JPH06275281A - Manufacture of plated nonwoven fabric electrode substrate - Google Patents

Abstract

PURPOSE:To manufacture a nickel-plated nonwoven fabric electrode substrate excellent in the tensile strength characteristic and having large porosity without using an adhesive constituted of binder fibers and an organic solvent. CONSTITUTION:Nickel plating is applied to a web mainly made of organic fibers to manufacture a nickel-plated nonwoven fabric electrode substrate. Nickel electric plating is applied after a steam entangling treatment is applied to the web made of conductive organic fibers. The nickel-plated nonwoven fabric electrode substrate excellent in the tensile strength characteristic, suppressing the falling or fuzzing of fibers, and having large porosity can be manufactured.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a nickel-plated porous non-woven electrode substrate used as an electrode substrate for a nickel-cadmium alkaline battery.

[0002]

2. Description of the Related Art Conventionally, electrodes used in nickel-cadmium alkaline batteries are those obtained by electrolytic reduction of a substrate obtained by sintering nickel powder and impregnated with cadmium nitrate, or a substrate made of non-woven nickel fiber. Although the one coated with cadmium oxide paste is used, the void utilization rate is only about 80%, it is impossible to increase the capacity of the battery, and the one with a large void ratio is required. There is.

When a non-woven fabric of nickel fibers is used, the tensile strength is weak, fluffing of the fibers or dropping of the fibers occurs, and there is a possibility of short circuit between electrodes when the battery is constructed. As an improvement to this, a non-woven fabric formed by applying an epoxy resin as an interfiber binder to a fiber assembly composed of organic fibers and adhesively coating the portions where the web constituent fibers intersect and contact each other and the interfiber surface. A substrate obtained by electroless nickel plating is disclosed in JP-A-3-17957. This plated non-woven substrate is excellent in the strength of the electrodes and is porous and has achieved a high capacity. Although this method improves the tensile strength of the electrodes, it does not improve the organic properties such as the application and curing of epoxy resin. Since treatment with a solvent-based compound is required, if the strength is to be increased, the treatment amount must be increased inevitably, resulting in filling the original voids of the non-woven fabric before treatment, and there is a limit to increasing the capacity. In addition, there was a problem in terms of environmental pollution due to the release of the organic solvent.

Further, recently, a foam metal plate of nickel has come to be used as an electrode substrate and contributes to a high capacity of the battery. However, since the opening diameter is large, there is a limit to the further capacity increase. . Further, since the elongation rate is small and the flexibility is poor, there is a problem such as cracking and breakage of the substrate when rolled up into a cylindrical shape during manufacturing. Furthermore, since the elasticity of the substrate is poor, as the temperature rises and falls due to charge and discharge,
There has been a problem that the electrode active material and the substrate are separated from each other and the life of the battery is limited.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides a method for producing an electrode substrate having a relatively large porosity, which is obtained by subjecting a fiber assembly composed of organic fibers to metal plating to obtain a tensile strength without using an organic solvent. An object of the present invention is to provide a manufacturing method for manufacturing a metal-plated non-woven fabric electrode substrate that is strong, has flexibility, eliminates fiber fluffing, and is capable of achieving high capacity, and is capable of eliminating falling off.

[0006]

Means for Solving the Problems The present inventors have diligently studied the above problems. As a result, a web made of electrically conductive fibers is subjected to a three-dimensional entanglement treatment (by a high-pressure columnar water flow), and then electroplated to provide a strong tensile strength and a fiber fluff without using an organic solvent, It has been found that a metal-plated non-woven electrode substrate having a large porosity that does not fall off can be manufactured.

That is, according to the present invention, after hydroentangling treatment is applied to a web containing an electrically conductive organic fiber as a main component,
A method for manufacturing a metal-plated non-woven fabric electrode substrate for electroplating.

