JP2014043602A - Facility and method for producing fibrous electrode - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a facility and a method for producing a fibrous electrode, with which an active material layer is uniformly formed by holding an opening state of a fibrous material.SOLUTION: In a production facility which is a facility (M) for producing a fibrous electrode to be used for a battery, and which includes: an opening unit (1) to open a bundle of fibrous current collectors being core bodies of the fibrous electrode; and an electrode production unit (3) to produce the fibrous electrode by forming an active material layer on the fibrous current collectors opened with the opening unit (1), an opening state holding device (51), to convey the bundle (13) of fibrous current collectors while holding the opening state, is installed on the electrode production unit (3).

Description

  The present invention relates to equipment and a method for producing a fiber-like electrode that can be used in batteries such as alkaline batteries and non-aqueous batteries, and that enables high output of the battery.

  In recent years, as a solution to energy problems and environmental problems, the use of chemical batteries has expanded, such as mounting a storage battery in a vehicle, and accordingly, higher output of the battery is required. Conventionally, for example, a block shape, a plate shape, a sheet shape or the like has been generally used as an electrode structure. However, as an electrode structure for realizing higher output of a battery, a fiber shape such as a carbon fiber is used. A fiber electrode manufactured by using a current collector as a material and forming an active material layer on the surface thereof has been proposed (see, for example, Patent Document 1).

  In the fiber electrode manufacturing process, as a preparatory process for uniformly forming an active material layer on each of the fiber materials such as carbon fibers as the core, a step of opening a bundle of fiber materials Is required (see, for example, Patent Document 2).

JP 2003-317794 A Japanese Patent No. 3064019

  However, in the electrode manufacturing process, after the fiber-like material bundle that functions as a current collector is once opened, many processes such as a conductive layer and active material layer forming process and a cleaning process are performed. . In the post-process of these fiber-opening processes, the fiber-like material may be immersed in various liquids, and the fiber-like materials are reattached due to the surface tension of the liquid and the fiber-opening state is maintained. It becomes difficult. As a result, there is a problem that the active material layer cannot be formed uniformly. On the other hand, it is conceivable to apply tension to the fibrous material in order to maintain the opened state in the post-opening process. However, if excessive tension is applied, the fibrous material will break or fluff. Also, it becomes difficult to form a uniform active material layer.

  In order to solve the above problems, an object of the present invention is to provide a fiber electrode manufacturing facility and a manufacturing method capable of uniformly forming an active material layer while maintaining a fiber material in an opened state. It is in.

  In order to achieve the above object, a fiber electrode manufacturing facility according to the present invention is a device for manufacturing a fiber electrode used in a battery, and is a fiber current collector that is a core of the fiber electrode. An opening unit that opens a bundle of bodies, and an electrode manufacturing unit that forms an active material layer on the fiber-shaped current collector opened by the opening unit to manufacture the fiber-shaped electrode, The electrode manufacturing unit includes a fiber-opening state holding device that conveys the fiber-shaped current collector or fiber-shaped electrode while holding the fiber-opening state. In addition, the fiber electrode manufacturing method according to the present invention includes a fiber-opening step of opening a bundle of fiber-shaped current collectors that are cores of the fiber-like electrode, and the fiber-like fiber opened by the fiber opening unit. An electrode manufacturing step of forming an active material layer on a current collector to manufacture the fiber-shaped electrode, while the electrode manufacturing step maintains the opened state of the fiber-shaped current collector or fiber-shaped electrode. It has the process of conveying.

  According to this configuration, the fiber-shaped current collector or the fiber-shaped electrode opened by the fiber-spreading unit can form an active material layer while maintaining the fiber-opened state even in the subsequent process of the electrode manufacturing unit. An active material layer can be uniformly formed on each of the current collectors.

  In the manufacturing facility according to an embodiment of the present invention, the electrode manufacturing unit includes a plating apparatus that performs metal plating on the opened fiber-shaped current collector, and the opening is provided at least downstream of the plating apparatus. It is preferable that a fine state holding device is provided. By forming a metal plating film on the fibrous current collector, the electrical conductivity of the fibrous electrode can be improved. On the other hand, the fibrous current collector after the plating process is caused by the surface tension of the plating solution. It becomes easy to adhere to each other, and it may be particularly difficult to maintain the opened state. Therefore, by providing a spread state holding device downstream of the plating device, a uniform active material layer can be formed while improving the conductivity of the electrode.

  In the manufacturing facility according to an embodiment of the present invention, the spread state holding device has a transport roller row composed of three or more transport rollers of the same diameter that are rotatably supported and arranged in parallel to each other. The distance between the plane including the rotation axis of the conveyance roller located at both ends of the conveyance roller row and the rotation axis of each conveyance roller of the conveyance roller row is set to D / 3 or less, where D is the conveyance roller diameter. It is preferable. According to this configuration, by passing the fibrous current collector through the conveying roller array having three or more conveying rollers, it is possible to apply an appropriate tension to the fibrous current collector and maintain the opened state. . Moreover, since each of the transport rollers is arranged in a horizontal state of D / 3 or less with respect to the roller diameter D, it is possible to prevent the fiber current collector from being broken or fuzzed due to excessive tension. .

