WO2017056984A1 - リチウムイオン二次電池用負極の製造方法 - Google Patents
リチウムイオン二次電池用負極の製造方法 Download PDFInfo
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- WO2017056984A1 WO2017056984A1 PCT/JP2016/077057 JP2016077057W WO2017056984A1 WO 2017056984 A1 WO2017056984 A1 WO 2017056984A1 JP 2016077057 W JP2016077057 W JP 2016077057W WO 2017056984 A1 WO2017056984 A1 WO 2017056984A1
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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- 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
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- 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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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- 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
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- 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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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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- 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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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a method for producing a negative electrode for a lithium ion secondary battery.
- lithium ion secondary batteries Since lithium ion secondary batteries have high energy density and excellent charge / discharge cycle characteristics, they are widely used as power sources for small mobile devices such as mobile phones and laptop computers. Also, in recent years, due to consideration for environmental problems and increased awareness of energy saving, a large capacity and long life such as a storage battery for a vehicle such as an electric vehicle or a hybrid electric vehicle, and a power storage system such as a household power storage system are required. Demand for large power supplies is also increasing.
- Patent Document 1 describes a method for producing an electrode plate for a negative electrode of a non-aqueous secondary battery using a paste constituted by kneading and dispersing a carbon material mainly composed of graphite, a thickener, and a binder. Yes. It is described that carboxymethyl cellulose is used as a thickener, and a water-dispersible polymer having a polar group (a core-shell type rubber particle-based binder containing an acrylonitrile unit) is used as a binder.
- this manufacturing method includes an initial kneading step of adding and kneading an aqueous solution of a thickener to graphite, a dilution kneading step of diluting and kneading the kneaded product of this initial kneading step with an aqueous solution of the thickener, and this dilution kneading step. It is described that it includes at least three steps of a final kneading step of preparing a paste by adding a binder to the kneaded product and kneading.
- Patent Document 2 discloses a method for producing a mixture for a negative electrode of a non-aqueous secondary battery, comprising kneading and dispersing a negative electrode active material and a conductive agent, and a dispersion in which a binder is dispersed in a thickener solution.
- a fluorine resin polyvinylidene fluoride
- carboxymethylcellulose is used as a thickener
- SiSnO 3 is used as a negative electrode active material
- acetylene black and graphite are used as conductive agents.
- Secondary batteries are described as having long life characteristics.
- Patent Document 3 discloses a negative electrode coating film for a lithium ion secondary battery in which a negative electrode active material is a carbon material, a binder is a mixed hydrate of an acrylic copolymer (aqueous emulsion) and carboxymethyl cellulose, and an aqueous medium.
- a forming slurry is disclosed. Specifically, an example using an acrylic-styrene copolymer emulsion and carboxymethylcellulose ammonium salt is described. It is described that the negative electrode coating film of a battery formed using this slurry has excellent adhesion between carbon particles and between the carbon particles and the current collector, high discharge capacity, and excellent cycle life.
- An object of the present invention is to provide a production method capable of forming a negative electrode having a negative electrode active material layer having high productivity and excellent adhesion to a current collector and binding property between active material particles. .
- a method for producing a negative electrode for a lithium ion secondary battery comprising a current collector and a negative electrode active material layer on the current collector, Forming a slurry containing a negative electrode active material, a binder, a water-soluble polymer thickener, and an aqueous solvent; Applying the slurry onto a current collector, and drying to remove the aqueous solvent to form a coating layer that becomes a negative electrode active material layer,
- the step of forming the slurry includes Dissolving the water-soluble polymer thickener in the aqueous solvent to form a dispersion in which an acrylic binder is dispersed as the binder;
- a method for producing a negative electrode for a lithium ion secondary battery comprising a step of forming and stirring a mixture containing a powder material containing the negative electrode active material and the dispersion.
- a manufacturing method capable of forming a negative electrode having a negative electrode active material layer that is highly productive and has excellent adhesion to a current collector and excellent binding between active material particles. be able to.
- a method for manufacturing a negative electrode for a lithium ion secondary battery includes a negative electrode active material, a binder, a water-soluble polymer thickener (for example, carboxymethylcellulose, hereinafter “CMC”), and an aqueous solvent (for example, water).
- CMC carboxymethylcellulose
- aqueous solvent for example, water
- the step of forming a slurry includes a step of forming a dispersion in which a water-soluble polymer thickener is dissolved in an aqueous solvent and an acrylic binder is dispersed, a powder material containing a negative electrode active material, and a mixture containing the dispersion Forming and stirring.
- This mixture may further contain other aqueous solvents and additives as required.
- the powder material can include other powder materials such as a conductive aid.
- the time required for the manufacturing process (especially the process of forming the slurry) can be shortened, and the negative electrode active material layer excellent in adhesion to the current collector and binding between the active material particles Can be formed.
- the step of forming a slurry includes a step of forming a first dispersion in which an acrylic binder is dispersed in an aqueous solvent, and a water-soluble polymer thickener is added to the first dispersion.
