JP5182789B2 - Hydrogen storage alloy-containing sheet, method for producing the same, and nickel metal hydride battery - Google Patents

Description

  The present invention relates to a hydrogen storage alloy-containing sheet, a manufacturing method thereof, and a nickel metal hydride battery.

  In recent years, hydrogen storage alloys have attracted attention as materials used for secondary batteries and fuel cells. Hydrogen storage alloys have the property of absorbing hydrogen by lowering the ambient temperature or increasing the surrounding hydrogen pressure and releasing hydrogen by raising the ambient temperature or lowering the surrounding hydrogen pressure. Taking advantage of these characteristics, they are used for hydrogen storage bodies such as fuel cells and hydrogen separation membranes, electrode materials for secondary batteries, hydrogen permeable membranes and hydrogen permeable electrodes for fuel cells, and the like.

  For example, a sealed nickel-metal hydride battery is mainly composed of a positive electrode, an alkaline electrolyte, a separator, a negative electrode, and a storage can that stores them, and is sealed. A negative electrode containing an alloy is used. Therefore, oxygen generated at the positive electrode during overcharge can be converted into water by reaction with the hydrogen storage alloy of the negative electrode, so that an increase in battery internal pressure can be suppressed.

  As this negative electrode, for example, a hydrogen storage alloy powder, a paste made of a binder such as polyvinyl alcohol or polytetrafluoroethylene, a conductive aid such as nickel powder or carbon powder, and a thickening aid such as CMC, A foamed nickel base material, a punching metal base material, or an expanded metal base material is generally coated and press-molded. However, such a negative electrode is generally hard and difficult to handle. For example, when used as a negative electrode for a cylindrical nickel-metal hydride battery, the negative electrode needs to be bent in a coil shape. However, when the hydrogen storage alloy is bent or cracked, the hydrogen storage alloy can be used as a separator. There were some problems such as penetration and easy occurrence of internal short circuits, the yield in battery manufacturing was poor, and there was a problem in terms of long-term reliability.

On the other hand, as a composite sheet that can be deformed and can be used as a negative electrode, “a sheet-like fiber structure in which fiber materials are intertwined and bonded by papermaking, and a hydrogen storage alloy fine particle dispersed and held inside the fiber structure” A "composite sheet body provided with powder" has been proposed (Patent Document 1). More specifically, a composite sheet body is proposed in which an aqueous solution in which a fiber material and a hydrogen storage alloy fine powder are mixed and dispersed is made into a sheet shape, and the formed sheet body is dried. In this composite sheet, since the hydrogen storage alloy fine powder is held in the gap formed by the fiber material, the amount of the hydrogen storage alloy fine powder is reduced if the hydrogen storage alloy fine powder is prevented from falling off. When the amount of fine powder was increased, it was easy to fall off from the composite sheet when deformed.
JP 2006-196280 A (Claim 1, claim 8, paragraph number 0025, etc.)

  The present invention was made in order to solve the above-described problems. A hydrogen-absorbing alloy-containing sheet excellent in deformability in which the hydrogen-absorbing alloy powder is difficult to fall off despite a large amount of the hydrogen-absorbing alloy powder. The purpose is to provide. It is another object of the present invention to provide a manufacturing method thereof and a nickel metal hydride battery using the same.

The invention according to claim 1 of the present invention is “a hydrogen storage alloy-containing sheet in which the fiber sheet constituting fiber inside the matrix , the hydrogen storage alloy powder surface, and the resin surface are coated with a porous metal film,” Is filled with hydrogen storage alloy powder in the voids of the fiber sheet, and some hydrogen storage alloy powder is bonded to the fiber sheet constituting fiber by resin, and some hydrogen storage alloy powder is adjacent to the hydrogen storage alloy by resin. A hydrogen storage alloy-containing sheet characterized by being bonded to an alloy powder. "

  The invention according to claim 2 of the present invention is characterized in that “the hydrogen storage alloy according to claim 1, wherein the hydrogen storage alloy powder is bonded to a part of the hydrogen storage alloy powder by fusing the resin constituting the fiber sheet constituting fiber. Alloy-containing sheet. "

  The invention according to claim 3 of the present invention is the “hydrogen-absorbing alloy-containing sheet according to claim 1 or 2, wherein the fiber sheet is made of a polyolefin-based nonwoven fabric”.

  The invention according to claim 4 of the present invention is the “powder filling step of filling the voids of the fiber sheet with the resin powder and the hydrogen storage alloy powder, the binding action of the filled resin powder, A matrix forming step of binding the storage alloy powder to the fiber sheet constituting fiber and combining a part of the hydrogen storage alloy powder with the adjacent hydrogen storage alloy powder to form a matrix, and dispersing fine particles other than metal in the matrix. A metal film coating step of coating the surface of the matrix with a porous metal film by performing electroless plating in a plating bath. "

  The invention according to claim 5 of the present invention is as follows: "The powder filling step is performed by supplying an air flow including a resin powder and a hydrogen storage alloy powder to the fiber sheet. It is a manufacturing method of an alloy containing sheet. "

  The invention according to claim 6 of the present invention is as follows: "The powder filling step includes supplying a gas stream to the fiber sheet in a state where the hydrogen storage alloy powder is heated above the melting point of the fiber constituting the fiber sheet; 5. The method for producing a hydrogen-absorbing alloy-containing sheet according to claim 4, further comprising: a second stage of supplying an air flow including the hydrogen-absorbing alloy powder to the fiber sheet.

  The invention according to claim 7 of the present invention is as follows: "The first stage in which the powder filling step supplies the hydrogen storage alloy powder to the fiber sheet by the air flow heated from the melting point of the fiber constituting the fiber sheet; the resin powder and the hydrogen storage 5. The method for producing a hydrogen-absorbing alloy-containing sheet according to claim 4, further comprising a second stage of supplying an airflow containing the alloy powder to the fiber sheet.

  The invention according to claim 8 of the present invention is characterized in that "in the matrix forming step, the resin powder and the resin constituting the surface of the fiber sheet constituting fiber are fused and the hydrogen storage alloy powder is bonded. The manufacturing method of the hydrogen storage alloy containing sheet | seat in any one of 4-7. "

  The invention according to claim 9 of the present invention is as follows: "In the metal film coating step, polytetrafluoroethylene fine particles are used as fine particles other than metal, and the hydrogen storage alloy according to any one of claims 4 to 8" Manufacturing method of containing sheet. "

  The invention according to claim 10 of the present invention is a “nickel metal hydride battery comprising the hydrogen storage alloy-containing sheet according to any one of claims 1 to 3 as a negative electrode”.

