WO2012133034A1 - 電池用電極およびそれを用いたリチウムイオン二次電池 - Google Patents
電池用電極およびそれを用いたリチウムイオン二次電池 Download PDFInfo
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- WO2012133034A1 WO2012133034A1 PCT/JP2012/057161 JP2012057161W WO2012133034A1 WO 2012133034 A1 WO2012133034 A1 WO 2012133034A1 JP 2012057161 W JP2012057161 W JP 2012057161W WO 2012133034 A1 WO2012133034 A1 WO 2012133034A1
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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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
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
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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
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- 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
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present invention relates to a battery electrode and a lithium ion secondary battery using the same.
- a lithium ion secondary battery generally includes a positive electrode in which a positive electrode active material layer including a positive electrode active material and a binder is formed on a current collector, and a negative electrode including a negative electrode active material and a binder on the current collector. It has a laminated structure including a negative electrode on which an active material layer is formed and a separator interposed between the positive and negative electrodes arranged so that the respective active material layers are opposed to each other.
- Some lithium ion secondary batteries have only one layer, and some lithium ion secondary batteries are stacked two or more.
- the battery is filled with an electrolyte composition containing an electrolyte salt containing lithium atoms and a non-aqueous solvent.
- the positive electrode active material lithium-containing metal compounds such as lithium-cobalt composite oxide and lithium iron phosphate are mainly used.
- the negative electrode active material a carbon material such as graphite having a multilayer structure in which lithium ions can be inserted / extracted between layers is mainly used.
- Each of the positive electrode and the negative electrode is prepared by kneading these active materials, a binder, a solvent, and, if necessary, further additives such as a conductive additive to prepare an active material slurry, which is applied to a current collector. The solvent is removed by drying to form an active material layer. Moreover, this is compressed with a roll press machine etc. as needed.
- non-aqueous solvent used in the electrolyte composition for example, carbonate compounds such as ethylene carbonate (EC) and propylene carbonate (PC) are used.
- EC ethylene carbonate
- PC propylene carbonate
- an electrolyte composition containing EC is widely used, but PC has an advantage that it has a lower melting point than EC and is excellent in use in a low temperature environment.
- Patent Document 1 describes a battery electrode using polymethacrylic acid as a binder.
- polymethacrylic acid has low solubility in water, and it is necessary to use an organic solvent as a solvent for preparing an active material slurry containing an active material and a binder.
- organic solvent as a solvent for preparing an active material slurry containing an active material and a binder.
- binder that can prepare an active material slurry without using it.
- Patent Documents 2 and 3 describe active material slurries using polyvinyl alcohol or polyacrylate as a binder and water as a solvent.
- polyvinyl alcohol is used as the binder, there is a problem that the polarization of the electrode increases. If the electrode polarization is large, the electrode resistance during charging / discharging is large, so lithium insertion / extraction does not occur smoothly, and the charge / discharge characteristics are poor.
- an acrylic polymer when used as the binder, the viscosity of the active material slurry becomes very high, and it is difficult to form a good active material layer. Moreover, since an acrylic polymer generally has a high glass transition point (Tg), it tends to be a hard and brittle active material layer, and when a battery is produced, there is a tendency that the productivity is deteriorated due to cracking.
- Tg glass transition point
- JP 2009-238681 A Japanese Patent Laid-Open No. 11-67216 JP 2009-80971 A
- the present invention has been made in order to solve the above-described problems, and uses a battery electrode capable of providing a battery that is easy to manufacture and has low polarization and excellent charge / discharge characteristics and cycle characteristics.
- An object is to provide a lithium ion secondary battery.
- the inventors of the present invention can easily produce an electrode having a small polarization when a block copolymer having a vinyl alcohol polymer block is used as a binder.
- the present invention was completed through further studies based on the findings.
- a battery electrode in which an active material layer containing a block copolymer having a vinyl alcohol polymer block and an active material is formed on the current collector surface [2]
- the vinyl alcohol polymer block is a polymer obtained by saponifying a vinyl ester polymer, and a polymer block corresponding to a polymer having a saponification degree of 75 to 99.95 mol%.
- the above-mentioned vinyl alcohol polymer block is a polymer block obtained by saponifying a vinyl ester polymer, and is a polymer block corresponding to a polymer having a polymerization degree of 200 to 3000.
- the block copolymer has at least one structural unit selected from the group consisting of an acrylic acid unit, an acrylate unit, an acrylate unit, a methacrylic acid unit, a methacrylate unit and a methacrylic acid ester unit.
- the battery electrode of the present invention can provide a battery with small polarization and excellent charge / discharge characteristics and cycle characteristics.
- the productivity of the electrode is excellent, and since the active material layer is difficult to break, the processability and yield are good in battery production and the battery productivity is excellent.
- the battery electrode of the present invention has an active material layer formed on the current collector surface.
- the active material layer includes a block copolymer having a vinyl alcohol polymer block and an active material.
- the number of polymer blocks is not particularly limited, but the block copolymer preferably has 2 to 5 polymer blocks because of easy production of the block copolymer. More preferably, it has 2 to 3 polymer blocks.
- bonding form of each block in a block copolymer Any of the coupling
- the above block copolymer can give a battery with more excellent charge / discharge characteristics and cycle characteristics, and also improves the productivity of electrodes and batteries, so that acrylic acid units, acrylate units, acrylic acid Polymer block containing at least one structural unit selected from the group consisting of an ester unit, a methacrylic acid unit, a methacrylate unit and a methacrylic acid ester unit [hereinafter referred to as “(meth) acrylic polymer block”] It is preferable to further include
- the above block copolymer having a (meth) acrylic polymer block may be composed of only a vinyl alcohol polymer block and a (meth) acrylic polymer block, but other polymers other than these. You may have a block further.
- the ratio of the total mass of the vinyl alcohol polymer block and the (meth) acrylic polymer block in the mass of the block copolymer is preferably 30% by mass or more, more preferably 60% by mass or more. More preferably, it is 90% by mass or more.
- the block copolymer can provide a battery having further excellent charge / discharge characteristics and cycle characteristics, and the productivity of the electrode and battery is further improved, one vinyl alcohol polymer block and one (meta) )
- a diblock copolymer in which an acrylic polymer block is linearly bonded is preferable.
- the mass ratio of the vinyl alcohol polymer block and the (meth) acrylic polymer block gives a battery with further excellent charge / discharge characteristics and cycle characteristics. Therefore, the mass ratio represented by [mass of vinyl alcohol polymer block] / [mass of (meth) acrylic polymer block] is preferably within a range of 100/1 to 100/100. Is more preferably in the range of 100/5 to 100/75, and still more preferably in the range of 100/10 to 100/50.
- the block copolymer has a plurality of vinyl alcohol polymer blocks and / or (meth) acrylic polymer blocks
- the total mass of the plurality of polymer blocks is determined based on the vinyl alcohol weight. The mass ratio is calculated as the mass of the combined block and / or the (meth) acrylic polymer block.
- the vinyl alcohol polymer block is not particularly limited as long as it is a polymer block containing vinyl alcohol units.
- a vinyl ester polymer block obtained by polymerizing a vinyl ester represented by vinyl acetate is used.
- examples thereof include a polymer block corresponding to a polymer obtained by saponifying a polymer in the presence of an acidic substance or an alkaline substance [hereinafter sometimes referred to as “polymer (a1)”].