  In the fiber electrode manufacturing facility according to an embodiment of the present invention, the opening unit has a suction device that opens the fiber-shaped current collector bundle by suction, and the suction device includes the suction device. It is preferable to have two opening direction suction ports for sucking the fibrous current collector in directions opposite to each other in the opening direction, and a longitudinal suction port for sucking in the traveling direction of the fibrous current collector. According to this configuration, the fiber-shaped current collector is opened by suction mainly from two opening direction suction ports, and more uniformly opened by applying suction from the longitudinal direction suction ports. Is possible.

  In the fiber electrode manufacturing facility according to an embodiment of the present invention, the opening unit has a sizing agent heater that heats and removes the sizing agent adhering to the fiber current collector bundle. It is preferable. According to this configuration, the sizing agent can be removed in a short time, and physical properties suitable as an electrode material can be obtained.

  In the fiber electrode manufacturing facility according to an embodiment of the present invention, the fiber opening unit includes a plurality of parallel cylindrical members that are supported in a non-rotatable manner, and applies tension to the fiber current collector bundle. It is preferable to have a tension applying mechanism. According to this configuration, the fiber-shaped current collector bundle is twisted by applying an appropriate tension to the fiber-shaped current collector bundle by passing the fiber-shaped current collector through a non-rotatably fixed cylindrical member. Can be effectively prevented. Thereby, the breakage and fluffing of the fibrous current collector are prevented, and the fiber opening can be performed efficiently.

  In one embodiment of the present invention, it is preferable that the tension applying mechanism is provided so as to be capable of reciprocating in parallel with the traveling direction of the fibrous current collector. According to this configuration, a flattening force acts on the fiber-shaped current collector bundle so that it can be processed into a flat shape, and twisting is more effectively suppressed and tension is maintained.

  Moreover, it is preferable that the reciprocating speed of the tension applying mechanism is set to 2 cm / s or less. According to this configuration, breakage and fluffing of the fiber-like current collector due to reciprocating friction can be prevented.

  In the fiber electrode manufacturing facility according to one embodiment of the present invention, the electrode preparation unit has an electrolytic deposition apparatus that forms an active material layer on the fiber current collector by electrolytic deposition, The electrolytic deposition apparatus preferably has an electrolytic deposition tank that performs electrolytic deposition treatment and a circulation mechanism that circulates the electrolytic deposition solution in the electrolytic deposition layer. The temperature of the electrolytic deposition solution in the electrolytic deposition tank is preferably in the range of 20 to 80 ° C., for example. By constituting in this way, it is possible to suppress the composition change of the electrolytic deposition solution in the electrolytic deposition tank and to perform the electrolytic deposition treatment while maintaining the liquid properties such as pH. It becomes possible to manufacture continuously over a long time.

  In the fiber electrode manufacturing facility according to an embodiment of the present invention, when the battery is an alkaline battery, an electrolytic deposition apparatus that forms an active material layer on the fiber current collector by electrolytic deposition; It is preferable to have an alkali cleaning device that performs alkali cleaning by directly introducing a fiber electrode that has been subjected to electrolytic deposition by the electrolytic deposition device. Here, “directly introducing the fiber electrode that has been subjected to electrolytic deposition treatment” means that it is introduced into the alkali cleaning apparatus without passing through other steps such as a water washing step. By washing the fiber electrode after electrolytic deposition treatment with alkali, the precipitate formed on the fiber-like current collector by electrolytic deposition is fixed as an active material layer by reaction with alkali. However, if the fiber electrode after the electrolytic deposition treatment is washed with water before alkali washing, a part of the electrolytically deposited active material is washed away before being stabilized as an active material layer. However, the fiber-like electrode derived from the electrolytic deposition apparatus was obtained by electrolytic deposition treatment by directly introducing it into the alkaline cleaning apparatus without passing through other steps such as a water washing step in the middle and performing alkali cleaning. The active material can be reliably fixed as an active material layer on the fibrous current collector.

  In the fiber electrode manufacturing facility according to an embodiment of the present invention, the electrode manufacturing unit may include a slurry application device that forms an active material layer by applying a slurry onto the fiber current collector. Good. According to this configuration, the production rate of the fiber electrode can be greatly improved. In addition, this configuration makes it possible to produce a fiber-like electrode by applying a powdery material, such as a hydrogen storage alloy, which is difficult to deposit by plating. For example, a negative electrode or lithium of a nickel-hydrogen secondary battery A fiber electrode used for a negative electrode of a nickel-metal hydride secondary battery or a positive electrode or a negative electrode of a lithium ion battery can be easily produced using powders used for manufacturing a positive electrode or a negative electrode of an ion battery.

