present invention is not limited to this, and may be a secondary battery having another shape such as a coin shape, a square shape, or a paper shape. There may be.
  • An electrode mixture according to an embodiment of the present invention includes an electrode active material provided on a current collector and a binder composition for binding the electrode active material to the current collector.
  • R 1 , R 2 and R 3 are each independently a hydrogen atom, a chlorine atom or an alkyl group having 1 to 5 carbon atoms, and X is a molecular weight having a main chain composed of 1 to 20 atoms. 500 or less atomic groups.
  • the electrode active material contains a lithium metal oxide, and the pH of the water when the lithium metal oxide is extracted with water is 10.5 or more. It is.
  • the copolymer contains 0.01 to 10 mol% (provided that the structural unit derived from the monomer represented by the formula (1) or (2)).
  • the total of the structural units derived from vinylidene fluoride and the structural units derived from the monomer represented by the formula (1) or (2) is preferably 100 mol%.
  • the copolymer contains 0.20-7 mol% (provided that the structural unit derived from the monomer represented by the formula (1) or (2)).
  • the total of the structural units derived from vinylidene fluoride and the structural units derived from the monomer represented by the formula (1) or (2) is preferably 100 mol%.
  • the copolymer contains 0.30 to 4 mol% (provided that the structural unit derived from the monomer represented by the formula (1) or (2)).
  • the total of the structural units derived from vinylidene fluoride and the structural units derived from the monomer represented by the formula (1) or (2) is preferably 100 mol%.
  • X represents the following formula (3): -COO-X'- (3) (In the formula, X ′ is an atomic group having a main chain of 1 to 18 atoms and a molecular weight of 456 or less.) It is preferable to be represented by
  • the monomer represented by the formula (1) is 2-carboxyethyl acrylate, acryloyloxyethyl succinic acid, or acryloyloxypropyl succinic acid. It is preferable.
  • the inherent viscosity ⁇ i of the copolymer is preferably 0.5 dl / g to 5.0 dl / g.
  • lithium metal oxide is following formula (4).
  • LiMO 2 (4) (Wherein M represents at least one selected from the group consisting of Ni, Co, Al, Fe, Mn, Cr and V) It is preferable to be represented by
  • lithium metal oxide is following formula (5).
  • LiNi x N1 y O 2 (5) (In the formula, N1 represents Co or Mn, and 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1)
  • a binary lithium metal oxide represented by the following formula (6) LiNi x Co y N2 z O 2 ⁇ (6) (Wherein N2 represents either Mn or Al, 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 1) It is preferable that it is a ternary lithium metal oxide represented by these.
  • the method for producing an electrode mixture according to an embodiment of the present invention includes vinylidene fluoride and the following formula (1) or the following formula (2).
  • R 1 , R 2 and R 3 are each independently a hydrogen atom, a chlorine atom or an alkyl group having 1 to 5 carbon atoms, and X is a molecular weight having a main chain composed of 1 to 20 atoms. 500 or less atomic groups.
  • R 1 , R 2 and R 3 are each independently a hydrogen atom, a chlorine atom or an alkyl group having 1 to 5 carbon atoms
  • An electrode structure according to an embodiment of the present invention is an electrode structure including a current collector and an electrode mixture layer provided on the current collector, and the electrode mixture layer includes at least a binder. It is a layer containing a composition and an electrode active material, and the binder composition comprises vinylidene fluoride and the following formula (1) or the following formula (2).
  • R 1 , R 2 and R 3 are each independently a hydrogen atom, a chlorine atom or an alkyl group having 1 to 5 carbon atoms, and X is a molecular weight having a main chain composed of 1 to 20 atoms. 500 or less atomic groups.
  • the electrode active material contains a lithium metal oxide, and the pH of the water when the lithium metal oxide is extracted with water is 10.5. That's it.
  • An electrode structure according to an embodiment of the present invention is an electrode structure including a current collector and an electrode mixture layer provided on the current collector, and the electrode mixture layer includes at least a binder. It is a layer containing a composition and an electrode active material, and the binder composition comprises vinylidene fluoride and the following formula (1) or the following formula (2).
