A cathode plate for electrolytic manganese dioxide and an electrode assembly

Abstract

The application provides a cathode plate for electrolyzing manganese dioxide and an electrode assembly, and relates to the field of manganese dioxide processing, and comprises an upper connecting rib plate, a copper pipe frame connected with the upper connecting rib plate, corrugated plates, the width direction of the corrugated plates being consistent with the length direction of the upper connecting rib plate, the length direction of the corrugated plates being perpendicular to the length direction of the upper connecting rib plate, and the corrugated plates being arranged at intervals along the length direction of the upper connecting rib plate, wherein the corrugated plates are made of conductive material, the traditional tubular cathode plate is improved into a copper plate with a corrugated shape in the application, the cathode surface area is increased by about 10% compared with the traditional tubular cathode plate, the electrolysis cross section reaction efficiency is effectively improved, the electric field distribution is optimized, and the current distribution characteristics of the electrolysis electric field are significantly improved.

Description

Technical Field

[0001] This utility model relates to the field of manganese dioxide processing, and in particular to a cathode plate and electrode assembly for electrolytic manganese dioxide. Background Technology

[0002] In the industrial production of electrolytic manganese dioxide, the cathode assembly serves as the core reaction carrier, and its structural design and material properties directly affect electrolysis efficiency, product quality, and equipment operating costs. Currently, the industry commonly employs two types of cathode technologies, both of which suffer from significant technical bottlenecks:

[0003] The first type is a copper tube cathode plate:

[0004] While constructing a conductive framework using copper tube arrays can meet basic conductivity requirements, its tubular geometry leads to the following systemic defects:

[0005] Corrosion failure risk: In a strongly acidic electrolyte environment (pH<1.5), the copper tube wall thickness is lost at a rate of 0.15-0.25 mm / thousand hours due to electrochemical corrosion (tested according to GB / T 16545 standard). The H+ / Cu²+ concentration gradient formed in the tube cavity triggers a local micro-battery effect, accelerating the tube perforation process (average life <8000h).

[0006] Deterioration of current distribution: The distortion of the edge electric field caused by the circular cross section caused the current density deviation in the effective reaction zone to reach ±18%, which in turn caused manganese dioxide crystals to grow dendrites along the tube wall, and the tap density of the product fluctuated by more than 0.2 g / cm³.

[0007] Operation and maintenance costs: A single cathode repair takes 12-15 hours. 2 Furthermore, a new corrosion-sensitive zone will form in the weld heat-affected zone (HV hardness decreases by 23%).

[0008] The second type is composite graphite cathode technology.

[0009] While hot pressing of graphite powder (particle size D50 = 45 μm) with epoxy resin (60 wt%) can avoid metal corrosion problems, it presents the following irreversible failure modes:

[0010] Interfacial delamination failure: Under cyclic thermal shock at 50-95℃, the resin-graphite interface generates shear stress due to the difference in CTE, resulting in a delamination rate of 5.2 times / thousand hours (refer to ISO 4624 test).

[0011] Conductive network degradation: Electrolyte penetration increased the interfacial resistivity of the carbon fiber (10wt%) and matrix by three orders of magnitude (from the initial value). Up to 1.2Ω·m);

[0012] Mechanical performance degradation: After 300 assembly and disassembly cycles, the bending strength of the cathode plate (100) decreased from the initial 126 MPa to 58 MPa (three-point bending test, ASTM D790).

[0013] Common technical defects

[0014] Both of the above-mentioned traditional technical solutions face the following industrialization challenges:

[0015] The effective reaction area of ​​the cathode is negatively correlated with the structural strength; for copper tube type, every 12% increase in area leads to a 35% reduction in service life.

[0016] There is an inverse relationship between electrical conductivity stability and corrosion resistance. Although the corrosion rate of graphite cathodes is reduced to 0.01 mm / a, the conductivity loss rate increases by 30% / year.

[0017] It is impossible to achieve both uniform current distribution (σ>15%) and manufacturing precision (flatness>0.8mm / m) in large-size cathode plates (>2m²).