  As described above, according to the fiber electrode manufacturing facility according to the present invention, the active material layer can be uniformly formed while maintaining the fiber-shaped material in the opened state.

It is a block diagram which shows schematic structure of the manufacturing equipment of the fiber electrode which concerns on 1st Embodiment of this invention. It is a figure which shows the structure of the preliminary opening apparatus of the manufacturing equipment of FIG. 1, (a) is a side view, (b) is a top view. It is a side view which shows schematic structure of the fiber opening apparatus of the manufacturing facility of FIG. It is a top view which shows schematic structure of the fiber opening apparatus of the manufacturing facility of FIG. It is a side view which shows the modification of the fiber-spreading apparatus of FIG. It is a schematic block diagram which shows the electrode preparation unit of the manufacturing equipment of FIG. It is the schematic which shows the principal part of the fiber-opening state holding | maintenance apparatus of FIG. It is the schematic which shows the principal part of the manufacturing equipment which concerns on 2nd Embodiment of this invention.

  Hereinafter, embodiments according to the present invention will be described with reference to the drawings. However, the present invention is not limited to the embodiments.

  In FIG. 1, schematic structure of the manufacturing equipment M of the fiber electrode which concerns on 1st Embodiment of this invention is shown. The manufacturing equipment M is an apparatus for manufacturing a fiber electrode used in a battery (a nickel metal hydride secondary battery that is an alkaline battery in the example of the present embodiment), and is a fiber that is a core body of the fiber electrode. An opening unit 1 that opens a bundle of the current collector, and an electrode manufacturing unit 3 that forms an active material layer on the fiber collector opened by the opening unit.

  In addition, as the fibrous current collector, a conductive fibrous material, for example, carbon fiber is preferable. In addition, for example, nickel wire, copper wire, aluminum wire, steel wire, metal-coated polyolefin, or the like can be used. .

  The fiber opening unit 1 unwinds the fiber-shaped current collector bundle from the bobbin around which the fiber-shaped current collector bundle is wound to make the fiber-shaped current collector bundle 13 easy to open. And a fiber opening device 7 for opening the fiber-shaped current collector bundle that has passed through the preliminary fiber opening device 5.

  FIG. 2 shows the configuration of the preliminary opening device 5. In the following description, the traveling direction of the fiber current collector 11 in the manufacturing facility M (that is, the longitudinal direction of the fiber current collector 11) is referred to as the vertical direction X, and the fiber current collector bundle is opened. The direction may be referred to as the horizontal direction Y.

  In the preliminary opening device 5, the bundle 13 of the fibrous current collector 11 is unwound from the unwinder 15, conveyed by the plurality of preliminary opening conveying rollers 17, and then laterally by the U-shaped guide hook 19. Guided to the center of Y. The unwinder 15 of the present embodiment includes an unwinding roll 21 around which the fiber-shaped current collector bundle 13 is wound, and an unwinding support base 23 that rotatably supports the unwinding roll 21. As shown in FIG. 2B, the unwinding support base 23 is installed so as to be rotatable with respect to a rotation axis C <b> 1 orthogonal to the rotation axis of the unwinding roll 21. When the fiber-shaped current collector bundle 13 is unwound from the unwinding roll 21, the unwinding position of the unwinding roll 21 changes in the lateral direction Y. Therefore, the unwinding support base 23 is moved according to the unwinding position change. By rotating, the tension of the fiber-like current collector bundle 13 can be adjusted.

  The fiber-shaped current collector bundle 13 brought to the central portion by the guide hook 19 passes through a plurality of (three in the illustrated example) fixing bars 25 and then enters the sizing agent combustor 27. Each fixed bar 25 is a columnar member provided so as not to rotate. In the illustrated example, a plurality of fixing bars 25 are fixed to the fixing plates 29 positioned at both ends in the lateral direction Y in a ladder shape, that is, in parallel to each other at the same axial position. When the fibrous current collector bundle 13 passes through a plurality of fixing bars 25 arranged in parallel to each other, an appropriate tension is applied to the fibrous current collector bundle 13. That is, the plurality of fixing bars 25 function as a tension applying mechanism that applies tension to the fibrous current collector bundle 13, suppresses twisting of the fibrous current collector bundle 13, and preliminarily opens the fiber.

  Further, the plurality of fixing bars 25 are provided so as to be able to reciprocate integrally in the longitudinal direction X while being fixed to the fixing plate 29 in a ladder shape as described above. By reciprocating the plurality of fixing bars 25 in the longitudinal direction X, a flattening force is applied to the fiber-like current collector bundle 13 so that it can be processed into a flat shape, and twisting is more effectively suppressed. Tension is maintained. In order to prevent breakage and fluffing of the fiber current collector 11 due to the reciprocating friction of the fixed bar 25, the reciprocating speed is preferably 2 cm / s or less.