  • R 1 , R 2 and R 3 are each independently a hydrogen atom, a chlorine atom or an alkyl group having 1 to 5 carbon atoms, and X is a molecular weight having a main chain composed of 1 to 20 atoms. 500 or less atomic groups.
  • R 1 , R 2 and R 3 are each independently a hydrogen atom, a chlorine atom or an alkyl group having 1 to 5 carbon atoms
  • the pH of the water when the electrode mixture layer is extracted with water is 10.5 or more.
  • a method for producing an electrode structure according to an embodiment of the present invention includes applying an electrode mixture containing a copolymer, a lithium metal oxide, and a solvent to a current collector surface and drying the electrode mixture.
  • a step of forming a coating film on the surface of the electric body and a step of heat-treating the coating film, and the copolymer is vinylidene fluoride and the following formula (1) or the following formula (2)
  • R 1 , R 2 and R 3 are each independently a hydrogen atom, a chlorine atom or an alkyl group having 1 to 5 carbon atoms, and X is a molecular weight having a main chain composed of 1 to 20 atoms. 500 or less atomic groups.
  • R 1 , R 2 and R 3 are each independently a hydrogen atom, a chlorine atom or an alkyl group having 1 to 5 carbon atoms
  • the pH of the water when the lithium metal oxide is extracted with water is 10.5 or more.
  • this invention provides a secondary battery provided with the electrode structure which concerns on one Embodiment of this invention.
  • electrode structures were prepared using various binder compositions and subjected to a peel test.
  • a peel test As shown below, electrode structures were prepared using various binder compositions and subjected to a peel test.
  • each method of measurement of pH of lithium metal oxide, calculation of slurry viscosity, measurement of peel strength, and viscosity change rate (also simply referred to as a thickening rate) will be described.
  • the pH of the lithium metal oxide as the electrode active material was the pH of the water when 49 g of ultrapure water was added to 1 g of lithium metal oxide and extracted by stirring for 10 minutes.
  • a pH meter MODEL: F-21 manufactured by Horiba, Ltd. was used for the measurement of the pH of the water.
  • ⁇ i (1 / C) ⁇ ln ( ⁇ / ⁇ 0 )
  • ⁇ is the viscosity of the polymer solution
  • ⁇ 0 is the viscosity of the solvent N, N-dimethylformamide
  • C is 0.4 g / dl.
  • a single-side coated electrode with a single-sided weight of 200 g / m 2 was cut into a length of 50 mm and a width of 20 mm, and a tensile tester (“STA-1150 UNIVERSAL TESTING MACHINE” manufactured by ORIENTEC) was used according to JIS K-6854.
  • a 90 degree peel test was conducted at a head speed of 10 mm / min, and the peel strength was measured.
  • the viscosity change rate indicates the rate of change of viscosity with respect to the storage time of an electrode mixture composed of a binder composition, an electrode active material, a conductive aid, and a nonaqueous solvent, and is determined by the following method. be able to.
  • the viscosity of the electrode mixture consisting of binder composition, electrode active material, conductive additive and non-aqueous solvent, and at a predetermined temperature, precision thermostat manufactured by Yamato Scientific Co., Ltd. MODEL: nitrogen content in DH410: 7-10L / Min. After a predetermined time, the electrode mixture was allowed to cool to room temperature, stirred at 2000 rpm for 2 minutes, and then the viscosity was measured. Viscosity was measured using the E-type viscometer RE-550 MODEL: R, RC-550 manufactured by Toki Sangyo Co., Ltd., and the viscosity was measured when shearing for 300 seconds at a measurement temperature of 25 ° C and a shear rate of 20 sec- 1. It was measured. From the electrode mixture viscosity before storage and the electrode mixture viscosity after storage, the viscosity change rate (thickening rate) was calculated based on the following formula.