[0018] For the reasons mentioned above, the structure of the cathode plate urgently needs to be optimized. Utility Model Content

[0019] This invention provides a cathode plate and electrode assembly for electrolytic manganese dioxide, which aims to optimize the reaction efficiency of existing cathode plates in the electrolytic cross section and the current sharing characteristics of electrolytic power plants.

[0020] To achieve the above objectives, embodiments of this utility model provide a cathode plate for electrolytic manganese dioxide, comprising:

[0021] Upper connecting stiffener plate;

[0022] A copper tube frame, wherein the copper tube frame and the upper connecting stiffener form a sealed area around the copper tube frame;

[0023] A corrugated plate has a length direction and a width direction. The width direction of the corrugated plate is consistent with the length direction of the upper connecting stiffener. The length direction of the corrugated plate is perpendicular to the length direction of the upper connecting stiffener. Several corrugated plates are arranged at intervals along the length direction of the upper connecting stiffener.

[0024] The corrugated plate includes a first horizontal section in a straight line shape, and second horizontal sections are provided on both sides of the first horizontal section in the width direction. The first horizontal section and the second horizontal sections are parallel, and the first horizontal section and the two second horizontal sections are respectively connected by a first connecting section.

[0025] The corrugated plate is made of a conductive material.

[0026] Preferably, the first connecting part and the first horizontal part form an angle α, the angle α is an obtuse angle, the width c of the first horizontal part is 40mm-60mm, the width b of the corrugated plate is 100mm-120mm, and the spacing width between the corrugated plates is 24.2mm.

[0027] Preferably, the corrugated plate is made of copper.

[0028] Preferably, a conductive rod is also fixed on the upper connecting rib plate, and the other end of the conductive rod is connected to a square copper tube.

[0029] Preferably, at least two conductive rods are provided.

[0030] This application also provides an electrode assembly for electrolyzing manganese dioxide, including the aforementioned cathode plate and an anode plate;

[0031] The cathode plate is parallel to the plane containing the anode plate.

[0032] Preferably, the anode plate is composed of multiple anode units connected end to end. Each anode unit includes a third horizontal section and a fourth horizontal section disposed on both sides of the third horizontal section. The third horizontal section and the two fourth horizontal sections are respectively connected by a second connecting section, and the third horizontal section and the second connecting section form an obtuse angle.

[0033] Preferably, the width of the corrugated plate is the same as the width of the three anode units, and the distance between the planes where the cathode plate and the anode plate are located is 50mm-100mm.

[0034] The above-mentioned solution of this utility model has the following beneficial effects:

[0035] In this application, the traditional tubular cathode plate is improved by replacing it with a nearly corrugated copper plate, which increases the cathode surface area by approximately 10% and effectively enhances the reaction efficiency of the electrolytic cross section. At the same time, the crests (i.e., the second horizontal section) and troughs (i.e., the first horizontal section) can optimize the electric field distribution, reduce the relative deviation of the cathode current density, and significantly improve the current-sharing characteristics of the electrolytic electric field.

[0036] Other features and advantages of this invention will be described in detail in the following detailed description section. Attached Figure Description

[0037] Figure 1 This is a schematic diagram of the cathode plate;

[0038] Figure 2 This is a schematic diagram of a corrugated sheet;

[0039] Figure 3 This is a schematic diagram of the electrolytic current of the electrode assembly in this application;

[0040] Figure 4 This is a schematic diagram of the current in a traditional tubular anode electrolysis system.

[0041] [Explanation of Labels in the Attached Image]

[0042] 100 - Cathode plate, 110 - Upper connecting stiffener, 120 - Copper pipe frame

[0043] 130 - Corrugated plate, 131 - First horizontal section, 132 - Second horizontal section

[0044] 140 - Conductive rod, 150 - Square copper tube

[0045] 200 - Anode plate, 210 - Anode unit Detailed Implementation

[0046] To make the technical problems, technical solutions and advantages of this utility model clearer, a detailed description will be given below in conjunction with the accompanying drawings and specific embodiments.