- the vinyl ester polymer may be a vinyl ester homopolymer, or may be a copolymer obtained by copolymerizing a vinyl ester and another monomer.
- the other monomer include olefins having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, and isobutylene; methyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, Vinyl ethers such as t-butyl vinyl ether, dodecyl vinyl ether, stearyl vinyl ether; acrylamide, methacrylamide, N-methyl acrylamide, N-methyl methacrylamide, N-ethyl acrylamide, N-ethyl methacrylamide, N, N-dimethyl acrylamide, N, N-dimethylmethacrylamide, diacetone acrylamide, diacetone methacrylamide
- the ratio of the structural unit derived from the other monomer to the total structural unit constituting the vinyl ester polymer is preferably 60 mol% or less, preferably 30 mol% or less, although it depends on the type of the other monomer. It is more preferable that it is 15 mol% or less.
- each structural unit may be arranged randomly or in a block form.
- the bonding mode of each structural unit may be a head-to-tail bond, a head-to-head bond, or a combination thereof. May be.
- the saponification degree of the polymer (a1) is preferably in the range of 75 to 99.95 mol%, more preferably 80 to 99.92, from the viewpoint of charge / discharge characteristics and cycle characteristics of the battery obtained. It is in the range of mol%, and more preferably in the range of 85 to 99.9 mol%.
- the “degree of saponification” means the ratio of the number of moles of vinyl alcohol units to the total number of moles of vinyl alcohol units and vinyl ester units.
- the degree of polymerization of the polymer (a1) is preferably within the range of 200 to 3000 as the average degree of polymerization measured according to the polyvinyl alcohol test method specified in JIS K6726-1994 from the viewpoint of electrode productivity and the like. More preferably, it is in the range of 230 to 2500, and more preferably in the range of 250 to 2000.
- the vinyl alcohol polymer block corresponds to a polymer obtained by acetalizing a part of the vinyl alcohol unit of the polymer (a1) [hereinafter sometimes referred to as “polymer (a2)”]. It may be a polymer block.
- Examples of the compound used for the acetalization include various aldehydes, complete acetalization products of various aldehydes, hemiacetalization products of various aldehydes, various vinyl esters, various vinyl ethers, and the like.
- Structural formulas: R—CHO, R— A compound represented by CH (OX) 2 or R—CH (OH) (OX) can be preferably used, and a compound represented by the structural formula: R—CHO can be more preferably used.
- R is a hydrogen atom, a halogen atom, or a substituent having one or more carbon atoms.
- X is a substituent having one or more carbon atoms.
- Examples of the substituent having one or more carbon atoms represented by R above include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
- Alkyl group having 1 to 20 carbon atoms such as n-pentyl group, n-hexyl group, n-octyl group and 1-ethylpentyl group; aryl group having 6 to 18 carbon atoms such as phenyl group and naphthyl group; benzyl And aralkyl groups having 7 to 20 carbon atoms such as 1-phenylethyl group and 2-phenylethyl group; cycloalkyl groups having 3 to 20 carbon atoms such as cyclopentyl group and cyclohexyl group.
- R is preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 18 carbon atoms, and is preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a 6 to 10 carbon atom.
- An aryl group is more preferable, a hydrogen atom, a methyl group, an n-propyl group, and a phenyl group are more preferable, and an n-propyl group is particularly preferable.
- Examples of X include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, and n-hexyl.
- n-octyl group 2-ethylhexyl group and other alkyl groups having 1 to 20 carbon atoms
- benzyl group 1-phenylethyl group, 2-phenyl Examples thereof include an aralkyl group having 7 to 20 carbon atoms such as an ethyl group.
- numerator when it has two or more X in a molecule
- numerator X may mutually be same or different.
- the degree of acetalization of the polymer (a2) is preferably in the range of 50 to 95 mol%, more preferably in the range of 55 to 90 mol%, and still more preferably in the range of 60 to 85 mol%. is there.
- the “degree of acetalization” means the ratio of the number of moles of the constituent unit constituting the acetal unit to the total number of moles of the constituent unit constituting the acetal unit, the vinyl alcohol unit and the vinyl ester unit.
- the number of moles of the structural unit constituting the acetal unit is usually twice the number of moles of the acetal unit.
- the degree of acetalization is represented by the following formula (1 ).
- Acetalization degree (mol%) 100 ⁇ [n III ⁇ 2] / [n I + n II + n III ⁇ 2] ... (1)
- Said (meth) acrylic-type polymer block is at least 1 type of structure chosen from the group which consists of an acrylic acid unit, an acrylate unit, an acrylate ester unit, a methacrylic acid unit, a methacrylate unit, and a methacrylic acid ester unit Includes units.
- the (meth) acrylic polymer block includes any one of an acrylate unit, an acrylate unit, a methacrylate unit, and a methacrylic ester unit, these structural units may be one type,
- the (meth) acrylic polymer block may contain two or more acrylate units even if it contains one acrylate unit. Even if it contains, either.
- those containing an acrylic acid unit and / or an acrylate unit are preferred because the preparation of the active material slurry is easy.
- the acrylate unit examples include a metal acrylate unit and an ammonium acrylate unit.
- a methacrylic acid metal salt unit, an ammonium methacrylate salt unit, etc. are mentioned, for example.
- the metal constituting the acrylic acid metal salt unit and the methacrylic acid metal salt unit include alkali metals such as lithium (Li), sodium (Na), and potassium (K); beryllium (Be), magnesium (Mg), and calcium.
- Group 2 metals such as (Ca); chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), ruthenium (Ru), rhodium (Rh) ), Palladium (Pd), silver (Ag), platinum (Pt), gold (Au) and other transition metals; aluminum (Al), zinc (Zn), mercury (Hg) and other typical element metals; lanthanum (La) And lanthanoids such as neodymium (Nd) and europium (Eu).
- alkali metals and metals of Group 2 of the periodic table are preferable, alkali metals are more preferable, and lithium, sodium, and potassium are more preferable.
- ester in the acrylic ester unit and the methacrylic ester unit examples include, for example, methyl ester, ethyl ester, n-propyl ester, isopropyl ester, n-butyl ester, isobutyl ester, sec-butyl ester, tert-butyl ester, alkyl esters having 1 to 20 carbon atoms such as n-pentyl ester, n-hexyl ester, n-octyl ester and 2-ethylhexyl ester; aryl esters having 6 to 18 carbon atoms such as phenyl ester and naphthyl ester; benzyl ester, 1 -Aralkyl esters having 7 to 20 carbon atoms such as phenylethyl ester and 2-phenylethyl ester.
- alkyl esters having 1 to 20 carbon atoms are preferable, alkyl esters having 1 to 8 carbon
- the (meth) acrylic polymer block is at least one component selected from the group consisting of acrylic acid units, acrylate units, acrylate ester units, methacrylic acid units, methacrylate units and methacrylic acid ester units. Although it may be comprised only from the unit, you may have further other structural units other than these.