A detailed description of the present invention will be given below with reference to nickel plating. In the present invention, first, a base material web containing an organic fiber having electroconductivity as a main component is produced, and then the base material web is three-dimensionally entangled, and then electroplated to obtain a nickel-plated non-woven fabric electrode substrate. And

The fibers used in the non-woven fabric substrate are polyvinyl chloride, polyacrylonitrile, polyamide, polyester, polyvinyl alcohol fibers, organic fibers such as regenerated cellulose fibers, or inorganic fibers such as glass fibers. Although there are fibers such as fibers, in the present invention, since they are used as electrode substrates for nickel cadmium alkaline batteries and the like, those having strong alkali resistance and being inactive are desirable, and particularly polyolefin fibers such as polypropylene fibers and polyethylene fibers Are preferably fibers having a core-sheath structure. Further, a polyester-based core-sheath structure fiber having a sheath portion made of a polyolefin polymer can also be used. The above fibers may be mixed and used as needed.
In particular, in the case of the three-dimensional entangled non-woven fabric substrate of the present invention, binder fibers that can be dissolved and removed in the entanglement treatment stage, for example, polyvinyl alcohol-based fibers that dissolve and flow out in a water stream are mixed to strengthen the substrate. Preferably.

The cross-sectional shape of the fiber is not particularly limited and may be not only circular but also oval, triangular, star-shaped, T-shaped, Y-shaped, leaf-shaped, and so-called atypical cross-sectional shape. Rather, the use of fibers having a cross-sectional shape other than circular is preferable because the porosity and specific surface area of the non-woven fabric are improved. Further, a material having a void on the surface or a material having a branched structure may be used.

In the present invention, the above-mentioned various fibers are used by imparting conductivity. As a method of giving conductivity to the organic fiber, for example, a method of attaching a conductive polymer such as polypyrrole or polypyridine to the organic fiber, a method of attaching conductive carbon together with a binder polymer, a method of plating a metal by an electroless plating method Alternatively, there is a method of using carbon fiber which has conductivity itself. In the present invention, since the three-dimensional entanglement treatment is performed by the high-pressure water flow after the base material web is manufactured, the conductive fiber is preferably flexible so that the conductivity is not deteriorated even when the fiber is subjected to the high-pressure water flow. A fiber obtained by plating a metal on an organic short fiber by an electroless plating method is preferable. It is preferable that the conductivity of the fiber is high, but the value when the fiber is made into a sheet is 0.01 S / cm.
It is possible to carry out electroplating with the above conductivity.

Next, a method for electroless nickel plating of organic short fibers used in the present invention will be described. Generally, a method of forming a metal film on the surface of a support is roughly classified into a method by vapor deposition, a method by electroplating, a method by electroless plating and the like. In particular, electroless plating is performed on a non-conductive substrate. A thin conductive metal film can be formed on the surface of the fine organic short fibers of the present invention in that it has good adhesiveness and can be formed uniformly in blind holes with a high aspect ratio. It is a preferred method for forming a metal layer on the substrate.

The electroless nickel plating process is basically a two-step process of applying a catalyst and an electroless plating process.
Normally, a conditioning process for cleaning and degreasing the surface of the support with sodium hydroxide, etc., a micro-etching process with sulfuric acid, chromic acid, etc. for roughening to obtain an anchor effect for the plating layer, and prevention of deterioration of the catalyst solution A pre-dip step for activation, an activation step with an acid such as sulfuric acid and sodium hydroxide for activating the catalyst, and an alkali are added before and after that. If necessary, steps such as washing with water, draining, and drying are added between the steps to stabilize the treatment liquid and improve the adhesion and uniformity of the plating film.

As a method of producing electroconductive organic short fibers on the above organic short fibers by electroless plating, the above steps are continuously passed without cutting after fiber spinning, and plating is performed to form paper after plating. A method of producing by cutting into suitable short fibers, or after producing short fibers in advance, dipping the fibers in the treatment liquid of the above step, filtering the fibers after treatment, and immersing in the next treatment liquid It can be manufactured by repeating the process.

