WO2013005739A1 - リチウム二次電池用電極、リチウム二次電池及びリチウム二次電池用電極の製造方法 - Google Patents
リチウム二次電池用電極、リチウム二次電池及びリチウム二次電池用電極の製造方法 Download PDFInfo
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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Definitions
- the present invention relates to an electrode for a lithium secondary battery, a lithium secondary battery, and a method for producing an electrode for a lithium secondary battery.
- Lithium ion secondary batteries are currently used for applications such as mobile phones, laptop computers, and video cameras because of their high energy density.
- Small lithium-ion batteries generally use lithium cobaltate or lithium manganate as the positive electrode active material and graphite as the negative electrode.
- the positive electrode of a typical lithium ion secondary battery is composed of lithium cobaltate or lithium manganate, which is a positive electrode active material, and carbon particles having electronic conductivity fixed on a metal foil having a current collecting effect.
- Aluminum is common as the metal foil.
- PVDF polyvinylidene fluoride
- PTFE polytetrafluoroethylene
- the negative electrode is configured by fixing a negative electrode active material on a metal foil having a current collecting effect. Copper is common as the metal foil.
- PVDF polyvinylidene fluoride
- the power source is required to supply a large current. Along with this, the charging capacity of the battery is quickly reduced, so that it is necessary to finish charging in a short time. If the charging time is set long, the battery cannot be used during that time, so charging must be completed quickly with as much current as possible.
- the discharge performance and the charge performance at such a large current value are referred to as rapid charge / discharge characteristics and are important performance indexes of the secondary battery.
- JP 2001-266850 A Japanese Patent Publication 7-123053 Japanese Patent Publication No. 4-24831 JP-A-7-130356 JP 2005-222772 A JP 2007-005281 A JP 2009-222492 A JP 2006-261062 A JP 2001-351612 A
- the present invention has been made in view of the above circumstances, can be easily manufactured, enables rapid charge / discharge without adding a large amount of conductive particles to the electrode mixture layer, and has a large charge / discharge current condition.
- it aims at providing the manufacturing method of the electrode for lithium secondary batteries which can maintain a battery capacity maintenance factor highly, a lithium secondary battery, and the electrode for lithium secondary batteries.
- the present invention adopts the following configuration.
- An electrode having a metal foil and an electrode mixture laminated on the metal foil, comprising a binder and conductive particles between the metal foil and the electrode mixture.
- a coating layer is provided, and the electrode mixture includes an electrode active material and a conductive additive having a composition ratio in the electrode mixture of 0% by mass to 1.4% by mass.
- Electrode for lithium secondary battery [2]
- the electrode mixture includes an electrode material in which a carbon material is attached to part or all of the surface of the electrode active material particles, and substantially does not include a conductive additive.
- the electrode for a lithium secondary battery according to [1].
- the binder contains one or more selected from the group consisting of polysaccharides or derivatives thereof. electrode.
- the coating layer includes one or more selected from the group consisting of organic acids or organic acid derivatives. electrode.
- the electrode active material according to any one of [1] to [6], wherein the electrode active material is one or more of a lithium-containing composite oxide, a chalcogen compound, or a lithium-containing olivic acid salt. Electrode for lithium secondary battery. [8] The electrode active material contains any one or more of lithium cobalt oxide, lithium manganate, lithium nickelate, lithium cobalt manganese nickelate, titanium sulfide (TiS2), lithium iron olivine, and lithium manganese olivine.
- TiS2 titanium sulfide
- the electrode for a lithium secondary battery according to [7], wherein [9] The binder according to any one of [1] to [8], wherein the binder contains one or more selected from the group consisting of chitosan, chitin, cellulose, and derivatives thereof. Electrode for lithium secondary battery. [10]
- the organic acid or the organic acid derivative is at least one selected from the group consisting of trimellitic anhydride, pyromellitic anhydride, 1,2,3,4-butanetetracarboxylic acid, or derivatives thereof.
- a lithium secondary battery comprising the lithium secondary battery electrode according to any one of [1] to [11] and an electrolyte.
- a coating layer coating solution containing a binder, conductive particles, and a dispersion medium is applied to a metal foil, the dispersion medium is removed to form a coating layer, and then an electrode active material is formed on the coating layer.
- the lithium secondary battery electrode is a positive electrode for a lithium secondary battery having a metal foil and a positive electrode mixture laminated on the metal foil, Between the metal foil and the positive electrode mixture, a coating layer containing a binder and conductive particles is further provided,
- the positive electrode mixture is A positive electrode material made only of a positive electrode active material, or a positive electrode material in which a carbon material is attached to part or all of the surface of particles of the positive electrode active material;
- the positive electrode mixture includes a positive electrode material in which a carbon material is attached to part or all of the surfaces of the particles of the positive electrode active material, and substantially does not include the conductive additive [15]. ]
- the positive electrode material formed by adhering a carbon material to part or all of the surface of the positive electrode active material particles, A method of firing a mixture of the positive electrode active material and a carbon-forming material as a precursor of the carbon material at a temperature of 500 ° C. to 800 ° C.
- the metal foil is aluminum or aluminum alloy foil;
- the conductive particles in the coating layer are carbon particles, and the area ratio of the conductive particles is 50% or more and less than 100%,
- the binder in the coating layer includes a polysaccharide or a derivative thereof, an aromatic carboxylic acid or a derivative thereof,
- the positive electrode active material includes one selected from the group consisting of lithium iron olivicate, lithium manganese olivine, lithium cobaltate, lithium manganate, lithium nickelate, lithium cobalt manganese nickelate [17.
- the lithium secondary battery electrode is a positive electrode for a lithium secondary battery, After applying a coating layer coating solution containing a binder, conductive particles and a dispersion medium to a metal foil, forming the coating layer by removing the dispersion medium, On the coating layer, A positive electrode material made only of a positive electrode active material, or a positive electrode material in which a carbon material is attached to part or all of the surface of particles of the positive electrode active material; Applying a mixture coating liquid containing a conductive additive having a composition ratio of 0 to 1.4% by mass when formed into a positive electrode mixture and another dispersion medium, The method for producing an electrode for a lithium secondary battery according to [13] or [14], wherein the other dispersion medium is removed to form a positive electrode mixture.
- the positive electrode material is a positive electrode material in which a carbon material is attached to part or all of the surface of the positive electrode active material particles
- the method of attaching the carbon material is a method of firing a mixture of the positive electrode active material and a carbon forming material that is a precursor of the carbon material at a temperature of 500 ° C. to 800 ° C. under an inert condition or a reducing condition. Or a method of kneading the mixture of the positive electrode active material and the carbon material so as to apply compression, shear, and rolling action, wherein the lithium according to [13], [14] or [19] A method for producing an electrode for a secondary battery.
- the present invention can be easily produced, enables rapid charge / discharge without adding a large amount of conductive particles to the electrode mixture layer, and maintains a high battery capacity maintenance rate even under large charge / discharge current conditions.
- the electrode for lithium secondary batteries, the lithium secondary battery, and the manufacturing method of the electrode for lithium secondary batteries which can be performed can be provided.
- FIG. 1 is a graph showing the relationship between the capacity retention rate of the lithium secondary batteries of Example 1 and the comparative example and the discharge current rate.
- FIG. 2 is a graph showing the relationship between the capacity retention rate of the lithium secondary batteries of Example 2 and the comparative example and the discharge current rate.
- FIG. 3 is a graph showing the relationship between the capacity retention rate and the discharge current rate of the lithium secondary batteries of Example 3 and Comparative Example.
- FIG. 4 is a graph showing the relationship between the capacity retention rate and the discharge current rate of the lithium secondary batteries of Example 4 and Comparative Example.
- FIG. 4 is a graph showing the relationship between the capacity retention rate and the discharge current rate of the lithium secondary batteries of Example 4 and Comparative Example.
- FIG. 4 is a graph showing the relationship between the capacity retention rate and the discharge current rate of the lithium secondary batteries of Example 4 and Comparative Example.
- FIG. 5 is a graph showing the relationship between the capacity retention rate of the lithium secondary batteries of Example 5 and the comparative example and the discharge current rate.
- FIG. 6 is a graph showing the relationship between the capacity retention rate of the lithium secondary batteries of Example 6 and the comparative example and the discharge current rate.
- Electrode for lithium secondary battery An electrode for a lithium secondary battery according to an embodiment of the present invention was provided between a metal foil serving as a current collector, an electrode composite laminated on the metal foil, and the metal foil and the electrode composite. And a coating layer.
- the metal foil constituting the current collector may be a general foil not provided with openings, or may be a punched metal foil, a foil having an opening such as a metal net, or a porous foil. Further, the metal foil may have a smooth surface, or may be a foil roughened by electrical or chemical etching.
- the thickness of the metal foil is not particularly limited, but is preferably 5 ⁇ m to 200 ⁇ m. By setting it to such a thickness, the ratio of the current collector in the predetermined volume of the lithium secondary battery can be kept below a certain level, and the current collector and the electrode itself are given sufficient strength and handling properties are good. Can be.
- the material of the metal foil is preferably a metal having high electrical conductivity and high electrochemical corrosion resistance, and in particular, an aluminum or aluminum alloy foil is preferably used.
- the aluminum foil include pure aluminum-based A1085 material and A3003 material.
- the material of the metal foil when the electrode is a negative electrode is preferably copper or a copper alloy.
- the coating layer is configured to contain a binder and conductive particles.
- the coating layer may further contain one or more selected from the group consisting of organic acids or derivatives thereof.
- the coating layer may be formed on one side of the metal foil, or may be formed on both sides.
- the coating layer should just be formed between metal foil and electrode compound material, Preferably it is provided in contact with metal foil and electrode compound material.
- the conductive particles used in the coating layer are not particularly limited as long as they are electrically conductive particles, but are preferably those containing carbon element as a main component, that is, carbon particles.
- carbon particles carbon black, graphite, vapor grown carbon fiber, carbon nanotube, carbon nanofiber, and the like are suitable.