  In the invention according to claim 1 of the present invention, since the matrix already includes a fiber sheet having a form, the hydrogen storage alloy powder is less likely to fall off and has excellent deformability. Further, since the hydrogen storage alloy powder is bonded to the fiber sheet constituting fiber or the adjacent hydrogen storage alloy powder by the resin, it is difficult to cause a problem such as dropping even if the amount of the hydrogen storage alloy powder is large. In addition, since the matrix surface is covered with a porous metal film, it has a low resistance that allows electrons to move continuously, and does not hinder the hydrogen retention ability of the hydrogen storage alloy powder. Thus, since it is coat | covered with the porous metal film and the surface area of a metal film is large, when this hydrogen storage alloy containing sheet | seat is used as an electrode, an electrode reaction will be favorable.

  In the invention according to claim 2 of the present invention, since a part of the hydrogen storage alloy powder is bonded by the fusion of the resin constituting the fiber sheet constituting fiber, it falls off even if the amount of the hydrogen storage alloy powder is large. The problem is less likely to occur.

  The invention according to claim 3 of the present invention is excellent in chemical resistance and high in reliability because the fiber sheet is made of a polyolefin-based nonwoven fabric.

  In the invention according to claim 4 of the present invention, since the hydrogen storage alloy powder is filled in the voids of the already formed fiber sheet, the hydrogen storage alloy-containing sheet is excellent in deformability because the hydrogen storage alloy powder hardly falls off. The hydrogen storage alloy powder can be manufactured, and the hydrogen storage alloy powder is bonded to the fiber sheet constituting fiber or the adjacent hydrogen storage alloy powder by the binding action of the resin powder, so that it is difficult to fall off even if the amount of the hydrogen storage alloy powder is large. A hydrogen storage alloy-containing sheet can be produced. Further, since the matrix surface can be covered with a porous metal film, it is possible to produce a hydrogen storage alloy-containing sheet that can move electrons continuously and has low resistance, and that does not hinder the hydrogen retention ability of the hydrogen storage alloy powder. Furthermore, since the matrix fiber sheet is left, steps such as firing can be omitted.

  In the invention according to claim 5 of the present invention, the airflow containing the resin powder and the hydrogen storage alloy powder is supplied to the fiber sheet to fill the voids of the fiber sheet with the powder. A large amount of occlusion alloy powder can be filled.

  In the invention according to claim 6 of the present invention, a part of the hydrogen storage alloy powder is supplied by the first stage in which the hydrogen storage alloy powder is supplied to the fiber sheet in a state where the hydrogen storage alloy powder is heated more than the melting point of the fiber constituting the fiber sheet. Because it can be bonded to the fiber sheet constituent fiber in a buried state, the hydrogen storage alloy powder can be reliably bonded to the fiber sheet constituent fiber, and the void that can be filled with the hydrogen storage alloy powder can be widened as much as it is embedded. Further, the filling amount of the hydrogen storage alloy powder in the second stage in which the airflow including the subsequent resin powder and the hydrogen storage alloy powder is supplied to the fiber sheet can be increased. Further, in the first stage, a part of the hydrogen storage alloy powder can be bonded in a state where it is buried in the fiber sheet constituting fiber, and the hydrogen supplied in the subsequent second stage is improved by improving the denseness of the fiber sheet. Since the adhesiveness with the storage alloy powder becomes high, the performance of the hydrogen storage alloy powder can be exhibited more. For example, when a hydrogen storage alloy-containing sheet is used as the negative electrode of a cylindrical nickel-metal hydride battery, the capacity is large and the utilization rate of the hydrogen storage alloy is increased.

  The invention according to claim 7 of the present invention is such that a part of the hydrogen-absorbing alloy powder is formed into a fiber sheet by the first stage in which the hydrogen-absorbing alloy powder is supplied to the fiber sheet by an air flow heated from the melting point of the fiber constituting the fiber sheet. Since it can be bonded in the state of being buried in the fiber, the hydrogen storage alloy powder can be reliably bonded to the fiber sheet constituting fiber, and the void that can be filled with the hydrogen storage alloy powder can be widened as much as it is buried, so that the following resin It is possible to increase the filling amount of the hydrogen storage alloy powder in the second stage in which the airflow including the powder and the hydrogen storage alloy powder is supplied to the fiber sheet. Further, in the first stage, since the hydrogen storage alloy powder can be bonded to the fiber even at a temperature lower than the melting point of the fiber sheet constituent fiber, there is an effect that the oxidative deterioration of the hydrogen storage alloy powder can be suppressed. . Furthermore, in the first stage, a part of the hydrogen storage alloy powder can be bonded in a state where it is buried in the fiber sheet constituting fibers, and the denseness of the fiber sheet is improved, so that the hydrogen supplied in the subsequent second stage is increased. Since the adhesiveness with the storage alloy powder becomes high, the performance of the hydrogen storage alloy powder can be exhibited more. For example, when a hydrogen storage alloy-containing sheet is used as the negative electrode of a cylindrical nickel-metal hydride battery, the capacity is large and the utilization rate of the hydrogen storage alloy is increased.

  In the invention according to claim 8 of the present invention, since the hydrogen storage alloy powder is bonded by fusing the resin powder and the resin constituting the surface of the fiber sheet constituent fiber, the hydrogen storage alloy powder is strong. Is stably held and is less likely to fall off.

  In the invention according to claim 9 of the present invention, since the polytetrafluoroethylene fine particles are used as the fine particles other than the metal, a porous metal film is easily formed, and a hydrogen storage alloy-containing sheet having a large metal film surface area is produced. It's easy to do.

  Since the invention concerning Claim 10 of this invention is equipped with the above-mentioned hydrogen storage alloy containing sheet | seat, it is a nickel metal hydride battery which a short circuit does not generate | occur | produce easily.

  Since the hydrogen storage alloy-containing sheet of the present invention includes a fiber sheet having a form as a matrix, the hydrogen storage alloy powder is less likely to fall off and has excellent deformability. That is, when the fiber sheet is a woven fabric, the yarn or fiber is woven, so it is already in a form, and when the fiber sheet is a knitted fabric, the yarn or fiber is already knitted. When the fiber sheet is made of a non-woven fabric in a state having a form, the fiber is in a state of being bonded to each other, so that the fiber sheet is already in a form. The nonwoven fabric in which the fibers are bonded to each other is a nonwoven fabric manufactured by a chemical bond method, a nonwoven fabric manufactured by a thermal bond method, a nonwoven fabric manufactured by a needle punch method, or a fluid intertwining method such as a hydroentanglement method. Or a non-woven fabric produced by combining these bonding methods. Among the fiber sheets constituting such a matrix, the nonwoven fabric is preferable because the fibers can exist in a mesh state and the retention property of the hydrogen storage alloy powder is excellent.

