CN219689899U - Fence type titanium-based lead dioxide electrode plate - Google Patents
Fence type titanium-based lead dioxide electrode plate Download PDFInfo
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- CN219689899U CN219689899U CN202321174214.1U CN202321174214U CN219689899U CN 219689899 U CN219689899 U CN 219689899U CN 202321174214 U CN202321174214 U CN 202321174214U CN 219689899 U CN219689899 U CN 219689899U
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- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 title claims abstract description 360
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 288
- 239000010936 titanium Substances 0.000 title claims abstract description 286
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 286
- 239000002131 composite material Substances 0.000 claims abstract description 183
- 230000003014 reinforcing effect Effects 0.000 claims abstract description 85
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 44
- 230000007704 transition Effects 0.000 claims abstract description 38
- 229910052802 copper Inorganic materials 0.000 claims abstract description 28
- 239000010949 copper Substances 0.000 claims abstract description 28
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- 229910006529 α-PbO Inorganic materials 0.000 claims description 51
- 239000011159 matrix material Substances 0.000 claims description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 23
- 229910044991 metal oxide Inorganic materials 0.000 claims description 23
- -1 tin metal oxide Chemical class 0.000 claims description 19
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 12
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- 229910000978 Pb alloy Inorganic materials 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 11
- 239000011229 interlayer Substances 0.000 claims description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 6
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 6
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 6
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 6
- 235000011151 potassium sulphates Nutrition 0.000 claims description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 6
- 235000011152 sodium sulphate Nutrition 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 12
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 9
- 229910001887 tin oxide Inorganic materials 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000005416 organic matter Substances 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 7
- 229910003460 diamond Inorganic materials 0.000 description 7
- 239000010432 diamond Substances 0.000 description 7
- 238000004070 electrodeposition Methods 0.000 description 7
- 238000005868 electrolysis reaction Methods 0.000 description 6
- 238000010079 rubber tapping Methods 0.000 description 6
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- NPNMHHNXCILFEF-UHFFFAOYSA-N [F].[Sn]=O Chemical compound [F].[Sn]=O NPNMHHNXCILFEF-UHFFFAOYSA-N 0.000 description 2
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Abstract
The utility model relates to a fence-type titanium-based lead dioxide electrode plate, and belongs to the technical field of nonferrous metal electrometallurgical extraction. The fence-type titanium-based lead dioxide electrode plate comprises an electrode plate main body, wherein the electrode plate main body comprises a fence-type titanium-based composite lead dioxide plate body and conductive reinforcing ribs, and the fence-type titanium-based composite lead dioxide plate body comprises a plurality of vertical hollow titanium-based/lead dioxide composite pipes I, horizontal hollow titanium-based/lead dioxide composite pipes II and horizontal hollow titanium-based/lead dioxide composite pipes III; the top end of the transverse hollow titanium-based/lead dioxide composite pipe II is fixedly provided with a transition titanium plate, and the top end of the transition titanium plate is fixedly provided with a titanium-coated copper conductive beam. The fence-type titanium-based lead dioxide electrode plate can improve current density, reduce material cost and anode mud, improve cathode product quality and anode service life, and prevent aging deformation phenomenon caused by long-term soaking of insulating strips or plastic cards in electrolyte without adopting insulating strips or plastic cards.
Description
Technical Field
The utility model relates to a fence-type titanium-based lead dioxide electrode plate, and belongs to the technical field of nonferrous metal hydrometallurgy.
Background
Anode plates are used in the fields of hydrometallurgy nonferrous metal industry and the like, lead alloy anode plates are adopted in the current domestic metallurgy industry electrolysis, and the anode plates have high energy consumption and poor corrosion resistance in different degrees in the electrolysis process, and the materials of the anode plates are dissolvedThe quality of the product is reduced after the electrolyte is added, and the environment is greatly polluted in the production and the production process. The lead-base alloy anode has the disadvantages of large weight, low strength, easy bending deformation in use, short circuit, reduced current efficiency, necessity of lifting the deformed anode out of an electrolytic tank for hammering and leveling, high labor intensity, great drop of the anode surface layer, shortened service life of the anode and the like, and does not accord with energy conservation and emission reduction. In addition, because the area of the polar plate is large>0.5m 2 ) The low conductivity makes the current distribution on the surface of the polar plate uneven, the polarization degree of the polar plate is different at each position, the polarization degree at the electrolyte/air interface is highest, especially in the electrolyte containing high chloride ion and organic matter, the corrosion is more serious, and the polar plate is easy to break neck. In addition, the traditional plate anode plate is of an integral plate type, so that the flow of an electrolytic solution can be partially blocked in the electro-deposition process, and the concentration polarization is relatively large; the anode plate has small single-section area and low strength due to incomplete stress elimination in the rolling process, and is easy to deform and cause short circuit in the using process.
The aluminum-based lead alloy composite fence type anode plate is prepared by using aluminum to manufacture a plurality of aluminum bars, and then using wrapping equipment to wrap lead alloy on the aluminum bars. The method has the advantages that concentration polarization can be reduced, manufacturing materials are saved compared with a plate anode plate, and energy consumption is reduced; the anode plate has the defects that the anode plate cannot eliminate the heating phenomenon in the electrodeposition process, electrolyte is required to be cooled in the subsequent process, the structure stability of the anode plate is insufficient, the whole anode plate is easy to deform, the current of the composite rod is unevenly distributed, the conductive beam is corroded, and the like, and meanwhile, in the use process, the anode mud is difficult to clean, and the anode plate is easy to short-circuit due to excessive anode mud deposition. The fence-type anode plate adopting the insulating clamping strips to connect and fix the composite rod is complex and tedious in manufacturing process, affects production efficiency, and the insulating strips are easy to age and deform after being soaked in electrolyte for a long time, thus being unfavorable for the stability of the anode plate structure.
