JP6011488B2 - Anode and manufacturing method thereof - Google Patents

Description

  The present invention relates to an anode used for electrolysis and a method for producing the same, and more particularly to an anode used for electrolyzing a low melting point metal or a low melting point alloy and a method for producing the same.

  Electrolysis is an abbreviation for electrolysis. In a state where an anode and a cathode are paired and immersed in an electrolyte or molten salt, a direct current is passed through both to cause a chemical change on the electrode surface, which decomposes the substance. It is to purify.

  For example, metal refining or metal plating is an example of an electrolysis method in which a metal is decomposed at the anode surface on the cathode surface by applying voltage with the anode as an anode, and a coating is formed in a high purity state. .

  On the other hand, by adjusting the electrolyte to an appropriate pH condition, when the metal decomposed at the anode is dissolved in the electrolyte and moved to the cathode, it is simply precipitated as a hydroxide before being deposited on the cathode. They can also be separated (see, for example, Patent Document 1).

  In many cases, the anode used in the electrolysis is an anode 100 as shown in FIG. The anode 100 is molded into a single plate having a protrusion 101 on the top, and is electrically connected to the power supply unit 102 by hooking or hanging the protrusion 101 on the power supply unit 102.

  In such electrolysis using the anode 100, a heat generation phenomenon due to electric resistance occurs between the protrusion 101 of the anode 100 and the power feeding portion 102. In the anode 100, since this heat_generation | fever leads to an energy loss, it is suppressed as much as possible. However, it is impossible to prevent heat generation at all.

  Further, this exothermic phenomenon does not increase the temperature so as to soften or melt the anode formed of a general metal such as copper. However, when a metal or alloy having a low melting point, such as tin or indium, is used as the anode 100, when a large voltage or current is applied, the heat generation softens and deforms, or the protrusion 101 and the power supply portion 102 that are at the highest temperature. As a result, the protrusion 101 melts at the contact point, and the anode 100 itself cannot be supported, causing a problem of dropping into the electrolytic cell.

  In order to deal with such a problem, the normal integral-type anode 100 as shown in FIG. 10 has a very small contact area between the protrusion 101 and the power feeding portion 102, and therefore generates heat when a large voltage or current is passed. Cannot be kept low. For this reason, it becomes difficult to prevent the anode 100 from falling off. Therefore, in the anode 100, the electrolysis process must be completed in a short time until dropping off, the workability is deteriorated, and there is only a method of performing electrolysis while keeping the voltage and current low, and the metal deposition efficiency is poor. Become.

  In addition, in Patent Document 3, as shown in FIG. 11, holes 104 are formed in two upper portions of the electrode plate 103 for the anode, and are suspended from the power supply metal rod 106 through the conductive connection jig 105. And a method of electrically connecting the power feeding unit 107 is disclosed. Further, in Patent Document 4, as shown in FIG. 12, a ribbon-like metal suspension 109 is attached to an electrode plate 108 at two places and suspended from a power supply metal rod 110, and the metal rod 110 and the power supply portion 111 are connected. A method of electrical connection is disclosed.

  However, in the method described in Patent Document 3, since the conductive connection jig 105 and the electrode plate 103 are only in point contact with each hole, the temperature rise of the contact portion when a large voltage or current is passed is suppressed. However, when a low melting point metal such as tin or indium is used for the electrode plate 103 for the anode, it softens, melts and falls off.

  The method described in Patent Document 4 is a method that is often used as an electrode on the cathode side, but such a structure is also used for the anode. In the method described in Patent Document 4, a metal suspension 109 and an electrode plate 108 are joined at two locations by rivets as shown in FIG. This metal suspension 109 is made of thin metal with good workability in order to make a firm contact with the metal rod 110 and is easily deformed. It ’s hard to say. Also, for the purpose of using the suspension 109, it is common not to use a metal wider than necessary if the electrode plate 108 can be sufficiently held. In the method described in Patent Document 4, the electrode of a low-melting-point metal or low-melting-point alloy such as tin or indium is somewhat relaxed with respect to the temperature rise than the point contact as in the method described in Patent Document 3. The effect is not sufficient for the plate, softening occurs when a large voltage or current is applied, and the weight of the metal suspension 109 and the electrode plate 108 in the vicinity of the joined portion where there is no holding portion on the upper side is added. , It starts to deform due to its own weight and falls off.

Japanese Patent No. 2829556 Japanese Patent Laid-Open No. 11-229171 Japanese Patent No. 4911668 JP 2004-043846 A

  Therefore, the present invention has been proposed in view of such circumstances, and an electrode plate made of a low-melting-point metal or a low-melting-point alloy, and a holding member that holds the electrode plate and is electrically connected to the power feeding unit. It is an object of the present invention to provide an anode and a method for manufacturing the same, which can suppress the temperature rise at the connecting portion between the electrodes and allow long-term electrolysis without melting and dropping off the electrode plate. In particular, an object of the present invention is to provide an anode capable of long-term electrolysis without dropping off the electrode plate even when a large voltage or current is applied to the electrode plate, and a method for manufacturing the same.

The anode according to the present invention that achieves the above-described object is provided with a length of one side in the vicinity of one side of at least one main surface of an electrode plate made of a low melting point metal or low melting point alloy having a melting point of 100 ° C. or higher and 250 ° C. or lower. A holding member made of a metal or an alloy having the above length and having a melting point higher than the melting point of the electrode plate is attached by surface contact , and the holding member includes an electrode plate holding member that holds the electrode plate, and The electrode plate and the electrode plate holding member are electrically connected to each other, have a conductive connection member formed in a plate shape, and two side surfaces of the connection portion where the electrode plate and the electrode plate holding member are connected The electrode plate and the electrode plate holding member are sandwiched between two conductive connecting members, and the electrode plate and the electrode plate holding member are electrically connected via the conductive connecting member .