- carbon black include acetylene black and furnace black. Commercial products such as ketjen black can also be used. These carbon particles can be used alone or in combination of two or more.
- Examples of conductive particles other than carbon particles include metal powders such as gold, silver, copper, nickel, and aluminum, a mixture of these metal powders and carbon particles, or a coating of metal powder on the surface of carbon particles. And so on.
- the conductive particles may be spherical, scale-like, lump-like, or irregularly-shaped particles, or may be anisotropically-shaped particles such as needles, rods, or fibers.
- the conductive particles having a spherical shape, a scale shape, a lump shape, or an irregular shape preferably have an average primary particle size of 10 nm to 5 ⁇ m, and more preferably 10 nm to 100 nm.
- the average primary particle size of these conductive particles is calculated by measuring the particle size of 500 to 1000 particles using an electron microscope and averaging them on a number basis.
- the maximum particle diameter (longest diameter) is used as the particle diameter, and similarly, the average particle diameter is obtained by averaging these on a number basis.
- Anisotropic conductive particles have a large surface area per mass and a large contact area with the metal foil or electrode active material, so even when added in a small amount, between the metal foil and the electrode active material or between the electrode active materials. The electrical conductivity of can be increased.
- Particularly effective anisotropic conductive particles include vapor grown carbon fiber, carbon nanotube, or carbon nanofiber.
- the vapor grown carbon fiber, carbon nanotube or carbon nanofiber has an average fiber diameter of usually 0.001 to 0.5 ⁇ m, preferably 0.003 to 0.2 ⁇ m, and an average fiber length from the viewpoint of improving conductivity. Usually, it is 1 to 100 ⁇ m, preferably 1 to 30 ⁇ m.
- the average fiber diameter and the average fiber length are calculated by measuring the fiber diameter and fiber length of 500 to 1000 fibers using an electron microscope and averaging them on the basis of several numbers.
- the conductive particles preferably have a powder electrical resistance of 5.0 ⁇ 10 ⁇ 1 ⁇ ⁇ cm or less in a 100% green compact.
- the conductive particles are preferably contained in the coating layer in an amount of 30 to 90% by mass, more preferably 40 to 85% by mass, and still more preferably 60 to 80% by mass.
- the binder contained in the coating layer is not particularly limited as long as it can bind the metal foil and the conductive particles, but from the viewpoint of excellent adhesion to the metal foil and lithium ion ion permeability. And those containing at least one selected from the group consisting of polysaccharides and derivatives thereof.
- Polysaccharides are high molecular compounds in which monosaccharides or their derivatives are polymerized by glycosidic bonds.
- a polymer obtained by polymerizing 10 or more monosaccharides or derivatives thereof is generally called a polysaccharide, but even a polymer obtained by polymerizing 10 or less monosaccharides can be used.
- the monosaccharide constituting the polysaccharide may be a normal monosaccharide such as glucose having only a hydroxyl group as a basic skeleton, a uronic acid having a carboxyl group, or an amino sugar having an amino group or an acetylamino group.
- the polysaccharide may be either a homopolysaccharide or a heteropolysaccharide.
- polysaccharides include agarose, amylose, amylopectin, alginic acid, inulin, carrageenan, chitin, glycogen, glucomannan, keratan sulfate, colominic acid, chondroitin sulfate, cellulose, dextran, starch, hyaluronic acid, pectin, pectic acid, Examples include heparan sulfate, levan, lentinan, chitosan, pullulan and curdlan. Of these, chitin, chitosan, and cellulose are preferred because of their high adhesion to metal foils and electrode composites.
- polysaccharide derivatives include hydroxyalkylated polysaccharides, carboxyalkylated polysaccharides, sulfated polysaccharides, and the like.
- hydroxyalkylated polysaccharides are preferable because they can be highly dispersible in a solvent.
- the hydroxyalkylated polysaccharide can be produced by a known method.
- hydroxyalkyl chitosan examples include hydroxyethyl chitosan, hydroxypropyl chitosan, glycerylated chitosan and the like.
- hydroxyalkyl cellulose examples include hydroxyethyl cellulose and hydroxypropyl cellulose.
- carboxyalkyl chitosan examples include carboxymethyl chitosan and carboxyethyl chitosan.
- carboxyalkyl cellulose include carboxymethyl cellulose and carboxyethyl cellulose.
- binders other than polysaccharides include the following. Fluoropolymer: polyvinylidene fluoride, polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, ethylene-tetrafluoroethylene copolymer, etc .; Poly (olefin oxide): polyethylene oxide, polypropylene oxide, polyethylene oxide-propylene oxide copolymer, etc .; Elastomer: styrene butadiene block copolymer, acrylic acid-modified SBR resin, gum arabic, etc.
- the binder has a weight average molecular weight of preferably 1.0 ⁇ 10 4 to 2.0 ⁇ 10 5 , more preferably 5.0 ⁇ 10 4 to 2.0 ⁇ 10 5 .
- the weight average molecular weight is within this range, the performance of dispersing the conductive particles is high, so that the coating property of the coating liquid is good and the strength of the resulting coating layer is high.
- a weight average molecular weight can be calculated
- the amount of the binder in the coating layer is preferably 20 to 300 parts by mass, more preferably 40 to 200 parts by mass, and further preferably 60 to 100 parts by mass with respect to 100 parts by mass of the conductive particles.
- the coating layer further includes one or more selected from the group consisting of organic acids such as carboxylic acid and sulfonic acid and derivatives thereof.
- the organic acid or a derivative thereof acts as a cross-linking agent for the polysaccharide or the derivative thereof, and the conductive particles can be disposed more firmly on the metal foil.
- the organic acid or a derivative thereof one having a valence of 2 or more, more preferably a valence of 3 or more is preferably used from the viewpoint of a high crosslinking effect.
- carboxylic acid or its derivative is used preferably.
- the carboxylic acid and derivatives thereof include aromatic carboxylic acids, chain aliphatic carboxylic acids, and derivatives thereof. From the viewpoint of thermal stability, an aromatic carboxylic acid or a derivative thereof is preferable. From the viewpoint of solubility in water, a chain aliphatic carboxylic acid or a derivative thereof is preferable.
- organic acid derivatives include esters, acid chlorides, and acid anhydrides. An acid anhydride is preferable because the crosslinking reaction easily proceeds and there are few by-products.
- aromatic carboxylic acids and derivatives thereof divalent aromatic carboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid and derivatives thereof; trimellitic acid, pyromellitic acid, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, etc.
- trimellitic anhydride or pyromellitic anhydride is preferred.
- chain aliphatic carboxylic acids and derivatives thereof include divalent chain aliphatic carboxylic acids and derivatives thereof such as succinic acid, maleic acid, tartaric acid, malic acid, glutaric acid, itaconic acid, and adipic acid; citric acid, 1 , 2,3,4-butanetetracarboxylic acid and other trivalent or higher chain aliphatic carboxylic acids and derivatives thereof.
- divalent chain aliphatic carboxylic acids and derivatives thereof such as succinic acid, maleic acid, tartaric acid, malic acid, glutaric acid, itaconic acid, and adipic acid; citric acid, 1 , 2,3,4-butanetetracarboxylic acid and other trivalent or higher chain aliphatic carboxylic acids and derivatives thereof.
- 1,2,3,4-butanetetracarboxylic acid is preferred.
- organic acids and organic acid derivatives can be used singly or in combination of two or more.
- the amount of these organic acids and derivatives thereof used is preferably 30 to 300 parts by mass, more preferably 35 to 120 parts by mass, and still more preferably 40 to 85 parts by mass with respect to 100 parts by mass of the polysaccharide or derivative thereof. It is.
- the coating layer may be provided on a part of the surface of the metal foil, or may be provided uniformly on the entire surface.
- a form provided on a part of the surface of the metal foil a form provided in the central part excluding the edge part of the metal foil, a form provided in a pattern such as a dot shape, a stripe shape, a net shape, a lattice (grid) shape, a nested shape, a spiral shape, etc. Can be illustrated.
- the ratio A1 of the area of the coating layer to the area of the metal foil is preferably 50 to 100%, more preferably 60 to 100%, and particularly preferably 70 to 100%.
- the method for determining the ratio A1 of the area of the coating layer to the area of the metal foil is as follows.
- the pattern of the coating layer on the metal foil is observed from the normal direction through a microscope or the like at a low magnification according to the size of the pattern, and the observation images are photographed at three or more visual fields.
- the photograph is binarized by image analysis processing, and the area S a of the portion where the covering layer is reflected and the area S b of the portion where the covering layer is not reflected are obtained.
- the length may be measured using a caliper or the like, and the area ratio A1 of the coating layer may be obtained by calculation.
- the area of the metal foil is the area of both surfaces when the coating layer is provided on both surfaces of the metal foil, and the area of one surface when the coating layer is provided on one surface of the metal foil.
- the amount of the coating layer provided on the metal foil is preferably 0.2 to 5 g / m 2 , more preferably 0.5 to 3 g / m 2 , and most preferably 1 to 2 g / m 2 . With such an amount, the penetration resistance value of the current collector is significantly reduced, and a lithium secondary battery with low internal resistance and impedance can be configured by using this current collector.
- the thickness of the coating layer is 5 ⁇ m or less, more preferably 4 ⁇ m or less, and even more preferably 3 ⁇ m or less.
- the lower limit of the thickness of the coating layer is not particularly limited as long as the function of the coating layer is exhibited, but is preferably 0.1 ⁇ m. When the thickness of the coating layer is within the above range, the penetration resistance value of the coating layer is reduced, and the internal resistance and impedance of the lithium secondary battery can be reduced.
- the area ratio of the conductive particles in the coating layer is 50% or more and less than 100%, more preferably 60% or more and less than 100%, and still more preferably 70% or more and less than 100%.
- This area ratio is the ratio of the area of the conductive particles to the area of the coating layer.