  In some cases, the fiber-shaped current collector bundle 13 wound around the bobbin is attached with a converging agent that binds a large number of fiber-shaped current collectors 11 and converges in a bundle shape. In such a case, by removing the sizing agent adhering to the fiber-like current collector 11, it is possible to prevent the electrical conductivity of the electrode after being processed into the fiber-like electrode from being lowered, and to have better performance. An electrode can be obtained. The converging agent combustor 27 burns and removes the converging agent adhering to the fiber-like current collector 11 by heating the fiber-like current collector bundle 13. For example, an electric furnace is used as the converging agent combustor 27. Used. The electric furnace used as the sizing agent combustor 27 has a cylindrical shape having an axis substantially parallel to the traveling direction X of the fiber current collector 11.

  In the present embodiment, the fibrous current collector bundle 13 before the sizing agent is removed passes alternately above or below the three fixing bars 25. In the example shown in the drawing, the fiber-shaped current collector bundle 13 is provided at the lower part of the uppermost first fixing bar 25, the upper part of the second fixing bar 25 downstream thereof, and the lower part of the third fixing bar 25 of the most downstream side. Pass in order. As described above, the tension applying mechanism including the fixed bar 25 is arranged upstream of the sizing agent combustor 27 to prevent twisting of the fiber-shaped current collector bundle 13 in the previous stage of entering the sizing agent combustor 27. Therefore, when entering the sizing agent combustor 27, breakage or fluffing of the fiber-shaped current collector 11 due to contact with members constituting the sizing agent combustor 27 is prevented.

  The fiber-shaped current collector bundle 13 in which the binding agent is removed by the preliminary fiber opening device 5 and the fiber-shaped current collectors 11 are not bound to each other is conveyed to the fiber opening device 7 shown in FIG. The fiber opening device 7 of this embodiment opens the fiber-shaped current collector bundle 13 by sucking it from below. Specifically, the fiber opening device 7 includes a transport mechanism 31 that supports and transports the fiber-shaped current collector bundle 13, and an aspirator 33 provided below the transport mechanism 31. As shown in FIG. 4, the aspirator 33 includes three (one pair) suction ports 35 and 35 in the horizontal direction (opening direction) and one suction port 37 in the vertical direction (longitudinal direction). have.

  The two horizontal suction ports 35 are arranged side by side in the horizontal direction Y below the transport mechanism 31. The pair of lateral suction ports 35, 35 are installed so as to be inclined in opposite directions so as to face the central portion in the lateral direction Y of the fiber current collector bundle 13, respectively. On the other hand, the vertical suction port 37 is disposed on the downstream side of the two horizontal suction ports 35 and 35 and is inclined in the vertical direction X so as to face the upstream side.

  The fiber-shaped current collector bundle 13 is opened mainly by suction from the two horizontal suction ports 35 and 35 and is pulled in the vertical direction X by suction from the vertical suction port 37, whereby the horizontal direction Y Spread evenly. As described above, since the vertical suction port 37 is provided mainly for uniformly opening the fiber-shaped current collector bundle 13, the suction force of the vertical suction port 37 is set to each of the horizontal suction ports. It is preferable to set a value smaller than the attraction force, for example, about 1/2.

  Further, as a modification of the present embodiment, as shown in FIG. 5, air is intermittently supplied from above to the fiber current collector bundle 13 in addition to the suction device 33 or instead of the suction device 33. An intermittent blower mechanism 39 for spraying may be provided. In the illustrated example, the intermittent blower 39 is configured by providing an openable / closable shutter 39b at the blowout port of the blower 39a that performs continuous spraying. When fiber opening is performed by continuously blowing air onto the fiber-shaped current collector bundle 13, it is difficult to open the fiber uniformly due to the influence of turbulent flow generated by the air flow. By blowing air intermittently, the fibers can be spread uniformly.

  Furthermore, a tension adjusting mechanism 41 that adjusts the tension of the fiber-shaped current collector bundle 13 may be provided upstream of the transport mechanism 31 of the fiber opening device 7. In the illustrated example, as the tension adjusting mechanism 41, a slide mechanism is used that can move back and forth in the vertical direction with respect to the fiber-shaped current collector bundle 13, that is, in the direction Z orthogonal to the traveling direction X and the fiber opening direction Y. .

  In the present embodiment, the suction unit 33 has a total of three suction ports, that is, two (one pair) horizontal suction ports 35 and 35 and one vertical suction port 37 shown in FIG. However, the suction device 33 only needs to have at least one pair of lateral suction ports 35 and 35. Even if suction is performed using only the two lateral suction ports 35, 35, the fiber can be opened more efficiently and uniformly than when one suction port 37 is used.