  The fiber constituting the fiber sheet is not particularly limited, but is preferably excellent in chemical resistance, and polyolefin fibers or polyamide fibers can be suitably used. In particular, polyolefin fibers are chemically resistant. It is suitable because it has excellent properties and many have a relatively low melting point and is easily involved in the binding of the hydrogen storage alloy powder. Examples of suitable polyolefin fibers include high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene, ethylene-vinyl alcohol copolymer, ethylene-methacrylic acid copolymer, and other ethylene-based fibers. A resin, a propylene resin such as polypropylene, and a methylpentene resin such as polymethylpentene can be composed of one kind or two or more kinds. In particular, an ethylene-based resin is preferable because it has a low melting point and easily participates in bonding of the hydrogen storage alloy powder. In addition, when the polyolefin fiber is made of two or more types of resins having different melting points, and the resin having a low melting point occupies part or all of the fiber surface, the bonding of the hydrogen-absorbing alloy powder is performed without significantly reducing the fiber strength. It is suitable because it is easily involved in As such polyolefin-based fibers, those having a core-sheath type, a bonded type, a sea-island type, an orange type, and a multi-layered type can be used in the cross section of the fiber, particularly for bonding hydrogen storage alloy powders. The core-sheath type or sea-island type is preferred because the amount of resin that can be involved is large. Further, the fineness and fiber length of the fibers constituting the fiber sheet are not particularly limited, but the fineness is preferably 0.01 dtex to 30 dtex, more preferably 0.1 dtex to 10 dtex. On the other hand, the fiber length varies depending on the type of fiber sheet. In the case of a woven fabric or a knitted fabric, a continuous fiber or yarn of filament or spun yarn is used. In the case of a nonwoven fabric, the fiber length varies depending on the method of forming the fiber web. When forming a web, the fiber length is preferably 15 mm to 150 mm, more preferably 20 mm to 100 mm. Moreover, when forming a fiber web by a wet method, it is preferable that fiber length is 2 mm-50 mm, and it is more preferable that it is 3 mm-20 mm. Furthermore, when a fiber web is formed by the spunbond method, it is a continuous fiber.

  In addition, among the suitable nonwoven fabrics, since the nonwoven fabric manufactured by the thermal bond method does not generate | occur | produce an impurity from a nonwoven fabric, it can be used conveniently. For example, even when the hydrogen storage alloy-containing sheet of the present invention is used as an electrode, impurities are eluted in the electrolytic solution, which is suitable because there is no possibility of adversely affecting the battery reaction. In addition, a polyolefin-based nonwoven fabric in which the nonwoven fabric-constituting fibers consist only of polyolefin-based fibers is particularly suitable because it is particularly excellent in chemical resistance. In addition, although the formation method of the fiber web used as the origin of a nonwoven fabric is not specifically limited, It can form by direct methods, such as a dry method, a wet method, and a spun bond method.

Such fiber sheet having a basis weight is not particularly limited in thickness, weight per unit area is preferably a 30~300g / ^{m 2,} and more preferably 50 to 250 g / ^{m 2.} On the other hand, the thickness is preferably 0.05 to 5 mm, more preferably 0.1 to 3 mm.

  The matrix of the hydrogen-absorbing alloy-containing sheet of the present invention is such that the voids of the fiber sheet as described above are filled with the hydrogen-absorbing alloy powder, and some of the hydrogen-absorbing alloy powder is bonded to the fiber sheet constituting fibers by the resin. Some of the hydrogen storage alloy powders are bonded to the adjacent hydrogen storage alloy powder by the resin, so that even if the amount of the hydrogen storage alloy powder is large, it is difficult to fall off. That is, because the hydrogen storage alloy powder is bonded to the fiber sheet constituting fiber or the adjacent hydrogen storage alloy powder, even if there is an unbonded hydrogen storage alloy powder, the hydrogen storage alloy powder is bound to each other. This makes it difficult for the hydrogen storage alloy powder to fall off.

  In the matrix of the present invention, a part of the hydrogen storage alloy powder is bonded to the fiber sheet constituting fiber by the resin, and the hydrogen storage alloy powder does not easily fall off. The bond with the fiber by this resin may be bonded by fusion of the resin constituting the fiber sheet constituting fiber, or may be bonded by a resin not derived from the resin constituting the fiber sheet constituting fiber, Bonding by fusing the resin constituting the fiber sheet constituting fiber is a preferred embodiment because the bonding force between the fiber and the hydrogen storage alloy powder is strong and the hydrogen storage alloy powder is unlikely to fall off. In particular, when part of the hydrogen storage alloy powder is bonded in a state where it is buried in the fiber sheet constituting fiber, the hydrogen storage alloy powder is securely bonded, and even if the amount of the hydrogen storage alloy powder is large, the hydrogen storage alloy powder falls off. This is preferable because problems are less likely to occur. Further, the voids that can be filled with the hydrogen storage alloy powder are widened as much as the hydrogen storage alloy powder is buried, and the amount of the hydrogen storage alloy powder can be further increased, which is preferable.

  In addition, when the resin that binds the hydrogen storage alloy powder to the fiber is not derived from the resin that constitutes the fiber sheet constituting fiber, this resin is not particularly limited. It is preferable to consist of resin or a polyamide-type resin. Polyolefin resins are particularly suitable because of their excellent chemical resistance. For example, high density polyethylene, medium density polyethylene, low density polyethylene, linear low density polyethylene, ethylene-vinyl alcohol copolymer, ethylene-methacrylic acid. An ethylene resin such as a copolymer, a propylene resin such as polypropylene, and a methylpentene resin such as polymethylpentene can be suitably used. In particular, it is preferable to use a resin having the same composition as the resin constituting the fiber sheet constituting fiber, which has a high affinity with the fiber and a strong binding force. Therefore, it is more preferable that it consists of polyolefin resin, especially ethylene resin. In addition, when resin which couple | bonds hydrogen storage alloy powder with a fiber does not originate in resin which comprises a fiber sheet structure fiber, it can couple | bond by fusion | melting or aggregation of resin.

  In the matrix of the present invention, some of the hydrogen storage alloy powders are bonded to the adjacent hydrogen storage alloy powder by the resin, so that the hydrogen storage alloy powders are constrained and are unlikely to fall off. The bonding by the resin can be performed by fusion or aggregation of the resin. The resin involved in the bonding between the hydrogen storage alloy powders is not particularly limited, but is preferably made of a polyolefin resin or a polyamide resin so as to be excellent in chemical resistance. Polyolefin resins are particularly suitable because of their excellent chemical resistance. For example, high density polyethylene, medium density polyethylene, low density polyethylene, linear low density polyethylene, ethylene-vinyl alcohol copolymer, ethylene-methacrylic acid. An ethylene resin such as a copolymer, a propylene resin such as polypropylene, and a methylpentene resin such as polymethylpentene can be suitably used.