The manufacturing method of the anode according to the present invention that achieves the above-described object is a low melting point metal or low melting point obtained by cooling and solidifying a low melting point metal or low melting point alloy having a melting point of 100 ° C. or higher and 250 ° C. or lower in a mold. The alloy is removed from the mold to obtain an electrode plate, and has a length equal to or greater than the length of one side of at least one main surface of the obtained electrode plate, and a melting point higher than the melting point of the electrode plate. in the method for manufacturing install them anode in contact with the holding member surface made of a metal or alloy having, in a state in which low-melting-point metal or alloy in said mold is melted, insert the rod in the vicinity of the one side, Merged the The electrode plate is formed so that the rod portion becomes a through hole, the holding member is configured, a through hole is formed at an end of the electrode plate holding member that holds the electrode plate, and the electrode plate and the electrode plate Opposite the through hole of the holding member The electrode plate and the electrode are formed in a plate shape in which a through-hole is formed on the device, and the electrode plate and the electrode are constituted by two conductive connection members that constitute the holding member and electrically connect the electrode plate and the electrode plate holding member. The electrode plate holding member and the electrode plate are electrically connected by the conductive connection member with a side surface of a connection portion to which the plate holding member is connected interposed therebetween . Further, the anode manufacturing method according to the present invention comprises cooling and solidifying a low melting point metal or low melting point alloy having a melting point of 100 ° C. or higher and 250 ° C. or lower in a mold, and solidifying the solidified low melting point metal or low melting point alloy into the mold. An electrode plate is obtained by taking out the electrode plate, and has a length equal to or greater than the length of the one side in the vicinity of one side of at least one main surface of the obtained electrode plate, and has a melting point higher than the melting point of the electrode plate. In the method of manufacturing an anode for attaching a holding member made of a metal or an alloy so as to be in surface contact, the electrode plate having the groove formed by the convex portion on the outer periphery using the mold having the convex portion protruding from the inner wall Forming a holding member, forming a through hole at an end of the electrode plate holding member that holds the electrode plate, and facing the groove of the electrode plate and the through hole of the electrode plate holding member. Plate with through holes A connecting portion where the electrode plate and the electrode plate holding member are connected by two conductive connection members that constitute the holding member and electrically connect the electrode plate and the electrode plate holding member. And the electrode plate holding member and the electrode plate are electrically connected by the conductive connection member.

  In the present invention, a holding member having a length equal to or longer than the length of one side of at least one main surface of the electrode plate is attached to the electrode plate while being in surface contact with each other. By suppressing the temperature rise due to electrical resistance and preventing melting of the electrode plate, and holding the entire vicinity of one side of at least one main surface of the electrode plate even when some softening is caused by resistance heating, the electrode plate Can be prevented, and electrolysis can be performed for a long time. Furthermore, in the present invention, even when a large voltage or current is applied, the holding member is attached in surface contact to suppress the temperature rise due to electrical resistance and prevent the electrode plate from melting, so long-term electrolysis can be performed. It can be carried out.

  Further, in the present invention, the electrode plate can be easily melted by using a low melting point metal or low melting point alloy having a low melting point of 100 ° C. or more and 250 ° C. or less, and cooled and solidified to obtain an electrode plate by casting. Just by attaching a holding member to the vicinity of one side of at least one main surface of the electrode plate, a temperature rise due to electrical resistance at the connecting portion between the electrode plate and the holding member is suppressed, and melting of the electrode plate is prevented. In addition, it is possible to efficiently manufacture an anode that is prevented from dropping even when softening occurs due to resistance heating.

It is a perspective view of the anode to which this invention is applied. It is a disassembled perspective view of the same anode. It is a disassembled perspective view of the anode which has an electrode plate in which the groove part was formed. It is a figure which shows the relationship between a casting_mold | template and a fixed plate, (A) is a top view, (B) is a side view. It is a perspective view which shows the relationship between a casting_mold | template, a fixed plate, and a stick | rod. It is a perspective view of the casting_mold | template which manufactures the electrode plate which has a groove part. It is the schematic of an electrolysis apparatus. It is the schematic which shows arrangement | positioning of the electrode in an electrolytic vessel. It is a top view of the anode used by the comparative example. It is a top view of the conventional anode. It is a top view of the conventional anode. It is a top view of the conventional anode.

  Below, the anode to which the present invention is applied and the production thereof will be described in detail with reference to the drawings. Note that the present invention is not limited to the following detailed description unless otherwise specified.

<1. Anode>
The anode 1 shown in FIG. 1 and FIG. 2 to which the present invention is applied is an anode used for electrolysis, and is of a type that is hooked or hung on a power feeding part of an electrolysis apparatus. In the anode 1, a holding member 3 that holds the electrode plate 2 during electrolysis is attached to a holding member attachment surface 2 a that is located near one side of both main surfaces of the electrode plate 2.

  The electrode plate 2 is made of a low melting point metal or low melting point alloy having a melting point of 100 ° C. or higher and 250 ° C. or lower, and is formed in a square or rectangular plate shape, for example. Examples of the low melting point metal or low melting point alloy include tin, indium, an alloy of indium and tin (for example, In-9.6 wt% Sn), an alloy of indium and gallium (for example, In-6.3 wt% Ga), and the like. Can do.

  The thickness of the electrode plate 2 is appropriately determined from preventing the electrode plate 2 from falling off the holding member 3 due to the weight of the electrode plate 2 itself, and the thickness of the anode 1 becoming thinner as electrolysis proceeds. For example, the thickness of the electrode plate 2 is preferably 2 mm or more and 15 mm or less. A thickness of 2 mm or less is not preferable because it is thin and may be broken during handling, and the anode 1 for electrolysis is easily pitted. On the other hand, when the thickness is 15 mm or more, the electrode plate 2 becomes heavy and easily falls off, making it difficult to handle, and when the anode 1 becomes thin as the electrolysis progresses, the distance between the electrodes increases and the voltage rises significantly. This is not preferable.