Novel inert lead dioxide anode: the electrode is prepared by adopting titanium, graphite, plastic, ceramic and the like as matrix materials, and roughening the surface of the matrix, coating a bottom layer and alpha-PbO 2 Intermediate layer and electroplated beta-PbO 2 The basic process is that PbO is obtained by plating 2 An electrode. But PbO thus electroplated 2 The electrode acts as an insoluble anode, and the following problems occur in use: (1) PbO (PbO) 2 The deposited layer is not tightly combined with the surface of the electrode or is uneven; (2) PbO (PbO) 2 The lamination is porous and rough, and the internal stress is large; (3) PbO (PbO) 2 The deposited layer is easy to peel off or corrode, and the service life is not long. And doped with fluorine-containing resin and/or inert particulate PbO 2 The cell voltage of the electrode used in nonferrous metal electrodeposition is high. (4) When the large-size flat plate or corrugated polar plate is used, thermal deformation and bending are generated when the current is excessive, and the thermal bending deformation can lead to cathode-anode short-circuit breakdown, directly influence the quality of a finished product of a cathode and lead to PbO on the surface of an anode plate 2 The ceramic oxide falls off, so that the anode plate is scrapped, and the strength is poor in the process of knocking the anode plate to obtain a finished product.
The U-shaped cylindrical tube type water-cooled anode plate for electrodeposited metal adopts a hollow seamless cylindrical lead-aluminum alloy composite tube, so that the material consumption is greatly reduced, and the manufacturing cost of the anode plate is reduced by 30%; the strength of the anode plate is increased by the application of the cylindrical tubular structure, and the stability of the external dimension of the anode plate is ensured; the application of cooling water effectively controls the heating temperature of the anode plate during electrolytic deposition, reduces the tank voltage, reduces the electricity consumption and improves the electrodeposition efficiency. However, lead-aluminum alloy has complex preparation process and poor corrosion resistance, and particularly in electrolyte containing high chloride ions and organic matters, the corrosion is more serious.
Disclosure of Invention
Aiming at the defects of the existing electrolytic deposition anode plate, the utility model provides a fence-type titanium-based lead dioxide electrode plate, namely, a fence-type titanium-based composite lead dioxide plate body is reinforced by adopting two layers of transverse conductive reinforcing ribs and two longitudinal conductive reinforcing ribs, so that the mechanical strength of the whole anode plate is greatly improved, and the deformation resistance of the anode is remarkably improved. The fence-type titanium-based lead dioxide electrode plate has the advantages of corrosion resistance, high rigidity, deformation resistance, effective improvement of electrodeposition efficiency and long service life.
The utility model adopts the technical proposal for solving the technical problems that:
a fence-type titanium-based lead dioxide electrode plate comprises an electrode plate main body,
the electrode plate main body comprises a fence-type titanium-based composite lead dioxide plate body 3 and conductive reinforcing ribs 4, the conductive reinforcing ribs 4 comprise two layers of transverse conductive reinforcing ribs, a longitudinal conductive reinforcing rib I and a longitudinal conductive reinforcing rib II, the two layers of transverse conductive reinforcing ribs are horizontally and fixedly arranged in the middle of the fence-type titanium-based composite lead dioxide plate body 3, the longitudinal conductive reinforcing ribs I and the longitudinal conductive reinforcing ribs II are respectively and fixedly arranged at two sides of the fence-type titanium-based composite lead dioxide plate body 3, and two ends of the transverse conductive reinforcing ribs are respectively fixed on the longitudinal conductive reinforcing ribs I and the longitudinal conductive reinforcing ribs II;
the fence-type titanium-based composite lead dioxide plate body 3 comprises a plurality of vertical hollow titanium-based/lead dioxide composite pipes I, a plurality of horizontal hollow titanium-based/lead dioxide composite pipes II and a plurality of horizontal hollow titanium-based/lead dioxide composite pipes III, wherein the plurality of vertical hollow titanium-based/lead dioxide composite pipes I are equidistantly arranged, and the horizontal hollow titanium-based/lead dioxide composite pipes II and the horizontal hollow titanium-based/lead dioxide composite pipes III are respectively fixedly arranged at the top end and the bottom end of the hollow titanium-based/lead dioxide composite pipes I;
the top end of the transverse hollow titanium-based/lead dioxide composite pipe II is fixedly provided with a transition titanium plate 2, and the top end of the transition titanium plate 2 is fixedly provided with a titanium-coated copper conductive beam 1.
Preferably, the titanium base at the top end of the transverse hollow titanium base/lead dioxide composite tube II is welded with the bottom end of the transition titanium plate 2, and the top end of the transition titanium plate 2 is welded with the titanium outer layer at the bottom end of the titanium-coated copper conductive beam 1.
The conductive reinforcing rib 4 sequentially comprises a titanium matrix I41, a fluorine-doped tin metal oxide intermediate layer I42 and alpha-PbO from inside to outside 2 /β-PbO 2 Nano Ti 4 O 7 Composite active layer i 43.