- a powder material containing a negative electrode active material and an aqueous solution of a water-soluble polymer thickener are mixed in advance, and thereafter, a binder is added to the mixture and stirred. It takes extra time for the binder to mix well. In addition, the mechanical share is applied to the binder due to the agitation, and the binder function tends to be lowered.
- a binder (particularly a rubber-based binder such as SBR (styrene-butadiene rubber)) is added to the CMC aqueous solution in advance to form a binder dispersion, and then the binder dispersion and a powder material containing a negative electrode active material are mixed.
- SBR styrene-butadiene rubber
- an acrylic binder is used as the binder, and after forming the binder dispersion containing the binder and the thickener, the binder dispersion and the powder material (including the negative electrode active material). And stirring, the slurry preparation time can be shortened, and the decrease in the binder function due to the mechanical share during the stirring can be suppressed. As a result, a negative electrode including a negative electrode active material layer excellent in adhesion to the current collector and binding property between the active material particles can be produced with high productivity.
- a binder (acrylic binder) in an aqueous solvent in advance, and then add and dissolve a water-soluble polymer thickener (for example, CMC), so that the binder is uniformly dispersed.
- CMC water-soluble polymer thickener
- the stirring time for forming the dispersion can be shortened, and a decrease in the binder function due to the mechanical share during the stirring can be suppressed.
- the CMC aqueous solution is viscous, when a binder is added to such a CMC aqueous solution and stirred, it takes time to disperse uniformly, or the binder function tends to decrease due to the mechanical share being applied to the binder during stirring. There is.
- the time required for uniform dispersion can be shortened, and the decrease in the binder function can be suppressed.
- an acrylic binder and an aqueous solvent for example, water are mixed to form a first dispersion in which the acrylic binder is dispersed.
- acrylic binder examples include homopolymers or copolymers containing units of acrylic acid or methacrylic acid, esters or salts thereof (hereinafter referred to as “acrylic units”).
- copolymer examples include a copolymer containing an acrylic unit and a styrene unit, and a copolymer containing an acrylic unit and a silicone unit.
- the acrylic binder contains a styrene unit, the binding property between the active material particles can be enhanced.
- the acrylic binder one prepared in the state of an aqueous emulsion can be used.
- the acrylic binder preferably contains a surfactant or a dispersant, and may be one used during polymerization.
- the surfactant contained in the acrylic binder include an anionic surfactant and a nonionic surfactant, and preferably contains at least one.
- the amount of the acrylic binder added can be set in the range of 0.5 to 5% by mass with respect to the aqueous solvent, and preferably 1 to 3% by mass. If the amount of the binder added is too small, a sufficient binding effect cannot be obtained. On the other hand, if the addition amount is too large, uniform dispersion becomes difficult and the electrical resistance of the negative electrode active material layer increases.
- a water-soluble polymer thickener is added to the first dispersion to form a second dispersion in which the water-soluble polymer thickener is dissolved.
- the water-soluble polymer thickener may be added in a solid state such as a powder, or may be added in the form of an aqueous solution. However, from the viewpoint of workability and uniformity, the water-soluble polymer thickener may be added in a solid state such as a powder. It is preferable to add and dissolve.
- water-soluble polymer thickener examples include cellulose derivatives, polyvinyl alcohol or modified products thereof, starch or modified products thereof, polyvinyl pyrrolidone, polyacrylic acid or salts thereof, and polyethylene glycol.
- a cellulose derivative is preferable and carboxymethyl cellulose (CMC) is more preferable.
- CMC a sodium salt or an ammonium salt thereof can be used, and a sodium salt is preferable.
- the CMC sodium salt has a higher viscosity of the CMC solution having the same concentration than the CMC ammonium salt, and the dispersibility of the active material particles in the slurry can be improved by adding a relatively small amount.
- CMC ammonium salt when CMC ammonium salt is used, there is concern about corrosion of equipment due to alkaline water vapor during drying after application of slurry, but CMC sodium salt is free from such problems and easy to handle in production. .
- the amount of the water-soluble polymer thickener added can be set in the range of 0.5 to 5% by mass, preferably 1 to 5% by mass with respect to the aqueous solvent.
- the second dispersion and the powder material containing the negative electrode active material are mixed and stirred.
- This mixing step is preferably performed in two stages by changing the concentration of the mixture.
- the mixture containing the powder material and the second dispersion is blended and kneaded so that the solid content concentration is 50% by mass or more and 70% by mass or less.
- the solid content concentration of the mixture is more preferably 55% by mass or more and 65% by mass or less.
- the solid content concentration of the mixture (slurry) is lowered and stirred so that the solid content concentration is 40% by mass or more and less than 50% by mass.
- the solid content concentration of the mixture (slurry) is preferably 45% by mass or more, and preferably 48% by mass or less.
- the method for reducing the solid content concentration can be performed by adding water as an aqueous solvent, and in place of water, a water-soluble polymer thickener and other additives are dissolved in water.
- An aqueous solution may be used.