  The low melting point metal or low melting point alloy forming the electrode plate 2 is characterized by being softer as the purity is higher and the temperature is higher. For this reason, the electrode plate 2 obtained by molding the low melting point metal or the low melting point alloy into a plate shape has the holding member 3 having a large contact area attached to the holding member attaching surface 2a located above when the electrode plate 2 is attached to the electrolysis apparatus. The state suspended by the holding member 3 in the electrolytic solution is maintained.

  The holding member 3 is attached to the holding member mounting surface 2a of the electrode plate 2, holds the electrode plate 2 in an electrolytic solution during electrolysis, and electrically connects the electrode plate 2 and a power feeding unit provided in the electrolysis apparatus. Connect to.

  The holding member 3 is made of a metal or alloy having a melting point higher than that of the electrode plate 2 and high electrical conductivity. By using a metal or alloy having a melting point higher than the melting point of the electrode plate 2, the holding member 3 is melted before the electrode plate 2 even if the resistance increases at the contact portion with the electrode plate 2 and the temperature rises. Thus, the electrode plate 2 can be prevented from falling off. Examples of the metal or alloy forming the holding member 3 include silver, copper, gold, and alloys thereof. Among them, it is preferable to use copper that is inexpensive in terms of cost.

  The holding member 3 is preferably made of a metal or alloy having a high melting point and high electrical conductivity and coated with a metal having a low ionization tendency that does not cause corrosion by the electrolytic solution. Examples of the metal for coating include noble metals such as platinum and titanium in order to prevent the core material from forming a non-conductive film due to corrosion or the like. Among them, it is preferable to use titanium which is inexpensive in terms of cost. When the requirement for corrosion resistance by the electrolytic solution is not high, it is more preferable to select a metal having high electrical conductivity and wear resistance.

  The core material can be coated by a general method such as welding, plating, or cladding. There is no problem in partially covering only the portions where there is a risk of corrosion. If there is no concern about corrosion due to the electrolytic solution, only the uncovered core material may be used as the holding member 3.

  As the shape of the holding member 3, it is attached so as to be in surface contact with one side of at least one main surface of the electrode plate 2, that is, the holding member attaching surface 2 a, and holds the electrode plate 2. As long as they can be electrically connected, the shape is not particularly limited.

  Examples of the holding member 3 include those shown in FIGS. 1 and 2. The holding member 3 shown in FIG. 1 is electrically connected via the electrode plate 2 and the conductive connection member 6, electrically connects the electrode plate 2 and the power feeding unit, and holds the electrode plate 2 in the electrolyte. The electrode plate holding member 4, the conductive connection member 6 that electrically connects the electrode plate 2 and the electrode plate holding member 4, and the bolt 5 that attaches the conductive connection member 6 to the electrode plate 2 and the electrode plate holding member 4. Have.

  The lower end of the electrode plate holding member 4 is connected to the electrode plate 2 via the conductive connection member 6, and the upper end of the electrode plate holding member 4 is horizontally oriented so that the electrode plate 2 is hooked or hung on the power feeding portion. It has a structure with arms extended. This overhanging portion becomes a power supply connecting portion 4a that is electrically connected to the power supply portion. The power feeding connecting portion 4a may be formed in a horizontal bar shape or a plate shape. The shape of the power supply connection portion 4a is preferably a structure that can ensure a sufficient contact area with the power supply portion, and when the anode and cathode are alternately installed (see FIG. 8), the distance between the anode and cathode electrodes It should be something that does not become too wide.

  The conductive connecting member 6 has a length equal to or longer than the length of the holding member mounting surface 2a of the electrode plate 2 and the bolt 5 so as to be in contact with the entire holding member mounting surface 2a of the electrode plate 2 formed in a plate shape. And the electrode plate holding member 4 are formed in a plate shape having a sufficient width that can be connected integrally. It is preferable to use a metal having good conductivity for the conductive connecting member 6. Since the conductive connecting member 6 is connected to the electrode plate 2 by surface contact, heat is diffused even if the temperature rises due to electric resistance at the connection portion between the electrode plate 2 and the conductive connecting member 6, so that the electrode plate 2 is melted. The electrode plate 2 can be prevented from melting even when a large voltage or current is applied. Further, even if the temperature rises due to electric resistance and softening occurs somewhat, the entire holding member mounting surface 2a of the electrode plate 2 and the conductive connecting member 6 are connected, so that the electrode plate 2 can be prevented from falling off.

  As shown in FIGS. 1 and 2, the electrode plate 2 and the holding member 3 are connected in a state where the electrode plate holding member 4 is abutted against the electrode plate 2, and the connecting portion between the electrode plate 2 and the electrode plate holding member 4. Is sandwiched between two conductive connection members 6 from the side surfaces, that is, from both main surfaces of the electrode plate 2, and the electrode plate 2 and the two conductive connection members 6, and the electrode plate holding member 4 and the two conductive connection members 6. Bolts 5 are passed through each of them, and the bolts 5 and nuts (not shown) are fastened. At this time, one through hole 9 of the two conductive connecting members 6 is a screw hole corresponding to the bolt 5, and the electrode plate 2 and the electrode plate holding member 4 are connected to the conductive connecting member 6 without using a nut. You may fasten using the volt | bolt 5. FIG. Thereby, the electrode plate 2 and the holding member 3 having the electrode plate holding member 4 and the two conductive connection members 6 are integrated, and the electrode plate 2 and the electrode plate holding member 4 are connected by the bolt 5 and the conductive connection member 6. Are electrically connected. As shown in FIG. 2, the electrode plate 2, the electrode plate holding member 4 and the conductive connection member 6 are previously formed with through holes 7, 8, and 9 through which the bolts 5 are passed. In the case of connection by such a connection method, as shown in FIG. 1, an example in which four bolts 5 are attached to each of the electrode plate 2 and the electrode plate holding member 4 has been shown, but the present invention is limited to this. However, it is preferable to connect with a plurality of bolts 5, preferably three or more bolts 5, and particularly preferably three or four in order to firmly fix the electrode plate 2 to the holding member 3 and to avoid complicated operations. It is particularly preferable to do this. The distance between the bolts 5 may be sufficiently widened symmetrically and equally spaced.