[0047] like Figures 1-4 As shown, an embodiment of the present invention provides a cathode plate for electrolytic manganese dioxide, including an upper connecting rib plate 110, a copper tube frame 120 and a corrugated plate 130, wherein the upper connecting rib plate 110 and the copper tube frame 120 surround to form a sealed area, and the aforementioned corrugated tube is disposed in the sealed area.

[0048] Specifically, the copper tube frame 120 includes a lower connecting rib and a side tube. The lower connecting rib is parallel to the upper connecting rib 110. The side tube is fixedly connected to the upper connecting rib 110 at both ends of the lower connecting rib, so that a rectangular sealing area is formed between the copper tube frame 120 and the upper connecting rib 110.

[0049] The corrugated plate 130 has a length direction and a width direction. The width direction of the corrugated plate 130 is consistent with the length direction of the upper connecting stiffener 110, and the length direction of the corrugated plate 130 is perpendicular to the length direction of the upper connecting stiffener 110. A plurality of corrugated plates 130 are arranged at intervals along the length direction of the upper connecting stiffener 110. The upper and lower ends of the corrugated plates 130 are fixedly connected to the upper connecting stiffener 110 and the lower connecting stiffener, respectively.

[0050] In this application, the upper connecting stiffener 110 and the lower connecting stiffener are provided with grooves for the corrugated plate 130 to be inserted into. The two ends of the corrugated plate 130 are inserted into the corresponding grooves to fix the corrugated plate 130.

[0051] In this application, the corrugated plate 130 includes a first horizontal portion 131 and a second horizontal portion 132. Both the first horizontal portion 131 and the second horizontal portion 132 are straight. The two second horizontal portions 132 are located on both sides of the first horizontal portion 131, and the plane containing the two second horizontal portions 132 is parallel to the plane containing the first horizontal portion 131. The two ends of the first horizontal portion 131 are connected to the two second horizontal portions 132 respectively through a first connecting portion.

[0052] As described above, the corrugated plate 130 is approximately wave-shaped, with crests (i.e., the second horizontal section 132) and troughs (i.e., the first horizontal section 131). Both the crests and troughs are straight, which helps to alleviate the phenomenon of edge electric field distortion.

[0053] The corrugated plate 130 is made of a conductive material, preferably copper.

[0054] An angle α is formed between the first connecting part and the first horizontal part 131. The angle α is an obtuse angle. The width c of the first horizontal part 131 is 40mm-60mm, the width b of the corrugated plate 130 is 100mm-120mm, and the spacing between the corrugated plates 130 is 24.2mm.

[0055] Furthermore, a conductive rod 140 is also provided on the upper connecting stiffener 110. One end of the conductive rod 140 is fixed to the upper connecting stiffener 110, and the other end is connected to a square copper tube 150. At least two conductive rods 140 are provided. In this embodiment, two conductive rods 140 are provided. The conductive rods 140 can be used for conducting electricity and also serve to fix the square copper tube 150 and the upper connecting stiffener 110.

[0056] In this application, a corrugated plate 130 is used instead of a tubular structure, effectively increasing the surface area of ​​the cathode and enhancing the reaction efficiency of the electrolytic cross section. Simultaneously, by optimizing the electric field distribution through corrugated peaks and troughs, the relative deviation of the current density of the cathode plate 100 is reduced from ±15% in the traditional structure to ±8%, significantly improving the current sharing characteristics of the electrolytic power plant. Finally, this application overcomes the material limitations of traditional cathode structures, increasing the regularity of manganese dioxide to 98.7%, reducing the standard deviation of grain size to 0.24 μm, and achieving a product tap density of 1.92 g / cm³. 3 Industry-leading level.

[0057] This application also provides an electrode assembly for electrolyzing manganese dioxide, which includes, in addition to the aforementioned cathode plate 100, an anode plate 200, wherein the anode plate 200 is parallel to the plane on which the cathode plate 100 is located.