- the lithium ion secondary battery of this example includes a positive electrode current collector 3 made of a metal such as an aluminum foil and a positive electrode active material layer 1 containing a positive electrode active material provided thereon. And a negative electrode current collector 4 made of a metal such as copper foil and a negative electrode active material layer 2 containing a negative electrode active material provided thereon.
- the positive electrode and the negative electrode are laminated via a separator 5 made of a nonwoven fabric or a polypropylene microporous film so that the positive electrode active material layer 1 and the negative electrode active material layer 2 face each other.
- This electrode pair is accommodated in a container formed by the outer casings 6 and 7 made of an aluminum laminate film.
- a positive electrode tab 9 is connected to the positive electrode current collector 3
- a negative electrode tab 8 is connected to the negative electrode current collector 4, and these tabs are drawn out of the container.
- An electrolytic solution is injected into the container and sealed. It can also be set as the structure where the electrode group by which the several electrode pair was laminated
- a carbonaceous material can be used as the negative electrode active material.
- the carbonaceous material include graphite, amorphous carbon (for example, graphitizable carbon and non-graphitizable carbon), diamond-like carbon, fullerene, carbon nanotube, and carbon nanohorn.
- graphite natural graphite and artificial graphite can be used, and cheap natural graphite is preferable from the viewpoint of material cost.
- the amorphous carbon include those obtained by heat treatment of coal pitch coke, petroleum pitch coke, acetylene pitch coke, and the like.
- the average particle diameter of the negative electrode active material is preferably 2 ⁇ m or more, more preferably 5 ⁇ m or more, from the viewpoint of suppressing side reactions during charge / discharge and suppressing reduction in charge / discharge efficiency, and from the viewpoint of input / output characteristics and electrode production In view of (smoothness of the electrode surface, etc.), it is preferably 40 ⁇ m or less, more preferably 30 ⁇ m or less.
- the average particle diameter means a particle diameter (median diameter: D 50 ) at an integrated value of 50% in a particle size distribution (volume basis) by a laser diffraction scattering method.
- the negative electrode is prepared by applying a slurry containing a negative electrode active material and a binder, a water-soluble polymer thickener, an aqueous solvent, and a conductive auxiliary agent as necessary on the negative electrode current collector, drying, and pressing as necessary.
- the negative electrode current collector and negative electrode active material layer thereon
- the method for applying the negative electrode slurry include a doctor blade method, a die coater method, and a dip coating method. You may add additives, such as an antifoamer and surfactant, to a slurry as needed.
- the content of the binder in the negative electrode active material layer is preferably in the range of 0.5 to 15% by mass as the content of the negative electrode active material layer from the viewpoint of the binding force and energy density that are in a trade-off relationship.
- the range of 0.5 to 10% by mass is more preferable, and the range of 1 to 10% by mass is further preferable.
- the content of the water-soluble polymer thickener in the negative electrode active material layer is preferably in the range of 0.2 to 10% by mass, preferably in the range of 0.5 to 5% by mass as the content of the negative electrode active material layer. Is more preferable, and the range of 0.5 to 2% by mass is even more preferable.
- the content of the thickener is preferably 10% by mass or less from the viewpoint of the electric resistance of the negative electrode active material layer, and 0.2% by mass from the viewpoint of increasing the dispersibility and adhesion of the active material particles to obtain a sufficient binding force. % Or more is preferable.
- the negative electrode active material layer may contain a conductive aid as necessary.
- a conductive material generally used as a negative electrode conductive auxiliary agent such as carbonaceous material such as carbon black, ketjen black, and acetylene black can be used.
- the content of the conductive additive in the negative electrode active material layer is preferably in the range of 0.1 to 3.0% by mass as a content rate with respect to the negative electrode active material.
- the content of the conductive additive relative to the negative electrode active material is preferably 0.1% by mass or more, more preferably 0.3% by mass or more from the viewpoint of forming a sufficient conductive path, resulting from excessive addition of the conductive additive. 3.0 mass% or less is preferable and 1.0 mass% or less is more preferable from the point which suppresses the gas generation by electrolytic solution decomposition
- the average particle diameter (primary particle diameter) of the conductive additive is preferably in the range of 10 to 100 nm.
- the average particle diameter (primary particle diameter) of the conductive additive is preferably 10 nm or more, more preferably 30 nm or more, and a sufficient number of contact points from the viewpoint of uniformly dispersing the conductive additive in the negative electrode while suppressing excessive aggregation. 100 nm or less is preferable from the viewpoint of forming a good conductive path, and 80 nm or less is more preferable.
- the conductive additive is fibrous, those having an average diameter of 2 to 200 nm and an average fiber length of 0.1 to 20 ⁇ m can be mentioned.
- the average particle diameter of the conductive additive is the median diameter (D 50 ), which means the particle diameter at an integrated value of 50% in the particle size distribution (volume basis) by the laser diffraction scattering method.
- the negative electrode current collector copper, stainless steel, nickel, titanium, or an alloy thereof can be used.
- the shape include foil, flat plate, and mesh.
- lithium complex oxide which has a layered rock salt type structure or a spinel type structure, lithium iron phosphate which has an olivine type structure, etc.