  Next, the configuration of the electrode production unit 3 will be described. As shown in FIG. 6, the electrode manufacturing unit 3 includes a plating apparatus 51 that forms a coating layer by metal plating on the surface of the opened fiber-shaped current collector 11, and the fiber-shaped current collector 11 that has passed through the plating apparatus 51. On the fiber-shaped current collector (in this example, on the metal coating layer formed by the plating apparatus 51), which is conveyed to the subsequent process while maintaining the opened state. An active material layer forming device 55 for forming a material layer is provided as a main component.

  The plating apparatus 51 is provided in a plating bath 57 that performs metal plating on the fibrous current collector 11 and an introduction portion to the plating bath 57 and introduces a plating bath that guides the fibrous current collector 11 into the plating bath 57. A roller 59 and a plating bath derivation roller 61 that is provided in a lead-out portion from the plating bath 57 and guides the fiber-shaped current collector 11 subjected to the plating process out of the plating bath 57 are provided. Inside the plating bath 57, an upstream-side transport roller 63 and a downstream-side transport roller 65 that transport the fiber-shaped current collector in the plating bath 57 are provided. In the illustrated example, the fibrous current collector 11 passes from the upper part of the plating bath introducing roller 59 to the lower part of the upstream conveying roller 63, the lower part of the downstream conveying roller 65, and the upper part of the plating bath outlet roller 61. In the present embodiment, nickel plating is performed by the plating apparatus 51. As the plating solution used in the plating bath 57, a solution in which boric acid or nickel chloride is added based on an aqueous solution of nickel amidosulfate (nickel sulfamate) is used. Watt baths based on nickel sulfate can also be used. In order to obtain a uniform plating layer, the preferable range of the plating bath temperature is 40 to 80 ° C. If the plating bath temperature becomes too high, there is a concern about changes in the liquid concentration due to the influence of water evaporation. Specifically, when the plating solution concentration increases, the plating amount decreases. Conversely, when the plating solution concentration decreases, the plating amount increases. As a result, the amount of plating becomes non-uniform on the current collector, and the electrical conductivity also becomes non-uniform depending on the location on the current collector, so that the amount of active material deposited by electrolytic deposition described later becomes non-uniform. Therefore, even if the batteries are manufactured using the same lot of electrodes, the variation in the actual capacity of each battery increases. For this reason, if the amount of plating can be kept constant, it is not necessary to raise the temperature more than necessary. Therefore, a more preferable range of the plating bath temperature is 40 to 60 ° C.

  The active material layer forming apparatus 55 according to the present embodiment is configured as an electrolytic deposition apparatus 55A that forms an active material layer on the fibrous current collector 11 by electrolytic deposition. Specifically, the active material layer forming device 55 (electrolytic deposition device 55A) includes an active material layer forming tank 67 (electrolytic deposition bath 67A) for performing electrolytic deposition treatment on the fiber-like current collector 11, and an electric analysis. An electrolytic deposition bath introduction roller 69 provided in the introduction portion to the bathtub 67A and guiding the fiber-shaped current collector into the electrolytic deposition bath 67A, and a lead-out portion from the electrolytic deposition bath 67A are provided. An electrolytic deposition bath derivation roller 71 is provided for deriving the fiber-like current collector (electrode) 11 subjected to the analysis out process to the outside of the electrolytic deposition bath 67A. Inside the electrolytic deposition bath 67A, an upstream transport roller 73 and a downstream transport roller 75 that transport the fiber-shaped current collector 11 in the electrolytic deposition bath 67A are provided. In the illustrated example, the fiber-shaped current collector 11 extends from the upper part of the electrolytic deposition bath introducing roller 69 to the lower part of the upstream transport roller 73, the lower part of the downstream transport roller 75, and the upper part of the electrolytic deposition bath lead-out roller 71. Pass in order.

  As shown in the figure, the electrolytic deposition bath 67A is provided with a circulation mechanism 77 for circulating the electrolytic deposition solution. Although the circulation mechanism 77 may be omitted, by providing the circulation mechanism 77, the electrolytic deposition treatment is performed while suppressing the composition change of the electrolytic deposition solution in the electrolytic deposition bath 67A and maintaining the liquid properties such as pH. Therefore, it is possible to continuously manufacture electrodes having a certain quality over a long period of time.