  Further, as shown in FIG. 3, the electrode plate 2 may have a through hole 7 through which the bolt 5 is passed as a groove 7 a. The groove portion 7a is provided on the outer peripheral portion of the electrode plate 2 facing the electrode plate holding member 4, and the upper end portion side facing the electrode plate holding member 4 is opened, and is formed into a groove shape by cutting with a width equal to or larger than the diameter of the bolt 5. Has been. The shape of the groove portion 7a is not limited to the U-shaped groove portion shown in FIG. 3, but may be, for example, a triangular or quadrangular groove, and the bolt 5 is passed through the groove portion 7a of the electrode plate 2. Any shape may be used as long as it can be attached to the electrode plate holding member 4.

Even when the electrode plate 2 shown in FIG. 3 is used, the electrode plate 2 and the holding member 3 can be connected as in the case shown in FIG. Both main surfaces of the butted electrode plate 2 and electrode plate holding member 4 are sandwiched between two conductive connection members 6, and the groove 7a of the electrode plate 2, the two conductive connection members 6, and the electrode plate holding member 4 and two sheets. Bolts 5 are passed through each of the conductive connecting members 6 and the bolts 5 and nuts (not shown) are fastened. By sandwiching the electrode plate 2 between the two conductive connection members 6, the electrode plate 2 can be attached without dropping from the electrode plate holding member 4 even in the groove portion 7 a formed in a groove shape.

  In the electrode plate 2 shown in FIG. 3, the electrode plate 2 can be easily attached to and detached from the electrode plate holding member 4 by using a groove-like groove portion 7 a instead of a through-hole as a part through which the bolt 5 passes. For example, when replacing the electrode plate 2 during continuous operation, the bolt 5 is removed and the two conductive connecting members 6 are not completely separated from the electrode plate 2 and the electrode plate holding member 4, but only by loosening the bolt 5 The used electrode plate 2 can be easily removed from the holding member 3. Then, with the electrode plate 2 removed, the new electrode plate 2 is inserted between the conductive connection member 6 so that the bolt 5 fits into the groove portion 7a, and the bolt 5 is tightened to easily form the electrode. The plate 2 can be fixed. Thus, since the electrode plate 2 in which the groove part 7a is formed can be easily attached and detached, the working efficiency can be improved.

  In the holding member 3 shown in FIG. 1, the electrode plate 2 and the electrode plate holding member 4 are sandwiched between two conductive connection members 6, and the connection state is maintained by the bolts 5 and the conductive connection members 6, so that the electrode plate 2 is electrolyzed. Hold in liquid. In addition, the holding member 3 electrically connects the electrode plate 2 and the electrode plate holding member 4 via the conductive connection member 6, and electrically connects the electrode plate 2 and the power supply portion on which the power supply connection portion 4a is caught. Connecting.

  The holding member 3 is not limited to the one shown in FIG. 1, and as a simpler method, for example, a method of attaching and detaching with one touch using a pinching force using a spring or the like may be adopted. However, in this case, when the electrode plate 2 is sandwiched from the holding member 3 shown in FIG. Corrosion countermeasures become more important and maintenance becomes complicated. For this reason, when using for a long period of time, the holding member 3 using the bolt 5 shown in FIG. 1 having a simpler structure is preferable. The holding member 3 is attached only to the holding member mounting surface 2a of one main surface of the electrode plate 2 as long as the electrode plate 2 can be held and the electrode plate 2 and the power feeding portion can be electrically connected. It may be a thing.

  In the anode 1 having the above-described configuration, the electrode plate 2 and the holding member 3, for example, the conductive connection member 6 in FIG. 1 are in surface contact even if the electrode plate 2 is formed of a low melting point metal or a low melting point alloy. Therefore, even if resistance heating occurs in the connection portion, heat is diffused and the temperature rise is suppressed, so that melting of the electrode plate 2 can be prevented, and the holding member for the electrode plate 2 even if resistance heating causes some softening By holding the entire mounting surface 2a with the holding member 3, it is possible to prevent the electrode plate 2 from falling off and to perform electrolysis for a long time. In the anode 1, since the electrode plate 2 and the holding member 3 are in surface contact, even when a large voltage or current is passed through the electrode plate 2, the electrode plate 2 does not fall off, and for a long time. Electrolysis can be performed. Moreover, since the anode 1 is held without dropping from the holding member 3 even when the thickness of the electrode plate 2 is increased, for example, a thickness of 8 mm or more, it can be electrolyzed for a long time.

<2. Method for producing anode>
Regarding the manufacturing method of the anode 1, the manufacturing method of the electrode plate 2 will be described first. The electrode plate 2 is manufactured by casting using a mold that matches the shape of the electrode plate 2.

  Specifically, the electrode plate 2 used for the anode 1 shown in FIGS. 1 and 2 is equivalent to the size of the electrode plate 2 on a graphite carbon plate having a sufficient thickness, for example, as shown in FIGS. It forms using the casting_mold | template 10 in which the recessed part 10a to form was formed. By using the graphite carbon mold 10, the heat is easily transferred to the metal placed in the recess 10 a during heating, so that the metal is easily melted and the solidified metal from the mold 10 is easily taken out after cooling.