- lithium composite oxide examples include lithium manganate (LiMn 2 O 4 ); lithium cobaltate (LiCoO 2 ); lithium nickelate (LiNiO 2 ); and at least part of the manganese, cobalt, and nickel portions of these lithium compounds.
- lithium composite oxides may be used individually by 1 type, and 2 or more types may be mixed and used for them.
- lithium-containing composite oxide having a layered crystal structure examples include a lithium nickel-containing composite oxide.
- this lithium nickel-containing composite oxide one obtained by substituting a part of nickel at the nickel site with another metal can be used.
- the metal other than Ni occupying the nickel site include at least one metal selected from Mn, Co, Al, Mg, Fe, Cr, Ti, and In.
- This lithium nickel-containing composite oxide preferably contains Co as a metal other than Ni occupying nickel sites.
- the lithium nickel-containing composite oxide preferably contains Mn or Al in addition to Co, that is, lithium nickel cobalt manganese composite oxide (NCM) having a layered crystal structure, lithium nickel having a layered crystal structure Cobalt aluminum composite oxide (NCA) or a mixture thereof can be suitably used.
- NCM lithium nickel cobalt manganese composite oxide
- NCA Cobalt aluminum composite oxide
- lithium nickel-containing composite oxide having a layered crystal structure for example, one represented by the following formula can be used.
- Me1 is Mn or Al
- Me2 is at least one selected from the group consisting of Mn, Al, Mg, Fe, Cr, Ti, In (excluding the same type of metal as Me1), ⁇ 0.5 ⁇ a ⁇ 0.1, 0.1 ⁇ b ⁇ 1, 0 ⁇ c ⁇ 0.5, 0 ⁇ d ⁇ 0.5)
- the average particle diameter of the positive electrode active material is, for example, preferably from 0.1 to 50 ⁇ m, more preferably from 1 to 30 ⁇ m, and even more preferably from 2 to 25 ⁇ m, from the viewpoints of reactivity with the electrolytic solution and rate characteristics.
- the average particle diameter means a particle diameter (median diameter: D 50 ) at an integrated value of 50% in a particle size distribution (volume basis) by a laser diffraction scattering method.
- the positive electrode is composed of a positive electrode current collector and a positive electrode active material layer on the positive electrode current collector.
- the positive electrode is disposed so that the active material layer faces the negative electrode active material layer on the negative electrode current collector through the separator.
- the positive electrode active material layer can be formed as follows. First, it is formed by preparing a slurry containing a positive electrode active material, a binder and a solvent (and further a conductive aid if necessary), applying the slurry onto a positive electrode current collector, drying, and pressing as necessary. it can. N-methyl-2-pyrrolidone (NMP) can be used as a slurry solvent used in preparing the positive electrode.
- NMP N-methyl-2-pyrrolidone
- the positive electrode active material layer can contain a conductive additive in addition to the positive electrode active material and the binder.
- a conductive support agent There is no restriction
- binder those usually used as a binder for positive electrodes such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF) can be used.
- PTFE polytetrafluoroethylene
- PVDF polyvinylidene fluoride
- a higher proportion of the positive electrode active material in the positive electrode active material layer is preferable because the capacity per mass increases.
- a conductive auxiliary agent from the viewpoint of electrode strength.
- a binder it is preferable to add a binder. If the proportion of the conductive auxiliary agent is too small, it becomes difficult to maintain sufficient conductivity, and the resistance of the electrode is likely to increase. When the ratio of the binder is too small, it becomes difficult to maintain the adhesive force with the current collector, active material, and conductive additive, and electrode peeling may occur. From the above points, the content of the conductive additive in the active material layer is preferably 1 to 10% by mass, and the content of the binder in the active material layer is preferably 1 to 10% by mass.
- the positive electrode current collector aluminum, stainless steel, nickel, titanium, or an alloy thereof can be used.
- the shape include foil, flat plate, and mesh.
- an aluminum foil can be suitably used.
- the porosity of the positive electrode active material layer (not including the current collector) is preferably 10 to 30%, more preferably 20 to 25%.
- the porosity of the positive electrode active material layer is set to the above value, the discharge capacity during use at a high discharge rate is improved, which is preferable.
- a nonaqueous electrolytic solution in which a lithium salt is dissolved in one or two or more nonaqueous solvents can be used.
- Non-aqueous solvents include cyclic carbonates such as ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), vinylene carbonate (VC); dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), chain carbonates such as dipropyl carbonate (DPC); aliphatic carboxylic acid esters such as methyl formate, methyl acetate and ethyl propionate; ⁇ -lactones such as ⁇ -butyrolactone; 1,2-ethoxy Examples include chain ethers such as ethane (DEE) and ethoxymethoxyethane (EME); and cyclic ethers such as tetrahydrofuran and 2-methyltetrahydrofuran.