- Examples of such other structural units include olefins having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene and isobutylene; methyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, Vinyl ethers such as isobutyl vinyl ether, t-butyl vinyl ether, dodecyl vinyl ether, stearyl vinyl ether; acrylamide, methacrylamide, N-methyl acrylamide, N-methyl methacrylamide, N-ethyl acrylamide, N-ethyl methacrylamide, N, N-dimethyl acrylamide , N, N-dimethylmethacrylamide, diacetone acrylamide, diacetone methacrylamide, N-methylolacrylamide, N-methylo (Meth) acrylamides such as methacrylamide; structural units derived from vinyl halides such as vinyl chloride, vinyl
- the proportion of the acrylic acid unit, acrylate unit, acrylate unit, methacrylic acid unit, methacrylic acid unit and methacrylic acid ester unit to the total structural units constituting the (meth) acrylic polymer block is preferably It is 50 mol% or more, More preferably, it is 60 mol% or more, More preferably, it is 70 mol% or more.
- the arrangement order of the structural units in the (meth) acrylic polymer block is not particularly limited, and may be arranged randomly or in a block shape.
- the bonding mode of each structural unit may be a head-to-tail bond, a head-to-head bond, or a combination thereof. It may be a thing.
- a polymer (a1) which has a mercapto group at the terminal is a (meth) acrylic-type in presence of a polymerization initiator.
- the monomer for constituting the (meth) acrylic polymer block is added to carry out the polymerization, or the monomer for constituting the (meth) acrylic polymer block is polymerized, and then the vinyl ester and necessary
- other monomers may be added and polymerized, and then saponified to produce a block copolymer. It is.
- the block copolymer having a polymer block corresponding to the polymer (a2) is acetalized from the block copolymer having a polymer block corresponding to the polymer (a1) produced as described above. Can be manufactured.
- an aqueous solution of a block copolymer having a polymer block corresponding to the polymer (a1) and the compound (various aldehydes etc.) used for the acetalization in the presence of an acid catalyst are used.
- Examples thereof include a solvent method in which an acetalization reaction is performed with a compound used for acetalization (various aldehydes and the like), and a block copolymer is precipitated from the reaction solution with a poor solvent (such as water) for the obtained block copolymer.
- a poor solvent such as water
- the water medium method is preferable.
- the acid catalyst inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid and carbonic acid; organic acids such as acetic acid and propionic acid can be used. Of these, hydrochloric acid and nitric acid are particularly preferred.
- the block copolymer having a polymer block corresponding to the polymer (a2) constitutes a (meth) acrylic polymer block in the presence of a polymerization initiator in the polymer (a2) having a mercapto group at the terminal. It can also be produced by adding a monomer for radical polymerization.
- the block copolymer having a (meth) acrylic polymer block containing an acrylate unit and / or a methacrylate unit is a (meth) acrylic polymer block containing an acrylic acid unit and / or a methacrylic acid unit.
- the block copolymer having s is produced in advance, it can be produced by neutralizing with an alkaline substance such as a metal hydroxide.
- a block copolymer other than the block copolymer having a (meth) acrylic polymer block may be produced by appropriately using a known method.
- the content of the block copolymer in the active material layer of the battery electrode of the present invention is too low, the active material layer tends to be easily separated without sufficiently functioning as a binder, If it is too high, the charge / discharge characteristics of the resulting battery tend to be reduced or the discharge capacity per unit weight tends to be small. Therefore, it is preferably in the range of 1 to 10% by mass, more preferably 1. It is in the range of 5 to 9% by mass, more preferably in the range of 2 to 8% by mass.
- the type of active material used in the present invention is not particularly limited, but as the active material (positive electrode active material) when the battery electrode is used for the positive electrode, a granular active material capable of inserting and extracting lithium is preferable. Can be used. Specifically, for example, lithium-cobalt composite oxide, lithium-manganese composite oxide, lithium-nickel composite oxide, lithium-iron composite oxide, lithium-cobalt-manganese composite oxide, lithium-cobalt-nickel composite Lithium-transition metal composite oxides such as oxides, lithium-manganese-nickel composite oxides, lithium-cobalt-manganese-nickel composite oxides; lithium-transition metal phosphate compounds such as lithium-iron phosphate compounds; lithium- Examples include transition metal sulfate compounds.
- a positive electrode active material may be used individually by 1 type, and may use 2 or more types together.
- Examples of the active material (negative electrode active material) when the battery electrode is used for the negative electrode include materials capable of occluding and releasing lithium. Specifically, graphite, amorphous carbon, carbon fiber, coke, activated carbon And carbon materials such as lithium, silicon, tin and silver, oxides of these metals, alloys of these metals, and the like.
- a negative electrode active material may be used individually by 1 type, and may use 2 or more types together.
- the negative electrode active material preferably includes a carbon material and particularly preferably includes graphite because the cycle characteristics and the discharge capacity are more excellent.
- the active material content in the active material layer of the battery electrode of the present invention is preferably in the range of 90 to 99% by mass, more preferably in the range of 91 to 98.5% by mass, and still more preferably. Is in the range of 92 to 98% by mass.
- the active material layer of the battery electrode of the present invention may be composed only of the block copolymer and the active material, but may further contain additives other than these.
- the additive include a conductive aid.
- a conductive assistant is an additive blended to improve conductivity.
- the conductive assistant include powdery carbon materials such as acetylene black, ketjen black, and carbon black; fibrous carbon materials such as vapor grown carbon fiber (VGCF) and carbon nanotubes; polyacetylene, polyaniline, polythiophene, and polyparaffin. Examples thereof include conductive polymers such as phenylene, polyparaphenylene vinylene, and poly (3,4-ethylenedioxythiophene) (PEDOT).
- the active material layer can also contain additives other than the conductive additive.
- the total content of these additives in the active material layer of the battery electrode of the present invention is preferably in the range of 0.05 to 20% by mass, more preferably in the range of 0.1 to 15% by mass. More preferably, it is in the range of 0.5 to 10% by mass.
- a conductive member can be used, for example, metal such as gold, platinum, copper, aluminum, nickel, stainless steel, titanium, silver, palladium; polyacetylene, polyaniline, Examples thereof include conductive polymers such as polythiophene, polyparaphenylene, polyparaphenylene vinylene, and poly (3,4-ethylenedioxythiophene) (PEDOT).
- metal such as gold, platinum, copper, aluminum, nickel, stainless steel, titanium, silver, palladium
- polyacetylene, polyaniline examples thereof include conductive polymers such as polythiophene, polyparaphenylene, polyparaphenylene vinylene, and poly (3,4-ethylenedioxythiophene) (PEDOT).
- PEDOT poly (3,4-ethylenedioxythiophene)
- aluminum is preferably used as the positive electrode current collector
- copper is preferably used as the negative electrode current collector.
- an electrical power collector there is no restriction
- surface treatment such as plating or chromate treatment may be performed within a range not affecting the conductivity.
- the battery electrode of the present invention has an active material layer formed on the current collector surface.
- the active material layer may be formed only on a part of the current collector surface or may be formed on the entire current collector surface, for example, one of the current collectors having a foil shape or a plate shape. It may be formed on the surface or on both surfaces.
- an active material slurry is prepared by kneading an active material, the above block copolymer, a solvent in which the block copolymer can be dissolved, and an additive as necessary. Is applied to the current collector, and the active material layer can be formed on the surface of the current collector by a method of drying and removing the solvent.
- the solvent include water, N-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide (DMSO), N, N-dimethylformamide (DMF) and the like, depending on the type of block copolymer.
- water or a mixed solvent of water and the above solvent is preferable.
- a doctor blade method, an ink jet method, or the like can be employed.
- the battery electrode of the present invention is used as a component of a battery, preferably a lithium ion secondary battery.