- the area ratio of the conductive particles is less than 100%, there is a region that does not include the conductive particles in the coating layer. Since this region does not contain conductive particles, there is a concern that the electron conduction between the metal foil and the electrode mixture is reduced and the internal resistance is increased. However, in reality, the presence of this region can reduce the internal resistance and impedance of the electrode itself. This is presumed to be because lithium ions are exchanged between the electrode active material and the electrolytic solution in a portion not including conductive particles.
- the presence of the conductive particles between the metal foil and the electrode mixture further improves the electronic conductivity between the metal foil and the electrode mixture.
- the coating layer functions as an adhesive as described above, but the bonding strength may be slightly lowered due to the presence of the conductive particles.
- the electron conductivity compensates for the decrease in bonding strength, the internal resistance and impedance can be reduced even in the region where the conductive particles are present in the coating layer.
- the area ratio of the conductive particles in the coating layer is set to less than 100%, the bonding strength of the electrode mixture to the metal foil can be increased, and the internal resistance and impedance of the lithium secondary battery can be reduced. Further, by setting the area ratio of the conductive particles in the coating layer to 50% or more, the electronic conductivity between the metal foil and the electrode mixture can be improved, and the internal resistance and impedance of the lithium secondary battery can be reduced.
- the area ratio of electroconductive particle is computed as follows. First, the portion of the current collector on which the coating layer is provided is observed from the normal direction through a microscope or the like at a high magnification, and the observation images are photographed in three or more visual fields. The magnification is adjusted so that the number of conductive particles is preferably 100 or more, more preferably 200 or more, and still more preferably 300 or more in one field of view. The amount of light is adjusted so that the boundary between particles is clear and halation does not occur. In particular, care should be taken when a material that easily reflects light, such as an aluminum foil, is used for the metal foil.
- the gray level of the photographic image is digitized to 0 to 255.
- the area ratio can be controlled by changing the amount of the dispersion medium used when forming the coating layer, the method of preparing the coating liquid, the method of applying the coating liquid, and the like.
- the electrode of the present invention may be applied to either a positive electrode or a negative electrode of a lithium secondary battery.
- a positive electrode mixture is laminated on the metal foil
- the negative electrode mixture is laminated on the metal foil.
- the positive electrode mixture and the negative electrode mixture will be described.
- the positive electrode composite is configured to include a positive electrode material made of a positive electrode active material, or a positive electrode material in which a carbon material is attached to part or all of the surface of particles of the positive electrode active material.
- the positive electrode mixture includes a binder. Further, the positive electrode mixture may contain a conductive additive.
- the positive electrode active material constituting the positive electrode material is preferably at least one of a lithium-containing composite oxide, a chalcogen compound, or a lithium-containing olivic acid salt. More specifically, the positive electrode active material is at least one of lithium cobalt oxide, lithium manganate, lithium nickelate, lithium cobalt manganese nickelate, titanium sulfide (TiS2), lithium iron olivine, and lithium manganese olivine. It is preferable to contain.
- the average particle diameter D50 of the positive electrode active material is preferably 0.01 to 50 ⁇ m.
- An average particle size of 50 ⁇ m or less is preferable because the insertion and extraction of lithium inside and outside the particles become uniform. Moreover, if it is 0.01 micrometer or more, since crystallinity will increase and particle structure will not be disturb
- the average particle diameter D50 is preferably in the range of 0.01 to 0.5 ⁇ m.
- those having an average particle diameter D50 of 0.5 to 50 ⁇ m, preferably 1 to 50 ⁇ m are preferable.
- a carbon material is attached to part or all of the surface of the positive electrode active material particles.
- the carbon material to be attached to the particle surface may be in the form of a film or particles.
- a method for attaching the carbon material a mixture of the positive electrode active material and the carbon material is kneaded so as to apply compression, shear, and rolling, and the carbon material is attached to a part or all of the surface of the positive electrode active material particles.
- Examples of the carbon material in this case include graphite and carbon black.
- lithium cobaltate, lithium manganate, lithium nickelate, or lithium cobalt manganese nickelate is preferably used as the positive electrode active material in this case.
- a method of firing a mixture of the positive electrode active material and the carbon forming material under an inert condition or a reducing condition, preferably at a temperature of 500 ° C. to 800 ° C. can be exemplified.
- the carbon-forming material in this case include saccharides exemplified by sucrose and lactose, ascorbic acid, 1,6-hexanediol, polyethylene glycol, polyethylene oxide, and water-soluble organic substances such as carboxymethyl cellulose.
- the positive electrode active material in this case lithium iron oliate or lithium manganese olivine is preferably used as the positive electrode active material.
- the amount of the carbon material adhered to the positive electrode active material is preferably in the range of 1% by mass to 40% by mass, more preferably in the range of 3% by mass to 30% by mass, as the content of the carbon material in the positive electrode material.
- the range of 5% by mass or more and 20% by mass or less is more preferable. If the content rate of a carbon material is 1 mass% or more, a carbon material will not decrease too much and the electronic conductivity of a positive electrode compound will become sufficient. Moreover, if the content rate of a carbon material is 40 mass% or less, the charge / discharge capacity of a positive electrode material can be maintained high, without the content rate of a positive electrode active material falling relatively.
- the binder of the positive electrode mixture is polyethylene, polypropylene, ethylene propylene copolymer, ethylene propylene terpolymer, butadiene rubber, styrene butadiene rubber, butyl rubber, polytetrafluoroethylene, poly (meth) acrylate, polyvinylidene fluoride, polyethylene oxide, polypropylene oxide And polyepichlorohydrin, polyphasphazene, polyacrylonitrile, and the like.
- the addition amount of the binder is preferably 0.1 to 10% by mass with respect to the dry mass of the positive electrode mixture.
- the conductive additive need not be added as long as the electrical conductivity of the positive electrode mixture is sufficiently ensured by the carbon contained in the positive electrode material, but may be added to improve the performance of the positive electrode. However, if added excessively, the compounding ratio of the positive electrode material in the positive electrode mixture is relatively lowered and the charge / discharge capacity is lowered. Therefore, the presence or absence of the addition of the conductive additive may be determined by observing the characteristics of the positive electrode.
- the conductive aid include conductive metal powder such as silver powder; conductive carbon powder such as furnace black, ketjen black, and acetylene black.
- the addition amount is 1.4% by mass or less, preferably less than 1.4% by mass, more preferably 0.2% by mass or less, based on the dry mass of the positive electrode mixture. If the electrical conductivity of the material is sufficiently secured, it may not be added.
- the positive electrode mixture may contain an ion conductive compound, a thickener, a dispersant, a lubricant, and the like as necessary.
- the ion conductive compound include polysaccharides such as chitin and chitosan, or a cross-linked product of the polysaccharide.
- the thickener include carboxymethyl cellulose and polyvinyl alcohol.
- the amount of the positive electrode mixture formed on the metal foil is preferably 20 to 400 g / m 2 , more preferably 30 to 300 g / m 2 , and most preferably 50 to 200 g / m 2 . If it is this range, the charging / discharging capacity in a positive electrode will become sufficient, and peeling of a positive electrode compound material can also be suppressed.
- the negative electrode mixture as the electrode mixture laminated on the surface of the metal foil is a negative electrode mixture containing a negative electrode active material, a binder, and a conductive additive added as necessary, A sheet-like electrode composed of a negative electrode current collector bonded to the negative electrode mixture can be used.
- negative electrode active material conventionally known negative electrode active materials can be used.
- carbon materials such as artificial graphite and natural graphite, metals such as Sn and Si, or metalloid materials can be used.
- a lithium composite oxide or a metal oxide such as titanium oxide may be used as the negative electrode active material.
- a carbon material may be attached to the surface of the negative electrode active material as in the case of the positive electrode. In this case, it is particularly preferable to apply to metals such as Sn and Si, or metalloid materials.
- the binder the same binder as that used in the positive electrode can be used.
- the conductive additive may be added as necessary, or may not be added.
- conductive carbon powders such as furnace black, ketjen black, and acetylene black; carbon nanotubes, carbon nanofibers, vapor grown carbon fibers, and the like can be used.
- vapor grown carbon fiber is particularly preferable.
- the vapor grown carbon fiber preferably has a fiber diameter of 5 nm to 0.2 ⁇ m.
- the ratio of fiber length / fiber diameter is preferably 5 to 1000.
- the addition amount is 1.4% by mass or less, more preferably 0.4% by mass or less, still more preferably 0.2% by mass or less, based on the dry mass of the negative electrode mixture. If the electrical conductivity of the composite material is sufficiently ensured, it may not be added.
- the electrode manufacturing method of the present embodiment includes a step of applying a coating layer coating solution containing a binder, conductive particles, and a dispersion medium to a metal foil, removing the dispersion medium to form a coating layer, and a coating layer And forming an electrode mixture on top. Moreover, it is preferable to press the electrode mixture after forming the electrode mixture.
- the step of forming the coating layer is performed by applying a coating layer coating solution containing conductive particles, a binder and a dispersion medium and not containing an electrode active material to one or both sides of the metal foil, and then removing the dispersion medium. And a heat treatment process.
- the coating layer coating liquid preferably further contains one or more selected from the group consisting of organic acids and derivatives thereof.
- the dispersion medium used in the coating layer coating solution is not particularly limited as long as it can disperse the conductive particles, the binder, and the organic acid or derivative thereof contained as necessary.
- Water or an organic solvent is preferably used as the dispersion medium.
- the organic solvent include aprotic polar solvents and protic polar solvents.
- the aprotic polar solvent examples include ethers, carbonates, amides, esters and the like. Of these, amides and esters are preferred.
- the aprotic polar solvent is preferably one that evaporates at a temperature equal to or lower than the heat treatment temperature after coating.
- the boiling point at normal pressure is preferably 50 to 300 ° C., more preferably 100 to 220 ° C.
- the concentration of the coating layer coating solution is difficult to change during the coating operation, so that it is easy to obtain a coating layer having a predetermined thickness or coating amount. Further, the dispersion medium can be sufficiently removed by heat treatment.