Palladium is generally used as the above catalyst, and the catalyst is applied to the fiber surface by the following various methods. As a method of applying a catalyst, for example, after immersing in an aqueous solution of palladium chloride, then immersing in an aqueous solution of a reducing agent to precipitate the metal nuclei (JP-A-49-126999), palladium chloride and an activator are used. After adding a reducing agent to the aqueous solution containing it to form a colloidal dispersion of palladium metal, it is immersed in this aqueous solution to deposit palladium nuclei into catalyst nuclei (Chemicals and Industry, p430, vol.42). , 1989)
However, in the present invention, the sensitizing-activator method (“the latest surface treatment) in which the palladium metal nuclei are precipitated by preliminarily immersing in an aqueous solution of tin (II) chloride and then immersing in an aqueous solution of palladium (II) chloride "Technical overview" Industrial Technology Service Center p225, December 12, 1987), immersed in an aqueous solution of palladium (II) chloride colloidally dispersed in excess tin (II) chloride solution, and then an aqueous solution of sulfuric acid, sodium hydroxide, etc. Particularly preferred is the catalyst-accelerator method in which the palladium metal nuclei are precipitated by immersing in palladium ("Latest Surface Treatment Technology Guide", Industrial Technology Service Center, p225, December 12, 1987). It is sufficient that the amount of the catalyst metal attached is 0.1 g / m ² or less in terms of the weight of the catalyst metal. In recent years, there is also a plating grade fiber in which a metal or a functional group having a further catalytic action is previously added to the constituent polymer of the fiber and this is spun, but in this case, direct electroless plating is performed without further catalytic treatment. Is also possible.

Next, the electroless plating solution will be described. Generally, an electroless plating solution is prepared by using a metal ion source and a reducing agent as main components and a complexing agent, a pH adjusting agent, a buffering agent, an accelerator, a stabilizer, an improving agent, etc. as auxiliary components. . Usually, these chemicals are mixed to form a plating solution.
When the organic short fibers are plated in the present invention, the organic short fibers are previously dispersed in an aqueous solution of a complexing agent or the like, and an aqueous solution of a metal ion source and an aqueous solution of a reducing agent, a pH adjusting agent or the like are separately dropped into this dispersion. Then, the so-called dropping method of plating is preferred. By the dropping method, a thin uniform plating film can be obtained on the fiber surface with good adhesiveness.

In the present invention, when the electroless plating is used to provide conductivity, the base material web is subjected to a three-dimensional entanglement treatment, so that the thickness of the plating layer should be kept within a range that does not impair the flexibility of the fiber. And its thickness is 0.01-0.
1 μm is sufficient.

In the electroless nickel plating solution of the present invention, nickel sulfate, nickel chloride, nickel nitrate, nickel sulfamate or the like is used as the metal ion source.

As the reducing agent, sodium hypophosphite, sodium borohydride, potassium borohydride, Rochelle salt, dimethylamine borane, diethylamine borane,
Formalin and hydrazine derivatives such as hydrated hydrazine, hydrazine sulfate and hydrazinium chloride can be used.

Examples of complexing agents include sodium citrate, potassium citrate, organic acid salts such as Rochelle salt, thioglycolic acid, ammonia, triethanolamine, glycine,
Examples include ethylenediamine, ethylenediamine diacetate, o-aminophenol, and pyridine.

In the present invention, the amount of metal ions in the plating solution is 0.001 to 0.2 mol / l, and the amount of complexing agent is 0.001.
˜4.0 mol / l, and the reducing agent preferably ranges from 0.001 to 0.4 mol / l.