The outer surface of the titanium matrix I41 is in a zigzag shape, a diamond shape, a tapping shape or a twist shape, the tooth space is 0.1-1.0 mm, and the tooth depth is 0.05-0.8 mm; the thickness of the fluorine-doped tin metal oxide interlayer I42 is 1-3 mu m, alpha-PbO 2 /β-PbO 2 Nano Ti 4 O 7 The total thickness of the composite active layer II 33 is 0.1-2 mm, alpha-PbO 2 Layer thickness of alpha-PbO 2 /β-PbO 2 Nano Ti 4 O 7 20-50% of the total thickness of the composite active layer II 33.
The transverse conductive reinforcing ribs of the conductive reinforcing ribs 4 are vertical titanium-based/lead dioxide composite pipes IV, titanium-based/lead dioxide composite sheets or titanium-based/lead dioxide composite nets, and the longitudinal conductive reinforcing ribs I and the longitudinal conductive reinforcing ribs II are titanium-based/lead dioxide composite pipes V.
When the transverse conductive reinforcing ribs are vertical titanium-based/lead dioxide composite pipes IV, a plurality of vertical through holes are uniformly formed in the transverse conductive reinforcing ribs, and the vertical hollow titanium-based/lead dioxide composite pipes I of the fence-type titanium-based composite lead dioxide plate body 3 penetrate through the vertical through holes of the transverse conductive reinforcing ribs; when the transverse conductive reinforcing ribs are titanium-based/lead dioxide composite sheets or titanium-based/lead dioxide composite nets, the transverse conductive reinforcing ribs are horizontally attached and fixedly arranged in the middle of the fence-type titanium-based composite lead dioxide plate body 3.
Preferably, the vertical titanium-base/lead dioxide composite tube IV is a square tube, the section of the square tube is 8-40 mm long, the width is 5-30 mm, and the wall thickness is 0.5-3.0 mm.
Preferably, the heights of the titanium-based/lead dioxide composite sheet and the titanium-based/lead dioxide composite net are 5-100.0 mm, the titanium net is a diamond-shaped titanium net, the mesh length is 2-8 mm, and the net width is 1-5 mm.
Preferably, the titanium-based/lead dioxide composite sheet or the titanium-based/lead dioxide composite net is coated and welded on the front side and the rear side of the fence-type titanium-based composite lead dioxide plate body 3 through argon arc spot welding.
The fence-type titanium-based composite lead dioxide plate body 3 sequentially comprises a titanium tube substrate II 31, a fluorine-doped tin metal oxide intermediate layer II 32 and alpha-PbO from inside to outside 2 /β-PbO 2 Nano Ti 4 O 7 Composite active layer ii 33.
Preferably, the outer surface of the titanium tube substrate II 31 is in a zigzag shape, a diamond shape, a tapping shape or a twist shape, the tooth space is 0.1-1.0 mm, and the tooth depth is 0.05-0.8 mm; fluorine doped tin oxide intermediatesThe thickness of the layer is 1-5 mu m; alpha-PbO 2 /β-PbO 2 Nano Ti 4 O 7 The total thickness of the composite active layer II 33 is 0.1-2 mm, alpha-PbO 2 Layer thickness of alpha-PbO 2 /β-PbO 2 Nano Ti 4 O 7 20-50% of the total thickness of the composite active layer II 33.
Preferably, the vertical hollow titanium-base/lead dioxide composite pipe I, the horizontal hollow titanium-base/lead dioxide composite pipe II and the horizontal hollow titanium-base/lead dioxide composite pipe III are round pipes or oval pipes, the section length diameter is 5-20 mm, and the wall thickness is 0.5-3.0 mm; the distance between adjacent vertical hollow titanium-based/lead dioxide composite pipes I is 3-15 mm.
The titanium-coated copper conductive beam 1 sequentially comprises a copper core 11, a nickel transition layer 12 and a titanium outer layer 13 from inside to outside.
Preferably, the length of the titanium-coated copper conductive beam 1 is 1000-2000 mm, the copper core is rectangular, the material is selected as T2, the height of the cross section of the copper core is 10-80 mm, and the thickness is 6-50 mm; the thickness of the nickel transition layer is 5-20 mu m; the titanium outer layer is made of TA1 or TA2, and the thickness of the titanium outer layer is 0.5-4 mm.
The two ends of the titanium-coated copper conductive beam 1 are fixedly provided with conductive heads connected with a copper core 11.
Hollow cavities of the fence-type titanium-based composite lead dioxide plate body 3 and the conductive reinforcing ribs 4 are filled with sodium sulfate solution, lead alloy, magnesium sulfate solution, potassium sulfate solution or calcium sulfate solution; the sodium sulfate solution, the lead alloy, the magnesium sulfate solution, the potassium sulfate solution or the calcium sulfate solution can play a role in heat dissipation and increase weight, so that the plate is prevented from floating upwards or being greatly and laterally swung by liquid flow in the use process, and the filled substance does not introduce impurity ions to affect the deposition of cathode zinc copper.
Preferably, the transition titanium plate 2 is symmetrically provided with a rectangular opening I and a rectangular opening II on two sides of the vertical central axis.
Preferably, the height of the transition titanium plate 2 is 50-200 mm, the thickness is 3-10 mm, the distance between the rectangular opening I and the vertical central axis is 100-300 mm, the height of the rectangular opening I is 30-100 mm, and the width of the rectangular opening I is 50-200 mm.