- a lithium ion secondary battery in which the battery electrode of the present invention is used, for example, a pair of electrodes (positive electrode and negative electrode) having an active material layer are arranged so that the active material layers face each other with a separator interposed therebetween.
- at least one of the pair of electrodes is the battery electrode of the present invention.
- an electrode having only an active material layer is included in the electrode “having an active material layer”.
- the active material layers face each other means that at least a part of the active material layer of one electrode and at least a part of the active material layer of the other electrode face each other.
- the electrolyte composition containing an electrolyte salt containing a lithium atom is at least between each of the pair of electrodes and the separator (that is, between one electrode and the separator and between the other electrode and the separator).
- the lithium ion secondary battery may be either one having only one layer of the above laminated structure as a whole, or one having a plurality of the laminated structures laminated.
- the battery electrode of the present invention may be at least one of a pair of electrodes.
- one electrode is the battery electrode of the present invention and the other electrode is the same.
- the electrode for batteries of this invention may be sufficient as both electrodes.
- the configuration is not particularly limited, and the active material, current collector, and conventionally known binder described above in the description of the battery electrode of the present invention are used. What is manufactured using can be used.
- the separator is not particularly limited as long as it can prevent a short circuit due to physical contact between the positive electrode and the negative electrode while allowing ions such as lithium ions to pass through.
- a microporous polyethylene film And a microporous polyolefin film such as a microporous polypropylene film for example, a microporous polyethylene film And a microporous polyolefin film such as a microporous polypropylene film.
- the separator preferably has a function of blocking the current by closing the holes by heat melting at a predetermined temperature (for example, 120 ° C.) or higher to cut off the current.
- the electrolyte composition examples include those containing an electrolyte salt containing a lithium atom and a non-aqueous solvent. Such an electrolyte composition may further contain components other than the electrolyte salt containing a lithium atom and a non-aqueous solvent as necessary as long as the effects of the present invention are exhibited. Further, the above electrolyte composition may be a polymer electrolyte containing an electrolyte salt containing lithium atoms and a polymer. The polymer electrolyte is generally classified into a gel electrolyte that further includes a non-aqueous solvent and an intrinsic polymer electrolyte that does not include a non-aqueous solvent, but either polymer electrolyte may be used in the present invention.
- lithium hexafluorophosphate LiPF 6
- LiBF 4 lithium tetrafluoroborate
- LiClO 4 lithium perchlorate
- LiNO 3 lithium nitrate
- LiPF 6 , LiBF 4 , LiClO 4 , LiAsF 6 , CH 3 SO 3 Li, CF 3 SO 3 Li, LiN (SO 2 CF 3 ) 2 , and LiN (SO 2 C 2 F 5 ) 2 are preferable.
- LiPF 6 and LiBF 4 are particularly preferable.
- the electrolyte salt containing a lithium atom may be used alone or in combination of two or more.
- non-aqueous solvent examples include ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate, vinylene carbonate (VC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC).
- EC ethylene carbonate
- PC propylene carbonate
- PC butylene carbonate
- VC vinylene carbonate
- DMC dimethyl carbonate
- EMC ethyl methyl carbonate
- DEC diethyl carbonate
- These non-aqueous solvents may be used alone or in combination of two or more.
- carbonate ester and lactone are preferable, and EC, PC, DMC, EMC, DEC, and GBL are particularly preferable.
- a cyclic carbonate ester for example, EC, PC, etc.
- chain-like are used. It is preferable to use together with carbonate ester (for example, DMC, EMC, DEC, etc.).
- the content of the electrolyte salt containing lithium atoms in the electrolyte composition is not particularly limited, but when the electrolyte composition contains an electrolyte salt containing lithium atoms and a non-aqueous solvent, the electrolyte salt containing lithium atoms and the non-aqueous solvent
- the ratio of the number of moles of the electrolyte salt containing lithium atoms to the total of each mass of is preferably in the range of 0.1 to 10 mmol / g, more preferably in the range of 0.2 to 5 mmol / g. More preferably, it is in the range of 0.5 to 2 mmol / g.
- polyalkylene oxides such as polyethylene oxide (PEO) and polypropylene oxide (PPO); poly (vinylidene fluoride-hexafluoropropylene) copolymer (P (VDF-HFP)).
- PEO polyethylene oxide
- PPO polypropylene oxide
- PVDF-HFP poly (vinylidene fluoride-hexafluoropropylene) copolymer
- PAN polyacrylonitrile
- PMMA polymethyl methacrylate
- PVB polyvinyl butyral
- PVF polyvinyl formal
- copolymers thereof examples include polyalkylene oxides such as polyethylene oxide (PEO) and polypropylene oxide (PPO); poly (vinylidene fluoride-hexafluoropropylene) copolymer (P (VDF-HFP)).
- PAN polyacrylonitrile
- PMMA polymethyl methacrylate
- PVVB polyvinyl butyral
- PVF polyvinyl
- a battery such as a lithium ion secondary battery.
- a stacked structure as described above (a pair of electrodes having an active material layer is opposed to each other with a separator interposed therebetween)
- a lead wire for taking out the generated electricity can be connected to the electrode.
- the lead wire may be drawn to the outside of the battery case, or may be brought into contact with the battery case to take out electricity.
- limiting in particular in the shape of a battery case For example, a cylindrical shape, a flat shape, etc. are mentioned.
- a metal can may be used and a laminate film may be used.
- aqueous solution of a polyvinyl alcohol-polyacrylic acid graft copolymer (polymer K) was obtained. A part of the obtained aqueous solution was dried, dissolved in heavy water, and subjected to 1 H-NMR measurement at 270 MHz. As a result, it was expressed as [mass of vinyl alcohol unit] / [mass of (meth) acrylic acid unit]. The mass ratio was 100/20. Ion exchange water was further added to the aqueous solution of the above polymer K to adjust the solid content to 10% by mass.
- Example 1 Natural graphite (average particle diameter: 3 ⁇ m) as an active material for producing a battery electrode, and an aqueous solution of polymer A prepared in Production Example 1 (solid content: 8% by mass) as an aqueous solution containing a binder, 95 mass of natural graphite.
- An active material slurry was prepared by mixing 5 parts by mass of polymer A with respect to parts and further adding an appropriate amount of ion-exchanged water. Next, the active material slurry is applied to one surface of a nickel mesh (wire diameter: 0.1 mm, mesh size: 0.154 mm) as a current collector by the doctor blade method and dried, and the current is collected on the surface of the current collector.
- a battery electrode having a material layer formed thereon was produced. The thickness of the active material layer was 60 ⁇ m.
- Bipolar Beaker Type Lithium Ion Secondary Battery for Evaluation A lithium metal foil (a stack of five lithium metal foils having a thickness of 200 ⁇ m) was cut into a strip shape as a counter electrode of the battery electrode prepared above.
- the battery electrode 2 and the counter electrode 3 to which the lead wires 5 are connected are arranged so that the active material layer of the battery electrode and the counter electrode face each other, so that the active material layer is completely immersed in the electrolyte composition 4.
- An evaluation bipolar beaker-type lithium ion secondary battery 1 as schematically shown in FIG. 1 was produced.