As the pH adjusting agent, sodium hydroxide, ammonium hydroxide, inorganic acid, organic acid and the like are preferable. As a buffering agent, an organic acid, an inorganic acid alkali metal salt,
Sodium citrate, sodium acetate, ammonium chloride, ammonium sulfate, oxycarboxylic acid, dihydrogen phosphate, boric acid and carbonic acid are used to alleviate abrupt changes in pH during plating. The promoter is added to suppress the generation of hydrogen, and sulfides, fluorides, etc. are used. Lead chlorides, sulfides, and nitrates are added as stabilizers, and a trace amount of surfactants and the like are added as improvers.

The organic short fibers to which the conductivity has been imparted as described above are formed into a nonwoven web. Generally, the manufacturing method of a nonwoven fabric differs depending on the length of the fibers used. For example, when the fiber length is on the order of millimeters, the constituent fibers are called pulp. As in the case of producing paper from wood pulp, natural or synthetic fibers may be added, if necessary, to wood pulp or binder resin. It is manufactured by a wet method of mixing with and suspending in water to form a sheet by a papermaking method. When the fiber length is on the order of centimeters, the constituent fibers are called staples. Resin bond by resin bonding, needle punch using entanglement by needles, stitch bond woven by threads, or thermal bond bonded by heat. It is manufactured by a so-called dry method called a so-called “jet bond” in which high-pressure water is jetted from a nozzle to be entangled. Further, when the fiber length is long, the constituent fibers are called filaments and are produced by spunbonding into a sheet while directly spinning. It is also manufactured by melt-blowing in which a fine fiber is formed into a sheet while directly spinning, using the atomization principle. Depending on the production method, the thickness range, void ratio, void shape, pore size, homogeneity, flexibility, elasticity, fluffing, fiber dropout, and other properties of the resulting nonwoven fabric differ.

In the present invention, the fibers are not bound to each other because they are used as the base material for the three-dimensional entanglement treatment, or even if they are bound at the stage of the base material, the binder is not added at the stage of the three-dimensional entanglement treatment. A method for producing a non-woven fabric substrate to be dissolved and removed is preferable, and a wet method is preferable as the producing method. The wet method has high productivity and can produce a homogeneous web.

If necessary, the above-mentioned forming methods may be combined and the obtained webs may be laminated and entangled. Further, webs obtained by methods other than the above can be laminated as long as the performance of the nonwoven fabric of the present invention is not impaired.

When producing a web by the wet papermaking method,
The fiber length of the fibers that can be used is 1 to 50 mm. Fibers having a fiber length of more than 50 mm are not preferable because the fibers are entangled during the dispersion of the fibers. Furthermore, if the fibers are too short, they fall off during entanglement, and the entanglement becomes insufficient and the strength decreases, so in the present invention, considering the strength after entanglement, uniformity, etc., a range of 5 to 30 mm is preferable. .

The fiber diameter of the fibers used in the nonwoven fabric is not particularly limited, but in the present invention, if the fiber diameter is too thin, the nonwoven fabric becomes too dense, resulting in a decrease in void ratio, and when the electrode substrate is manufactured into an electrode. This is not preferable because the amount of active material retained decreases. Conversely, if it becomes too thick, the rigidity of the fiber will increase,
The confounding process becomes insufficient. Further, although the porosity increases, the specific surface area decreases, and the capacity of the electrode when used as a battery decreases, which is not preferable. In the present invention, the fiber diameter is preferably in the range of 5 to 20 μ.

Next, the three-dimensional confounding process will be described. Three
Dimensional entanglement treatment is a single layer of the above web, or a plurality of laminated, placed on a support, mechanical treatment to the web,
This is a method of three-dimensionally entangled fibers. Specific examples thereof include a needle punching method and a hydroentangling method. However, the hydroentangling method is preferable in the present invention because even the thin fibers can be uniformly entangled and the production rate is high. The hydroentanglement method is a method of injecting a waterflow from above the web to three-dimensionally entangle the fibers forming the web to develop strength.