- EC ethylene carbonate
- PC propylene carbonate
- BC butylene carbonate
- VVC vinylene carbonate
- DMC dimethyl carbonate
- DEC diethyl
- lithium salt dissolved in the nonaqueous solvent is not particularly limited, for example LiPF 6, LiAsF 6, LiAlCl 4 , LiClO 4, LiBF 4, LiSbF 6, LiCF 3 SO 3, LiCF 3 CO 2, Li (CF 3 SO 2 ) 2 , LiN (CF 3 SO 2 ) 2 , and lithium bisoxalatoborate are included. These lithium salts can be used individually by 1 type or in combination of 2 or more types. Moreover, a polymer component may be included as a non-aqueous electrolyte. The concentration of the lithium salt can be set in the range of 0.8 to 1.2 mol / L, preferably 0.9 to 1.1 mol / L.
- the electrolytic solution preferably contains a compound that is usually used as an additive for non-aqueous electrolytic solutions.
- a compound that is usually used as an additive for non-aqueous electrolytic solutions for example, carbonate compounds such as vinylene carbonate and fluoroethylene carbonate; acid anhydrides such as maleic anhydride; boron additives such as boronic esters; sulfite compounds such as ethylene sulfite; 1,3-propane sultone 1,2-propane sultone, 1,4-butane sultone, 1,2-butane sultone, 1,3-butane sultone, 2,4-butane sultone, 1,3-pentane sultone, and other cyclic monosulfonic acid esters; methylenemethane disulfonic acid Examples thereof include cyclic disulfonate compounds such as esters (1,5,2,4-dioxadithian-2,2,4,4-tetraoxide) and
- additives may be used individually by 1 type, and may use 2 or more types together.
- a cyclic sulfonic acid ester compound is preferable and a cyclic disulfonic acid compound is preferable from the viewpoint that a film can be more effectively formed on the positive electrode surface and battery characteristics can be improved.
- the content of the additive in the electrolytic solution is preferably 0.01 to 10% by mass from the viewpoint of obtaining a sufficient addition effect while suppressing an increase in the viscosity and resistance of the electrolytic solution. More preferably, it is mass%.
- the electrolytic solution contains sufficient cyclic sulfonic acid ester, a coating can be more effectively formed on the surface of the positive electrode, and battery characteristics can be improved.
- the cyclic sulfonic acid ester compound a cyclic disulfonic acid compound is preferable.
- a porous resin film, a woven fabric, a non-woven fabric, or the like can be used as the separator.
- the resin constituting the porous film include polyolefin resins such as polypropylene and polyethylene, polyester resins, acrylic resins, styrene resins, and nylon resins.
- a polyolefin-based microporous membrane is preferable because of its excellent ion permeability and performance of physically separating the positive electrode and the negative electrode.
- the separator may be formed with a layer containing inorganic particles.
- the inorganic particles include insulating oxides, nitrides, sulfides, carbides, etc. Among them, TiO. 2 or Al 2 O 3 is preferably included.
- a case made of a flexible film, a can case, or the like can be used for the exterior container, and a flexible film is preferably used from the viewpoint of reducing the weight of the battery.
- a film in which a resin layer is provided on the front and back surfaces of a metal layer serving as a base material can be used.
- a metal layer having a barrier property such as prevention of leakage of the electrolytic solution or entry of moisture from the outside can be selected, and aluminum, stainless steel, or the like can be used.
- a heat-fusible resin layer such as a modified polyolefin is provided.
- An exterior container is formed by making the heat-fusible resin layers of the flexible film face each other and heat-sealing the periphery of the portion that houses the electrode laminate.
- a resin layer such as a nylon film or a polyester film can be provided on the surface of the exterior body that is the surface opposite to the surface on which the heat-fusible resin layer is formed.
- Example 1 An acrylic binder was added to water and mixed sufficiently to prepare dispersion A. The amount of the acrylic binder added at this time was 1.7% by mass with respect to water.
- CMC sodium salt, manufactured by Nippon Paper Industries Co., Ltd., trade name: Sunrose MAC350HC
- the amount of CMC added at this time was 1.2% by mass with respect to water.
- a mixed powder composed of a negative electrode active material (natural graphite coated) and a conductive additive (carbon black) and dispersion B were mixed and kneaded.
- the solid content concentration (concentration of components excluding water) of the mixture at this time was 60% by mass.
- the slurry was applied to a current collector (copper foil), dried and pressed to obtain a negative electrode.
- the time from the mixing step of the mixed powder and dispersion B to obtaining the slurry was defined as the slurry preparation time.
- the preparation time of the dispersion A was 0.5 hours or less (about 10 minutes).
- Completion of slurry preparation was made when there was no aggregate of material and it became a predetermined viscosity (7000 cP). Judgment of the presence or absence of aggregates was made visually using a particle size gauge.
- a lithium ion secondary battery was produced as follows.
- This slurry was applied onto a current collector (aluminum foil) and dried.
- the slurry was applied to the other surface of the current collector, dried, and pressed to obtain a positive electrode in which a positive electrode active material layer was formed on both surfaces of the current collector.
- a porous polypropylene (PP) film (thickness 25 ⁇ m) by a dry method was used as a separator, and an electrode laminate was obtained by laminating in this order through the separator in the order of negative electrode / positive electrode / negative electrode.