  As the mold 10, in addition to graphite carbon, polytetrafluoroethylene or a refractory metal can be used from the viewpoint of heat resistance. However, in the case of polytetrafluoroethylene, since the thermal conductivity is poor, it takes time to melt the metal, which is not preferable. In the case of a high melting point metal, wettability with a molten low melting point metal or a low melting point alloy becomes high, and it becomes difficult to peel off from a mold when cooled and solidified, which is not preferable. Therefore, graphite carbon is preferable as a material having good thermal conductivity and less deformation due to thermal expansion and good peelability. The dimensions of the mold 10 are determined by the thickness and width dimensions of the electrode plate 2. In order to make it easier to take out the cooled and solidified electrode plate 2, the recess 10 a of the mold 10 may be provided with an angle so that the inner wall extends from the bottom surface toward the opening.

  At the time of casting using the mold 10 described above, the through hole 7 through which the bolt 5 for attaching the holding member 3 is passed is formed on the holding member attaching surface 2a to which the holding member 3 of the electrode plate 2 to be formed is attached. For example, as a method for forming the through hole 7, as shown in FIGS. 4 and 5, while the low melting point metal or the low melting point alloy is melted in the mold 10, it is the same as the bolt 5 from the opening side of the mold 10. By inserting the rod 11 having a diameter, the inserted rod 11 portion becomes the through hole 7. In order to fix the rod 11 in the molten low-melting-point metal or low-melting-point alloy, the fixing plate 13 is formed in a plate shape having a size almost the same as the width of the mold 10 and has a through hole 12 for passing the rod 11. Use.

  The fixing plate 13 is parallel to the mold 10 and covers the opening of the mold 10 without floating on the mold 10. In addition, the fixing plate 13 has a structure in which the positional accuracy is firmly maintained so that the fixing plate 13 is appropriately covered on the mold 10 every time casting is repeated. For this reason, as shown in FIG. 5, the fixed plate 13 has the same height as the thickness of the mold 10 on the bottom surface of one short side so as to be L-shaped. An accuracy maintaining member 14 having the same length is attached.

  The accuracy maintaining member 14 is fitted so as to slide along the outer surface of the mold 10 when the fixing plate 13 is put on the mold 10. Since the accuracy maintaining member 14 is formed at the same height as the mold 10, the accuracy of the height of the fixing plate 13 can be maintained, and the length is formed to be the same as the length of the fixing plate 13. By matching the end portion 14a with the corner portion 10b of the mold 10, the accuracy of the position of the through hole 12 through which the rod 11 is passed can be maintained. The accuracy maintaining member 14 is not limited to the above-described structure as long as high positional accuracy can be maintained.

  The rod 11 forming the through hole 7 is preferably heat resistant and has a poor wettability with the metal so that it can be easily removed even after the low melting point metal or low melting point alloy is solidified. For example, it is preferable to use a rod 11 made of polytetrafluoroethylene.

  The size of the rod 11 needs to have a length sufficient to penetrate the electrode plate 2 to be cast and a diameter corresponding to the diameter of the bolt 5. The number of rods 11 and the interval at which the rods 11 are inserted are adjusted to the number and position of the bolts 5.

  When the electrode plate 2 is manufactured using such a mold 10 or the like, the low melting point metal or low melting point alloy is heated to the melting point or higher in the mold 10 and the low melting point metal or low melting point alloy is sufficiently melted. The fixing plate 13 in a state where the rod 11 is passed through the hole 12 in a state of spreading in the mold 10 is placed on the mold 10 so that the rod 11 faces the portion where the through hole 7 is formed, and the rod is placed in the molten metal. 11 is inserted. Then, the metal is cooled and solidified by standing with the rod 11 inserted. Then, the rod 11 is extracted from the hole 12, and the solidified metal is removed from the mold 10 to obtain the electrode plate 2 in which the through hole 7 is formed. In this method of manufacturing the electrode plate 2, it is preferable to heat the mold 10 in order to maintain the molten state of the low melting point metal or the low melting point alloy until the rod 11 is inserted.

  And the through-hole 8 is formed in the edge part connected with the conductive connection member 6 of the electrode plate holding member 4, and the through-hole 7 of the electrode plate 2 of the conductive connection member 6 and the through-hole 8 of the electrode plate holding member 4 are opposed. A through-hole 9 through which the bolt 5 is passed is formed at a position where it is to be performed. Examples of the method for forming the through holes 8 and 9 include cutting with a general drill.

  Next, the holding member 3 is attached to the holding member attaching surface 2a of the electrode plate 2 obtained as described above, and the anode 1 is manufactured. The electrode plate 2 and the electrode plate holding member 4 are abutted, and the abutted portion is sandwiched between two conductive connecting members 6 from both sides, and the electrode plates 2, the electrode plate holding member 4, and the through holes 7 and 8 of the conductive connecting member 6. 9, the bolt 5 is passed through and the bolt 5 and the nut are fastened, whereby the electrode plate 2 and the holding member 3 are integrated, and the anode 1 is obtained.

  Although the above-described method for manufacturing the anode 1 has been described with respect to the case where the holding member 3 is as shown in FIG. 1, the attachment method suitable for each structure is used depending on the structure of the holding member 3.

  In the above, the manufacturing method of the anode 1 using the electrode plate 2 having the through hole 7 has been described. Next, the manufacturing method of the anode 1 using the electrode plate 2 having the groove 7a will be described.

  The electrode plate 2 having the groove 7a can be manufactured using a mold 15 shown in FIG. The mold 15 has a sufficiently thick graphite carbon plate formed with a recess 15a corresponding to the size of the electrode plate 2, and a protrusion 15b protruding from the inner wall at a position corresponding to the groove 7a. In order to make it easier to take out the cooled and solidified electrode plate 2, the recess 15 a of the mold 15 may be provided with an angle so that the inner wall extends from the bottom surface toward the opening.

  When manufacturing the electrode plate 2, the low melting point metal or low melting point alloy is heated to the melting point or higher in the mold 15, and the low melting point metal or low melting point alloy is sufficiently melted and spread in the mold 15. Allow to cool and solidify. Then, the solidified metal is removed from the mold 15 to obtain the electrode plate 2 in which the groove 7a is formed.