- Examples of the aprotic polar solvent having the boiling point as described above include N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-pyrrolidone, and ⁇ -butyrolactone. Of these, N-methyl-2-pyrrolidone is preferred.
- examples of the protic polar solvent include alcohols and polyhydric alcohols.
- the coating layer coating solution contains a protic polar solvent, the wettability of the coating layer coating solution with respect to the current collector can be improved, and the area ratio of the conductive particles can be made uniform within the above range. .
- the protic polar solvent evaporates at a temperature lower than the heat treatment temperature after coating.
- the protic polar solvent preferably has a boiling point of 100 ° C. or less at normal pressure.
- Preferred protic polar solvents include alcohols. More preferred protic polar solvents include ethanol, isopropyl alcohol, and n-propyl alcohol.
- the amount of the dispersion medium in the coating layer coating solution is preferably 20 to 99% by mass, more preferably 65 to 98% by mass, and still more preferably 80 to 95% by mass.
- the amount of the protic polar solvent is not particularly limited, but is preferably 1 to 20% by mass based on the total mass of the dispersion medium.
- the coating liquid has an appropriate viscosity, so that the coating workability is excellent, the coating amount, the thickness of the coating layer, and the area ratio of the conductive particles are within the above range. It is easy to adjust inside and can be made uniform in the coating surface.
- the amount of the dispersion medium used is increased, the area ratio of the conductive particles and the thickness of the coating layer are reduced.
- the amount of the dispersion medium is decreased, the area ratio of the conductive particles and the thickness of the coating layer are increased.
- the viscosity of the coating layer coating solution is preferably 100 to 50000 mPa ⁇ s, more preferably 100 to 10000 mPa ⁇ s, and still more preferably 100 to 5000 mPa ⁇ s at normal temperature. Viscosity is measured using a B-type viscometer by selecting a rotor and rotation speed suitable for the viscosity range to be measured. For example, when measuring the viscosity of a coating solution of several hundred mPa ⁇ s, the rotor No. 2, 60 rpm.
- the coating layer coating solution used in the present invention includes a dispersant, a thickener, an anti-settling agent, an anti-skinning agent, an antifoaming agent in addition to the above-described conductive particles, binder and organic acid and derivatives thereof.
- additives such as an electrostatic coating property improving agent, an anti-sagging agent, a leveling agent, an anti-repelling agent, and a crosslinking catalyst may be contained. Any known additive can be used, and the additive amount is 10 parts by mass or less with respect to 100 parts by mass of the total amount of the conductive particles, the binder, the organic acid and the derivative thereof. It is preferable.
- the coating liquid can be produced by mixing conductive particles, a binder, a dispersion medium, and an organic acid or an additive added as necessary using a mixer.
- the mixing order of the components contained in the coating liquid is not particularly limited, but from the viewpoint of easily obtaining a uniform coating liquid, firstly prepared a liquid in which a binder and a dispersion medium are mixed. It is preferable to add and mix conductive particles.
- the method for applying the coating layer coating liquid to the metal foil is not particularly limited.
- a casting method, a bar coater method, a dip method, a printing method, and the like can be given.
- methods for adjusting the area ratio include pattern design of a coating roll of a gravure coater, use of a stencil type or wire mesh type mask, and the like.
- the heat treatment is performed to remove the dispersion medium.
- the method of heat treatment is not particularly limited, but a method using hot air is more preferable.
- the heat treatment temperature is preferably 100 to 300 ° C, more preferably 120 to 250 ° C.
- the heating time is preferably 10 seconds to 10 minutes. Moreover, you may press a coating layer with a roll or a flat plate at the time of heat processing.
- the electrode mixture is formed by applying a mixture coating solution containing an electrode material and another solvent on the coating layer and removing another dispersion medium.
- a binder and, if necessary, a conductive additive are added to the mixture coating solution.
- a known solvent can be used as long as it does not alter the previously formed coating layer.
- the electrode mixture is preferably pressed with a roll or a flat plate. By pressing, the adhesion between the metal foil and the electrode mixture can be enhanced.
- the pressing pressure is preferably about 1 t / cm 2 to 3 t / cm 2 .
- a lithium secondary battery according to a preferred embodiment of the present embodiment includes a positive electrode, a negative electrode, and a nonaqueous electrolyte.
- either the positive electrode or the negative electrode may be the electrode according to the present invention, and the other may be the conventional electrode. Both the positive electrode and the negative electrode in the lithium secondary battery are the present invention. It is good also as an electrode concerning. As a result, a lithium secondary battery capable of rapid charge / discharge and capable of maintaining a high battery capacity retention rate even under a large charge / discharge current condition can be obtained. Since the positive electrode and the negative electrode have already been described, the non-aqueous electrolyte constituting the lithium secondary battery will be described here.
- Non-aqueous electrolyte examples include a non-aqueous electrolyte in which a lithium salt is dissolved in an aprotic solvent.
- the aprotic solvent is preferably at least one or a mixed solvent selected from the group consisting of ethylene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate, propylene carbonate, butylene carbonate, ⁇ -butyrolactone, and vinylene carbonate.
- the lithium salt include LiClO 4 , LiPF 6 , LiAsF 6 , LiBF 4 , LiSO 3 CF 3 , CH 3 SO 3 Li, and CF 3 SO 3 Li.
- a so-called solid electrolyte or gel electrolyte can also be used as the nonaqueous electrolyte.
- the solid electrolyte or gel electrolyte include polymer electrolytes such as sulfonated styrene-olefin copolymers, polymer electrolytes using polyethylene oxide and MgClO4, and polymer electrolytes having a trimethylene oxide structure.
- the inorganic solid electrolyte include those based on sulfide-based glass.
- glass ceramics having a combination of at least one member selected from the group consisting of silicon sulfide, germanium sulfide, phosphorus sulfide, and boron sulfide can be given.
- a combination of lithium sulfide and phosphorus sulfide is preferable because of its high conductivity.
- the non-aqueous solvent used for the polymer electrolyte is preferably at least one selected from the group consisting of ethylene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate, propylene carbonate, butylene carbonate, ⁇ -butyrolactone, and vinylene carbonate.
- a molten electroelectrolyte can also be used.
- a molten salt electrolyte for example, a combination of methylpropylimidazolium bisfluorosulfonylamide and lithium bistrifluoromethanesulfonic acid amide can be used.
- the lithium secondary battery according to a preferred embodiment of the present embodiment is not limited to the positive electrode, the negative electrode, and the nonaqueous electrolyte, and may include other members as necessary.
- the positive electrode and the negative electrode are isolated.
- a separator may be provided.
- the separator is essential when the non-aqueous electrolyte is not a polymer electrolyte, and examples thereof include nonwoven fabrics, woven fabrics, microporous films, and combinations thereof. More specifically, the separator is porous.
- a polypropylene film, a porous polyethylene film, etc. can be used suitably.
- the lithium secondary battery is enclosed in an exterior material. Examples of the exterior material include a metal can and a laminate film of a metal and a resin, but a laminate film is preferable from the viewpoint of battery size reduction.
- the lithium secondary battery according to a preferred embodiment of the present embodiment can be used in various fields.
- Electric and electronic devices such as digital cameras, digital video, AV equipment and vacuum cleaners; electric vehicles, hybrid vehicles, electric bikes, hybrid bikes, electric bicycles, electric assist bicycles, railway engines, aircraft, ships, etc .
- Examples include power generation systems such as power generation systems, wind power generation systems, tidal power generation systems, geothermal power generation systems, heat differential power generation systems, and vibration power generation systems.
- the lithium secondary battery that enables rapid charge / discharge and maintains a high battery capacity maintenance rate even under a large charge / discharge current condition can be configured.
- the method for manufacturing an electrode for a lithium secondary battery of the present embodiment for a lithium secondary battery that enables rapid charge / discharge and can maintain a high battery capacity retention rate even under a large charge / discharge current condition. Can be manufactured.
- rapid charge / discharge is possible, and the battery capacity retention rate can be maintained high even under a large charge / discharge current condition.
- Example 1 In a dispersion medium composed of 80 parts by mass of N-methyl-2-pyrrolidone and 5 parts by mass of isopropyl alcohol, 5 parts by mass of carbon black as conductive particles, 5 parts by mass of glycerylated chitosan as a polysaccharide, and pyromellitic anhydride 5 parts by mass was placed in a dissolver type stirrer and mixed at a rotation speed of 300 rpm for 10 minutes. Subsequently, it processed for 30 seconds at 20000 rpm using the homogenizer (the product name PRO200 by Ieda Trading Co., Ltd.), and obtained the coating layer coating liquid by which the electroconductive particle etc. were disperse
- the homogenizer the product name PRO200 by Ieda Trading Co., Ltd.
- an aluminum foil having a thickness of 30 ⁇ m made of alkali-cleaned A1085 material was prepared.
- the above coating layer coating solution was applied to both surfaces of the aluminum foil by a casting method. Then, it heat-processed for 3 minutes at 180 degreeC, it was made to dry and the electrical power collector provided with the coating layer was obtained.
- a separator made by POLYPORE International, Inc., trade name Celgard 2500 was incorporated between the positive electrode and the negative electrode, and the required number of sheets was alternately stacked for a design capacity of 1 Ah.
- the lithium secondary battery of the example was obtained by sealing the opening of the aluminum laminate packaging material with a vacuum sealer.
- Example 2 A lithium secondary battery of Example 2 was obtained in the same manner as Example 1 by using lithium manganese phosphate synthesized by a hydrothermal method as the positive electrode active material particles.
- Example 3 90 parts by mass of lithium cobaltate as positive electrode active material particles, 3 parts by mass of graphite (made by Timcal Ltd., trade name KS6L) as carbon material and 2 parts by mass of carbon (made by Timcal Ltd., trade name Super P-Li) Were processed with a powder processing apparatus (product name: Nobilta NOB-130, manufactured by Hosokawa Micron Corporation) to obtain a positive electrode material combined with 5 parts by mass of carbon. A lithium secondary battery of Example 2 was obtained in the same manner as Example 1 using this positive electrode material.