The hydrogen storage alloy powder constituting the matrix is not particularly limited. For example, AB ₅ type (rare earth) alloy, AB / A ₂ B type (titanium) alloy, AB ₂ type (Laves phase) alloy, etc. One type or a mixture of two or more types can be used. More specifically, as AB ₅ type (rare earth) alloy, LaNi ₅ , LaNi ₄ Cu, LaNi ₄ Al, LaNi _2.5 Co _2.5 , La _0.8 Nd _0.2 Ni ₂ Co ₃ , La _0.7 Nd _0.2 Ti _0.1 Ni _2.5 Co _2.4 Al _0.1 , La _0.8 Nd _0.2 Ni _2.5 Co _2.4 Si _0.1 , La _0.9 Zr _0.1 Ni _4.5 Al _0.5 , MmNi ₅ (Mm = Misch metal), MmNi _3.55 Co _0.75 Mn _0.4 Al _0.3 , MmNi _4.2 Mn _0.6 Al _0.2 , MmNi ₃ Co _1.5 Al _0.5 , MmB _x (x = 4.55 to 4.76, B = Ni, Co, Mn, Al), AB / A ₂ B type (titanium system) ) as an _{alloy, TiNi, Ti 2 Ni, TiMn} 1 _{5, Ti} 2 Ni-TiNi based multi-component alloys (V, Cr, Zr, Mn , Co, Cu, partial substitution of Ni, etc. _{Fe); Ti 1-y Zr} y Ni x (x = 0.5~1. 45, y = 0 to 1), and the like. As the AB type ₂ (Laves phase) alloy, Ti _2-x Zr _x V _4-y Ni _y , Ti _1-x Cr _x V _2-y Ni _y ZrV _0.4 Ni _1.6 , ZrMn _0.6 Cr _0.2 Ni _1.2 , Ti ₁₇ Zr ₁₅ V ₂₂ Ni ₃₉ Cr ₇ , LaNi ₂ , CeNi _{2 and the} like. The hydrogen storage alloy powder is preferably obtained by mechanically pulverizing and classifying the ingot and using a uniform particle size, and an average particle size of 0.01 μm to 2 mm can be used. 0.1 to 100 μm is preferable. The hydrogen storage alloy powder can be previously plated. As the plating treatment in this case, for example, a plating treatment method described in JP-A-9-106817 can be used.

As described above, the matrix of the present invention is a fiber sheet void filled with hydrogen storage alloy powder. Even if the filling amount is 500 g / m ² or more, the matrix is not easily dropped and has excellent deformability. It is.

  In the hydrogen storage alloy-containing sheet of the present invention, the surface of the matrix as described above (that is, the fiber surface, the hydrogen storage alloy powder surface, and the resin surface) is covered with a porous metal film. In addition, it has a low resistance to move and can exhibit the hydrogen retention ability of the hydrogen storage alloy powder. Furthermore, there is an effect that the oxidation of the hydrogen storage alloy powder can be suppressed.

  The metal constituting the metal film is not particularly limited. For example, Ni, Ni alloy, Cu, Cu alloy, Sn, Cr, Zn, Co, Ti, Al, Au, Ag, Pt, Pt And alloys selected from the group consisting of Pd, Rh, and Ru, or alloys such as Ni—P, Ni—B, Ni—Cu—P, Ni—Co—P, and Ni—Cu—B. be able to. Among these, since Ni is excellent in chemical resistance, it is a suitable metal film constituent metal.

  The hydrogen storage alloy-containing sheet of the present invention has a large amount of hydrogen storage alloy powder, and the hydrogen storage alloy powder does not easily fall off and has excellent deformability. Therefore, a hydrogen storage body such as a fuel cell, a hydrogen separation membrane, and a secondary battery The electrode material, the hydrogen permeable membrane of a fuel cell, the hydrogen permeable electrode, and the like can be suitably used as a hydrogen storage body such as a fuel cell and a negative electrode of a nickel metal hydride battery.

  Such a hydrogen storage alloy-containing sheet of the present invention is, for example, a powder filling step of filling a resin sheet and a hydrogen storage alloy powder in the voids of a fiber sheet, and exhibiting the binding action of the filled resin powder. A matrix forming step of binding a part of the hydrogen storage alloy powder to the fiber sheet constituting fiber and combining a part of the hydrogen storage alloy powder with an adjacent hydrogen storage alloy powder to form a matrix; In particular, by performing electroless plating in a plating bath in which hydrophobic fine particles are dispersed, the matrix surface can be manufactured by a metal film coating step in which the surface of the matrix is coated with a porous metal film. As described above, since the matrix fiber sheet is left, steps such as firing can be omitted, and the workability is excellent.

  More specifically, first, in order to perform a powder filling step of filling the resin sheet and the hydrogen storage alloy powder into the voids of the fiber sheet, the fiber sheet as described above (particularly a polyolefin-based nonwoven fabric), Such hydrogen storage alloy powder and resin powder are prepared. The resin powder binds the hydrogen storage alloy powders, and the hydrogen storage alloy powder and the fiber sheet constituent fibers. As described above, the resin is preferably a polyolefin resin or a polyamide resin, and particularly an ethylene resin. Can be suitably used. The average particle size of the resin powder is not particularly limited, but can be effectively bonded (particularly fused) with the hydrogen storage alloy powder, so as not to hinder the hydrogen absorption and hydrogen release performance of the hydrogen storage alloy powder. It is preferable that it is 0.1-100 micrometers, and it is more preferable that it is 1-50 micrometers.

  Next, the voids of the fiber sheet are filled with the resin powder and the hydrogen storage alloy powder. However, in a method of simply spreading the resin powder and the hydrogen storage alloy powder, a sufficient amount of the hydrogen storage alloy powder is placed inside the fiber sheet. Since the air gap cannot be filled, it is preferable to forcibly fill the fiber sheet by supplying an air flow (preferably an air flow) containing the resin powder and the hydrogen storage alloy powder to the fiber sheet. For forced filling, a flow rate of 20 m / sec. It is preferable to supply the airflow as described above. If an air flow having a high flow rate is supplied to fill the resin powder and the hydrogen storage alloy powder, the resin powder and the hydrogen storage alloy powder permeate the gaps in the fiber sheet, and a sufficient amount of the hydrogen storage alloy powder is obtained. Since filling may not be possible, it is preferable to supply the airflow in a state where a shielding material that does not allow the resin powder and the hydrogen storage alloy powder to pass through is disposed on the surface opposite to the airflow supply surface of the fiber sheet. As this shielding material, a film, a metal plate, a glass plate, etc. can be used, for example.