[0058] The anode plate 200 is composed of multiple anode units 210 connected end to end. The anode unit 210 has a structure similar to that of the corrugated plate 130, including a third horizontal part and a fourth horizontal part disposed on both sides of the third horizontal part. The third horizontal part and the fourth horizontal parts on both sides are connected by a second connecting part, and the third horizontal part and the second connecting part form an obtuse angle.

[0059] Understandably, the cathode plate 100 is electrically connected to the cathode of the power supply, and the anode plate 200 is electrically connected to the anode of the power supply. To fix the anode plate 200, it can also be fixed and conductive using an upper connecting rib plate 110 and a copper tube frame 120.

[0060] Preferably, the width of the corrugated plate 130 is the same as the width of the three anode units 210, that is, each corrugated plate 130 corresponds to three anode units 210. In this application, the corrugated plate 130 effectively enhances the overall strength of the cathode plate 100, and compared with the conventional copper tube cathode, it effectively increases the area and improves the uniformity of current during electrolysis. At the same time, the use of the corrugated plate 130 effectively avoids the occurrence of perforation and extends the service life of the corrugated plate 130. The spacing between the cathode plate 100 and the anode plate 200 is between 50-100mm, ensuring that the current resistance damage of the cathode plate 100 and the anode plate 200 is small, while fully considering the growth space for electrolytic manganese dioxide.

[0061] The above description is the preferred embodiment of this utility model. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of this utility model, and these improvements and modifications should also be considered within the protection scope of this utility model.

Claims

1. A cathode plate for electrolytic manganese dioxide, characterized in that, include: Upper connecting stiffener plate (110); A copper tube frame (120) and the upper connecting stiffener (110) surround each other to form a sealed area; The corrugated plate (130) has a length direction and a width direction. The width direction of the corrugated plate (130) is consistent with the length direction of the upper connecting stiffener (110). The length direction of the corrugated plate (130) is perpendicular to the length direction of the upper connecting stiffener (110). A plurality of the corrugated plates (130) are arranged at intervals along the length direction of the upper connecting stiffener (110). The corrugated plate (130) includes a first horizontal section (131) in a straight line shape, and second horizontal sections (132) are provided on both sides of the first horizontal section (131) in the width direction. The first horizontal section (131) and the second horizontal sections (132) are parallel, and the first horizontal section (131) and the two second horizontal sections (132) are respectively connected by a first connecting part. The corrugated plate (130) is made of conductive material.

2. The cathode plate for electrolytic manganese dioxide according to claim 1, characterized in that: The first connecting part and the first horizontal part (131) form an angle α, which is an obtuse angle. The width c of the first horizontal part (131) is 40mm-60mm, the width b of the corrugated plate (130) is 100mm-120mm, and the spacing between the corrugated plates (130) is 24.2mm.

3. The cathode plate for electrolytic manganese dioxide according to claim 1, characterized in that: The corrugated plate (130) is made of copper.

4. The cathode plate for electrolytic manganese dioxide according to claim 1, characterized in that: A conductive rod (140) is also fixed on the upper connecting rib plate (110), and the other end of the conductive rod (140) is connected to a square copper tube (150).

5. The cathode plate for electrolytic manganese dioxide according to claim 4, characterized in that: At least two conductive rods (140) are provided.

6. An electrode assembly for electrolyzing manganese dioxide, comprising the cathode plate (100) according to any one of claims 1-5, characterized in that: It also includes an anode plate (200); The cathode plate (100) is parallel to the plane containing the anode plate (200).

7. The electrode assembly for electrolytic manganese dioxide according to claim 6, characterized in that: The anode plate (200) is composed of multiple anode units (210) connected end to end. The anode unit (210) includes a third horizontal part and a fourth horizontal part disposed on both sides of the third horizontal part. The third horizontal part and the two fourth horizontal parts are respectively connected by a second connecting part. The third horizontal part and the second connecting part form an obtuse angle.

8. The electrode assembly for electrolytic manganese dioxide according to claim 7, characterized in that: The width of the corrugated plate (130) is the same as the width of the three anode units (210), and the distance between the planes where the cathode plate (100) and the anode plate (200) are located is 50mm-100mm.

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