- This electrode laminate was wrapped with an aluminum laminate film, and an electrolyte was injected and sealed.
- the negative electrode peel strength, battery contact resistance, charge transfer resistance, and capacity retention rate were measured according to the following methods. The results are shown in Table 1.
- Example 2 In the same manner as in Example 1, this slurry was applied to a current collector (copper foil), dried and pressed to obtain a negative electrode. A battery was obtained in the same manner as in Example 1.
- the time from the mixing step of the mixed powder and the CMC aqueous solution to obtaining the slurry was defined as the slurry preparation time.
- the negative electrode peel strength, battery contact resistance, charge transfer resistance, and capacity retention rate were measured according to the following methods. The results are shown in Table 1.
- Comparative Example 2 A slurry was formed, a negative electrode was produced, and a battery was obtained in the same manner as in Comparative Example 1, except that the same type of acrylic binder as in Example 1 was used instead of the SBR binder.
- Example 1 water was added to lower the solid content concentration of the mixture to 45% by mass and further stirred to obtain a slurry for forming a negative electrode active material layer.
- the CMC concentration and binder concentration in the obtained slurry are the same as in Example 1.
- this slurry was applied to a current collector (copper foil), dried and pressed to obtain a negative electrode.
- a battery was obtained in the same manner as in Example 1.
- the time from the mixing step of the mixed powder and the SBR binder dispersion to obtaining the slurry was defined as the slurry preparation time.
- the negative electrode peel strength, battery contact resistance, charge transfer resistance, and capacity retention rate were measured according to the following methods. The results are shown in Table 1.
- Capacity maintenance rate / cycle test As the charge / discharge conditions, CC-CV charge: upper limit voltage 4.2V, current 1C, CV time: 1.5 hours, CC discharge: lower limit voltage 3.0V, current 1C, environmental temperature during charge / discharge: 25 ° C, A cycle test was conducted. The capacity retention rate was the ratio of the discharge capacity at the 500th cycle to the discharge capacity at the first cycle.
- Example 1 Comparison between Example 1 and Comparative Example 1:
- an SBR binder rubber-based binder
- this SBR binder was added after mixing the powder material containing the negative electrode active material and the CMC aqueous solution.
- an acrylic binder is used as the binder, and a binder dispersion is formed in advance before adding the powder material (particularly, the binder and water are mixed before adding CMC). According to this, it can be seen that the slurry preparation time can be shortened, the peel strength is high, the contact resistance and the charge transfer resistance are low, and the capacity retention rate is further improved.