The utility model has the beneficial effects that:
(1) According to the utility model, the barrier-type titanium-based composite lead dioxide plate body is reinforced by adopting two layers of transverse conductive reinforcing ribs and two longitudinal conductive reinforcing ribs, so that the mechanical strength of the whole plate is greatly improved, and the deformation resistance of the anode is remarkably improved;
(2) The utility model roughens the surface of the titanium matrix into a zigzag shape, a diamond shape, a tapping shape or a twist shape, and then sequentially arranges the fluorine-doped tin oxide intermediate layer and the alpha-PbO 2 Inner layer and beta-PbO 2 Nano Ti 4 O 7 A composite outer layer; can solve the problems of titanium matrix and alpha-PbO 2 With interfacial resistance, alpha-PbO 2 beta-PbO tightly bonded with fluorine tin oxide but having poor corrosion resistance and good corrosion resistance 2 The technical problems of poor adhesion with a matrix and the like, and the service life of the electrode plate is prolonged;
(3) Compared with the traditional fence-type titanium rod matrix, the fence-type anode plate provided by the utility model has the advantages that the material cost is low, the prepared electrode is low, the electrode distance between the cathode and the anode is shortened under the same specific surface area, the metal ion deposition speed is high, the improvement of the current efficiency of a cathode product and the increase of the yield are facilitated;
(4) beta-PbO of the utility model 2 Nano Ti 4 O 7 The composite outer layer has high catalytic activity and low internal stress, so that the electrode has low energy consumption and long service life in the electrodeposition process;
(5) The titanium plate is used as the transition plate at the liquid interface of the anode plate, so that corrosion of impurity chloride ions or organic matters in the electrolyte to the anode plate can be prevented, and the service life of the anode plate can be prolonged; especially in the sulfate electrolyte of high chloride ion and organic matter, compared with the traditional lead alloy anode, the service life is obviously prolonged, the produced anode mud is less, and the quality of the obtained cathode product is high;
(6) According to the novel fence-type titanium-based lead dioxide electrode plate, the titanium-coated copper conductive beam is provided with the intermediate transition layer nickel, so that the copper and titanium are prevented from being oxidized in the hot rolling process, and the interface resistance of the conductive beam is reduced;
(7) The fence type structure of the utility model does not adopt the insulating clamping strips or the plastic cards to connect and fix the composite rods, thereby avoiding complex and complicated manufacturing process, preventing the aging deformation phenomenon from easily occurring due to the long-term soaking of the insulating strips or the plastic cards in electrolyte and ensuring the stability of the anode plate structure.
Drawings
FIG. 1 is a schematic diagram of the structure of a fence-type titanium-based lead dioxide electrode plate of examples 1-2;
FIG. 2 is a schematic view in section A-A of FIG. 1;
FIG. 3 is a schematic view of section B-B of FIG. 1;
FIG. 4 is a schematic view of section C-C of FIG. 1;
FIG. 5 is a schematic view of section D-D of FIG. 1;
FIG. 6 is a schematic diagram of the structure of a novel barrier-type titanium-based lead dioxide electrode plate of example 5;
FIG. 7 is a schematic view of section D-D of FIG. 6;
FIG. 8 is a schematic diagram of the structure of a novel barrier-type titanium-based lead dioxide electrode plate of example 6;
in the figure: 1-titanium-coated copper conductive beam, 11-copper core, 12-nickel transition layer, 13-titanium outer layer, 2-titanium matrix, 3-fence-type titanium-based composite lead dioxide plate body, 31-titanium tube matrix II, 32-fluorine-doped tin metal oxide intermediate layer II and 33-alpha-PbO 2 /β-PbO 2 Nano Ti 4 O 7 Composite active layer II, 4-conductive reinforcing rib, 41-titanium matrix I, 42-fluorine-doped tin metal oxide intermediate layer I, 43-alpha-PbO 2 /β-PbO 2 Nano Ti 4 O 7 Composite active layer I.
Detailed Description
The utility model will be further described with reference to the following specific embodiments.
Example 1: as shown in fig. 1, a barrier-type titanium-based lead dioxide electrode plate, comprises an electrode plate body,
the electrode plate main body comprises a fence-type titanium-based composite lead dioxide plate body 3 and conductive reinforcing ribs 4, the conductive reinforcing ribs 4 comprise two layers of transverse conductive reinforcing ribs, a longitudinal conductive reinforcing rib I and a longitudinal conductive reinforcing rib II, the two layers of transverse conductive reinforcing ribs are horizontally and fixedly arranged in the middle of the fence-type titanium-based composite lead dioxide plate body 3, the longitudinal conductive reinforcing ribs I and the longitudinal conductive reinforcing ribs II are respectively and fixedly arranged at two sides of the fence-type titanium-based composite lead dioxide plate body 3, and two ends of the transverse conductive reinforcing ribs are respectively fixed on the longitudinal conductive reinforcing ribs I and the longitudinal conductive reinforcing ribs II;
the fence-type titanium-based composite lead dioxide plate body 3 comprises a plurality of vertical hollow titanium-based/lead dioxide composite pipes I, a plurality of horizontal hollow titanium-based/lead dioxide composite pipes II and a plurality of horizontal hollow titanium-based/lead dioxide composite pipes III, wherein the plurality of vertical hollow titanium-based/lead dioxide composite pipes I are equidistantly arranged, and the horizontal hollow titanium-based/lead dioxide composite pipes II and the horizontal hollow titanium-based/lead dioxide composite pipes III are respectively fixedly arranged at the top end and the bottom end of the hollow titanium-based/lead dioxide composite pipes I;
a transition titanium plate 2 is fixedly arranged at the top end of the transverse hollow titanium-based/lead dioxide composite pipe II, and a titanium-coated copper conductive beam 1 is fixedly arranged at the top end of the transition titanium plate 2; the titanium base at the top end of the transverse hollow titanium base/lead dioxide composite tube II is welded with the bottom end of the transition titanium plate 2, and the top end of the transition titanium plate 2 is welded with the titanium outer layer at the bottom end of the titanium-coated copper conductive beam 1;
the barrier-type titanium-based composite lead dioxide plate body is reinforced by adopting two layers of transverse conductive reinforcing ribs and two longitudinal conductive reinforcing ribs, so that the mechanical strength of the whole plate is greatly improved, and the deformation resistance of the anode is remarkably improved; compared with the traditional fence-type titanium rod matrix, the hollow titanium matrix is adopted, the material cost is low, the prepared electrode is low in price, and the electrode distance between the cathode and the anode is shortened under the same specific surface area, so that the metal ion deposition speed is high, the improvement of the current efficiency of a cathode product and the increase of the yield are facilitated; the insulating edge clamping strips or the plastic cards are not used for connecting and fixing the composite rods, so that complex and complicated manufacturing processes are avoided, the phenomenon that the insulating strips or the plastic cards are easy to age and deform due to long-term soaking in electrolyte is prevented, and the stability of the anode plate structure is ensured.