  • Viscosity change rate (thickening rate) (%) ((Electrode mixture viscosity after storage / electrode mixture viscosity before storage) -1) ⁇ 100
  • Apparatus manufactured by Bruker. AVANCE AC 400FT NMR spectrum meter Measurement conditions Frequency: 400 MHz Measuring solvent: DMSO-d6 Measurement temperature: 25 ° C
  • the amount of the structural unit derived from the vinylidene fluoride of the polymer and the amount of the structural unit derived from the comonomer were calculated from the 1 H NMR spectrum. Specifically, it was calculated based on the integrated intensity of signals mainly derived from comonomer and signals observed at 2.24 ppm and 2.87 ppm mainly derived from vinylidene fluoride.
  • a comonomer having a structure derived from acrylic acid When a comonomer having a structure derived from acrylic acid is used as a comonomer, the amount of the structural unit containing a structure derived from acrylic acid in the polymer is neutralized with a sodium hydroxide aqueous solution of 0.03 mol / l. Determined by More specifically, a solution to be titrated was prepared by dissolving 0.3 g of a polymer in 9.7 g of acetone at about 80 ° C. and then adding 3 g of pure water. As an indicator, phenolphthalein was used, and neutralization titration was performed using a 0.03 mol / l aqueous sodium hydroxide solution at room temperature.
  • a vinylidene fluoride copolymer (VDF / APS) was dissolved in N-methyl-2-pyrrolidone (hereinafter referred to as NMP) to prepare a 5% by weight vinylidene fluoride solution.
  • NMP N-methyl-2-pyrrolidone
  • Carbon nanotubes were added as a conductive additive to the vinylidene fluoride solution and kneaded at 2000 rpm for 3 minutes, and then NCM111 and NMP as electrode active materials were added and kneaded at 2000 rpm for 5 minutes. Further, NMP was added so that the solid content concentration was 62%, and the mixture was kneaded at 2000 rpm for 1 minute to obtain an electrode mixture.
  • the conductive support agent contained in an electrode mixture was 2 weight part
  • the binder composition was 1.5 weight part.
  • Electrode structure ⁇ Production of electrode structure>
  • the electrode mixture obtained as described above was applied on a 15 ⁇ m thick aluminum foil (current collector) with a bar coater, and this was heated and dried at 110 ° C. for 30 minutes and further at 130 ° C. for 2 hours, An electrode structure having a basis weight of the electrode mixture in a dry state of about 200 g / m 2 was produced.
  • Example 2 An electrode mixture was prepared in the same manner as in Example 1 except that the electrode active material was changed to NCM523, and an electrode structure was produced.
  • Example 3 An electrode mixture was prepared in the same manner as in Example 1 except that the inherent viscosity of the vinylidene fluoride copolymer (VDF / APS) was 1.8 dl / g, and an electrode structure was produced.
  • VDF / APS vinylidene fluoride copolymer
  • Example 4 Into an autoclave having an internal volume of 2 liters, each amount of 900 g of ion-exchanged water, 0.4 g of hydroxypropylmethylcellulose, 2 g of butylperoxypivalate, 396 g of vinylidene fluoride, and 0.2 g of initial addition amount of acrylic acid was charged at 50 ° C. Heated. A 1% by weight aqueous acrylic acid solution containing acrylic acid was continuously fed to the reaction vessel under the condition that the pressure was kept constant during the polymerization. The obtained polymer slurry was dehydrated and dried to obtain a vinylidene fluoride copolymer (VDF / AA) containing a polar group. A total of 4 g of acrylic acid was added, including the amount added initially.
  • VDF / AA vinylidene fluoride copolymer
  • An electrode mixture was prepared in the same manner as in Example 1 except that the obtained vinylidene fluoride copolymer (VDF / AA) was used, and an electrode structure was produced.
  • Example 5 An electrode mixture was prepared in the same manner as in Example 4 except that the electrode active material was changed to NCM523, and an electrode structure was produced.
  • Example 6 ⁇ Electrode mixture> (Preparation of electrode mixture) A vinylidene fluoride copolymer (VDF / APS) was dissolved in N-methyl-2-pyrrolidone (hereinafter referred to as NMP) to prepare a 5% by weight vinylidene fluoride solution. Using NCA811 as the electrode active material and carbon black as the conductive assistant, the above-mentioned vinylidene fluoride solution was added to a solid content concentration of 84%, and kneaded at 2000 rpm for 1 minute.