- Example 4 A lithium secondary battery of Example 4 was obtained in the same manner as Example 3 using lithium manganate as the positive electrode active material particles.
- Example 5 A lithium secondary battery of Example 5 was obtained in the same manner as Example 3 using lithium nickelate as the positive electrode active material particles.
- Example 6 A lithium secondary battery of Example 6 was obtained in the same manner as Example 3 using lithium cobalt manganese nickelate as the positive electrode active material particles.
- Comparative Example 1 A lithium secondary battery of Comparative Example 1 was obtained with the same specifications as in Example 1 except that a coating layer was not provided on an aluminum foil made of alkali-cleaned A1085 material having a thickness of 30 ⁇ m.
- Comparative Example 2 A current collector was prepared without providing a coating layer on a 30 ⁇ m-thick aluminum foil made of alkali-cleaned A1085 material. 90 parts by mass of lithium iron phosphate as positive electrode active material particles synthesized by the hydrothermal method, 5 parts by mass of carbon black, 5 parts by mass of polyvinylidene fluoride (trade name KF polymer # 1120 manufactured by Kureha Co., Ltd.), and N- 100 parts by mass of methyl-2-pyrrolidone (industrial grade) was mixed to obtain a positive electrode slurry. A battery of Comparative Example 2 was obtained with the same specifications as in Example 1 except that the positive electrode obtained by applying this positive electrode slurry to the current collector was used.
- Comparative Example 3 A lithium secondary battery of Comparative Example 1 was obtained with the same specifications as Example 2 except that a coating layer was not provided on a 30 ⁇ m thick aluminum foil made of alkali-cleaned A1085 material.
- Comparative Example 4 A current collector was prepared without providing a coating layer on a 30 ⁇ m-thick aluminum foil made of alkali-cleaned A1085 material. 90 parts by mass of lithium manganese phosphate as positive electrode active material particles synthesized by the hydrothermal method, 5 parts by mass of carbon black, 5 parts by mass of polyvinylidene fluoride (trade name KF polymer # 1120 manufactured by Kureha Corporation), and N- 100 parts by mass of methyl-2-pyrrolidone (industrial grade) was mixed to obtain a positive electrode slurry. A battery of Comparative Example 2 was obtained with the same specifications as in Example 2 except that the positive electrode obtained by applying this positive electrode slurry to the current collector was used.
- Comparative Example 5 A lithium secondary battery of Comparative Example 1 was obtained with the same specifications as in Example 3 except that a coating layer was not provided on an aluminum foil made of alkali-cleaned A1085 material having a thickness of 30 ⁇ m.
- Comparative Example 6 A current collector was prepared without providing a coating layer on a 30 ⁇ m-thick aluminum foil made of alkali-cleaned A1085 material. 90 parts by mass of lithium cobaltate as positive electrode active material particles, 5 parts by mass of carbon black, 5 parts by mass of polyvinylidene fluoride (manufactured by Kureha Co., Ltd., trade name KF polymer # 1120), and N-methyl-2-pyrrolidone (Industry) Grade) Positive electrode slurry was obtained by mixing 100 parts by mass. A battery of Comparative Example 2 was obtained with the same specifications as in Example 3 except that the positive electrode obtained by applying this positive electrode slurry to the current collector was used.
- Comparative Example 7 A lithium secondary battery of Comparative Example 1 was obtained with the same specifications as in Example 4 except that a coating layer was not provided on a 30 ⁇ m-thick aluminum foil made of alkali-cleaned A1085 material.
- Comparative Example 8 A current collector was prepared without providing a coating layer on a 30 ⁇ m-thick aluminum foil made of alkali-cleaned A1085 material. 90 parts by mass of lithium manganate as positive electrode active material particles, 5 parts by mass of carbon black, 5 parts by mass of polyvinylidene fluoride (manufactured by Kureha Co., Ltd., trade name KF polymer # 1120), and N-methyl-2-pyrrolidone (Industry Grade) Positive electrode slurry was obtained by mixing 100 parts by mass. A battery of Comparative Example 2 was obtained with the same specifications as in Example 4 except that the positive electrode obtained by applying this positive electrode slurry to the current collector was used.
- Comparative Example 9 A lithium secondary battery of Comparative Example 1 was obtained with the same specifications as in Example 5 except that a coating layer was not provided on an aluminum foil made of alkali-cleaned A1085 material having a thickness of 30 ⁇ m.
- Comparative Example 10 A current collector was prepared without providing a coating layer on a 30 ⁇ m-thick aluminum foil made of alkali-cleaned A1085 material. 90 parts by mass of lithium nickelate as positive electrode active material particles, 5 parts by mass of carbon black, 5 parts by mass of polyvinylidene fluoride (manufactured by Kureha Co., Ltd., trade name KF polymer # 1120), and N-methyl-2-pyrrolidone (Industry Grade) Positive electrode slurry was obtained by mixing 100 parts by mass. A battery of Comparative Example 2 was obtained with the same specifications as in Example 5 except that the positive electrode obtained by applying this positive electrode slurry to the current collector was used.