In the electrolytic deposition in this embodiment, nickel hydroxide (Ni (OH) ₂ ) is formed as the active material layer. Therefore, a nickel nitrate solution is used as an electrolytic deposition solution used in the electrolytic deposition bath 67A. Moreover, the preferable range of the temperature of an electrolytic deposition liquid is 20-80 degreeC. Depending on the temperature of the electrolytic deposition solution, the battery characteristics of the attached active material may be affected. For example, even when electrolytic deposition is performed at a low temperature, the deposition amount is kept constant, but the discharge capacity of the obtained electrode tends to decrease. Further, at low temperatures, unevenness of electrolytic deposition occurs, making it difficult to produce high quality electrodes. For this reason, it is better to raise temperature moderately, and the more preferable range of the temperature of an electrolytic deposition liquid is 40-80 degreeC. In addition, even when the temperature of the electrolytic deposition solution is high, the amount of electrolytic deposition tends to be kept constant, but as with the plating solution, it is easily affected by changes in concentration and the amount of liquid. The amount of active material deposited changes, and battery capacity tends to vary. Therefore, it is not preferable to raise the temperature more than necessary, and a more preferable range of the temperature of the electrolytic deposition solution is 40 ° C to 60 ° C.

Further, during electrolytic deposition, NO ₃ ⁻ (nitrate ions) are decomposed during electrolytic deposition and ammonia (alkali) is generated, so that the pH tends to increase. Therefore, the pH can be adjusted by dropping nitric acid or the like. preferable. When the pH shifts from acidity and falls below 3, the acidity increases and the amount of electrolytic deposition decreases. On the other hand, if the electrolytic deposition is continued without adjusting the pH, the pH continues to rise by shifting to the alkali side. If the pH exceeds 6.5, precipitation occurs and is affected by the change in the concentration of the liquid. Therefore, the pH is preferably in the range of 3 to 6.5. However, since the pH of the electrolytic deposition solution is likely to fluctuate, the pH of the electrolytic deposition solution can be kept constant, and the pH of the electrolytic deposition solution should not be affected even if pH fluctuation occurs. More preferably, it is in the range of 4-6, and more preferably in the range of 4-5.5. Circulating the electrolytic deposition solution by providing the circulation mechanism 77 as described above is also preferable from the viewpoint of causing a flow in the liquid so that the dropped nitric acid is uniformly distributed throughout the electrolytic deposition solution.

  Between the plating apparatus 51 and the active material layer forming apparatus 55, a spread state holding apparatus 53 is provided. Specifically, the spread state holding device 53 is in a state where the fiber-shaped current collector bundle 13 is opened by a transport roller row 83 including a plurality of (in this embodiment, five) transport rollers 81 that are rotatably provided. Transport while holding. In the present embodiment, as shown in FIG. 7, the transport rollers 81 constituting the transport roller row 83 have the same roller diameter D, and each transport roller 81 has a rotational axis C2 thereof. It arrange | positions so that distance S1 from the plane P1 containing the rotating shaft center C2 of the conveyance rollers 81 and 81 located in both ends may be D / 3 or less. A more preferable range of the distance S1 from the plane P1 of the rotation axis C2 of each conveyance roller 81 is D / 5 or less. In the example of FIG. 6, the rotation axes C2 of all the conveyance rollers 81 are substantially in the same plane. It is arranged to be located.

  Further, as shown in FIG. 7, each transport roller 81 has a distance S2 from a plane P2 including the rotation axis of the lead-out roller of the plating bath 57 and the rotation axis of the introduction roller of the electrolytic deposition bath 67A. It arrange | positions so that it may become 3 or less. A more preferable range of the distance S2 from the line segment L2 of the rotation axis of each conveyance roller is D / 5 or less. In the example of FIG. 6, the rotation axes C2 of all the conveyance rollers are located substantially in the plane P2. Are arranged as follows.

  The spread state holding device 53 may further include a dryer and a spread mechanism downstream of the transport roller row 83. Moreover, in the fiber-opening state holding device 53, it is preferable to wash the fiber-shaped current collector bundle 11 with droplets.

  An alkali cleaning device 85 is further provided downstream of the active material layer forming device 55. The alkali cleaning device 85 is provided in an alkali cleaning bath 87 that performs electrolytic deposition treatment on the fiber-shaped current collector and an introduction portion to the alkali cleaning bath 87, and guides the fiber-shaped current collector into the alkali cleaning bath 87. An alkali cleaning bath introducing roller 89 and an alkali cleaning bath deriving roller 91 that is provided in a lead-out portion from the alkali cleaning bath 87 and guides the fiber electrode 11 subjected to the alkali cleaning treatment out of the alkali cleaning bath 87. ing.

  In the alkali cleaning device 85, the electrode 11 was formed by electrolytic deposition by subjecting the fiber electrode 11 after electrolytic deposition treatment to alkaline cleaning with an alkaline solution (pH about 12 to 14) such as potassium hydroxide or sodium hydroxide. The precipitate is fixed as an active material layer (nickel hydroxide) by reaction with alkali. However, if the fiber electrode 11 after the electrolytic deposition treatment is washed with water before alkali washing, a part of the electrolytically deposited active material is washed away before being stabilized as an active material layer. In this embodiment, since the fiber electrode led out from the electrolytic deposition apparatus 55A is introduced into the alkali cleaning apparatus 85 directly, that is, without passing through other processes such as a water washing process, alkali analysis is performed. The active material obtained by the extraction treatment can be reliably fixed as an active material layer on the fiber current collector 11.