  In addition, the mass ratio of the resin powder and the hydrogen storage alloy powder is 1:10 to 500 so as not to impair the binding action by the resin powder and also to prevent the hydrogen absorption and hydrogen release performance of the hydrogen storage alloy powder. Is more preferable, and 1:50 to 200 is more preferable.

  In addition, if the resin powder and the hydrogen storage alloy powder are not uniformly mixed, the binding action of the resin derived from the resin powder becomes non-uniform, and the hydrogen storage alloy powder easily falls off. Before supplying to the airflow, it is preferable to uniformly mix with various mixers such as a mixer.

  A first stage of supplying an air flow including the powder filling process to the fiber sheet in a state in which the hydrogen storage alloy powder is heated above the melting point of the fiber constituting the fiber sheet, and an air flow including the resin powder and the hydrogen storage alloy powder. When implemented in the second stage to be supplied to the sheet, in the first stage, the hydrogen storage alloy powder can be bonded in a state where a part of the hydrogen storage alloy powder is buried in the fiber sheet constituent fiber. In addition, the void can be widened by filling the portion corresponding to the buried portion, and the filling amount of the hydrogen storage alloy powder in the subsequent second stage can be increased. Further, in the first stage, a part of the hydrogen storage alloy powder can be bonded in a state where it is buried in the fiber sheet constituting fiber, and the hydrogen supplied in the subsequent second stage is improved by improving the denseness of the fiber sheet. Since the adhesiveness with the storage alloy powder becomes high, the performance of the hydrogen storage alloy powder can be exhibited more. For example, when a hydrogen storage alloy-containing sheet is used as the negative electrode of a cylindrical nickel-metal hydride battery, the capacity is large and the utilization rate of the hydrogen storage alloy is increased.

  The heating of the hydrogen storage alloy powder in the first stage can indirectly heat the hydrogen storage alloy powder by heating the gas constituting the airflow, but in this case, the fiber sheet constituent fibers are melted. Therefore, it is preferable to heat and supply the hydrogen storage alloy powder itself because the voids tend to decrease. The heating temperature is not particularly limited as long as it is higher than the melting point of the fiber sheet constituting fiber, but it is preferably heated to a temperature higher by 20 ° C. or higher than the melting point of the fiber sheet constituting fiber, and the temperature higher by 50 ° C. or higher. It is more preferable to heat up to.

  As another powder filling step, a first stage of supplying the hydrogen storage alloy powder to the fiber sheet by an air flow heated from the melting point of the fiber constituting the fiber sheet, and an air flow including the resin powder and the hydrogen storage alloy powder to the fiber sheet When implemented in the second stage of supply, in the first stage, since a part of the hydrogen storage alloy powder can be bonded in a state of being embedded in the fiber sheet constituent fiber, the hydrogen storage alloy powder is reliably attached to the fiber sheet constituent fiber. In addition, the voids that can be filled with the hydrogen-absorbing alloy powder can be widened, and the amount of filling of the hydrogen-absorbing alloy powder in the subsequent second stage can be increased. Further, in this first stage, since the fibers are melted by the heated airflow, the hydrogen storage alloy powder does not need to be heated to the melting point of the fiber sheet constituting fiber, and therefore the effect that the hydrogen storage alloy powder is not easily deteriorated by oxidation. Also play. Furthermore, in the first stage, a part of the hydrogen storage alloy powder can be bonded in a state where it is buried in the fiber sheet constituting fibers, and the denseness of the fiber sheet is improved, so that the hydrogen supplied in the subsequent second stage is increased. Since the adhesiveness with the storage alloy powder becomes high, the performance of the hydrogen storage alloy powder can be exhibited more. For example, when a hydrogen storage alloy-containing sheet is used as the negative electrode of a cylindrical nickel-metal hydride battery, the capacity is large and the utilization rate of the hydrogen storage alloy is increased.

  In this case, in order to prevent the fiber sheet from shrinking due to the airflow, the fiber sheet constituting fiber includes two or more kinds of resins having different melting points, and includes a composite fiber in which a resin having a low melting point occupies the fiber surface. It is preferable that it consists only of such a composite fiber. As described above, the two or more kinds of resins having different melting points are preferably made of a polyolefin resin or a polyamide resin, and the resin having a low melting point is preferably an ethylene resin. Moreover, it is preferable that arrangement | positioning of resin in a fiber cross section is a core-sheath type or a sea island type. The heating temperature of the airflow is not particularly limited as long as it is higher than the melting point of the fiber sheet constituting fiber, but it is preferably 20 ° C. or more higher than the melting point of the fiber sheet constituting fiber, and higher by 50 ° C. or more. It is preferable that the temperature is below.

  The “melting point of the fiber sheet constituting fiber” in the present invention means the melting point of the resin constituting the surface of the fiber sheet constituting fiber, and when there are two or more kinds of resins constituting the surface of the fiber sheet constituting fiber, Based on the melting point of a resin having a high melting point, the melting point refers to a melting temperature obtained from a differential thermal analysis curve (DTA curve) obtained by differential thermal analysis specified in JIS K 7121-1987.

  The method for supplying the airflow containing the resin powder and the hydrogen storage alloy powder to the fiber sheet in the second step following the first step is performed in the same manner as the above-described method in any case following the first step. be able to. That is, it is preferable that an air flow (preferably an air flow) containing the resin powder and the hydrogen storage alloy powder is supplied to the fiber sheet to which the hydrogen storage alloy powder is fused and bonded to forcibly fill. For forced filling, a flow rate of 20 m / sec. It is preferable to supply by the above. Moreover, it is preferable to supply an airflow in a state where a shielding material is disposed on the opposite surface of the fiber sheet to an air supply surface so that a sufficient amount of the hydrogen storage alloy powder can be filled. In addition, it is preferable that it is 1: 10-500, and, as for the mass ratio of resin powder and hydrogen storage alloy powder, it is more preferable that it is 1: 50-200.