- Comparative Example 11 A lithium secondary battery of Comparative Example 1 was obtained with the same specifications as in Example 6 except that a coating layer was not provided on an aluminum foil made of alkali-cleaned A1085 material having a thickness of 30 ⁇ m.
- Comparative Example 12 A current collector was prepared without providing a coating layer on a 30 ⁇ m-thick aluminum foil made of alkali-cleaned A1085 material. 90 parts by mass of lithium cobalt manganese nickelate as positive electrode active material particles, 5 parts by mass of carbon black, 5 parts by mass of polyvinylidene fluoride (manufactured by Kureha Co., Ltd., trade name KF polymer # 1120), and N-methyl-2-pyrrolidone (Industrial grade) 100 parts by mass were mixed to obtain a positive electrode slurry. A battery of Comparative Example 2 was obtained with the same specifications as in Example 6 except that the positive electrode obtained by applying this positive electrode slurry to the current collector was used.
- the charge / discharge characteristics of the obtained battery were evaluated by the following method. Using a charging / discharging device (manufactured by Toyo System Co., Ltd.), changing the current rate to 0.2C, 0.5C, 1C, 2C, 5C, 10C, 20C, and measuring the constant current discharge capacity from the fully charged state did.
- the fully charged state refers to a state in which one hour has elapsed after the end of charging with a battery voltage of 4.0 V at 0.2 C constant current charging.
- FIG. 1 shows the result of calculating the capacity at each discharge current rate as the capacity maintenance rate based on the capacity at 0.2C.
- the batteries of Examples 1 to 6 are Comparative Examples 1 and 2, Comparative Examples 3 and 4, Comparative Examples 5 and 6, Comparative Examples 7 and 8, Comparative Examples 9 and 10, respectively.
- the capacity retention rate is higher at a current rate of 1 C or higher.
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Abstract
Description
本願は、2011年7月6日に、日本に出願された特願2011-150135号に基づき優先権を主張し、その内容をここに援用する。
また、負極は、負極活物質が、集電効果のある金属箔上に固定化されて構成されている。金属箔としては銅が一般的である。また、負極活物質の固定化に用いるバインダーとしてはポリフッ化ビニリデン(PVDF)が用いられている。
また特に正極においては、現在一般的に用いられている電極活物質は導電性が低いため、通常、炭素材料などの導電性粒子を正極合材中に数%~10%程度、添加して電極合材を調製されている(例えば特許文献7~9)。しかし電池のエネルギー密度向上の観点からは、導電性粒子の添加はなるべく少なくする必要がある。そこで、導電性粒子の添加を少なくしても、電池の内部抵抗を小さくできるように、例えば特許文献4~6のような試みがなされている。
[1] 金属箔と、該金属箔上に積層されてなる電極合材とを有する電極であって、該金属箔と電極合剤との間に、結着剤と、導電性粒子とを含む被覆層が備えられ、前記電極合材には、電極活物質と、前記電極合材中における組成比が0質量%~1.4質量%である導電助材とが含まれることを特徴とするリチウム二次電池用電極。
[2] 前記電極合材は、前記電極活物質の粒子の表面の一部または全部に炭素材料が付着されてなる電極材料を含み、かつ導電助材を実質的に含まないことを特徴とする[1]に記載のリチウム二次電池用電極。
[3] 前記被覆層における前記導電性粒子の面積率が50%以上100%未満であることを特徴とする[1]または[2]に記載のリチウム二次電池用電極。
[4] 前記導電性粒子が炭素粒子であることを特徴とする[1]乃至[3]の何れか一項に記載のリチウム二次電池用電極。
[5] 前記結着剤が、多糖類またはその誘導体からなる群より選ばれる一種以上を含むものであることを特徴とする[1]乃至[4]の何れか一項に記載のリチウム二次電池用電極。
[6] 前記被覆層に、有機酸または有機酸誘導体からなる群より選ばれる1種以上を含むことを特徴とする[1]乃至[5]の何れか一項に記載のリチウム二次電池用電極。
[7] 前記電極活物質が、リチウム含有複合酸化物、カルコゲン化合物またはリチウム含有オリビン酸塩のうちの1種以上であることを特徴とする[1]乃至[6]の何れか一項に記載のリチウム二次電池用電極。
[8] 前記電極活物質が、コバルト酸リチウム、マンガン酸リチウム、ニッケル酸リチウム、コバルトマンガンニッケル酸リチウム、硫化チタン(TiS2)、オリビン酸鉄リチウムまたはオリビン酸マンガンリチウムのうちいずれか一種以上を含むことを特徴とする[7]に記載のリチウム二次電池用電極。
[9] 前記結着剤が、キトサン、キチン、セルロースおよびそれらの誘導体からなる群より選ばれる1種以上を含むものであることを特徴とする[1]乃至[8]の何れか一項に記載のリチウム二次電池用電極。
[10] 前記有機酸または前記有機酸誘導体が、無水トリメリット酸、無水ピロメリット酸、1,2,3,4-ブタンテトラカルボン酸またはこれらの誘導体からなる群より選ばれる1種以上であることを特徴とする[6]乃至[9]の何れか一項に記載のリチウム二次電池用電極。
[11] 前記被覆層に含まれる前記導電性粒子の含有率が30~90質量%の範囲であることを特徴とする[1]乃至[10]の何れか一項に記載のリチウム二次電池用電極。
[12] [1]乃至[11]の何れか一項に記載のリチウム二次電池用電極と、電解質とを有することを特徴とするリチウム二次電池。
[13] 結着剤と導電性粒子と分散媒を含む被覆層塗工液を金属箔に塗布し、前記分散媒を除去して被覆層を形成した後、前記被覆層上に、電極活物質と、電極合材にしたときの組成比が0~1.4質量%となる導電助材と、別の分散媒とを含む合材用塗工液を塗布し、前記別の分散媒を除去して電極合材を形成することを特徴とするリチウム二次電池用電極の製造方法。
[14] 前記電極合材を成形した後に、前記電極合材をプレスすることを特徴とする[13]に記載のリチウム二次電池用電極の製造方法。
[15]
前記リチウム二次電池用電極が、金属箔と、該金属箔上に積層されてなる正極合材とを有するリチウム二次電池用正極であり、
該金属箔と正極合剤との間に、さらに、結着剤と、導電性粒子とを含む被覆層が備えられ、
前記正極合材は、
正極活物質のみからなる正極材料、又は正極活物質の粒子の表面の一部または全部に炭素材料が付着されてなる正極材料と、
前記正極合材中における組成比が0質量%~1.4質量%である導電助材とを含むことを特徴とする[1]乃至[11]に記載のリチウム二次電池用電極。
[16]
前記正極合材は、前記正極活物質の粒子の表面の一部または全部に炭素材料が付着されてなる正極材料を含み、かつ前記導電助材を実質的に含まないことを特徴とする[15]に記載のリチウム二次電池用電極。
[17]
前記正極活物質の粒子の表面の一部または全部に炭素材料が付着されてなる前記正極材料が、
前記正極活物質と、前記炭素材料の前駆体としての炭素形成材料の混合物を、不活性条件下または還元条件下で、500℃~800℃の温度で焼成する方法、 または、前記正極活物質と前記炭素材料の混合物を、圧縮、せん断、圧延作用を加えるように混練する方法で得られた
ことを特徴とする[16]に記載のリチウム二次電池用電極。
[18]
前記金属箔がアルミニウムまたはアルミニウム合金の箔であり、
前記被覆層における前記導電性粒子が炭素粒子であり、前記導電性粒子の面積率が50%以上100%未満であり、
前記被覆層における前記結着剤が多糖類又はその誘導体と、芳香族カルボン酸又はその誘導体とを含み、
前記正極活物質がオリビン酸鉄リチウム、オリビン酸マンガンリチウム、コバルト酸リチウム、マンガン酸リチウム、ニッケル酸リチウム、コバルトマンガンニッケル酸リチウムからなる群から選択される1種を含む
ことを特徴とする[17]に記載のリチウム二次電池用電極。
[19]
前記リチウム二次電池用電極が、リチウム二次電池用正極であり、
結着剤と導電性粒子と分散媒を含む被覆層塗工液を金属箔に塗布し、前記分散媒を除去して被覆層を形成した後、
前記被覆層上に、
正極活物質のみからなる正極材料、又は正極活物質の粒子の表面の一部または全部に炭素材料が付着されてなる正極材料と、
正極合材にしたときの組成比が0~1.4質量%となる導電助材と、別の分散媒と
を含む合材用塗工液を塗布し、
前記別の分散媒を除去して正極合材を形成する
ことを特徴とする[13]又は[14]に記載のリチウム二次電池用電極の製造方法。
[20]
前記正極材料が正極活物質の粒子の表面の一部または全部に炭素材料が付着されてなる正極材料であり、
前記炭素材料を付着させる方法は、前記正極活物質と前記炭素材料の前駆体である炭素形成材料の混合物を、不活性条件下または還元条件下で、500℃~800℃の温度で焼成する方法、または、前記正極活物質と前記炭素材料の混合物を、圧縮、せん断、圧延作用を加えるように混練する方法を含むことを特徴とする[13]、[14]又は[19]に記載のリチウム二次電池用電極の製造方法。
本発明の実施形態であるリチウム二次電池用の電極は、集電体として働く金属箔と、金属箔上に積層された電極合材と、金属箔と電極合材との間に備えられた被覆層とを具備して構成されている。