  • NMP N-methyl-2-pyrrolidone
  • a vinylidene fluoride solution and NMP were added so as to have a solid concentration of 70%, and kneaded at 2000 rpm for 5 minutes to obtain an electrode mixture.
  • an electrode active material was 100 weight part
  • the conductive support agent contained in an electrode mixture was 2 weight part
  • the binder composition was 2 weight part.
  • Electrode structure ⁇ Production of electrode structure>
  • the electrode mixture obtained as described above was applied on a 15 ⁇ m thick aluminum foil (current collector) with a bar coater, and this was heated and dried at 110 ° C. for 30 minutes and further at 130 ° C. for 2 hours, An electrode structure having a basis weight of the electrode mixture after drying of approximately 200 g / m 2 was produced.
  • Example 7 (Preparation of binder composition) In an autoclave having an internal volume of 2 liters, 1096 g of ion-exchanged water, 0.2 g of Metroze 90SH-100 (manufactured by Shin-Etsu Chemical Co., Ltd.), 2.2 g of a 50 wt% diisopropyl peroxydicarbonate-fluorocarbon 225 cb, 426 g of vinylidene fluoride, and Each amount of 0.2 g of initial addition amount of acryloyloxypropyl succinic acid was charged, and the temperature was raised to 26 ° C. over 1 hour.
  • An electrode mixture was prepared in the same manner as in Example 6 except that the obtained vinylidene fluoride copolymer (VDF / APS) was used to prepare an electrode structure.
  • the viscosity of the obtained electrode mixture was measured by the same method as the viscosity measurement described above except that the shear rate was 2 sec- 1 .
  • Example 8 An electrode mixture was prepared in the same manner as in Example 7 except that the vinylidene fluoride copolymer used in Example 1 was used, and an electrode structure was produced. The viscosity of the obtained electrode mixture was measured by the same method as in Example 7.
  • Example 9 (Preparation of binder composition) In an autoclave having an internal volume of 2 liters, 1096 g of ion-exchanged water, 0.2 g of Metroze 90SH-100 (manufactured by Shin-Etsu Chemical Co., Ltd.), 2.2 g of a 50 wt% diisopropyl peroxydicarbonate-fluorocarbon 225 cb, 426 g of vinylidene fluoride, and Each amount of 0.2 g of initial addition amount of acryloyloxypropyl succinic acid was charged, and the temperature was raised to 26 ° C. over 1 hour.
  • An electrode mixture was prepared in the same manner as in Example 6 except that the obtained vinylidene fluoride copolymer (VDF / APS) was used to prepare an electrode structure.
  • the viscosity of the obtained electrode mixture was measured by the same method as in Example 7.
  • Example 10 (Preparation of binder composition) In an autoclave having an internal volume of 2 liters, 1096 g of ion exchange water, 0.4 g of Metroze 90SH-100 (manufactured by Shin-Etsu Chemical Co., Ltd.), 2.2 g of a 50 wt% diisopropyl peroxydicarbonate-fluorocarbon 225 cb solution, 426 g of vinylidene fluoride, and Each amount of 0.2 g of initial addition amount of carboxyethyl acrylate was charged and heated to 45 ° C. in 2 hours.
  • Metroze 90SH-100 manufactured by Shin-Etsu Chemical Co., Ltd.
  • 2.2 g of a 50 wt% diisopropyl peroxydicarbonate-fluorocarbon 225 cb solution 426 g of vinylidene fluoride
  • An electrode mixture was prepared in the same manner as in Example 6 except that the obtained vinylidene fluoride copolymer (VDF / CEA) was used to prepare an electrode structure.
  • the viscosity of the obtained electrode mixture was measured by the same method as in Example 7.
  • Example 1 Example 1 except that the vinylidene fluoride copolymer was changed to KF # 7200 (excluding monomers other than VDF; hereinafter also referred to as PVDF) manufactured by Kureha Co., Ltd., and the solid content concentration was 65%.