  Subsequently, the bonding action of the filled resin powder is exerted to bond a part of the hydrogen storage alloy powder to the fiber sheet constituting fiber, and a part of the hydrogen storage alloy powder is combined with the adjacent hydrogen storage alloy powder. Form a matrix. The method for exerting the binding action of the resin powder is not particularly limited. For example, the fiber sheet filled with the resin powder and the hydrogen storage alloy powder is heated, and the resin powder is melted and cooled to be solidified. A coagulation method in which a resin sheet and a solvent capable of dissolving the resin powder are added to the fiber sheet filled with the hydrogen storage alloy powder, the resin powder is dissolved, and the resin is aggregated by removing the solvent. Can be mentioned. Among these, the fusion method is more preferable because the covering area of the hydrogen storage alloy powder with the resin is small and the function of the hydrogen storage alloy powder is easily exhibited. In the case of this suitable fusing method, it is preferable to heat the resin powder at a melting point or higher than the melting point to ensure fusing, and it is more preferable to heat at a temperature higher than the melting point by 5 ° C. or more. In addition, since it will become difficult to exhibit the function of a hydrogen storage alloy powder if it presses strongly at the time of a heating, it is preferable to heat-process in the state which is not strongly pressurized. For example, it is preferable to heat with an oven, hot air, infrared rays, a heating roll, and the like. In particular, when heat treatment is performed using a heating roll under a weak pressure of about 1 to 500 N / cm, the resin powder forms a resin film. However, it is preferable because the hydrogen storage alloy powder can be firmly bonded (fused) to the fiber sheet constituting fiber and the adjacent hydrogen storage alloy powder.

  In addition, the amount of the fixed hydrogen storage alloy powder is large, and the resin constituting the surface of the fiber sheet constituting fiber and the melting point of the resin having the highest melting point among the resin powders or higher temperature ( It is preferable that the hydrogen storage alloy powder is bonded by heating at a temperature higher than the melting point by 5 ° C. or more so as to exhibit the fusing force of the resin constituting the fiber sheet constituting fiber in addition to the fusing force of the resin powder. . Also in this case, it is preferable to heat-treat in a state where it is not strongly pressurized. In particular, the heat treatment is performed under a weak pressure of about 1 to 500 N / cm using a heating roll, and the resin powder and the fiber constituting the fiber sheet are formed into a resin film. It is preferable that the hydrogen storage alloy powder is firmly bonded (fused) to the fiber sheet constituting fiber and the adjacent hydrogen storage alloy powder without forming the film.

  In the case where the powder filling step includes the first stage, and the hydrogen storage alloy powder is already fused and bonded to the fiber sheet constituting fiber, the resin constituting the surface of the fiber sheet constituting fiber and Both resin powders may be melted and fused, or only the resin powder may be fused. In any of these cases, it is preferable to heat-treat in a state where the pressure is not strongly applied, and in particular, heat treatment is performed using a heating roll under a weak pressure of about 1 to 500 N / cm, so that the resin powder and the fiber sheet constituting fiber However, it is preferable to firmly bond (fuse) the hydrogen storage alloy powder to the fiber sheet constituting fiber and the adjacent hydrogen storage alloy powder without forming a resin film.

  Then, by performing electroless plating in a plating bath in which fine particles other than metal (particularly hydrophobic fine particles) are dispersed in the matrix, a metal film coating step for covering the matrix surface with a porous metal film is performed, A hydrogen storage alloy-containing sheet can be produced. In this way, the presence of fine particles other than metal makes it difficult for the plating solution to exist, and it is difficult to form a metal film locally, that is, many voids are formed, resulting in the formation of a porous metal film. Easy to be done. Therefore, the fine particles other than the metal are preferably made of hydrophobic fine particles in which the plating solution is difficult to exist.

  The fine particles other than the metal are not particularly limited, but polytetrafluoroethylene (PTFE), polyethylene (PE), polypropylene (PP), ABS resin, polyamide (PA), polysulfone (PSU), AS resin, polystyrene (PS), vinylidene chloride resin (PVDC), vinylidene fluoride resin, PFA resin, polyphenylene ether (PFE), methylpentene resin, methacrylic acid resin, carbon (C), catalyst-supporting fine particles, or thermosetting resin In particular, since the polytetrafluoroethylene fine particles have strong hydrophobicity and can easily form a porous metal film, they can be used particularly preferably. The average particle diameter of the fine particles other than metal is preferably 0.01 μm to 500 μm, more preferably 0.05 μm to 500 μm, and still more preferably 0.1 μm to 50 μm.

  Electroless plating is a conventionally well-known method, and is generally a method of reducing nickel with a reducing agent in a plating bath containing nickel salts such as nickel nitrate, nickel chloride, nickel sulfate and the like. A complexing agent, a pH adjusting agent, a buffering agent, a stabilizer and the like are added to the plating bath as necessary. In the present invention, the metal film formed by plating becomes porous by adding and dispersing fine particles (particularly hydrophobic fine particles) other than the metal as described above in the plating bath. The electroless plating can be performed on the matrix by, for example, immersing the matrix in a plating bath. Although the matrix of the present invention is porous even though the fiber sheet is filled with hydrogen storage alloy powder, the plating solution penetrates quickly and the matrix surface, that is, the fiber sheet constituting fiber surface, the hydrogen storage alloy. A porous metal film is formed on the powder surface and the resin surface. If necessary, after the metal film is formed by electroless plating, an electrolytic plating treatment can be performed.

  The nickel-metal hydride battery of the present invention is provided with the hydrogen storage alloy-containing sheet as described above as a negative electrode. Although the hydrogen storage alloy-containing sheet of the present invention has a large amount of hydrogen storage alloy powder, the hydrogen storage alloy powder is Since it is difficult to drop off and is excellent in deformability, even in the case of a cylindrical nickel-metal hydride battery, the separator is not damaged by the negative electrode, and a short circuit is unlikely to occur. In addition, since it can be a hydrogen storage alloy-containing sheet with a high hydrogen storage alloy powder content, it can quickly react with oxygen generated at the positive electrode during overcharge to form water, thus stabilizing the increase in battery internal pressure. It can be suppressed.

  The nickel-metal hydride battery of the present invention can have the same configuration except that the hydrogen storage alloy-containing sheet as described above is provided as the negative electrode. For example, as a positive electrode, a nickel hydroxide powder can be made into a paste together with a binder and a conductive auxiliary agent, filled into a foamed nickel base material or a nickel fiber base material, and pressure-molded and used as an alkaline electrolyte. As a separator, a two-component system of potassium hydroxide / lithium hydroxide or a three-component system of potassium hydroxide / sodium hydroxide / lithium hydroxide can be used as a separator. A polyolefin-based nonwoven fabric hydrophilized by treatment, graft polymerization treatment of vinyl monomer, surfactant treatment, discharge treatment, hydrophilic resin application treatment, or the like can be used.

  Examples of the present invention will be described below, but the present invention is not limited to the following examples.