集電体を構成する金属箔は、開孔が設けられていない一般的な箔でもよいし、パンチングメタル箔、金属網の如く開口部を有する箔または多孔質の箔でもよい。また、金属箔は、表面が平滑なものであってもよいし、電気的または化学的なエッチング処理などによって粗面化された箔でもよい。
電極が負極の場合の金属箔の材質は、銅または銅の合金が好ましい。
次に被覆層は、結着剤と、導電性粒子とが含有されて構成されている。被覆層には更に、有機酸またはその誘導体からなる群より選ばれる1種以上を含んでいてもよい。被覆層は、金属箔の片面に形成されていても良いし、両面に形成されていてもよい。また被覆層は、金属箔と電極合材との間に形成されていればよく、好ましくは金属箔と電極合材とに接して設けられる。
被覆層に用いられる導電性粒子は、電気伝導性を有する粒子であれば、特に制限されないが、炭素元素を主構成成分とするもの、すなわち炭素粒子であることが好ましい。炭素粒子としては、カーボンブラック、グラファイト、気相法炭素繊維、カーボンナノチューブ、カーボンナノファイバーなどが好適である。カーボンブラックの例としては、アセチレンブラックやファーネスブラックなどが挙げられる。また、ケッチェンブラックなどの市販品を用いることができる。これらの炭素粒子は1種単独でまたは2種以上を組み合わせて用いることができる。炭素粒子以外の導電性粒子としては、金、銀、銅、ニッケル、アルミニウムなどの金属の粉末、これら金属粉末と炭素粒子を混合したもの、または炭素粒子の表面に金属粉末をコーティングして成るものなどを挙げることができる。
球状、鱗片状、塊状、不定形状などの導電性粒子は、平均一次粒径が10nm~5μmのものが好ましく、10nm~100nmのものがより好ましい。これら導電性粒子の平均一次粒径は、電子顕微鏡を用いて500~1000個の粒子の粒径を計測し、これらを数基準で平均することによって算出される。なお、球状以外の形状の場合は、最大径(最長径)をもって粒径とし、同様にこれらを数基準で平均することで平均粒径とする。
異方形状の導電性粒子は質量あたりの表面積が大きく、金属箔や電極活物質などとの接触面積が大きくなるので、少量の添加でも金属箔と電極活物質との間もしくは電極活物質同士間の導電性を高くすることができる。特に効果的な異方形状の導電性粒子としては、気相法炭素繊維、カーボンナノチューブ若しくはカーボンナノファイバーが挙げられる。気相法炭素繊維、カーボンナノチューブ若しくはカーボンナノファイバーは、導電性向上の観点から、平均繊維径が通常0.001~0.5μm、好ましくは0.003~0.2μmであり、平均繊維長が通常1~100μm、好ましくは1~30μmである。なお、平均繊維径および平均繊維長は、電子顕微鏡を用いて500~1000個の繊維の繊維径および繊維長を計測し、これらを数基準で平均することによって算出される。
導電性粒子は、被覆層の中に、好ましくは30~90質量%、より好ましくは40~85質量%、さらに好ましくは60~80質量%含まれる。これにより、金属箔や電極合材との密着性に優れた被覆層を備えた集電体を得ることができる。
次に、被覆層に含まれる結着剤は、金属箔と導電性粒子とを結着できるものであれば特に限定されないが、金属箔との密着性やリチウムイオンのイオン透過性に優れる点から、多糖類およびその誘導体からなる群より選ばれる一種以上を含むものが好ましい。
含フッ素重合体:ポリビニリデンフルオライド、ポリテトラフルオロエチレン、テトラフルオロエチレン-パーフルオロアルキルビニルエーテル共重合体、テトラフルオロエチレン-ヘキサフルオロプロピレン共重合体、エチレン-テトラフルオロエチレン共重合体など;
ポリ(オレフィンオキサイド):ポリエチレンオキサイド、ポリプロピレンオキサイド、ポリエチレンオキサイド-プロピレンオキサイド共重合体など;
エラストマー:スチレンブタジエンブロック共重合体、アクリル酸変性SBR樹脂、アラビアゴムなど。
金属箔上の被覆層のパターンを、法線方向から顕微鏡等を通してパターンの大きさに応じて低倍率で観察し、3ヶ所以上の視野で観察像を写真撮影する。該写真を画像解析処理にて二値化し、被覆層が写っている部分の面積Saと写っていない部分の面積Sbを求める。式:A1=(Sa)/(Sa+Sb)×100%にて、金属箔の面積に対する被覆層の面積の割合A1を算出する。
被覆層における導電性粒子の面積率は、50%以上100%未満、より好ましくは60%以上100%未満、さらに好ましくは70%以上100%未満である。この面積率は、被覆層の面積に対する導電性粒子の面積の割合である。当該面積率を上記範囲にすることによって、集電体の貫通抵抗値が小さくなり、この集電体を用いて得られるリチウム二次電池の内部抵抗やインピーダンスを小さくすることができる。
まず、集電体の被覆層が設けられている部分を法線方向から顕微鏡等を通して、高倍率で観察し、3ヶ所以上の視野で観察像を写真撮影する。導電性粒子が、一視野に、好ましくは100個以上、より好ましくは200個以上、さらに好ましくは300個以上、写るように倍率を調整する。なお、粒子の境界が明確になるように、またハレーションが生じないように光量を調節する。特に金属箔にアルミニウム箔などの光を反射しやすい材料を用いている場合には注意を要する。該写真を画像解析処理にて二値化し、導電性粒子が写っている部分の面積S1と写っていない部分の面積S0を求める。式:A2=(S1)/(S1+S0)×100%にて、被覆層の面積に対する導電性粒子の面積の割合A2を算出する。このA2を導電性粒子の面積率とする。二値化処理では、写真画像の濃淡レベルを0~255にデジタル値化する。
本発明の電極は、リチウム二次電池の正極、負極のいずれに適用しても良い。電極が正極の場合は、金属箔に正極合材を積層し、電極が負極の場合は、金属箔に負極合材を積層する。以下、正極合材および負極合材について説明する。
正極合材は、正極活物質からなる正極材料、または正極活物質の粒子の表面の一部または全部に炭素材料が付着されてなる正極材料を具備して構成されている。正極合材には、正極材料の他にバインダが含まれる。また、正極合材には、導電助材が含まれていても良い。
正極材料を構成する正極活物質は、リチウム含有複合酸化物、カルコゲン化合物またはリチウム含有オリビン酸塩のうちの1種以上であることが好ましい。より具体的には、正極活物質は、コバルト酸リチウム、マンガン酸リチウム、ニッケル酸リチウム、コバルトマンガンニッケル酸リチウム、硫化チタン(TiS2)、オリビン酸鉄リチウムまたはオリビン酸マンガンリチウムのうちいずれか一種以上を含むことが好ましい。
炭素材料を付着させる方法としては、正極活物質と炭素材料の混合物を、圧縮、せん断、圧延作用を加えるように混練して正極活物質の粒子の表面の一部または全部に炭素材料を付着させる方法を例示できる。この場合の炭素材料としては、黒鉛、カーボンブラック等を例示できる。また、この場合の正極活物質としては、コバルト酸リチウム、マンガン酸リチウム、ニッケル酸リチウム、またはコバルトマンガンニッケル酸リチウムが好適に用いられる。
導電助材としては、銀粉などの導電性金属粉;ファーネスブラック、ケッチェンブラック、アセチレンブラックなどの導電性カーボン粉などが挙げられる。導電助材を添加する場合の添加量は正極合材の乾燥質量に対して1.4質量%以下であり、1.4質量%未満が好ましく、0.2質量%以下がより好ましく、正極合材の電気伝導性が十分に確保されていれば添加しなくてもよい。
次に、金属箔の表面に積層される電極合材としての負極合材は、負極活物質、結着剤及び必要に応じて添加される導電助材とが含有されてなる負極合材と、負極合材に接合される負極集電体とからなるシート状の電極を用いることができる。
また、負極活物質の表面にも、正極と同様に、炭素材料を付着させても良い。この場合、特に、Sn、Si等の金属または半金属材料に適用するとよい。
更に導電助材は、必要に応じて添加してもよく、添加しなくても良い。例えば、ファーネスブラック、ケッチェンブラック、アセチレンブラックなどの導電性カーボン粉;カーボンナノチューブ、カーボンナノファイバー、気相法炭素繊維などを用いることができる。導電助剤としては気相法炭素繊維が特に好ましい。気相法炭素繊維は、その繊維径が5nm以上0.2μm以下であることが好ましい。繊維長さ/繊維径の比が5~1000であることが好ましい。
導電助材を添加する場合の添加量は負極合材の乾燥質量に対して1.4質量%以下であり、0.4質量%以下がより好ましく、0.2質量%以下が更に好ましく、負極合材の電気伝導性が十分に確保されていれば添加しなくてもよい。
本実施形態の電極の製造方法は、結着剤と導電性粒子と分散媒を含む被覆層塗工液を金属箔に塗布し、分散媒を除去して被覆層を形成する工程と、被覆層上に電極合材を形成する工程とからなる。また、電極合材を成形した後に、電極合材をプレスすることが好ましい。
非プロトン性極性溶媒は、塗布後、熱処理の温度以下で蒸発するものが望ましい。具体的には、常圧での沸点が50~300℃のものが好ましく、100~220℃のものがより好ましい。このような沸点を持つ非プロトン性極性溶媒を用いると、塗工作業中に被覆層塗工液の濃度が変化し難いので、所定の厚さまたは塗布量を有する被覆層を得やすい。また、熱処理により分散媒を十分に除去することができる。上記のような沸点を有する非プロトン性極性溶媒としては、N,N-ジメチルアセトアミド、N-メチル-2-ピロリドン、N-エチル-ピロリドン、γ-ブチロラクトンが挙げられる。これらのうち、N-メチル-2-ピロリドンが好ましい。
面積率を調整するための手法として、グラビアコーターのコーティングロールのパターン設計、ステンシルタイプやワイヤーメッシュタイプのマスクの使用などが挙げられる。
本実施形態の好ましい実施態様に係るリチウム二次電池は、正極と負極と非水電解質とを具備して構成されている。本実施形態のリチウム二次電池においては、正極、負極のいずれか一方を本発明に係る電極とし、いずれか他方を従来の電極としてもよく、リチウム二次電池における正極、負極の両方を本発明に係る電極としてもよい。これにより、急速充放電を可能とし、充放電電流が大きな条件でも電池容量維持率を高く維持することが可能なリチウム二次電池が得られる。正極及び負極については既に説明しているので、ここでは、リチウム二次電池を構成する非水電解質について説明する。
非水電解質としては、例えば、非プロトン性溶媒にリチウム塩が溶解されてなる非水電解質を例示できる。
また、リチウム塩には、LiClO4、LiPF6、LiAsF6、LiBF4、LiSO3CF3、CH3SO3Li、CF3SO3Li等が挙げられる。
あるいは溶融電電解質を用いることもできる。溶融塩電解質としては、例えば、メチルプロピルイミダゾリウムビスフルオロスルホニルアミドと、リチウムビストリフルオロメタンスルホン酸アミドを組み合わせたものを用いることができる。
また通常、リチウム二次電池は外装材に封入されている。外装材としては、金属缶や金属と樹脂とのラミネートフィルムが挙げられるが、電池の小型化の観点から、ラミネートフィルムであることが好ましい。
また、本実施形態のリチウム二次電池用電極の製造方法によれば、急速充放電を可能とし、充放電電流が大きな条件でも電池容量維持率を高く維持することが可能なリチウム二次電池用の電極を製造できる。
更に、本実施形態のリチウム二次電池によれば、急速充放電を可能とし、充放電電流が大きな条件でも電池容量維持率を高く維持できる。
N-メチル-2-ピロリドン80質量部及びイソプロピルアルコール5質量部からなる分散媒に、導電性粒子であるカーボンブラック5質量部と、多糖類であるグリセリル化キトサン5質量部と、無水ピロメリット酸5質量部とを、ディゾルバータイプの撹拌機に入れて、回転数300rpmで10分間混合した。次いで、ホモジナイザー(家田貿易(株)製、製品名PRO200)を用いて20000rpmで30秒間処理し、分散媒中に導電性粒子等が均一に分散された被覆層塗工液を得た。
正極活物質粒子として、水熱法により合成された燐酸マンガンリチウムを用いて、実施例1と同様にして実施例2のリチウム二次電池を得た。
正極活物質粒子であるコバルト酸リチウム90質量部と、炭素材料としての黒鉛(Timcal Ltd.製、商品名KS6L)3質量部およびカーボン(Timcal Ltd.製、商品名Super P‐Li)2質量部とを粉体処理装置(ホソカワミクロン社製、製品名ノビルタNOB-130)にて処理して炭素分5質量部と複合化された正極材料を得た。この正極材料を用いて実施例1と同様にして実施例2のリチウム二次電池を得た。