  • an electrode mixture was prepared to produce an electrode structure.
  • An electrode mixture was prepared in the same manner as in Example 1 except that the obtained vinylidene fluoride copolymer was used and the solid content concentration was 65% to prepare an electrode structure.
  • Example 7 An electrode mixture and an electrode were prepared in the same manner as in Example 6 except that the vinylidene fluoride copolymer was changed to KF # 7200 (excluding monomers other than VDF, hereinafter also referred to as PVDF) manufactured by Kureha Co., Ltd. A structure was produced.
  • VDF vinylidene fluoride copolymer
  • Example 8 The electrode mixture and electrode were the same as in Example 7 except that the vinylidene fluoride copolymer was changed to KF # 7200 (excluding monomers other than VDF, hereinafter also referred to as PVDF) manufactured by Kureha Co., Ltd. A structure was produced.
  • VDF vinylidene fluoride copolymer
  • the binding strength of the aluminum foil and the electrode mixture layer of the electrodes obtained in Examples 1 to 10 and Comparative Examples 1 to 9 is that of the electrode structure formed by applying the electrode mixture to the current collector surface.
  • the upper surface and the plate thickness of plastic (made of acrylic resin, thickness 5 mm) were bonded together and evaluated as 90 ° peel strength determined in accordance with JIS K6854. The results are shown in Table 1.
  • Example 1 when Example 1 is compared with Example 4 and Examples 2 and 5, respectively, when VDF / APS is used as a copolymer, peeling is higher than when VDF / AA is used as a copolymer. Intensity was shown.
  • FIG. 3 is a graph based on the graph showing the rate of change in viscosity (thickening rate) of the electrode mixture when NCM111 is used as the electrode active material.
  • FIG. 4 is a graph based on the graph showing the rate of change in viscosity (thickening rate) of the electrode mixture when NCM523 is used as the electrode active material. More specifically, FIG. 3 corresponds to the viscosity change rate of each electrode mixture of Example 1 and Comparative Example 1, and FIG. 4 shows the viscosity change of each electrode mixture of Example 2 and Comparative Example 2. Corresponding to 3 and 4, the vertical axis represents the rate of change in viscosity (%) of the electrode mixture, and the horizontal axis represents the storage time (hour) of the electrode mixture.
  • the electrode mixture of the present invention can be suitably used as a material for producing a positive electrode of a lithium ion secondary battery.

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Abstract

L'invention concerne un mélange d'électrodes capable d'empêcher la gélification d'une bouillie de mélange d'électrodes, et capable d'obtenir une force de liaison élevée entre un collecteur et une substance active d'électrode. Ce mélange d'électrodes comprend : une composition de liant contenant un copolymère de fluorure de vinylidène et au moins un monomère représenté par la formule (1) ou la formule (2); et une substance active d'électrode contenant un oxyde métallique de lithium qui, lorsque extraite avec de l'eau, amène le pH de l'eau à être de 10,5 ou plus. (1) (2)
PCT/JP2017/040408 2016-11-15 2017-11-09 Mélange d'électrodes, procédé de production de mélange d'électrodes, corps de structure d'électrode, procédé de production de corps de structure d'électrode et batterie secondaire WO2018092676A1 (fr)

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CN113782750A (zh) * 2021-09-17 2021-12-10 广西鑫锋环保科技有限公司 一种金属@共聚复合板栅及其制备和在铅酸电池中的应用
CN114514639A (zh) * 2019-10-11 2022-05-17 东亚合成株式会社 二次电池电极用粘合剂、二次电池电极合剂层用组合物、二次电池电极和二次电池

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JP2005142165A (ja) * 1999-07-29 2005-06-02 Toshiba Corp 薄型非水電解質二次電池
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CN113782750A (zh) * 2021-09-17 2021-12-10 广西鑫锋环保科技有限公司 一种金属@共聚复合板栅及其制备和在铅酸电池中的应用
CN113782750B (zh) * 2021-09-17 2023-05-02 广西鑫锋环保科技有限公司 一种金属@共聚复合板栅及其制备和在铅酸电池中的应用

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