That is, in the case where the entanglement treatment is not performed, the fibers are arranged in layers in the cross section of the non-woven fabric, and unless a binder is added, the fibers become separated after drying and the tensile strength cannot be obtained. The binder is usually not conductive, and even after electroplating the non-woven fabric, this portion remains unplatable. Further, even if a conductive binder is added to fix the fibers to each other, the voids have a shape that linearly intersects at an acute angle, and the void ratio cannot be increased. The electrode active material is not filled up to the corners of the voids, leaving voids, and the filling rate cannot be increased. On the other hand, when the entanglement treatment is performed as in the present invention, the upper and lower fibers are entangled with each other, and the strength is exhibited even if the binder is not added. Moreover, as a result of the fibers being bent and entangled in the upper and lower parts, the voids also expand in the upper and lower parts, resulting in a flexible nonwoven fabric rich in fluffy voids. Furthermore, the shape of the voids is remarkably rounded as compared with that before the entanglement. As a result, when the electrode substrate is used after plating, the filling rate of the electrode active material is improved and the battery capacity can be improved.

The conditions for strongly and properly performing the entanglement by the hydroentanglement method will be described below. The diameter of the nozzle for jetting the water flow is preferably in the range of 10 to 500 μm. The distance between the nozzles is preferably 10 to 1500 μm. Further, the shape of the nozzle is preferably circular, and a so-called columnar water jet is preferable. The support on which the web is loaded is preferably a porous support of about 50 to 200 mesh.

These nozzles need a range that covers the width of the sheet to be processed in the direction orthogonal to the papermaking direction. Considering the papermaking direction, the type of web, the basis weight, the processing speed, and the water pressure, The number of nozzle heads can be changed and used within a range where sufficient entanglement can be obtained.

The water pressure is preferably used in the range of 10 to 250 kg / cm ² . More preferably 50-250 kg /
It is cm ² . The processing speed is preferably used in the range of 5 to 200 m / s.

The water pressure is preferably increased from the beginning of the process to the end thereof so that the surface quality is improved. In addition, it is also possible to successively reduce the nozzle diameter or the nozzle spacing, or both the nozzle diameter and the nozzle spacing, which is also preferable in that the surface quality of the nonwoven fabric is improved. Further, the surface quality can be further improved by rotating the header of the nozzle or by vibrating the wire to the left and right. Also, insert a wire between the nozzle and the web to spray the water flow,
The surface quality can also be improved by using a fan-shaped water stream.

The entanglement processing can be performed on only one side or on both sides. It is also possible to stack the webs after the entanglement and then entangle the webs.

In the present invention, the conductive non-woven fabric substrate that has been three-dimensionally entangled as described above is further electroplated with nickel to form an electrode substrate. The electroplating has a simpler composition of the plating solution than the electroless plating, is stable, is easy to manage the solution, and the growth of the plating layer is fast, and the amount of the plating can be controlled by the applied current.
The nickel plated layer formed by electroplating has high purity and excellent conductivity.

As the electric nickel plating solution, there are plating solutions generally known as Watts bath, chloride bath and sulfamic acid bath, and the constituents thereof are the nickel salts used in the above electroless nickel plating solution as the metal ion source. Used in addition to pH adjusting agents such as boric acid, saccharin, 1,
A small amount of brightening agents such as 5-naphthalenesulfonic acid, formalin, and 1,4-butynediol, and surfactants are added.
In electroplating, the conductive non-woven fabric is immersed in the plating solution at 20 to 80 ° C., the non-woven fabric is connected to the negative electrode, and the nickel counter electrode plate is connected to the positive electrode.
It is flow-plated in the range of 5 A / dm ² .

The heat-fusible conductive sheet of the present invention has voids, and the void diameter is determined by the bubble point method and the mean flow point method described in ASTM F-316.
It can be measured as an average void diameter. Further, these porosities can be evaluated by calculation from the magnitude of the pressure loss when air flows through the sheet.