Example 1
A slurry in which a composite fiber (fineness: 0.8 dtex, fiber length: 5 mm) in which a core component is made of polypropylene and a sheath component is made of high-density polyethylene (melting point: 125 ° C.) is provided with a short net and a circular net. Wet fiber web (random orientation, basis weight: 30 g / m ² ) fed to a paper machine and made by a short mesh and wet fiber web (unidirectional orientation, basis weight: 20 g / m) made by a circular mesh m ² ) in a wet state to form a laminated wet fiber web, and then heat-treated the laminated wet fiber web with a hot air dryer set at a temperature of 135 ° C. and fused with the sheath component of the composite fiber. (A basis weight: 50 g / m < ² >, thickness: 0.2 mm) was formed.

On the other hand, as the hydrogen-absorbing alloy _{powder, MmNi 4.27 Al 0 · 30 Mn} 0.24 Co 0.45 ( average particle diameter: Mean 30 [mu] m), as a resin powder, high density polyethylene (Sumitomo Seika Chemicals Co., Ltd., registered trademark : Flow beads HE-3040, average particle size: 12 μm, melting point: 135 ° C.) were prepared.

Next, after placing the wet nonwoven fabric on a polyester film, the high density polyethylene powder and the hydrogen storage alloy powder are put into a super mixer at a mass ratio of 1:94, and a mixed powder obtained by mixing these powders. Is 40 m / sec. By an air flow at room temperature (temperature: about 20 ° C.). Were sprayed alternately on both sides of the wet nonwoven fabric at a flow rate of 5 to fill the voids of the wet nonwoven fabric with the mixed powder. Thereafter, heat treatment is performed with a continuous bonding machine set at a temperature of 140 ° C. (pressurization with a pair of rubber rolls at 9.8 N / cm), and a part of the hydrogen storage alloy powder is bonded by the fusion action of the composite fibers, Part of the hydrogen storage alloy powder is bonded by the fusion action of the adjacent hydrogen storage alloy powder and the high-density polyethylene resin powder to form a matrix (weight: 576 g / m ² , hydrogen storage alloy powder amount: 520 g / m ² ). Formed.

Next, the matrix is subjected to electroless plating by the following method, the matrix surface is covered with a porous nickel film, and the hydrogen storage alloy-containing sheet of the present invention (weight per unit: 706 g / m ² , film thickness: 1 μm) is applied. Manufactured.

  The matrix was immersed in the next plating bath, subjected to electroless plating treatment under the following conditions, then thoroughly washed with water, and dried under vacuum under reduced pressure for 5 hours to produce the hydrogen storage alloy-containing sheet of the present invention.

<Plating bath>
Nickel sulfate 15 g / liter Sodium hypophosphite 14 g / liter Sodium hydroxide 8 g / liter Glycine 20 g / liter PTFE (average particle size: 0.3 μm) 15 g / liter Surfactant 0.5 g / liter

<Conditions>
pH 9.5
Bath temperature 40 ℃
Stirring time 40 minutes

(Example 2)
Similar wet-laid nonwoven fabric as in Example 1 (basis weight: 50g / ^{m 2,} thickness: 0.2 mm), as a hydrogen absorbing alloy _{powder, MmNi 4.27 Al 0 · 30 Mn} 0.24 Co 0.45 ( average particle size : Average 30 μm) and high density polyethylene (manufactured by Sumitomo Seika Co., Ltd., registered trademark: Flow Beads HE-3040, average particle size: 12 μm, melting point: 135 ° C.) were prepared as resin powders.

Next, after placing the wet nonwoven fabric on a polyester film, the high-density polyethylene powder and the hydrogen storage alloy powder are put into a super mixer at a mass ratio of 1:94. The mixed powder mixture was heated to 60 ° C. and then 40 m / sec. By an air flow heated to 160 ° C. Were alternately sprayed onto both surfaces of the wet nonwoven fabric, and 150 g / m ² of hydrogen storage alloy powder was fused to the surface of the wet nonwoven fabric.

  Next, as the second stage, the same mixed powder as described above was applied at 40 m / sec. By an air flow at normal temperature (temperature: about 20 ° C.). The hydrogen storage alloy powder fused with the hydrogen storage alloy powder was alternately sprayed on both surfaces at a flow rate of, and the mixed powder was filled into the voids of the wet nonwoven fabric fused with the hydrogen storage alloy powder.

Then, heat treatment was performed with a continuous bonding machine set at a temperature of 140 ° C. (pressurized with a pair of rubber rolls at 9.8 N / cm), and the adjacent hydrogen storage alloy powder mainly due to the fusion action of high-density polyethylene resin powder. They were bonded together to form a matrix (weight per unit: 576 g / m ² , hydrogen storage alloy powder amount: 520 g / m ² ). In this matrix, some hydrogen storage alloy powders are bonded by the fusion action of composite fibers, and some hydrogen storage alloy powders are bonded by the fusion action of adjacent hydrogen storage alloy powder and high-density polyethylene resin powder. I was in a state.

Then, electroless plating is performed in the same procedure as in Example 1, the matrix surface is covered with a porous nickel film, and the hydrogen storage alloy-containing sheet of the present invention (weight per unit: 706 g / m ² , film thickness: 1 μm) Manufactured.

(Comparative Example 1)
The core component comprises polypropylene, sheath component is high-density polyethylene (melting point: 125 ° C.) composite fibers comprising (fineness: 0.5 dtex, fiber length: 5 mm) and the hydrogen storage alloy powder _(MmNi 4.27 _{Al 0 · 30} (Mn _0.24 Co _0.45 , average particle size: about 30 μm) was mixed and dispersed at a mass ratio of 56: 520 to a paper machine equipped with a short mesh, and the paper was made by the short mesh The wet fiber web (randomly oriented) was heat treated with a continuous bonding machine (pressed at 9.8 N / cm with a pair of rubber rolls) at a temperature of 140 ° C. In addition, a matrix (weight: 576 g / m ² , thickness: 0.5 mm, hydrogen storage alloy powder amount: 520 g / m ² ) was formed by fusing the composite fiber and the hydrogen storage alloy powder.

Next, the matrix was subjected to electroless plating in the same manner as in Example 1, the matrix surface was covered with a porous nickel film, and a hydrogen storage alloy-containing sheet (weight per unit: 706 g / m ² , film thickness: 1 μm) ) Was manufactured.

(Comparative Example 2)
A paste containing a hydrogen storage alloy powder, carboxymethylcellulose as a thickener, and polytetrafluoroethylene as an adhesive is filled in a foamed nickel sheet (weight: 450 g / m ² , thickness: 0.5 mm) and dried. Then, it was rolled at room temperature to produce a hydrogen storage alloy-containing sheet (weight per unit: 576 g / m ² , thickness: 0.5 mm, hydrogen storage alloy powder amount: 520 g / m ² ).