- Example 1 and Comparative Example 2 Comparison between Example 1 and Comparative Example 2: In both Example 1 and Comparative Example 2, an acrylic binder is used, but in Comparative Example 2, the binder is mixed with the powder material containing the negative electrode active material and the CMC aqueous solution. It is added after. Compared to such Comparative Example 2, according to Example 1 in which the binder dispersion is formed in advance before adding the powder material (particularly, the binder and water are mixed before CMC addition), the slurry preparation time can be shortened. It can also be seen that the peel strength is high, the contact resistance and the charge transfer resistance are low, and the capacity retention rate is further improved.
- Example 1 Comparison of Example 1 and Comparative Example 3:
- an SBR binder rubber-based binder
- this SBR binder was mixed with an aqueous CMC solution, and then a powder material containing a negative electrode active material and its mixed liquid And are mixed.
- the peel strength was high, and the contact It can be seen that the resistance and the charge transfer resistance are lowered, and the capacity retention rate is further improved.
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Abstract
Description
集電体と、該集電体上の負極活物質層とを含むリチウムイオン二次電池用負極の製造方法であって、
負極活物質とバインダと水溶性高分子増粘剤と水系溶媒を含むスラリーを形成する工程と、
前記スラリーを集電体上に塗布し、前記水系溶媒を除去する乾燥を行って負極活物質層となる塗布層を形成する工程とを含み、
前記スラリーを形成する工程は、
前記水系溶媒に前記水溶性高分子増粘剤が溶解し、前記バインダとしてアクリル系バインダが分散した分散液を形成する工程と、
前記負極活物質を含む粉体材料と前記分散液とを含む混合物を形成し攪拌する工程とを含む、リチウムイオン二次電池用負極の製造方法が提供される。
リチウムイオン二次電池の一例(ラミネート型)の断面図を図1に示す。図1に示すように、本例のリチウムイオン二次電池は、アルミニウム箔等の金属からなる正極集電体3と、その上に設けられた正極活物質を含有する正極活物質層1とからなる正極、及び銅箔等の金属からなる負極集電体4と、その上に設けられた負極活物質を含有する負極活物質層2とからなる負極を有する。正極および負極は、正極活物質層1と負極活物質層2とが対向するように、不織布やポリプロピレン微多孔膜などからなるセパレータ5を介して積層されている。この電極対は、アルミニウムラミネートフィルムからなる外装体6、7で形成された容器内に収容されている。正極集電体3には正極タブ9が接続され、負極集電体4には負極タブ8が接続され、これらのタブは容器の外に引き出されている。容器内には電解液が注入され封止される。複数の電極対が積層された電極群が容器内に収容された構造とすることもできる。
負極活物質としては、炭素質材料を用いることができる。炭素質材料としては、黒鉛、非晶質炭素(例えば易黒鉛化性炭素、難黒鉛化性炭素)、ダイヤモンド状炭素、フラーレン、カーボンナノチューブ、カーボンナノホーンなどが挙げられる。黒鉛としては、天然黒鉛、人造黒鉛を用いることができ、材料コストの観点から安価な天然黒鉛が好ましい。非晶質炭素としては、例えば、石炭ピッチコークス、石油ピッチコークス、アセチレンピッチコークス等を熱処理して得られるものが挙げられる。
正極活物質としては、特に制限されるものではないが、例えば、層状岩塩型構造又はスピネル型構造を有するリチウム複合酸化物や、オリビン型構造を有するリン酸鉄リチウムなどを用いることができる。リチウム複合酸化物としては、マンガン酸リチウム(LiMn2O4);コバルト酸リチウム(LiCoO2);ニッケル酸リチウム(LiNiO2);これらのリチウム化合物のマンガン、コバルト、ニッケルの部分の少なくとも一部をアルミニウム、マグネシウム、チタン、亜鉛など他の金属元素で置換したもの;マンガン酸リチウムのマンガンの一部を少なくともニッケルで置換したニッケル置換マンガン酸リチウム;ニッケル酸リチウムのニッケルの一部を少なくともコバルトで置換したコバルト置換ニッケル酸リチウム;ニッケル置換マンガン酸リチウムのマンガンの一部を他の金属(例えばアルミニウム、マグネシウム、チタン、亜鉛の少なくとも一種)で置換したもの;コバルト置換ニッケル酸リチウムのニッケルの一部を他の金属元素(例えばアルミニウム、マグネシウム、チタン、亜鉛、マンガンの少なくとも一種)で置換したものが挙げられる。これらのリチウム複合酸化物は一種を単独で使用してもよいし、二種以上を混合して用いてもよい。
Li1+a(NibCocMe1dMe21-b-c-d)O2
(式中、Me1はMn又はAlであり、Me2は、Mn、Al、Mg、Fe、Cr、Ti、Inからなる群から選択される少なくとも1種であり(Me1と同種の金属を除く)、-0.5≦a<0.1、0.1≦b<1、0<c<0.5、0<d<0.5)
電解液には、非水電解液用添加剤として通常使用されている化合物を含むことが好ましい。例えば、ビニレンカーボネート、フルオロエチレンカーボネート等のカーボネート系化合物;マレイン酸無水物等の酸無水物;ボロン酸エステル等のホウ素系添加剤;エチレンサルファイト等のサルファイト系化合物;1,3-プロパンスルトン、1,2-プロパンスルトン、1,4-ブタンスルトン、1,2-ブタンスルトン、1,3-ブタンスルトン、2,4-ブタンスルトン、1,3-ペンタンスルトン等の環状モノスルホン酸エステル;メチレンメタンジスルホン酸エステル(1,5,2,4-ジオキサジチアン-2,2,4,4-テトラオキシド)、エチレンメタンジスルホン酸エステル等の環状ジスルホン酸エステル化合物が挙げられる。これらの添加剤は、1種を単独で用いてもよいし、2種以上を併用してもよい。特に、正極表面に被膜をより効果的に形成でき、電池特性を向上できる点から、環状スルホン酸エステル化合物が好ましく、環状ジスルホン酸化合物が好ましい。