  In the manufacturing method of this electrode plate 2, since it is not necessary to form the through-hole 7 as described above, it is not necessary to melt and hold the low melting point metal or low melting point alloy of the electrode material in the mold 15, After melting the low melting point metal or the low melting point alloy in the container, the electrode plate 2 may be obtained by pouring into the recess 15a of the mold 15.

In the electrode plate 2 in which the groove portion 7a is formed, since the convex portion 15b that forms the groove portion 7a is formed in the mold 15, the low melting point metal or the low melting point alloy is melted in the mold 15 and cooled or solidified. The low-melting-point metal or low-melting-point alloy can be poured and the metal can be cooled and solidified. Thereby, the electrode plate 2 in which the groove part 7a was formed can be manufactured more easily and efficiently than the electrode plate 2 in which the through-hole 7 was formed.

When using the electrode plate 2 in which the groove portion 7a is formed, the bolt 5 is first passed through the through holes 8 and 9 of the electrode plate holding member 4 and the conductive connection member 6, and the bolt 5 and the nut are tightened loosely. Then, after inserting the bolt 5 into the groove portion 7a of the electrode plate 2, the bolt 5 and the nut may be firmly tightened to obtain the anode 1 in which the electrode plate 2 and the holding member 3 are integrated.

  In the manufacturing method of the anode 1 described above, the electrode plate 2 can be easily melted by using a low melting point metal or low melting point alloy having a low melting point of 100 ° C. or more and 250 ° C. or less. The electrode plate 2 is obtained by molding with a mold, and the electrode plate 2 can be obtained simply by attaching the holding member 3, for example, the conductive connecting member 6 in FIG. The anode 1 is efficiently produced in which the temperature rise due to the resistance is suppressed at the connection portion between the holding member 3 and the holding member 3, the electrode plate 2 is not melted, and is prevented from falling off even if it is somewhat softened by resistance heating. can do. Further, in the method for manufacturing the anode 1, even when a large voltage or current is passed, the temperature rise due to the electrical resistance is suppressed by attaching the holding member 3 in surface contact, and the electrode plate 2 does not melt, The anode 1 that is prevented from falling off can be efficiently manufactured.

  Moreover, in the manufacturing method of the anode 1, when manufacturing the anode 1 shown in FIG. 1 with the structure shown in FIG. 2, as shown in FIG.4 and FIG.5, the through-hole 7 which lets the volt | bolt 5 of the electrode plate 2 pass is formed. At this time, the electrode plate 2 in which the through-holes 7 are formed can be easily manufactured simply by inserting the rod 11 positioned by the fixing plate 13 into the molten low melting point metal or low melting point alloy. Thereby, when the anode 1 shown in FIG. 1 is manufactured with the configuration shown in FIG. 2, the conductive connecting member 6 is connected to the electrode plate 2 with the bolt 5 by using the electrode plate 2 having the through hole 7. Therefore, the anode 1 can be manufactured efficiently.

  When the anode 1 having the structure shown in FIG. 3 is manufactured, the electrode plate 2 in which the groove portion 7a is formed is obtained simply by pouring a molten low melting point metal or low melting point alloy into the mold 15 as shown in FIG. Therefore, the electrode plate 2 can be manufactured more easily. Further, when the anode 1 is manufactured with the configuration shown in FIG. 3, the electrode plate 2 is made to be electrically conductive with the bolt 5 loosened without completely separating the conductive connection member 6 from the electrode plate holding member 4. The electrode plate 2 and the electrode plate holding member 4 can be connected by inserting the bolt 5 between the connecting members 6 so as to enter the groove portion 7 a and then tightening the bolt 5 firmly. When the electrode plate 2 in which the groove 7a is formed is used, the anode 1 can be manufactured more efficiently because it can be easily replaced especially when the used electrode plate 2 is replaced with a new electrode plate 2. Can do.

  Specific examples to which the present invention is applied will be described below, but the present invention is not limited to these examples.

<Example 1>
In Example 1, the anode shown in FIG. 1 was produced with the same configuration as the anode using the electrode plate in which the through hole shown in FIG. 2 was formed.

  An indium electrode plate having a thickness of 4 mm and a size of 27 cm in length and width was prepared by melt casting using a mold (see FIG. 5).

  The mold was manufactured by adding a concave portion having a depth of 15 mm and a length and width of 27 cm to carbon graphite having a thickness of 30 mm and a length and width of 30 cm. The fixing plate was prepared by scraping a carbon graphite lump having a length of 65 mm, a width of 35 cm, and a height of 35 mm into a plate shape having a length of 60 mm, a width of 30 mm, and a height of 30 mm. The dimension d (see FIG. 4) of the accuracy maintaining member attached to the fixed plate was set to 30 mm, which was the same as the thickness of the carbon graphite, and the length was set to be the same as the horizontal 30 mm of the fixed plate. In the fixing plate, four through holes having a diameter of 5 mm were formed at equal intervals. Here, the positions of the through holes were arranged so as to be at an interval of 6.8 cm on a line having a distance of 15 mm from the upper side of the electrode plate. Also, four rods made of Teflon having a diameter of 5 mm and a length of 3 cm were prepared as the rods for forming the bolt through holes.

  An indium electrode plate was cast as follows using the mold and the like produced as described above. The prepared mold was placed on a large hot plate (HP-A2234M, 30 cm × 30 cm) manufactured by AS ONE, and 2000 g of indium metal was placed thereon. In this state, the hot plate was heated to about 300 ° C. and held. When the indium metal was completely dissolved, the end of the accuracy maintaining member attached to the fixed plate was placed on one corner of the mold, and a Teflon rod was inserted into the four through holes to cool down. . After the indium metal cooled to room temperature, the Teflon rod was pulled out, the fixing plate was removed, and the mold was turned over. The solidified indium metal could be quickly peeled off from the mold. The thickness of the obtained indium electrode plate was about 4 mm.