Example 2: the fence-type titanium-based lead dioxide electrode plate of this example is substantially the same as the fence-type titanium-based lead dioxide electrode plate of example 1, except that: the conductive reinforcing rib 4 sequentially comprises a titanium matrix I41 and fluorine-doped tin metal oxide from inside to outsideInterlayer I42 and alpha-PbO 2 /β-PbO 2 Nano Ti 4 O 7 Composite active layer i 43;
the outer surface of the titanium matrix I41 is in a zigzag shape, a diamond shape, a tapping shape or a twist shape, the tooth spacing is 0.1-1.0 mm, and the tooth depth is 0.05-0.8 mm; the thickness of the fluorine-doped tin metal oxide interlayer I42 is 1-3 mu m, alpha-PbO 2 /β-PbO 2 Nano Ti 4 O 7 The total thickness of the composite active layer II 33 is 0.1-2 mm, alpha-PbO 2 Layer thickness of alpha-PbO 2 /β-PbO 2 Nano Ti 4 O 7 20-50% of the total thickness of the composite active layer II 33;
the transverse conductive reinforcing ribs of the conductive reinforcing ribs 4 are vertical titanium-based/lead dioxide composite pipes IV, titanium-based/lead dioxide composite sheets or titanium-based/lead dioxide composite nets, and the longitudinal conductive reinforcing ribs I and the longitudinal conductive reinforcing ribs II are titanium-based/lead dioxide composite pipes V;
when the transverse conductive reinforcing ribs are vertical titanium-based/lead dioxide composite pipes IV, a plurality of vertical through holes are uniformly formed in the transverse conductive reinforcing ribs, and the vertical hollow titanium-based/lead dioxide composite pipes I of the fence-type titanium-based composite lead dioxide plate body 3 penetrate through the vertical through holes of the transverse conductive reinforcing ribs; when the transverse conductive reinforcing ribs are titanium-based/lead dioxide composite sheets or titanium-based/lead dioxide composite nets, the transverse conductive reinforcing ribs are horizontally attached and fixedly arranged in the middle of the fence-type titanium-based composite lead dioxide plate body 3;
the vertical titanium-base/lead dioxide composite pipe IV is a square pipe, the section of the square pipe is 8-40 mm long, the width is 5-30 mm, and the wall thickness is 0.5-3.0 mm;
the heights of the titanium-based/lead dioxide composite sheet and the titanium-based/lead dioxide composite net are 5-100.0 mm, the titanium net is a diamond-shaped titanium net, the mesh length is 2-8 mm, and the net width length is 1-5 mm;
the titanium-based/lead dioxide composite sheet or the titanium-based/lead dioxide composite net is coated and welded on the front side and the rear side of the fence-type titanium-based composite lead dioxide plate body 3 through argon arc spot welding;
the fence-type titanium-based composite lead dioxide plate body 3 sequentially comprises a titanium tube substrate II 31, a fluorine-doped tin metal oxide intermediate layer II 32 and alpha-P from inside to outsidebO 2 /β-PbO 2 Nano Ti 4 O 7 A composite active layer II 33;
the outer surface of the titanium tube substrate II 31 is in a zigzag shape, a diamond shape, a tapping shape or a twist shape, the tooth space is 0.1-1.0 mm, and the tooth depth is 0.05-0.8 mm; the thickness of the fluorine-doped tin oxide intermediate layer is 1-5 mu m; alpha-PbO 2 /β-PbO 2 Nano Ti 4 O 7 The total thickness of the composite active layer II 33 is 0.1-2 mm, alpha-PbO 2 Layer thickness of alpha-PbO 2 /β-PbO 2 Nano Ti 4 O 7 20-50% of the total thickness of the composite active layer II 33;
the vertical hollow titanium-based/lead dioxide composite pipe I, the horizontal hollow titanium-based/lead dioxide composite pipe II and the horizontal hollow titanium-based/lead dioxide composite pipe III are round pipes or oval pipes, the section length diameter is 5-20 mm, and the wall thickness is 0.5-3.0 mm; the distance between adjacent vertical hollow titanium-based/lead dioxide composite pipes I is 3-15 mm;
the surface of the titanium matrix is roughened into a zigzag shape, a diamond shape, a tapping shape or a twist shape, and then the fluorine-doped tin oxide intermediate layer and the alpha-PbO are sequentially arranged 2 Inner layer and beta-PbO 2 Nano Ti 4 O 7 A composite outer layer; can solve the problems of titanium matrix and alpha-PbO 2 With interfacial resistance, alpha-PbO 2 beta-PbO tightly bonded with fluorine tin oxide but having poor corrosion resistance and good corrosion resistance 2 The technical problems of poor adhesion with a matrix and the like, and the service life of the electrode plate is prolonged; beta-PbO 2 Nano Ti 4 O 7 The composite outer layer has high catalytic activity and low internal stress, so that the electrode has low energy consumption and long service life in the electrodeposition process.