- the charging / discharging evaluation of the bipolar electrode beaker type lithium ion secondary battery for evaluation produced above was performed. That is, the current was set to 100 mA / g with respect to the graphite active material, and constant current charging was performed up to 0V. After charging, the current was set to 100 mA / g with respect to the graphite active material, and constant current discharge was performed up to 2V. From the above operations, the initial charge / discharge polarization, initial charge capacity, initial discharge capacity, and initial charge / discharge efficiency values were determined. Further, assuming the above operation as one cycle, the value of the discharge capacity at the 30th cycle when the 30th cycle is repeated is obtained, and divided by the maximum value of the discharge capacities up to the 30th cycle, the discharge capacity retention rate at the 30th cycle Was calculated.
- Example 2 In Example 1, instead of the aqueous solution of polymer A (solid content: 8% by mass), the aqueous solution of polymer B (solid content: 8% by mass) was used to convert natural graphite and the aqueous solution of polymer B to 95% of natural graphite.
- a battery electrode and a bipolar beaker type lithium ion secondary battery for evaluation were prepared by the same method as in Example 1 except that the polymer B was mixed to 5 parts by mass with respect to parts, and charge / discharge Evaluation was performed.
- Example 3 In Example 1, a battery electrode was prepared in the same manner as in Example 1 except that natural graphite and an aqueous solution of polymer A were mixed with 92 parts by mass of natural graphite so that polymer A was 8 parts by mass. And the bipolar beaker type lithium ion secondary battery for evaluation was produced, and charging / discharging evaluation was performed.
- Example 4 In Example 1, a battery electrode was prepared in the same manner as in Example 1 except that natural graphite and an aqueous solution of polymer A were mixed so that 97 parts by mass of natural graphite was 3 parts by mass of polymer A. And the bipolar beaker type lithium ion secondary battery for evaluation was produced, and charging / discharging evaluation was performed.
- Example 5 In Example 1, instead of the aqueous solution of polymer A (solid content: 8% by mass), the aqueous solution of polymer C (solid content: 8% by mass) was used to convert natural graphite and the aqueous solution of polymer C to 92% by mass of natural graphite.
- a battery electrode and a bipolar beaker type lithium ion secondary battery for evaluation were prepared by the same method as in Example 1 except that the polymer C was mixed to 8 parts by mass with respect to parts, and charge / discharge Evaluation was performed.
- Example 6 In Example 1, instead of the aqueous solution of polymer A (solid content: 8% by mass), the aqueous solution of polymer D (solid content: 8% by mass) was used to convert natural graphite and the aqueous solution of polymer D to 95% by mass of natural graphite.
- a battery electrode and a bipolar beaker type lithium ion secondary battery for evaluation were prepared in the same manner as in Example 1 except that the polymer D was mixed to 5 parts by mass with respect to parts, and charge / discharge Evaluation was performed.
- Example 7 In Example 1, instead of the aqueous solution of polymer A (solid content: 8% by mass), the aqueous solution of polymer E (solid content: 8% by mass) was used to convert natural graphite and the aqueous solution of polymer E to 92% by mass of natural graphite.
- a battery electrode and an evaluation bipolar beaker-type lithium ion secondary battery were prepared in the same manner as in Example 1 except that the polymer E was mixed to 8 parts by mass with respect to parts, and charge / discharge Evaluation was performed.
- Example 8 In Example 1, instead of using propylene carbonate (PC) alone as a non-aqueous solvent, 60 parts by mass of propylene carbonate (PC), 20 parts by mass of ethylene carbonate (EC) and 20 parts by mass of dimethyl carbonate (DMC) A bipolar beaker type lithium ion secondary battery for evaluation was prepared in the same manner as in Example 1 except that the mixture was used, and charge / discharge evaluation was performed.
- PC propylene carbonate
- EC ethylene carbonate
- DMC dimethyl carbonate
- Example 1 In Example 1, instead of the aqueous solution of polymer A (solid content: 8% by mass), an aqueous solution of polyvinyl alcohol (polymerization degree: 2400, saponification degree: 98.5 mol%) (polymer F) (solid content: 10% by mass).
- the battery electrode and evaluation were carried out in the same manner as in Example 1 except that natural graphite and an aqueous solution of polymer F were mixed so that polymer F was 5 parts by mass with respect to 95 parts by mass of natural graphite.
- Bipolar beaker-type lithium ion secondary batteries for use were prepared and evaluated for charge and discharge.
- Comparative Example 2 In Comparative Example 1, a battery electrode was prepared in the same manner as in Comparative Example 1, except that natural graphite and an aqueous solution of polymer F were mixed so that polymer F was 8 parts by mass with respect to 92 parts by mass of natural graphite. And the bipolar beaker type lithium ion secondary battery for evaluation was produced, and charging / discharging evaluation was performed.
- Comparative Example 3 In Comparative Example 1, a battery electrode was prepared in the same manner as in Comparative Example 1, except that natural graphite and an aqueous solution of polymer F were mixed so that 97 parts by mass of natural graphite was 3 parts by mass of polymer F. And the bipolar beaker type lithium ion secondary battery for evaluation was produced, and charging / discharging evaluation was performed.
- Example 4 In Example 1, instead of the aqueous solution of polymer A (solid content: 8% by mass), an aqueous solution of polyvinyl alcohol (polymerization degree: 500, saponification degree: 98.5 mol%) (polymer G) (solid content: 10% by mass).
- the battery electrode and evaluation were conducted in the same manner as in Example 1 except that natural graphite and an aqueous solution of polymer G were mixed so that polymer G was 8 parts by mass with respect to 92 parts by mass of natural graphite.
- Bipolar beaker-type lithium ion secondary batteries for use were prepared and evaluated for charge and discharge.
- Example 5 In Example 1, instead of an aqueous solution of polymer A (solid content: 8% by mass), an aqueous solution of polyvinyl alcohol (polymerization degree: 1500, saponification degree: 99.9 mol%) (polymer H) (solid content: 10% by mass).
- the battery electrode and evaluation were carried out in the same manner as in Example 1 except that natural graphite and an aqueous solution of polymer H were mixed so that polymer H was 5 parts by mass with respect to 95 parts by mass of natural graphite.
- Bipolar beaker-type lithium ion secondary batteries for use were prepared and evaluated for charge and discharge.
- Example 6 In Example 1, instead of the aqueous solution of polymer A (solid content: 8% by mass), an aqueous solution of polyvinyl alcohol (polymerization degree: 300, saponification degree: 88 mol%) (polymer I) (solid content: 10% by mass) was used.
- the battery electrode and the evaluation electrode were prepared in the same manner as in Example 1, except that natural graphite and an aqueous solution of polymer I were mixed so that 92 parts by mass of natural graphite was 8 parts by mass of polymer I.
- a polar beaker type lithium ion secondary battery was prepared and evaluated for charge and discharge.
- Example 7 In Example 1, instead of the aqueous solution of polymer A (solid content: 8% by mass), polyvinyl alcohol-polyacrylic acid random copolymer (TSP515 manufactured by Bowdal Chemical Co., Ltd .: polymerization degree 1500, saponification degree 98.5 mol%, [ The mass ratio represented by [mass of vinyl alcohol unit] / [mass of (meth) acrylic acid unit] is 100/20, and this is referred to as “polymer J”) (solid content 10 mass%), Natural graphite and an aqueous solution of polymer J are mixed with 95 parts by mass of natural graphite so that polymer J is 5 parts by mass, and a mixture (volume) of ethylene carbonate (EC) and dimethyl carbonate (DMC) as a non-aqueous solvent.