[0038]

EXAMPLES The present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

Example 1 1 part of 97 parts of nickel-plated vinylon fiber (manufactured by Nichibi Co., Ltd.) having a fiber density of 2 d (fiber diameter of 15 μm) and a fiber length of 20 mm
% Nonionic dispersant solution. Then, 3 parts of hot water-soluble polyvinyl alcohol (PVA) fiber was impregnated into a 1% solution of the nonionic dispersant. This was put into water, stirred for 3 minutes with a high-speed mixer to disaggregate the fibers, and then gently stirred in a chest equipped with a reciprocating rotary stirrer (Agitator, manufactured by Shimazaki Seisakusho). Then, a 0.1% aqueous solution of polyacrylamide (sticky agent) was rapidly added, and the mixture was gently stirred. In this way, a uniform slurry was prepared. Using the slurry, a web having a width of 50 cm and a basis weight of 50 g / m ² was made by a cylinder-making method.

Two layers of the web were laminated and three nozzle heads were used.
Entangling was performed with a columnar water flow using the head. The nozzle of the first head has a nozzle diameter of 120 μm, the nozzle interval is 1.2 mm, the water pressure is 100 kgf / cm ^{2 in} two rows, and the nozzle diameter of the second head is 120 μm.
m, nozzle spacing 0.6 mm, water pressure 100 kgf / cm ² in one row,
The third head has a nozzle diameter of 100 μm and a nozzle spacing of 0.6 m
The water pressure is 120 kg / cm ² per m. A 100 mesh support made of stainless steel was placed under the laminated web, and the laminated web was passed under the water flow to entangle the fibers, and the polyvinyl alcohol binder was eluted. Similarly, the same processing was performed on the back surface. The entanglement speed was 20 m / min. This entangled sheet was dried at 100 ° C. using a suction through dryer, and a hydroentangled conductive nonwoven fabric could be obtained.

The above hydroentangled nonwoven fabric is 50 cm long and 50 c wide.
Cut into m size, sandwich the perimeter with a frame, nickel sulfate 240g / l, nickel chloride 45g / l, boric acid 3
A container in which an electro nickel plating solution containing 0 g / l, saccharin 2 g / l, and 1,4-butynediol 0.2 g / l is circulated at 50 ° C. (height / width 70 cm, depth 20 c
m) soaked in the center and placed 1 between the nickel counter electrodes on both sides.
An electric current of 00 A was applied for 15 minutes to perform electro nickel plating.

Example 2 A polyolefin-based composite fiber (Cisso EA, core part PP, sheath part EV) having a fiber diameter of 2d (fiber diameter 15 μm) and a fiber length of 15 mm.
A) is immersed in a 40-fold diluted aqueous solution of MK-160 (cleaner / conditioner manufactured by Muromachi Chemical Co., Ltd.) at 25 ° C for 1 minute while being dispersed, filtered, washed with water, and then MK
The fiber was immersed in a 3-fold diluted aqueous solution of -660 (manufactured by Muromachi Chemical Co., Ltd.) at 50 ° C for 5 minutes while being dispersed, and the fiber was filtered and washed with water. Next, the fiber is immersed in a pre-dip solution of a 2N hydrochloric acid aqueous solution, the fiber is filtered, and MK-
It is immersed in a 32-fold dilution of 260 (Muromachi Chemical Catalyst Liquid) at 25 ° C for 10 minutes while dispersing, filtered, washed with water, and further MK-360 (Muromachi Chemical Accelerator).
It was immersed in a 10-fold diluted liquid of 30 ° C. for 8 minutes while dispersing, filtered, washed with water, and catalyzed. Next, this fiber was dispersed in an aqueous solution of 20 g / l of sodium citrate and 2 g / l of sodium hypophosphite to obtain 224 g / l of nickel sulfate.
And an aqueous solution of 226 g / l of sodium hypophosphite and 85 g / l of sodium hydroxide are simultaneously added dropwise.
After stirring and applying electroless nickel plating by the dropping method,
It was filtered and washed with water to obtain conductive organic short fibers. At this time, the temperature of the plating solution was 50 ° C.