Example 3: the fence-type titanium-based lead dioxide electrode plate of this example is substantially the same as the fence-type titanium-based lead dioxide electrode plate of example 2, except that: the titanium-coated copper conductive beam 1 sequentially comprises a copper core 11, a nickel transition layer 12 and a titanium outer layer 13 from inside to outside; the titanium-coated copper conductive beam is provided with the intermediate transition layer nickel, so that the copper and titanium are prevented from being oxidized in the hot rolling process, and the interface resistance of the conductive beam is reduced;
the length of the titanium-coated copper conductive beam 1 is 1000-2000 mm, the copper core is rectangular, the material is T2, the height of the cross section of the copper core is 10-80 mm, and the thickness is 6-50 mm; the thickness of the nickel transition layer is 5-20 mu m; the titanium outer layer is made of TA1 or TA2, and the thickness of the titanium outer layer is 0.5-4 mm;
the two ends of the titanium-coated copper conductive beam 1 are fixedly provided with conductive heads connected with a copper core 11;
rectangular openings I and II are symmetrically formed in the two sides of the vertical central axis of the transition titanium plate 2; the height of the transition titanium plate 2 is 50-200 mm, the thickness is 3-10 mm, the distance between the rectangular opening I and the vertical central axis is 100-300 mm, the height of the rectangular opening I is 30-100 mm, and the width is 50-200 mm; the titanium plate is used as a transition plate at the interface of the anode plate and the liquid, so that corrosion of impurity chloride ions or organic matters in the electrolyte to the electrode plate can be prevented, and the service life of the electrode plate can be prolonged; especially in the sulfate electrolyte of high chloride ion and organic matter, compared with the traditional lead alloy anode, the service life is obviously prolonged, the produced anode mud is less, and the quality of the obtained cathode product is high;
the hollow cavities of the fence-type titanium-based composite lead dioxide plate body 3 and the conductive reinforcing ribs 4 are filled with sodium sulfate solution, lead alloy, magnesium sulfate solution, potassium sulfate solution or calcium sulfate solution; the sodium sulfate solution, the lead alloy, the magnesium sulfate solution, the potassium sulfate solution or the calcium sulfate solution can play a role in heat dissipation and increase weight, so that the plate is prevented from floating upwards or being greatly and laterally swung by liquid flow in the use process, and the filled substance does not introduce impurity ions to influence the deposition of cathode zinc and copper;
the preparation method of the fence-type titanium-based lead dioxide electrode plate comprises the following specific steps:
1) Preparing a conductive beam and a transition titanium plate: two rectangular openings are symmetrically punched on a transitional titanium plate along a central axis, chemical nickel plating is performed on the surface of a conductive copper bar by adopting a conventional method, titanium is sleeved on the surface of the conductive copper bar, and is subjected to hot extrusion drawing compounding to obtain a titanium-coated copper conductive beam, then conductive copper heads are exposed at two ends of a milling cutter, and the titanium-coated copper conductive beam is metallurgically welded with the top end of the transitional titanium plate;
2) Preparation of a hollow tube of the metal oxide interlayer barrier-type titanium base plate 3: coating a fluorine-doped tin oxide intermediate layer on the surface of a hollow titanium tube with saw-tooth, diamond-shaped, tapped or twist-shaped teeth on the surface;
3) Preparation of conductive reinforcing ribs containing metal oxide intermediate layers: the surface of the titanium tube, the titanium sheet or the titanium mesh is coated with a fluorine-doped tin oxide intermediate layer, and hollow cavities of the fence-type titanium-based composite lead dioxide plate body 3 and the conductive reinforcing ribs 4 are filled with sodium sulfate solution, lead alloy, magnesium sulfate solution, potassium sulfate solution or calcium sulfate solution;
4) Welding a hollow tube of the fence-type titanium base plate 3 containing the metal oxide interlayer and a conductive reinforcing rib containing the metal oxide interlayer into a whole to obtain a main body of the titanium matrix polar plate;
5) Welding a titanium-coated copper conductive beam, a transition titanium plate and a titanium matrix polar plate main body, and then adopting a conventional method to sequentially electrodeposit alpha-PbO 2 And beta-PbO 2 Nano Ti 4 O 7 Obtaining a novel fence-type titanium-based lead dioxide electrode plate;
the utility model discloses novel titanium-based lead dioxide electrode plate of fence type compares traditional titanium-based lead dioxide net flat board with, at electrolytic zinc liquid 50g LZn 2+ +150g/LH 2 SO 4 +1g/LC1 - In +20mg/L organic matter (calculated by TOC), chloride ions and organic matter electrolyte, under the same electrolysis condition, the material cost is reduced by 10%, the service life is prolonged by 1 time, the cell voltage can be reduced by 50mV, the conductive current efficiency is improved by more than 1%, and the phenomenon of titanium mesh deformation caused by short circuit burning plate is avoided.