セパレータとしては、樹脂製の多孔質膜、織布、不織布等を用いることができる。多孔質膜を構成する樹脂としては、例えばポリプロピレンやポリエチレン等のポリオレフィン樹脂、ポリエステル樹脂、アクリル樹脂、スチレン樹脂、またはナイロン樹脂等が挙げられる。特にポリオレフィン系の微多孔膜は、イオン透過性と、正極と負極とを物理的に隔離する性能に優れているため好ましい。また、必要に応じて、セパレータには無機物粒子を含む層を形成してもよく、無機物粒子としては、絶縁性の酸化物、窒化物、硫化物、炭化物などを挙げることができ、なかでもTiO2やAl2O3を含むことが好ましい。
外装容器には可撓性フィルムからなるケースや、缶ケース等を用いることができ、電池の軽量化の観点からは可撓性フィルムを用いることが好ましい。
水にアクリル系バインダを添加して十分に攪拌混合して分散液Aを作製した。このときのアクリル系バインダの添加量は、水に対して1.7質量%とした。
正極活物質としてLiMn2O4、導電助剤としてアセチレンブラック、バインダーとしてポリフッ化ビニリデンを溶媒に分散してスラリーを調製し(正極活物質:導電助剤:バインダ=85:5:10(質量比))、このスラリーを集電体(アルミニウム箔)上に塗布し、乾燥した。集電体の他方の面にも同様にスラリーを塗布し、乾燥し、プレスを行って、集電体の両面に正極活物質層が形成された正極を得た。
CMCの水溶液(水に対するCMCの添加量:1.2質量%)と、実施例1と同様にして調製した混合粉末とを混合し、混練した。このときの混合物の固形分濃度(水を除く成分の濃度)は60質量%とした。
SBRバインダに代えて、実施例1と同種のアクリル系バインダを用いた以外は、比較例1と同様にして、スラリーを形成し、負極を作製し、電池を得た。
CMCの水溶液(水に対するCMCの添加量:1.2質量%)にSBRバインダを添加して、十分に混合した。このときのSBRバインダの添加量は、水に対して1.7質量%とした。
得られたスラリーを目付け10mg/cm2となるように銅箔の片面に塗布し、60℃で5分間、加熱乾燥し、続いて110℃で5分間、乾燥させて、試験用の電極を作製した。この電極とSUS板とを両面テープにて張り合わせ、180度剥離試験を実施した(剥離幅10mm、剥離速度10mm/min)。
得られた電池の交流インピーダンス測定を行い、結果を解析することにより、接触抵抗および電荷移動抵抗を算出した。交流インピーダンス測定は、環境温度:25℃、電池の状態:SOC(state of charge)100%(電圧4.2V)で行った。
充放電条件として、CC-CV充電:上限電圧4.2V、電流1C、CV時間:1.5時間、CC放電:下限電圧3.0V、電流1C、充放電時の環境温度:25℃で、サイクル試験を行った。容量維持率は、1サイクル目の放電容量に対する500サイクル目の放電容量の割合とした。
2 負極活物質層
3 正極集電体
4 負極集電体
5 セパレータ
6 ラミネート外装体
7 ラミネート外装体
8 負極タブ
9 正極タブ
Claims (12)
- 集電体と、該集電体上の負極活物質層とを含むリチウムイオン二次電池用負極の製造方法であって、
負極活物質とバインダと水溶性高分子増粘剤と水系溶媒を含むスラリーを形成する工程と、
前記スラリーを集電体上に塗布し、前記水系溶媒を除去する乾燥を行って負極活物質層となる塗布層を形成する工程とを含み、
前記スラリーを形成する工程は、
前記水系溶媒に前記水溶性高分子増粘剤が溶解し、前記バインダとしてアクリル系バインダが分散した分散液を形成する工程と、
前記負極活物質を含む粉体材料と前記分散液とを含む混合物を形成し攪拌する工程とを含む、リチウムイオン二次電池用負極の製造方法。 - 前記スラリーを形成する工程は、
前記アクリル系バインダが水系溶媒に分散した第1の分散液を形成する工程と、
前記第1の分散液に水溶性高分子増粘剤を添加して、該水溶性高分子増粘剤が溶解した第2の分散液を形成する工程と、
前記負極活物質を含む粉体材料と前記第2分散液とを含む混合物を形成し攪拌する工程とを含む、請求項1に記載のリチウムイオン二次電池用負極の製造方法。 - 前記混合物を形成し攪拌する工程は、
固形分濃度が50質量以上70質量%以下の混合物を攪拌する工程と、
固形分濃度を40質量%以上50質量%未満に低下させた混合物を攪拌する工程を含む、請求項1又は2に記載の製造方法。 - 前記アクリル系バインダの水系媒体に対する添加量が0.5~5質量%である、請求項1から3のいずれか一項に記載の製造方法。
- 前記水溶性高分子増粘剤の水系媒体に対する添加量が0.5~5質量%である、請求項1から4のいずれか一項に記載の製造方法。
- 前記水溶性高分子増粘剤はカルボキシメチルセルロースを含む、請求項1から5のいずれか一項に記載の製造方法。
- 前記カルボキシメチルセルロースはナトリウム塩である、請求項6に記載の製造方法。
- 前記負極活物質は炭素質材料である、請求項1から7のいずれか一項に記載の製造方法。
- 前記炭素質材料は黒鉛系材料である、請求項8に記載の製造方法。
- 前記負極活物質の平均粒径は2~40μmである、請求項1から9のいずれか一項に記載の製造方法。
- 前記粉体材料は導電助剤を含む、請求項1から10のいずれか一項に記載の製造方法。
- 前記導電助剤は炭素質材料である、請求項11に記載の製造方法。
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- 2016-09-14 CN CN201680053751.7A patent/CN108028365A/zh active Pending
- 2016-09-14 US US15/751,055 patent/US20180233735A1/en not_active Abandoned
- 2016-09-14 JP JP2017543102A patent/JPWO2017056984A1/ja active Pending
- 2016-09-14 WO PCT/JP2016/077057 patent/WO2017056984A1/ja active Application Filing
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WO2018184466A1 (zh) * | 2017-04-07 | 2018-10-11 | 惠州拓邦电气技术有限公司 | 一种锂离子电池负极浆料的制备方法 |
JP2018190501A (ja) * | 2017-04-28 | 2018-11-29 | トヨタ自動車株式会社 | リチウムイオン二次電池 |
Also Published As
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US20180233735A1 (en) | 2018-08-16 |
CN108028365A (zh) | 2018-05-11 |
JPWO2017056984A1 (ja) | 2018-07-12 |
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