(Evaluation)
1. Deformability;
Each hydrogen storage alloy-containing sheet was cut into a 5 cm × 30 cm rectangular shape to prepare a tape-shaped test piece. Subsequently, each tape-shaped test piece was wound up in a longitudinal direction in the longitudinal direction, and then spread back into a tape shape. At this time, the case where the amount of falling off of the hydrogen storage alloy powder was hardly recognized was evaluated as 、, the case where the falling off was clearly recognized was evaluated as も の, and the case where the falling amount was large and was observed as a lump was evaluated as ×. The results are shown in Table 1.

2. Evaluation of battery performance;
First, a paste type nickel positive electrode (41 mm × 70 mm length) using a foamed nickel base material and each of the hydrogen storage alloy-containing sheets (40 mm × 100 mm length) described above were prepared as the negative electrode. Further, a separator obtained by sulfonating a wet non-woven fabric made of polyolefin fibers (weight per unit: 55 g / m ² , thickness: 0.15 mm), 5N-potassium hydroxide and 1N-lithium hydroxide, and an outer can as an electrolyte solution Prepared.

  Next, each separator was sandwiched between a positive electrode and a negative electrode and wound in a spiral shape to produce an electrode group, and this electrode group was housed in an outer can. Next, the electrolytic solution was poured into an outer can and sealed to produce a cylindrical nickel-hydrogen battery (AA 800 mAh).

  After the activation of the cylindrical nickel-hydrogen battery, the battery was charged at 120% at a charging rate of 0.1 C, paused for 15 minutes, and discharged at a discharging rate of 0.2 C until a final voltage of 0.8 V was reached. The charge / discharge cycle was repeated, and the number of charge / discharge cycles required until the discharge capacity was less than 80% of the initial capacity was measured. For the measurement of the number of charge / discharge cycles, 10 batteries were prepared using each hydrogen storage alloy-containing sheet, and the arithmetic average value was calculated. The results are shown in Table 1. The capacity is the capacity when 120% charged at a charging rate of 0.1 C after activation, rested for 15 minutes, and discharged at a discharging rate of 0.2 C until the final voltage is 1 V. The active material utilization rate is It is a percentage with respect to the theoretical capacity obtained from the mass of the active material (hydrogen storage alloy powder) having the capacity.

  As can be seen from Table 1, the hydrogen storage alloy-containing sheets of Examples 1 and 2 were excellent in deformability in which the active material (hydrogen storage alloy powder) was prevented from falling off. In addition, a battery having a large number of cycles and having a long life is manufactured because a fine short circuit due to the active material (hydrogen storage alloy powder) particles entering the separator is suppressed without breaking through the separator when the battery group is configured. I was able to. Furthermore, since the filling amount of the hydrogen storage alloy powder was large and the adhesiveness between the active materials (hydrogen storage alloy powder) was high, the capacity and the active material utilization rate were high. In addition, the hydrogen storage alloy-containing sheet of Example 2 is less affected by heat during production, is not oxidized, and has high adhesion between active materials (hydrogen storage alloy powders). A battery with even better utilization could be produced.

  On the other hand, when the hydrogen storage alloy-containing sheet of Comparative Example 1 was deformed, the active material (hydrogen storage alloy powder) was likely to fall off. Moreover, since the adhesiveness between the active materials (hydrogen storage alloy powder) is low, the capacity and the active material utilization rate are low. Furthermore, a fine short-circuit due to the active material (hydrogen storage alloy powder) particles entering the separator tends to occur, and only a battery with a short cycle number and a short life could be produced.

  Further, when the hydrogen storage alloy-containing sheet of Comparative Example 2 was deformed, the active material (hydrogen storage alloy powder) was observed to fall off. Moreover, it was a thing with a low capacity | capacitance by the low adhesiveness of active materials (hydrogen storage alloy powder).

Claims (10)

The fiber sheet constituting the fiber sheet inside the matrix , the hydrogen storage alloy powder surface, and the resin surface are coated with a porous metal film. The matrix is filled with hydrogen storage alloy powder in the voids of the fiber sheet. A part of the hydrogen storage alloy powder is bonded to the fiber sheet constituting fiber by a resin, and a part of the hydrogen storage alloy powder is bonded to an adjacent hydrogen storage alloy powder by the resin. Hydrogen storage alloy-containing sheet.   The hydrogen-absorbing alloy-containing sheet according to claim 1, wherein the hydrogen-absorbing alloy-containing sheet is bonded to a part of the hydrogen-absorbing alloy powder by fusing resin constituting the fiber sheet constituting fiber.   The hydrogen storage alloy-containing sheet according to claim 1 or 2, wherein the fiber sheet is made of a polyolefin-based nonwoven fabric. A powder filling step of filling the voids of the fiber sheet with resin powder and hydrogen storage alloy powder;
The bonding effect of the filled resin powder is exerted so that a part of the hydrogen storage alloy powder is bonded to the fiber sheet constituting fiber, and a part of the hydrogen storage alloy powder is bonded to the adjacent hydrogen storage alloy powder to form a matrix. Matrix forming step to form,
A metal film coating step in which the matrix surface is coated with a porous metal film by performing electroless plating in a plating bath in which fine particles other than metal are dispersed;
The manufacturing method of the hydrogen storage alloy containing sheet | seat containing these.   The method for producing a hydrogen-absorbing alloy-containing sheet according to claim 4, wherein the powder filling step is performed by supplying an air stream containing resin powder and hydrogen-absorbing alloy powder to the fiber sheet.   The powder filling step includes a first step of supplying an air flow including the hydrogen storage alloy powder in a state heated to a melting point of the fiber constituting the fiber sheet to the fiber sheet, and an air flow including the resin powder and the hydrogen storage alloy powder. The method for producing a hydrogen-absorbing alloy-containing sheet according to claim 4, further comprising a second stage of supplying to the sheet.   The powder filling step supplies the fiber sheet with an air flow including a first stage of supplying the hydrogen storage alloy powder to the fiber sheet by an air flow heated from the melting point of the fiber constituting the fiber sheet, and the resin powder and the hydrogen storage alloy powder. The method for producing a hydrogen storage alloy-containing sheet according to claim 4, further comprising a second stage.   The hydrogen storage alloy according to any one of claims 4 to 7, wherein in the matrix formation step, the resin powder and the resin constituting the surface of the fiber sheet constituting fiber are fused to bond the hydrogen storage alloy powder. Production method of containing sheet.   The method for producing a hydrogen storage alloy-containing sheet according to any one of claims 4 to 8, wherein in the metal film coating step, polytetrafluoroethylene fine particles are used as fine particles other than metal.   A nickel-metal hydride battery comprising the hydrogen storage alloy-containing sheet according to claim 1 as a negative electrode.