  An ultrasonic cleaning device 93 is provided downstream of the alkali cleaning device 85. The ultrasonic cleaning apparatus 93 shakes off nickel hydroxide having a weak holding power by performing ultrasonic cleaning in a state where the fiber electrode is bathed in water.

  As shown in FIG. 6, the spread state holding device 53 is also provided between the alkali cleaning device 85 and the ultrasonic cleaning device 93 and also downstream of the ultrasonic cleaning device 93. As described above, the opened state holding device 53 may be provided at any position in the electrode manufacturing unit 3, but in particular, it is preferably provided at least downstream of the plating device 51. By forming a metal plating film on the fiber-shaped current collector 11, the conductivity of the fiber-shaped electrode can be improved. On the other hand, the fiber-shaped current collector 11 after the plating process is applied to the surface of the plating solution. It becomes easy to adhere to each other due to the tension, and it becomes particularly difficult to maintain the opened state. Therefore, by providing a spread state holding device downstream of the plating device 51, a uniform active material layer can be formed while improving the conductivity of the electrode.

  According to the manufacturing equipment M and the manufacturing method using the same according to the present embodiment, the fiber-shaped current collector bundle 13 opened by the opening unit maintains the opened state even in the subsequent process of the electrode manufacturing unit. However, since the active material layer can be formed, the active material layer can be formed uniformly on each of the fibrous current collectors 11.

  In FIG. 8, the principal part of the fiber electrode manufacturing equipment M which concerns on 2nd Embodiment of this invention is shown. In the second embodiment, as the active material layer forming device 55 of the electrode manufacturing unit in the first embodiment of FIG. 1, a slurry applying device 55B shown in FIG. 8 is used instead of the electrolytic deposition device 55A of the first embodiment. use. The slurry application device 55B applies a slurry prepared by preparing an electrode active material in a paste form together with a binder, a thickener, a conductive agent, etc. to the surface of the opened fiber-shaped current collector 11, thereby collecting a fiber-shaped collector. An active material layer is formed on the electric body 11.

  Specifically, the active material layer forming device 55 (slurry coating device 55B) includes an active material layer forming tank 67 (slurry immersing tank 67B) that immerses the fibrous current collector in the slurry and applies the slurry. . A removal mechanism 95 for removing excess slurry, such as a doctor blade or a scraper, is provided in the vicinity of the lead-out portion of the slurry immersion tank 67B. By passing this removal mechanism 95, the amount of slurry applied is adjusted. The active material layer is fixed by drying the fibrous current collector 11 that has passed through the slurry applying device 55 </ b> B by the slurry dryer 97.

  Moreover, in this embodiment, in the spread state holding | maintenance apparatus 53 downstream of the plating apparatus 51, the water washing by a water drop is performed. Further, as in the first embodiment, a dryer and a fiber opening mechanism are provided between the fiber-opening state holding device 53 and the slurry coating device 55B. Good.

  In order to form an active material layer as in this embodiment, the slurry coating apparatus 55B is provided to perform slurry coating, thereby greatly increasing the production rate of the electrode compared with the case where the active material layer is formed by electrolytic deposition. Can be improved. Further, the slurry application device 55B enables application of a powdery material such as a hydrogen storage alloy or carbon powder. For example, a material that is difficult to be plated or electrolytically deposited, such as a negative electrode of a nickel metal hydride secondary battery. Fiber electrode production is also possible.

  In each of the above embodiments, an apparatus for producing an electrode (positive electrode) mainly used for a nickel hydride secondary battery has been described as an example. However, the present invention is not limited to this, and various primary batteries and secondary batteries are used. For example, in addition to manganese batteries, silver-zinc batteries, nickel-cadmium batteries, nickel-zinc batteries, nickel-iron batteries, it also applies to manufacturing facilities for electrodes (positive and negative electrodes) used for non-aqueous batteries such as lithium ion batteries. It is possible.

  For example, in an embodiment in which the manufacturing equipment and manufacturing method of the present invention are applied to a fiber electrode for a lithium ion battery, a plating layer such as aluminum or copper may be formed on the fiber current collector 11 by the plating device 51. Good. A positive electrode for a lithium battery can also be obtained by electrolytically depositing a hydroxide or oxide such as Ni, Co, or Mn on a carbon fiber and then hydrothermally treating it in a Li salt. Moreover, what is necessary is just to electroplate on a carbon fiber, when depositing the Cu-Sn alloy and Ag-Sn alloy for negative electrodes. Further, the carbon fiber itself functions as a negative electrode.