Example 4: the fence-type titanium-based lead dioxide electrode plate of this example is substantially the same as the fence-type titanium-based lead dioxide electrode plate of example 2, except that:
the length of the titanium-coated copper conductive beam 1 is 1500mm, the copper core is rectangular, the material is T2, the height of the cross section of the copper core is 50mm, and the thickness is 20mm; the thickness of the nickel transition layer is 10 mu m; the titanium outer layer is made of TA1, and the thickness of the titanium outer layer is 2mm;
rectangular openings I and II are symmetrically formed in the two sides of the vertical central axis of the transition titanium plate 2; the height of the transition titanium plate 2 is 100mm, the thickness is 4mm, the distance from the rectangular opening I to the vertical central axis is 200mm, the height of the rectangular opening I is 60mm, and the width is 100mm;
the transverse conductive reinforcing ribs are vertical titanium-based/lead dioxide composite tubes IV (see fig. 1 and 5), a plurality of vertical through holes are uniformly formed in the transverse conductive reinforcing ribs, and the vertical hollow titanium-based/lead dioxide composite tubes I of the fence-type titanium-based composite lead dioxide plate body 3 penetrate through the vertical through holes of the transverse conductive reinforcing ribs; the vertical titanium-base/lead dioxide composite pipe IV is a square pipe, the section of the square pipe is 28mm long, the width is 20mm, and the wall thickness is 2.0mm;
the conductive reinforcing rib 4 sequentially comprises a titanium matrix I41, a fluorine-doped tin metal oxide intermediate layer I42 and alpha-PbO from inside to outside 2 /β-PbO 2 Nano Ti 4 O 7 Composite active layer i 43; the outer surface of the titanium matrix I41 is zigzag, the tooth spacing is 0.5mm, and the tooth depth is 0.3mm; the thickness of the fluorine-doped tin metal oxide interlayer I42 is 2 mu m, alpha-PbO 2 /β-PbO 2 Nano Ti 4 O 7 The total thickness of the composite active layer I43 is 1mm, and alpha-PbO 2 Layer thickness of alpha-PbO 2 /β-PbO 2 Nano Ti 4 O 7 20% of the total thickness of the composite active layer II 33;
the fence-type titanium-based composite lead dioxide plate body 3 sequentially comprises a titanium tube substrate II 31, a fluorine-doped tin metal oxide intermediate layer II 32 and alpha-PbO from inside to outside 2 /β-PbO 2 Nano Ti 4 O 7 A composite active layer II 33;
the vertical hollow titanium-based/lead dioxide composite pipe I, the horizontal hollow titanium-based/lead dioxide composite pipe II and the horizontal hollow titanium-based/lead dioxide composite pipe III are round pipes, the diameter of the section is 10mm, and the wall thickness is 2.0mm; the distance between adjacent vertical hollow titanium-based/lead dioxide composite pipes I is 10mm; the outer surface of the titanium tube substrate II 31 is zigzag, the tooth space is 0.5mm, and the tooth depth is 0.3mm; the thickness of the fluorine-doped tin oxide intermediate layer is 3 mu m; alpha-PbO 2 /β-PbO 2 Nano Ti 4 O 7 The total thickness of the composite active layer II 33 is 1mm, and alpha-PbO 2 Layer thickness of alpha-PbO 2 /β-PbO 2 Nano Ti 4 O 7 20% of the total thickness of the composite active layer II 33;
compared with the traditional titanium-based lead dioxide mesh, the titanium-based composite lead dioxide mesh electrode plate of the embodimentPlate, in electrolytic zinc liquid 50g/LCu 2+ +200g/LH 2 SO 4 +40mg/LC1 - In +20mg/L organic matter (calculated as TOC), under the same electrolysis condition, the service life is prolonged by 1 time, the cell voltage can be reduced by 100mV, the conducting current efficiency is improved by more than 1.5%, and the phenomenon of titanium mesh deformation caused by short circuit burning plate is avoided.
Example 5: the fence-type titanium-based lead dioxide electrode plate of this example is substantially the same as the fence-type titanium-based lead dioxide electrode plate of example 2, except that:
the length of the titanium-coated copper conductive beam 1 is 2000mm, the copper core is rectangular, the material is T2, the height of the cross section of the copper core is 80mm, and the thickness is 50mm; the thickness of the nickel transition layer is 20 mu m; the titanium outer layer is made of TA1, and the thickness of the titanium outer layer is 4mm;
rectangular openings I and II are symmetrically formed in the two sides of the vertical central axis of the transition titanium plate 2; the height of the transition titanium plate 2 is 200mm, the thickness is 10mm, the distance from the rectangular opening I to the vertical central axis is 300mm, the height of the rectangular opening I is 100mm, and the width is 200mm;
the transverse conductive reinforcing ribs are vertical titanium-based/lead dioxide composite sheets (see figures 1, 6 and 7) and are horizontally attached and fixedly arranged in the middle of the fence-type titanium-based composite lead dioxide plate body 3; the height of the titanium-based/lead dioxide composite sheet is 100.0mm; the titanium-based/lead dioxide composite sheet is coated and welded on the front side and the rear side of the fence-type titanium-based composite lead dioxide plate body 3 through argon arc spot welding; the vertical titanium-base/lead dioxide composite pipe IV is a square pipe, the section of the square pipe is 28mm long, the width is 20mm, and the wall thickness is 3.0mm;