- a battery electrode and an evaluation bipolar beaker type lithium ion secondary battery were prepared in the same manner as in Example 1 except that the ratio 1: 1) was used, and charge / discharge evaluation was performed.
- Example 8 In Example 1, an aqueous solution of polyvinyl alcohol-polyacrylic acid graft copolymer (polymer K) (solid content of 10% by mass) was used in place of the aqueous solution of polymer A (solid content of 8% by mass). Graphite and an aqueous solution of polymer K are mixed with 95 parts by mass of natural graphite so that polymer K is 5 parts by mass, and a mixture (volume ratio) of ethylene carbonate (EC) and dimethyl carbonate (DMC) as a non-aqueous solvent.
- EC ethylene carbonate
- DMC dimethyl carbonate
- a battery electrode and an evaluation bipolar beaker type lithium ion secondary battery were prepared by the same method as in Example 1 except that 1: 1) was used, and charge / discharge evaluation was performed.
- Example 9 an aqueous solution of polyvinyl alcohol-polyacrylic acid graft copolymer (polymer L) (solid content of 10% by mass) was used in place of the aqueous solution of polymer A (solid content of 8% by mass).
- Graphite and an aqueous solution of polymer L are mixed so that polymer L is 5 parts by mass with respect to 95 parts by mass of natural graphite, and a mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC) as a non-aqueous solvent (volume ratio).
- EC ethylene carbonate
- DMC dimethyl carbonate
- a battery electrode and an evaluation bipolar beaker type lithium ion secondary battery were prepared by the same method as in Example 1 except that 1: 1) was used, and charge / discharge evaluation was performed.
- Comparative Examples 1 to 6 in which only the polyvinyl alcohol homopolymer is used in the active material layer, the initial charge / discharge polarization is large, so that the electrical resistance during charge / discharge is large, and as a result, the initial charge / discharge efficiency is low. It was.
- Comparative Example 7 using a polyvinyl alcohol-polyacrylic acid random copolymer in the active material layer and Comparative Examples 8 and 9 using a polyvinyl alcohol-polyacrylic acid graft copolymer the discharge capacity at the 30th cycle was maintained. The rate declined. This is presumably because the crystallinity of polyvinyl alcohol was lowered and polyvinyl alcohol contained a large amount of water molecules, so that the deterioration of the binder due to the decomposition of water was caused by repeated cycle tests.
Abstract
Description
[1]ビニルアルコール系重合体ブロックを有するブロック共重合体と活物質とを含む活物質層が集電体表面に形成されてなる、電池用電極、
[2]前記ビニルアルコール系重合体ブロックが、ビニルエステル系重合体をけん化して得られる重合体であって、けん化度が75~99.95モル%である重合体に相当する重合体ブロックである、上記[1]の電池用電極、
[3]前記ビニルアルコール系重合体ブロックが、ビニルエステル系重合体をけん化して得られる重合体であって、重合度が200~3000である重合体に相当する重合体ブロックである、上記[1]または[2]の電池用電極、
[4]前記ブロック共重合体が、アクリル酸単位、アクリル酸塩単位、アクリル酸エステル単位、メタクリル酸単位、メタクリル酸塩単位およびメタクリル酸エステル単位からなる群より選ばれる少なくとも1種の構成単位を含む重合体ブロックをさらに有する、上記[1]~[3]のいずれか1つの電池用電極、
[5]前記活物質層における前記ブロック共重合体の含有率が1~10質量%である、上記[1]~[4]のいずれか1つの電池用電極、
[6]前記活物質が黒鉛を含む、上記[1]~[5]のいずれか1つの電池用電極、
[7]活物質層を有する一対の電極がセパレータを介して当該活物質層同士が対向するように配置されるとともに、リチウム原子を含む電解質塩を含む電解質組成物が当該一対の電極およびセパレータの各間を満たす積層構造を有するリチウムイオン二次電池であって、前記一対の電極のうちの少なくとも一方は、上記[1]~[6]のいずれか1つの電池用電極である、リチウムイオン二次電池、
[8]前記電解質組成物が炭酸プロピレンを含む、上記[7]のリチウムイオン二次電池、
に関する。
本発明の電池用電極は活物質層が集電体表面に形成されてなる。そして当該活物質層はビニルアルコール系重合体ブロックを有するブロック共重合体と活物質とを含む。
アセタール化度(モル%)=100×[nIII×2]/[nI+nII+nIII×2]
・・・(1)
また、上記の電解質組成物は、リチウム原子を含む電解質塩と高分子とを含むポリマー電解質であってもよい。ポリマー電解質は、一般に、非水系溶媒をさらに含むゲル電解質と、非水系溶媒を含まない真性ポリマー電解質とに分類されるが、本発明においてはどちらのポリマー電解質であってもよい。
ポリビニルアルコール-(b)-ポリアクリル酸共重合体(重合体A)の製造