  In addition, although not included in the scope of the present invention, each of the above-described preliminary opening device (process), opening device (process), active material layer forming device (process), alkali cleaning device (process), etc. Even if it does not combine with the fiber-opening state holding | maintenance apparatus made into essential constituent requirements by this invention, the manufacturing equipment and the manufacturing method including any of the processes have the above-described effects.

  As described above, the preferred embodiments of the present invention have been described with reference to the drawings, but various additions, modifications, or deletions can be made without departing from the spirit of the present invention. Therefore, such a thing is also included in the scope of the present invention.

DESCRIPTION OF SYMBOLS 1 Opening unit 3 Electrode preparation unit 5 Preliminary opening device 7 Opening device 11 Fiber-shaped current collector 13 Fiber-shaped current collector bundle 51 Plating device 53 Opening state holding device 55 Active material layer forming device 81 Conveying roller 83 Conveying Roller array 85 Alkali cleaning device C2 Conveying roller rotational axis D Conveying roller diameter M Manufacturing equipment P1 Plane plane including conveying roller rotational axis C2 located at both ends Distance from the rotation axis of the transport roller

Claims (13)

A facility for producing fiber electrodes used in batteries,
An opening unit for opening a bundle of fiber-shaped current collectors that is a core of the fiber-shaped electrode;
An electrode production unit for producing the fiber electrode by forming an active material layer on the fiber current collector opened by the fiber opening unit;
The manufacturing apparatus of the fiber-shaped electrode which has the open state holding | maintenance apparatus which the said electrode preparation unit conveys, hold | maintaining the open state of the said fiber-shaped collector bundle.   In Claim 1, the said electrode preparation unit has a plating apparatus which performs metal plating to the said opened fiber-shaped electrical power collector, The said opening state holding | maintenance apparatus is provided at least downstream of this plating apparatus. Manufacturing equipment for fiber electrode.   3. The spread state holding device according to claim 1 or 2, wherein the spread state holding device includes a conveyance roller row composed of three or more conveyance rollers having the same diameter, which are rotatably supported and arranged in parallel to each other. A fiber electrode in which the distance between the plane including the rotation axis of the conveyance roller located at both ends and the rotation axis of each conveyance roller in the conveyance roller row is set to D / 3 or less with the conveyance roller diameter as D Manufacturing equipment.   4. The fiber opening unit according to claim 1, wherein the fiber opening unit has a suction device that opens the fiber-like current collector bundle by sucking the fiber-like current collector bundle. A fiber electrode manufacturing facility having two opening direction suction ports for sucking an electric body in directions opposite to each other in the opening direction, and a longitudinal suction port for sucking in the traveling direction of the fiber current collector.   5. The fiber electrode according to claim 1, wherein the fiber opening unit includes a sizing agent heater that heats and removes the sizing agent attached to the fiber current collector bundle. production equipment.   The tension applying mechanism according to any one of claims 1 to 5, wherein the opening unit includes a plurality of parallel cylindrical members that are supported so as not to rotate. A fiber electrode manufacturing facility.   7. The fiber electrode manufacturing facility according to claim 6, wherein the tension applying mechanism is provided so as to be capable of reciprocating in parallel with the traveling direction of the fiber current collector.   The fiber electrode manufacturing facility according to claim 7, wherein the reciprocating speed of the tension applying mechanism is set to 2 cm / s or less.   The electrode deposition unit according to any one of claims 1 to 6, further comprising an electrolytic deposition apparatus that forms an active material layer by electrolytic deposition on the fibrous current collector. A fiber electrode manufacturing facility in which the apparatus has an electrolytic deposition tank for performing electrolytic deposition treatment and a circulation mechanism for circulating the electrolytic deposition liquid in the electrolytic deposition layer.   The fiber electrode manufacturing facility according to claim 9, wherein the temperature of the electrolytic deposition solution in the electrolytic deposition tank is in the range of 20 to 80 ° C.   The electrolytic deposition apparatus according to any one of claims 1 to 10, wherein the battery is an alkaline battery, and the electrode manufacturing unit forms an active material layer by electrolytic deposition on the fiber-shaped current collector. A fiber electrode manufacturing facility comprising: an alkali cleaning device that directly introduces a fiber electrode subjected to electrolytic deposition treatment by the electrolytic deposition device and performs alkali cleaning.   The fiber electrode manufacturing method according to any one of claims 1 to 6, wherein the electrode manufacturing unit includes a slurry application device that forms an active material layer by applying a slurry onto the fiber current collector. Facility. A method of manufacturing a fiber electrode used in a battery,
A fiber-opening step of opening a bundle of fiber-shaped current collectors that is a core of the fiber-shaped electrode;
An electrode preparation step for forming the fiber electrode by forming an active material layer on the fiber collector opened by the opening unit;
The manufacturing method of the fiber electrode which has the process which the said electrode preparation process conveys, hold | maintaining the opening state of the said fiber-shaped collector or fiber electrode.

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