正極活物質粒子として、マンガン酸リチウムを用いて、実施例3と同様にして実施例4のリチウム二次電池を得た。
正極活物質粒子として、ニッケル酸リチウムを用いて、実施例3と同様にして実施例5のリチウム二次電池を得た。
正極活物質粒子として、コバルトマンガンニッケル酸リチウムを用いて、実施例3と同様にして実施例6のリチウム二次電池を得た。
アルカリ洗浄されたA1085材からなる厚さ30μmのアルミニウム箔に被覆層を設けないことを除き、実施例1と同一の仕様にて比較例1のリチウム二次電池を得た。
アルカリ洗浄されたA1085材からなる厚さ30μmのアルミニウム箔に被覆層を設けずに集電体とした。
水熱法により合成された正極活物質粒子である燐酸鉄リチウム90質量部、カーボンブラック5質量部、ポリフッ化ビニリデン((株)クレハ製、商品名KFポリマー#1120)5質量部、およびN-メチル-2-ピロリドン(工業用グレード)100質量部を混合して正極スラリーを得た。この正極スラリーを上記の集電体に塗工して得た正極を用いた以外は実施例1と同一の仕様にて比較例2の電池を得た。
アルカリ洗浄されたA1085材からなる厚さ30μmのアルミニウム箔に被覆層を設けないことを除き、実施例2と同一の仕様にて比較例1のリチウム二次電池を得た。
アルカリ洗浄されたA1085材からなる厚さ30μmのアルミニウム箔に被覆層を設けずに集電体とした。
水熱法により合成された正極活物質粒子である燐酸マンガンリチウム90質量部、カーボンブラック5質量部、ポリフッ化ビニリデン((株)クレハ製、商品名KFポリマー#1120)5質量部、およびN-メチル-2-ピロリドン(工業用グレード)100質量部を混合して正極スラリーを得た。この正極スラリーを上記の集電体に塗工して得た正極を用いた以外は実施例2と同一の仕様にて比較例2の電池を得た。
アルカリ洗浄されたA1085材からなる厚さ30μmのアルミニウム箔に被覆層を設けないことを除き、実施例3と同一の仕様にて比較例1のリチウム二次電池を得た。
アルカリ洗浄されたA1085材からなる厚さ30μmのアルミニウム箔に被覆層を設けずに集電体とした。
正極活物質粒子であるコバルト酸リチウム90質量部、カーボンブラック5質量部、ポリフッ化ビニリデン((株)クレハ製、商品名KFポリマー#1120)5質量部、およびN-メチル-2-ピロリドン(工業用グレード)100質量部を混合して正極スラリーを得た。この正極スラリーを上記の集電体に塗工して得た正極を用いた以外は実施例3と同一の仕様にて比較例2の電池を得た。
アルカリ洗浄されたA1085材からなる厚さ30μmのアルミニウム箔に被覆層を設けないことを除き、実施例4と同一の仕様にて比較例1のリチウム二次電池を得た。
アルカリ洗浄されたA1085材からなる厚さ30μmのアルミニウム箔に被覆層を設けずに集電体とした。
正極活物質粒子であるマンガン酸リチウム90質量部、カーボンブラック5質量部、ポリフッ化ビニリデン((株)クレハ製、商品名KFポリマー#1120)5質量部、およびN-メチル-2-ピロリドン(工業用グレード)100質量部を混合して正極スラリーを得た。この正極スラリーを上記の集電体に塗工して得た正極を用いた以外は実施例4と同一の仕様にて比較例2の電池を得た。
アルカリ洗浄されたA1085材からなる厚さ30μmのアルミニウム箔に被覆層を設けないことを除き、実施例5と同一の仕様にて比較例1のリチウム二次電池を得た。
アルカリ洗浄されたA1085材からなる厚さ30μmのアルミニウム箔に被覆層を設けずに集電体とした。
正極活物質粒子であるニッケル酸リチウム90質量部、カーボンブラック5質量部、ポリフッ化ビニリデン((株)クレハ製、商品名KFポリマー#1120)5質量部、およびN-メチル-2-ピロリドン(工業用グレード)100質量部を混合して正極スラリーを得た。この正極スラリーを上記の集電体に塗工して得た正極を用いた以外は実施例5と同一の仕様にて比較例2の電池を得た。
アルカリ洗浄されたA1085材からなる厚さ30μmのアルミニウム箔に被覆層を設けないことを除き、実施例6と同一の仕様にて比較例1のリチウム二次電池を得た。
アルカリ洗浄されたA1085材からなる厚さ30μmのアルミニウム箔に被覆層を設けずに集電体とした。
正極活物質粒子であるコバルトマンガンニッケル酸リチウム90質量部、カーボンブラック5質量部、ポリフッ化ビニリデン((株)クレハ製、商品名KFポリマー#1120)5質量部、およびN-メチル-2-ピロリドン(工業用グレード)100質量部を混合して正極スラリーを得た。この正極スラリーを上記の集電体に塗工して得た正極を用いた以外は実施例6と同一の仕様にて比較例2の電池を得た。
得られた電池の充放電特性を次のような手法で評価した。
充放電装置(東洋システム(株)製)を用いて、電流レートを0.2C、0.5C、1C、2C、5C、10C、20Cと変えて、満充電状態からの定電流放電容量を測定した。
なお、満充電状態とは、0.2C定電流充電にて電池電圧が4.0Vを示して充電終了した後、1時間経過した状態をいう。
図1~図6に示すように、実施例1~6の電池は、それぞれ比較例1と2、比較例3と4、比較例5と6、比較例7と8,比較例9と10,比較例11と12の電池に比べて、1C以上の電流レートにおいて容量維持率が高くなっていることがわかる。
Claims (19)
- 金属箔と、該金属箔上に積層されてなる電極合材とを有する電極であって、
該金属箔と電極合剤との間に、結着剤と、導電性粒子とを含む被覆層が備えられ、
前記電極合材には、電極活物質と、前記電極合材中における組成比が0質量%~1.4質量%である導電助材とが含まれる
ことを特徴とするリチウム二次電池用電極。 - 前記電極合材は、前記電極活物質の粒子の表面の一部または全部に炭素材料が付着されてなる電極材料を含み、かつ導電助材を実質的に含まないことを特徴とする請求項1に記載のリチウム二次電池用電極。
- 前記被覆層における前記導電性粒子の面積率が50%以上100%未満であることを特徴とする請求項1または請求項2に記載のリチウム二次電池用電極。
- 前記導電性粒子が炭素粒子であることを特徴とする請求項1乃至請求項3の何れか一項に記載のリチウム二次電池用電極。
- 前記結着剤が、多糖類またはその誘導体からなる群より選ばれる一種以上を含むものであることを特徴とする請求項1乃至請求項4の何れか一項に記載のリチウム二次電池用電極。
- 前記被覆層に、有機酸または有機酸誘導体からなる群より選ばれる1種以上を含むことを特徴とする請求項1乃至請求項5の何れか一項に記載のリチウム二次電池用電極。
- 前記電極活物質が、リチウム含有複合酸化物、カルコゲン化合物またはリチウム含有オリビン酸塩のうちの1種以上であることを特徴とする請求項1乃至請求項6の何れか一項に記載のリチウム二次電池用電極。
- 前記電極活物質が、コバルト酸リチウム、マンガン酸リチウム、ニッケル酸リチウム、コバルトマンガンニッケル酸リチウム、硫化チタン(TiS2)、オリビン酸鉄リチウムまたはオリビン酸マンガンリチウムのうちいずれか一種以上を含むことを特徴とする請求項7に記載のリチウム二次電池用電極。
- 前記結着剤が、キトサン、キチン、セルロースおよびそれらの誘導体からなる群より選ばれる1種以上を含むものであることを特徴とする請求項1乃至請求項8の何れか一項に記載のリチウム二次電池用電極。
- 前記有機酸または前記有機酸誘導体が、無水トリメリット酸、無水ピロメリット酸、1,2,3,4-ブタンテトラカルボン酸またはこれらの誘導体からなる群より選ばれる1種以上であることを特徴とする請求項6乃至請求項9の何れか一項に記載のリチウム二次電池用電極。
- 前記被覆層に含まれる前記導電性粒子の含有率が30~90質量%の範囲であることを特徴とする請求項1乃至請求項10の何れか一項に記載のリチウム二次電池用電極。
- 請求項1乃至請求項11の何れか一項に記載のリチウム二次電池用電極と、電解質とを有することを特徴とするリチウム二次電池。
- 結着剤と導電性粒子と分散媒を含む被覆層塗工液を金属箔に塗布し、前記分散媒を除去して被覆層を形成した後、前記被覆層上に、電極活物質と、電極合材にしたときの組成比が0~1.4質量%となる導電助材と、別の分散媒とを含む合材用塗工液を塗布し、前記別の分散媒を除去して電極合材を形成することを特徴とするリチウム二次電池用電極の製造方法。
- 前記リチウム二次電池用電極が、金属箔と、該金属箔上に積層されてなる正極合材とを有するリチウム二次電池用正極であり、
該金属箔と正極合剤との間に、さらに、結着剤と、導電性粒子とを含む被覆層が備えられ、
前記正極合材は、
正極活物質のみからなる正極材料、又は正極活物質の粒子の表面の一部または全部に炭素材料が付着されてなる正極材料と、
前記正極合材中における組成比が0質量%~1.4質量%である導電助材とを含むことを特徴とする請求項1乃至請求項11の何れか一項に記載のリチウム二次電池用電極。 - 前記正極合材は、前記正極活物質の粒子の表面の一部または全部に炭素材料が付着されてなる正極材料を含み、かつ前記導電助材を実質的に含まないことを特徴とする請求項14に記載のリチウム二次電池用電極。
- 前記正極活物質の粒子の表面の一部または全部に炭素材料が付着されてなる前記正極材料が、
前記正極活物質と、前記炭素材料の前駆体としての炭素形成材料の混合物を、不活性条件下または還元条件下で、500℃~800℃の温度で焼成する方法、 または、前記正極活物質と前記炭素材料の混合物を、圧縮、せん断、圧延作用を加えるように混練する方法で得られた
ことを特徴とする請求項15に記載のリチウム二次電池用電極。 - 前記金属箔がアルミニウムまたはアルミニウム合金の箔であり、
前記被覆層における前記導電性粒子が炭素粒子であり、前記導電性粒子の面積率が50%以上100%未満であり、
前記被覆層における前記結着剤が多糖類又はその誘導体と、芳香族カルボン酸又はその誘導体とを含み、
前記正極活物質がオリビン酸鉄リチウム、オリビン酸マンガンリチウム、コバルト酸リチウム、マンガン酸リチウム、ニッケル酸リチウム、コバルトマンガンニッケル酸リチウムからなる群から選択される1種を含む
ことを特徴とする請求項16に記載のリチウム二次電池用電極。 - 前記リチウム二次電池用電極が、リチウム二次電池用正極であり、
結着剤と導電性粒子と分散媒を含む被覆層塗工液を金属箔に塗布し、前記分散媒を除去して被覆層を形成した後、
前記被覆層上に、
正極活物質のみからなる正極材料、又は正極活物質の粒子の表面の一部または全部に炭素材料が付着されてなる正極材料と、
正極合材にしたときの組成比が0~1.4質量%となる導電助材と、
別の分散媒と
を含む合材用塗工液を塗布し、
前記別の分散媒を除去して正極合材を形成する
ことを特徴とする請求項13に記載のリチウム二次電池用電極の製造方法。 - 前記正極材料が正極活物質の粒子の表面の一部または全部に炭素材料が付着されてなる正極材料であり、
前記炭素材料を付着させる方法は、前記正極活物質と前記炭素材料の前駆体である炭素形成材料の混合物を、不活性条件下または還元条件下で、500℃~800℃の温度で焼成する方法、または、前記正極活物質と前記炭素材料の混合物を、圧縮、せん断、圧延作用を加えるように混練する方法
を含むことを特徴とする請求項18に記載のリチウム二次電池用電極の製造方法。
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Also Published As
Publication number | Publication date |
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US20140120423A1 (en) | 2014-05-01 |
JPWO2013005739A1 (ja) | 2015-02-23 |
EP2731177A4 (en) | 2014-12-31 |
EP2731177A1 (en) | 2014-05-14 |
CN103636032A (zh) | 2014-03-12 |
KR20140015589A (ko) | 2014-02-06 |
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