  Next, the indium electrode plate was attached to the holding member manufactured as follows. The holding member is a copper material having the same shape as the holding member shown in FIG. 1, and an electrode plate holding member and a conductive connecting member, which are molded into a shape with an upper side length of 40 cm and a lower side reduced to 27 cm, are prepared. Was coated with titanium. Four through-holes for passing 5 mm bolts were formed on the line with a distance of 15 mm upward from the lower side of the electrode plate holding member so that the centers became 6.8 cm apart. Bolts were passed through the through holes of the holding member and the indium electrode plate, and the bolts and nuts were used to join them at four locations. The length from the top to the bottom of the anode in which the indium electrode plate and the holding member were integrated was 40 cm.

Electrolysis was performed using the anode produced as described above. As the electrolysis apparatus 20, the apparatus shown in FIG. 7 was used. The electrolyte solution 21 was prepared by preparing 100 L of a 1 mol / L ammonium nitrate aqueous solution and adding nitric acid thereto to adjust the pH to 4.0. This was put into an electrolytic cell 23 provided with a liquid dispersion plate 22 to keep the electrolytic solution 21 at 25 ° C. Further, four anodes 24 and five cathodes 25 are arranged as shown in FIG. 8 so that the distance between the pole centers is 2.0 cm, and the anode 24 and the cathode 25 are connected to a two-core VV cable (JIS C 3342 allowable current 200A, nominal cross-sectional area 100mm ² ), and connected to a rectifier.

  In the electrolyzer 20, a 1 mol / L ammonium nitrate aqueous solution having a pH of 4.0 is contained in a regulating tank 27 provided adjacent to the electrolytic tank 23. The adjustment tank 27 is connected to the electrolytic tank 23 by a circulation pump 28 and circulates the electrolytic solution 21. The adjustment tank 27 includes a stirring rod 29 for stirring the electrolytic solution 21, a pH electrode 30 for measuring pH, a temperature adjusting heater 31 for controlling and maintaining the temperature of the electrolytic solution 21, and a cooler 32.

In the electrolysis apparatus 20 having such a configuration, electrolysis was performed while maintaining the current so that the current density was 15 A / dm ² .

  During electrolysis, the contact temperature between the indium electrode plate and the conductive connecting member changed between 50 ° C. and 80 ° C., and no deformation of the indium electrode plate was observed due to the temperature rise. In Example 1, it was possible to continuously generate indium hydroxide in the electrolytic solution for 6 hours by electrolysis, and the obtained slurry could be solid-liquid separated.

<Example 2>
In Example 2, the anode shown in FIG. 1 was produced with the same structure as the anode using the electrode plate in which the groove part shown in FIG. 3 was formed.

  An indium electrode plate having a thickness of 8 mm, a length of 349 mm, and a width of 260 mm was produced by melt casting using a mold (see FIG. 6).

  The mold was manufactured by attaching a concave portion having a depth of 15 mm, a bottom portion of 349 mm length, and a width of 260 mm inside carbon graphite having a thickness of 30 mm, a length of 400 mm, and a width of 300 mm. More specifically, the inner wall of the mold was inclined so as to be 355 mm long and 266 mm wide at a depth of 8 mm. Moreover, the convex part which protrudes from one short side is formed in the casting_mold | template. The convex portion has a shape having an angle such that the width is 14 mm, the length is 17 mm, and the depth is 8 mm at the bottom position of the concave portion of the mold, and the width is 8 mm and the length is 14 mm. Three convex portions were provided at equal intervals. The convex portion was formed in a U shape with the other end not connected to the short side of the mold being arcuate.

  Then, a 2 L stainless steel pan was placed on a large hot plate (HP-A2234M, 30 cm × 30 cm) manufactured by ASONE Co., and 5000 g of indium metal was put thereon. In this state, the hot plate was heated to about 300 ° C. and held to completely dissolve the indium metal. This molten indium was poured into the aforementioned mold. Then, after solidifying by cooling at room temperature for 15 minutes, the mold was turned over. The solidified indium metal could be quickly peeled off from the mold. Three grooves were formed on one side of the electrode plate without any problem, and an indium electrode plate having a thickness of 8 mm, a length of 349 mm, and a width of 260 mm was obtained.

  Attachment to the holding member was performed in the same manner as in Example 1 except that the number of attachment bolts was reduced from four to three. Electrolysis was also performed in the same manner as in Example 1.

  In Example 2, indium hydroxide could be generated for 12 hours by electrolysis, and the resulting slurry could be solid-liquid separated.

<Example 3>
In Example 3, an anode using an electrode plate in which the groove formed in the U shape in Example 2 was formed into a triangular V shape was produced. The other conditions were the same as in Example 2.

  In Example 3 as well, indium hydroxide could be generated for 12 hours by electrolysis, and the resulting slurry could be solid-liquid separated.

<Comparative example>
As shown in FIG. 9, the comparative example has a portion 40 a that protrudes to the left and right by 6.5 cm in the lateral direction above the anode 40 having a width of 27 cm, a length of 40 cm, and a thickness of 4 mm, and includes the protruding portion 40 a. An anode 40 made of indium metal having a shape with a total length of 40 cm was molded. The overhanging portion 40a of the anode 40 was hooked on the power feeding portion 41 and electrolysis was performed under the same conditions as in Example 1.

  Immediately after the start of electrolysis, the temperature in the vicinity of the contact point between the protrusion 40a of the anode 40 and the power feeding portion 41 starts to gradually increase, and indium softens and melts immediately before reaching 150 ° C. after 30 minutes, and the anode 40 falls. At this point, electrolysis had to be terminated.