還流冷却管、撹拌翼を備え付けた3L四つ口セパラブルフラスコに、イオン交換水737g、および、分子末端にメルカプト基を有するポリビニルアルコール(重合度1500、けん化度98.5モル%)100gを仕込み、撹拌下90℃まで加熱して該ポリビニルアルコールを溶解した後、室温まで冷却した。該水溶液にアクリル酸19.8gを撹拌下添加した後、70℃まで加温し、また、水溶液中に窒素をバブリングしながら30分間系内を窒素置換した。窒素置換後、上記水溶液に過硫酸カリウムの2.5質量%水溶液37.6mLを90分かけて逐次的に添加してブロック共重合反応を開始、進行させた後、系内温度を75℃に60分維持して重合をさらに進行させ、ついで冷却して、固形分13質量%のポリビニルアルコール-(b)-ポリアクリル酸共重合体(重合体A)の水溶液を得た。得られた水溶液の一部を乾燥した後、重水に溶解し、270MHzでの1H-NMR測定を行った結果、[ビニルアルコール系重合体ブロックの質量]/[(メタ)アクリル系重合体ブロックの質量]で示される質量割合は100/18であった。上記の重合体Aの水溶液にさらにイオン交換水を添加し、固形分が8質量%となるように調整した。
ポリビニルアルコール-(b)-ポリアクリル酸塩共重合体(重合体B)の製造
水酸化リチウム(LiOH)を1モル/Lとなるようにイオン交換水に添加して水酸化リチウム水溶液を調製した。次いで、製造例1と同様にして製造した固形分13質量%の重合体Aの水溶液を攪拌下、これに、重合体A中のアクリル酸単位のカルボキシル基が全て中和される量に対して0.4倍量の上記水酸化リチウム水溶液を添加して、ポリビニルアルコール-(b)-ポリアクリル酸塩共重合体(重合体B)の水溶液を得た。pH試験紙で水溶液の酸性度を測定すると、pH6であった。これにさらにイオン交換水を添加し、固形分が8質量%となるように調整した。
ポリビニルアルコール-(b)-ポリアクリル酸共重合体(重合体C)の製造
製造例1において、分子末端にメルカプト基を有するポリビニルアルコール(重合度1500、けん化度98.5モル%)の代わりに、分子末端にメルカプト基を有するポリビニルアルコール(重合度500、けん化度98.5モル%)を用いたこと以外は、製造例1と同様の方法により、ポリビニルアルコール-(b)-ポリアクリル酸共重合体(重合体C)の水溶液を得た。これにさらにイオン交換水を添加し、固形分が8質量%となるように調整した。
ポリビニルアルコール-(b)-ポリアクリル酸共重合体(重合体D)の製造
製造例1において、分子末端にメルカプト基を有するポリビニルアルコール(重合度1500、けん化度98.5モル%)の代わりに、分子末端にメルカプト基を有するポリビニルアルコール(重合度1500、けん化度99.9モル%)を用いたこと以外は、製造例1と同様の方法により、ポリビニルアルコール-(b)-ポリアクリル酸共重合体(重合体D)の水溶液を得た。これにさらにイオン交換水を添加し、固形分が8質量%となるように調整した。
ポリビニルアルコール-(b)-ポリアクリル酸共重合体(重合体E)の製造
製造例1において、分子末端にメルカプト基を有するポリビニルアルコール(重合度1500、けん化度98.5モル%)の代わりに、分子末端にメルカプト基を有するポリビニルアルコール(重合度300、けん化度88モル%)を用いたこと以外は、製造例1と同様の方法により、ポリビニルアルコール-(b)-ポリアクリル酸共重合体(重合体E)の水溶液を得た。これにさらにイオン交換水を添加し、固形分が8質量%となるように調整した。
ポリビニルアルコール-ポリアクリル酸グラフト共重合体(重合体K)の製造
還流冷却管、撹拌翼を備え付けた3L四つ口セパラブルフラスコに、イオン交換水737g、60%アクリル酸水溶液12g、ギ酸ナトリウム1.0gを加えて、均一な混合溶液とした。該混合溶液を攪拌しながら、これにポリビニルアルコール(重合度1700、けん化度98.5モル%)100gを加え、窒素置換しながら70℃に内部温度を上昇させた。窒素置換を30分間行った後、上記混合溶液に10%2,2’-アゾビス(2-メチルプロピオンアミジン)二塩化水素化物5.0g添加し重合を開始させた。別途、60%アクリル酸水溶液48gにギ酸ナトリウム1.0gを加えた溶液を反応開始後から5時間かけて上記混合溶液に滴下しながら重合を行った。反応開始から5時間後、再度10%2,2’-アゾビス(2-メチルプロピオンアミジン)二塩化水素化物5.0gを上記混合溶液に添加し、更に17時間重合を進行させ、ついで冷却して、ポリビニルアルコール-ポリアクリル酸グラフト共重合体(重合体K)の水溶液を得た。得られた水溶液の一部を乾燥した後、重水に溶解し、270MHzでの1H-NMR測定を行った結果、[ビニルアルコール単位の質量]/[(メタ)アクリル酸単位の質量]で示される質量割合は100/20であった。上記の重合体Kの水溶液にさらにイオン交換水を添加し、固形分が10質量%となるように調整した。
ポリビニルアルコール-ポリアクリル酸グラフト共重合体(重合体L)の製造
製造例6において、けん化度の異なるポリビニルアルコール(重合度1700、けん化度88モル%)を用いたこと以外は、製造例6と同様の方法により、ポリビニルアルコール-ポリアクリル酸グラフト共重合体(重合体L)の水溶液を得た。1H-NMR測定を行った結果、[ビニルアルコール系単位の質量]/[(メタ)アクリル酸単位の質量]で示される質量割合は100/20であった。これにさらにイオン交換水を添加し、固形分が10質量%となるように調整した。
電池用電極の作製
活物質として天然黒鉛(平均粒子経3μm)と、結着剤を含む水溶液として製造例1で調製した重合体Aの水溶液(固形分8質量%)とを、天然黒鉛95質量部に対し重合体Aが5質量部となるように混合し、さらにイオン交換水を適量添加して、活物質スラリーを調製した。次に、集電体としてニッケルメッシュ(線径0.1mm、目開き0.154mm)の一方の表面に、上記の活物質スラリーをドクターブレード法で塗布して乾燥し、集電体表面に活物質層を形成した電池用電極を作製した。活物質層の厚さは60μmであった。
非水系溶媒としての炭酸プロピレン(PC)に、リチウム原子を含む電解質塩として過塩素酸リチウム(LiClO4)を0.79ミリモル/gの濃度になるように添加して、電解質組成物を調製した。
上記で作製した電池用電極の対極としてリチウム金属箔(厚さ200μmのリチウム金属箔を5枚重ねたもの)を帯状に切り抜いた。リード線5が接続された電池用電極2、対極3を、電池用電極の活物質層と対極が対向するように配置して、電解質組成物4に活物質層が完全に浸漬するようにし、図1にその概略図を示すような評価用二極式ビーカー型リチウムイオン二次電池1を作製した。
上記で作製した評価用二極式ビーカー型リチウムイオン二次電池の充放電評価を行った。すなわち、黒鉛活物質に対して100mA/gの電流になるように設定し、0Vまで定電流充電を行った。充電後、黒鉛活物質に対して100mA/gの電流になるように設定し、2Vまで定電流放電を行った。以上の操作から、初回充放電分極、初回充電容量、初回放電容量および初回充放電効率の各値を求めた。また、上記の操作を1サイクルとして、30サイクル繰り返したときの30サイクル目の放電容量の値を求め、30サイクル目までの放電容量のうちの最大値で除して30サイクル目放電容量保持率を算出した。
実施例1において、重合体Aの水溶液(固形分8質量%)の代わりに重合体Bの水溶液(固形分8質量%)を用いて、天然黒鉛と重合体Bの水溶液とを天然黒鉛95質量部に対し重合体Bが5質量部となるように混合したこと以外は、実施例1と同様の方法により電池用電極および評価用二極式ビーカー型リチウムイオン二次電池を作製し、充放電評価を行った。
実施例1において、天然黒鉛と重合体Aの水溶液とを天然黒鉛92質量部に対し重合体Aが8質量部となるように混合したこと以外は、実施例1と同様の方法により電池用電極および評価用二極式ビーカー型リチウムイオン二次電池を作製し、充放電評価を行った。
実施例1において、天然黒鉛と重合体Aの水溶液とを天然黒鉛97質量部に対し重合体Aが3質量部となるように混合したこと以外は、実施例1と同様の方法により電池用電極および評価用二極式ビーカー型リチウムイオン二次電池を作製し、充放電評価を行った。
実施例1において、重合体Aの水溶液(固形分8質量%)の代わりに重合体Cの水溶液(固形分8質量%)を用いて、天然黒鉛と重合体Cの水溶液とを天然黒鉛92質量部に対し重合体Cが8質量部となるように混合したこと以外は、実施例1と同様の方法により電池用電極および評価用二極式ビーカー型リチウムイオン二次電池を作製し、充放電評価を行った。