Next, using the above-mentioned conductive fibers, a hydroentangled conductive nonwoven fabric was obtained in the same manner as in Example 1. Next, electroplating was performed in the same manner as in Example 1.

Comparative Example The slurry of Example 1 was further mixed with polyester binder fibers (Melty 4080, core-sheath type, sheath melting point 11).
0 ° C., manufactured by Unitika Ltd.) was mixed and dried, and then adjusted so that polypropylene fiber / polyester binder fiber = 80/20. A web with a basis weight of 80 g / m ² is made with a cylinder paper machine and dried at 130 ° C. with a Yankee dryer.
A wet papermaking nonwoven fabric was obtained. This non-woven fabric was immediately subjected to nickel electroplating in the same manner as in Example 1 without hydroentangling treatment. At this time, no plating film was formed on the polyester binder fiber portion.

With respect to the nickel-plated non-woven fabrics obtained in Examples 1 and 2 and Comparative Example above, a sample having a thickness, a basis weight, an electric conductivity and a tensile strength (a width of 20 mm and a length of 150 mm was used as a span 1
When the sample is pulled at a speed of 200 mm / min at a speed of 200 mm, the longitudinal direction is measured at the maximum load value until the sample breaks, and the tape adhesiveness is evaluated (when a cellophane tape with a width of 1.5 cm is stuck with a finger and peeled off). Table 1 summarizes the fiber loss, the evaluation of the peeling of the plating), the fiber fluffing evaluation, and the overall evaluation as an electrode substrate.

[0046]

[Table 1] * Tape adhesion: Missing ○: No fibers are missing. Δ: Some fibers were missing. X: Many fibers are missing. * Fuzziness: ○ ・ ・ ・ No trouble ×: There is trouble ＊ Comprehensive evaluation: ○ ・ ・ ・ Can be used as an electrode. ×: Cannot be used as an electrode. The electrode substrates obtained in Examples 1 and 2 have a large porosity and, although manufactured without using a binder, the tensile strength is improved as compared with the Comparative Example, and the fibers are missing or fluffed. Highly conductive, with all the substrate fibers plated,
It can be seen that a porous nickel electrode substrate can be obtained.

[0047]

[Effects of the Invention] A three-dimensional entanglement treatment is applied to a web containing electrically conductive short organic fibers as a main component, and then nickel electroplating is applied to eliminate the use of binder fibers or organic solvent adhesives. It is possible to manufacture a nickel-plated non-woven fabric electrode substrate having a large void ratio, in which the tensile strength characteristics are improved and the fibers are prevented from falling out and fuzzing is suppressed.

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[Procedure amendment]

[Submission date] March 26, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0023

[Correction method] Change

[Correction content]

The organic short fibers to which the conductivity has been imparted as described above are formed into a nonwoven web. Nonwoven web manufacturing method
As the method, using the above fibers, a wet papermaking method or a dry heat method is used.
Or wet heat bonding method, card method, cross layer method, lander
For well-known manufacturing methods such as Mwebber method and spunbond method
Therefore, it can be manufactured, and if necessary, needle punch,
The fibers should be fixed by a treatment method such as the next water entanglement treatment.
You can The thickness range of the non-woven fabric formed by the manufacturing method, porosity, shape of the voids, pore size, homogeneity, flexibility,
It has different properties such as elasticity, fluff, and fiber loss.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0038

[Correction method] Change

[Correction content]

[0038]

EXAMPLES The present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. In the examples,
All parts and percentages are by weight.

Claims (1)

[Claims] 1. A method for producing a metal-plated non-woven fabric electrode substrate, which comprises subjecting a web containing a conductive organic fiber as a main component to hydroentangling treatment and then electroplating.