  From the above examples and comparative examples, when the melting temperature is low, such as indium, and the electrode plate and the holding member are in surface contact as in Examples 1-3, the electrode plate can be prevented from melting. It can be seen that long-term electrolysis is possible.

  On the other hand, as in the comparative example, when the electrode plate and the power feeding part are in contact with each other in a small area, a material having a low melting point such as indium melts, electrolysis time is shortened, and the metal can be sufficiently deposited. I understand that I can't.

  DESCRIPTION OF SYMBOLS 1 Anode, 2 Electrode plate, 2a Holding member attachment surface, 3 Holding member, 4 Electrode plate holding member, 5 Bolt, 6 Conductive connection member, 7 Through hole, 7a Groove part, 8 Through hole, 9 Through hole, 10 Mold, 10a Concave part, 10b corner part, 11 bar, 12 through hole, 13 fixing plate, 14 accuracy maintaining member, 14a end part, 15 mold, 15a concave part, 15b convex part, 20 electrolysis device, 21 electrolytic solution, 22 liquid dispersion plate, 23 Electrolyzer, 24 Anode, 25 Cathode, 26 Conductor, 27 Conditioner, 28 Circulating Pump, 29 Stirring Rod, 30 pH Electrode, 31 Heater, 32 Cooler

Claims (13)

In the vicinity of one side of at least one main surface of an electrode plate made of a low melting point metal or low melting point alloy having a melting point of 100 ° C. or more and 250 ° C. or less, the melting point of the electrode plate A holding member made of a metal or alloy having a higher melting point is attached by surface contact ;
The holding member has an electrode plate holding member for holding the electrode plate, and electrically connecting the electrode plate and the electrode plate holding member, and a conductive connection member formed in a plate shape,
The side surface of the connection portion where the electrode plate and the electrode plate holding member are connected is sandwiched between two conductive connection members, and the electrode plate and the electrode plate holding member are electrically connected via the conductive connection member. An anode characterized by being made . The upper Symbol electrode plate and the electrode plate holding member and two of the conductive connecting member and the above electrode plate and the electrode plate holding member and the above conductive connection member by caulking the bolts passed through so as to be integrated The anode according to claim 1, wherein the anode is electrically connected to the anode.   The anode according to claim 2, wherein the electrode plate has a through hole or a groove at a portion through which the bolt penetrates.   The anode according to any one of claims 1 to 3, wherein the electrode plate has a thickness of 2 mm or more and 15 mm or less.   The anode according to any one of claims 1 to 4, wherein the low-melting-point metal is indium or tin.   The anode according to any one of claims 1 to 5, wherein the holding member is made of copper.   The anode according to any one of claims 1 to 6, wherein a surface of the holding member is coated with a metal that is not corroded by an electrolytic electrolyte. A low melting point metal or low melting point alloy having a melting point of 100 ° C. or higher and 250 ° C. or lower was cooled and solidified in a mold, and the solidified low melting point metal or low melting point alloy was taken out of the mold to obtain an electrode plate. A holding member made of a metal or alloy having a melting point higher than the melting point of the electrode plate is brought into surface contact in the vicinity of one side of at least one principal surface of the electrode plate. in the method for manufacturing install them anode,
In a state where the low melting point metal or low melting point alloy in the mold is melted, a rod is inserted in the vicinity of the one side, and the electrode plate is formed so that the inserted rod portion becomes a through hole,
Constituting the holding member, forming a through hole at an end of the electrode plate holding member holding the electrode plate,
The electrode plate and the electrode plate holding member have a plate-like shape in which a through hole is formed at a position facing the through hole of the electrode plate and constitutes the holding member, and electrically connects the electrode plate and the electrode plate holding member. Sandwiching the side surface of the connecting portion where the electrode plate and the electrode plate holding member are connected by two conductive connecting members to be connected;
A method for producing an anode, wherein the electrode plate holding member and the electrode plate are electrically connected by the conductive connecting member . Upper Symbol electrode plate bolt to penetrate into the through hole of the through-holes and the two conductive connecting member through-hole and the electrode plate holding member of caulking, the electrode plate and the electrode plate holding member and two above 9. The method for producing an anode according to claim 8, wherein a conductive connecting member is integrated, and the electrode plate holding member and the electrode plate are electrically connected by the conductive connecting member.   10. The method for manufacturing an anode according to claim 8, wherein the mold is made of graphite carbon.   The method of manufacturing an anode according to claim 9 or 10, wherein the rod is made of polytetrafluoroethylene. A low melting point metal or low melting point alloy having a melting point of 100 ° C. or higher and 250 ° C. or lower was cooled and solidified in a mold, and the solidified low melting point metal or low melting point alloy was taken out of the mold to obtain an electrode plate. A holding member made of a metal or alloy having a melting point higher than the melting point of the electrode plate is brought into surface contact in the vicinity of one side of at least one principal surface of the electrode plate. In the manufacturing method of the anode attached to
Using the mold having a convex portion protruding from the inner wall, forming the electrode plate having a groove portion formed by the convex portion portion on the outer peripheral portion,
Constituting the holding member, forming a through hole at an end of the electrode plate holding member holding the electrode plate,
A plate-like shape in which a through hole is formed at a position facing the groove portion of the electrode plate and the through hole of the electrode plate holding member, constituting the holding member, and electrically connecting the electrode plate and the electrode plate holding member. Sandwiching the side surface of the connecting portion to which the electrode plate and the electrode plate holding member are connected by two conductive connecting members that are connected together,
Method of manufacturing an anode, characterized by connecting the electrode plate holding member and the electrode plate above Kishirubeden connecting member electrically. A bolt is passed through the groove of the electrode plate, the through hole of the electrode plate holding member, and the through hole of the two conductive connection members, and the electrode plate, the electrode plate holding member, and the two conductive connections. 13. The method for producing an anode according to claim 12, wherein a member is integrated, and the electrode plate holding member and the electrode plate are electrically connected by the conductive connection member.

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