実施例1において、重合体Aの水溶液(固形分8質量%)の代わりに重合体Dの水溶液(固形分8質量%)を用いて、天然黒鉛と重合体Dの水溶液とを天然黒鉛95質量部に対し重合体Dが5質量部となるように混合したこと以外は、実施例1と同様の方法により電池用電極および評価用二極式ビーカー型リチウムイオン二次電池を作製し、充放電評価を行った。
実施例1において、重合体Aの水溶液(固形分8質量%)の代わりに重合体Eの水溶液(固形分8質量%)を用いて、天然黒鉛と重合体Eの水溶液とを天然黒鉛92質量部に対し重合体Eが8質量部となるように混合したこと以外は、実施例1と同様の方法により電池用電極および評価用二極式ビーカー型リチウムイオン二次電池を作製し、充放電評価を行った。
実施例1において、非水系溶媒として炭酸プロピレン(PC)を単独で用いたことに代えて、炭酸プロピレン(PC)60質量部、炭酸エチレン(EC)20質量部および炭酸ジメチル(DMC)20質量部の混合物を用いたこと以外は、実施例1と同様の方法により評価用二極式ビーカー型リチウムイオン二次電池を作製し、充放電評価を行った。
実施例1において、重合体Aの水溶液(固形分8質量%)の代わりにポリビニルアルコール(重合度2400、けん化度98.5モル%)(重合体F)の水溶液(固形分10質量%)を用いて、天然黒鉛と重合体Fの水溶液とを天然黒鉛95質量部に対し重合体Fが5質量部となるように混合したこと以外は、実施例1と同様の方法により電池用電極および評価用二極式ビーカー型リチウムイオン二次電池を作製し、充放電評価を行った。
比較例1において、天然黒鉛と重合体Fの水溶液とを天然黒鉛92質量部に対し重合体Fが8質量部となるように混合したこと以外は、比較例1と同様の方法により電池用電極および評価用二極式ビーカー型リチウムイオン二次電池を作製し、充放電評価を行った。
比較例1において、天然黒鉛と重合体Fの水溶液とを天然黒鉛97質量部に対し重合体Fが3質量部となるように混合したこと以外は、比較例1と同様の方法により電池用電極および評価用二極式ビーカー型リチウムイオン二次電池を作製し、充放電評価を行った。
実施例1において、重合体Aの水溶液(固形分8質量%)の代わりにポリビニルアルコール(重合度500、けん化度98.5モル%)(重合体G)の水溶液(固形分10質量%)を用いて、天然黒鉛と重合体Gの水溶液とを天然黒鉛92質量部に対し重合体Gが8質量部となるように混合したこと以外は、実施例1と同様の方法により電池用電極および評価用二極式ビーカー型リチウムイオン二次電池を作製し、充放電評価を行った。
実施例1において、重合体Aの水溶液(固形分8質量%)の代わりにポリビニルアルコール(重合度1500、けん化度99.9モル%)(重合体H)の水溶液(固形分10質量%)を用いて、天然黒鉛と重合体Hの水溶液とを天然黒鉛95質量部に対し重合体Hが5質量部となるように混合したこと以外は、実施例1と同様の方法により電池用電極および評価用二極式ビーカー型リチウムイオン二次電池を作製し、充放電評価を行った。
実施例1において、重合体Aの水溶液(固形分8質量%)の代わりにポリビニルアルコール(重合度300、けん化度88モル%)(重合体I)の水溶液(固形分10質量%)を用いて、天然黒鉛と重合体Iの水溶液とを天然黒鉛92質量部に対し重合体Iが8質量部となるように混合したこと以外は、実施例1と同様の方法により電池用電極および評価用二極式ビーカー型リチウムイオン二次電池を作製し、充放電評価を行った。
実施例1において、重合体Aの水溶液(固形分8質量%)の代わりに、ポリビニルアルコール-ポリアクリル酸ランダム共重合体(バウダル化学製 TSP515:重合度1500、けん化度98.5モル%、[ビニルアルコール単位の質量]/[(メタ)アクリル酸単位の質量]で示される質量割合は100/20、これを「重合体J」とする)の水溶液(固形分10質量%)を用いて、天然黒鉛と重合体Jの水溶液とを天然黒鉛95質量部に対し重合体Jが5質量部となるように混合し、非水系溶媒として炭酸エチレン(EC)および炭酸ジメチル(DMC)の混合物(体積比1:1)を用いたこと以外は、実施例1と同様の方法により電池用電極および評価用二極式ビーカー型リチウムイオン二次電池を作製し、充放電評価を行った。
実施例1において、重合体Aの水溶液(固形分8質量%)の代わりに、ポリビニルアルコール-ポリアクリル酸グラフト共重合体(重合体K)の水溶液(固形分10質量%)を用いて、天然黒鉛と重合体Kの水溶液とを天然黒鉛95質量部に対し重合体Kが5質量部となるように混合し、非水系溶媒として炭酸エチレン(EC)および炭酸ジメチル(DMC)の混合物(体積比1:1)を用いたこと以外は、実施例1と同様の方法により電池用電極および評価用二極式ビーカー型リチウムイオン二次電池を作製し、充放電評価を行った。
実施例1において、重合体Aの水溶液(固形分8質量%)の代わりに、ポリビニルアルコール-ポリアクリル酸グラフト共重合体(重合体L)の水溶液(固形分10質量%)を用いて、天然黒鉛と重合体Lの水溶液とを天然黒鉛95質量部に対し重合体Lが5質量部となるように混合し、非水系溶媒として炭酸エチレン(EC)および炭酸ジメチル(DMC)の混合物(体積比1:1)を用いたこと以外は、実施例1と同様の方法により電池用電極および評価用二極式ビーカー型リチウムイオン二次電池を作製し、充放電評価を行った。
2 電池用電極
3 対極
4 電解質組成物
5 リード線
Claims (8)
- ビニルアルコール系重合体ブロックを有するブロック共重合体と活物質とを含む活物質層が集電体表面に形成されてなる、電池用電極。
- 前記ビニルアルコール系重合体ブロックが、ビニルエステル系重合体をけん化して得られる重合体であって、けん化度が75~99.95モル%である重合体に相当する重合体ブロックである、請求項1に記載の電池用電極。
- 前記ビニルアルコール系重合体ブロックが、ビニルエステル系重合体をけん化して得られる重合体であって、重合度が200~3000である重合体に相当する重合体ブロックである、請求項1または2に記載の電池用電極。
- 前記ブロック共重合体が、アクリル酸単位、アクリル酸塩単位、アクリル酸エステル単位、メタクリル酸単位、メタクリル酸塩単位およびメタクリル酸エステル単位からなる群より選ばれる少なくとも1種の構成単位を含む重合体ブロックをさらに有する、請求項1~3のいずれか1項に記載の電池用電極。
- 前記活物質層における前記ブロック共重合体の含有率が1~10質量%である、請求項1~4のいずれか1項に記載の電池用電極。
- 前記活物質が黒鉛を含む、請求項1~5のいずれか1項に記載の電池用電極。
- 活物質層を有する一対の電極がセパレータを介して当該活物質層同士が対向するように配置されるとともに、リチウム原子を含む電解質塩を含む電解質組成物が当該一対の電極およびセパレータの各間を満たす積層構造を有するリチウムイオン二次電池であって、前記一対の電極のうちの少なくとも一方は、請求項1~6のいずれか1項に記載の電池用電極である、リチウムイオン二次電池。
- 前記電解質組成物が炭酸プロピレンを含む、請求項7に記載のリチウムイオン二次電池。
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KR20140044802A (ko) | 2014-04-15 |
CN103688393A (zh) | 2014-03-26 |
EP2690688A4 (en) | 2014-12-24 |
US20140045054A1 (en) | 2014-02-13 |
KR101880029B1 (ko) | 2018-07-20 |
CN103688393B (zh) | 2016-09-28 |
JP6010788B2 (ja) | 2016-10-19 |
JPWO2012133034A1 (ja) | 2014-07-28 |
US9276262B2 (en) | 2016-03-01 |
EP2690688B1 (en) | 2018-02-28 |
EP2690688A1 (en) | 2014-01-29 |
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