the conductive reinforcing rib 4 sequentially comprises a titanium matrix I41, a fluorine-doped tin metal oxide intermediate layer I42 and alpha-PbO from inside to outside 2 /β-PbO 2 Nano Ti 4 O 7 Composite active layer i 43; the outer surface of the titanium matrix I41 is zigzag, the tooth spacing is 1.0mm, and the tooth depth is 0.8mm; the thickness of the fluorine-doped tin metal oxide interlayer I42 is 1 mu m, alpha-PbO 2 /β-PbO 2 Nano Ti 4 O 7 The total thickness of the composite active layer I43 is 2mm, alpha-PbO 2 Layer thickness of alpha-PbO 2 /β-PbO 2 Nano Ti 4 O 7 50% of the total thickness of the composite active layer II 33;
the fence-type titanium-based composite lead dioxide plate body 3 sequentially comprises a titanium tube substrate II 31, a fluorine-doped tin metal oxide intermediate layer II 32 and alpha-PbO from inside to outside 2 /β-PbO 2 Nano Ti 4 O 7 A composite active layer II 33;
the vertical hollow titanium-based/lead dioxide composite pipe I, the horizontal hollow titanium-based/lead dioxide composite pipe II and the horizontal hollow titanium-based/lead dioxide composite pipe III are round pipes, the diameter of the section is 20mm, and the wall thickness is 3.0mm; the distance between adjacent vertical hollow titanium-based/lead dioxide composite pipes I is 10mm; the outer surface of the titanium tube substrate II 31 is zigzag, the tooth space is 1.0mm, and the tooth depth is 0.8mm; the thickness of the fluorine-doped tin oxide intermediate layer is 5 mu m; alpha-PbO 2 /β-PbO 2 Nano Ti 4 O 7 The total thickness of the composite active layer II 33 is 2mm, alpha-PbO 2 Layer thickness of alpha-PbO 2 /β-PbO 2 Nano Ti 4 O 7 50% of the total thickness of the composite active layer II 33;
compared with the traditional titanium-based lead dioxide net plate, the titanium-based composite lead dioxide net plate in the embodiment has the advantages that the electrolytic zinc liquid is 50g/LCu 2+ +200g/LH 2 SO 4 +40mg/LC1 - In +20mg/L organic matter (calculated as TOC), under the same electrolysis condition, the service life is prolonged by 0.5 times, the cell voltage can be reduced by 100mV, the conducting current efficiency is improved by more than 1.5%, and the phenomenon of titanium mesh deformation caused by short circuit burning plate is avoided.
Example 6: the fence-type titanium-based lead dioxide electrode plate of this example is substantially the same as the fence-type titanium-based lead dioxide electrode plate of example 2, except that:
the length of the titanium-coated copper conductive beam 1 is 2000mm, the copper core is rectangular, the material is T2, the height of the cross section of the copper core is 80mm, and the thickness is 50mm; the thickness of the nickel transition layer is 20 mu m; the titanium outer layer is made of TA1, and the thickness of the titanium outer layer is 4mm;
rectangular openings I and II are symmetrically formed in the two sides of the vertical central axis of the transition titanium plate 2; the height of the transition titanium plate 2 is 200mm, the thickness is 10mm, the distance from the rectangular opening I to the vertical central axis is 300mm, the height of the rectangular opening I is 100mm, and the width is 200mm;
the transverse conductive reinforcing ribs are vertical titanium-based/lead dioxide composite diamond-shaped nets (see fig. 1 and 8), and are horizontally attached and fixedly arranged in the middle of the fence-type titanium-based composite lead dioxide plate body 3; the height of the titanium-based/lead dioxide composite diamond-shaped net is 100.0mm, the mesh length is 6mm, and the width of the net is 2mm; the titanium-based/lead dioxide composite diamond-shaped net is coated and welded on the front side and the rear side of the fence-type titanium-based composite lead dioxide plate body 3 through argon arc spot welding; the vertical titanium-base/lead dioxide composite pipe IV is a square pipe, the section of the square pipe is 8mm long, the width is 5mm, and the wall thickness is 0.5mm;
the conductive reinforcing rib 4 sequentially comprises a titanium matrix I41, a fluorine-doped tin metal oxide intermediate layer I42 and alpha-PbO from inside to outside 2 /β-PbO 2 Nano Ti 4 O 7 Composite active layer i 43; the outer surface of the titanium matrix I41 is provided with diamond teeth, the tooth spacing is 0.1mm, and the tooth depth is 0.05mm; the thickness of the fluorine-doped tin metal oxide interlayer I42 is 1 mu m, alpha-PbO 2 /β-PbO 2 Nano Ti 4 O 7 The total thickness of the composite active layer I43 is 0.1mm, alpha-PbO 2 Layer thickness of alpha-PbO 2 /β-PbO 2 Nano Ti 4 O 7 30% of the total thickness of the composite active layer II 33;
the fence-type titanium-based composite lead dioxide plate body 3 sequentially comprises a titanium tube substrate II 31, a fluorine-doped tin metal oxide intermediate layer II 32 and alpha-PbO from inside to outside 2 /β-PbO 2 Nano Ti 4 O 7 A composite active layer II 33;
the vertical hollow titanium-based/lead dioxide composite pipe I, the horizontal hollow titanium-based/lead dioxide composite pipe II and the horizontal hollow titanium-based/lead dioxide composite pipe III are round pipes, the diameter of the section is 5mm, and the wall thickness is 0.5mm; the distance between adjacent vertical hollow titanium-based/lead dioxide composite pipes I is 3mm; the outer surface of the titanium tube substrate II 31 is zigzag, the tooth space is 0.1mm, and the tooth depth is 0.05mm; the thickness of the fluorine-doped tin oxide intermediate layer is 3 mu m; alpha-PbO 2 /β-PbO 2 Nano Ti 4 O 7 The total thickness of the composite active layer II 33 is 1mm, and alpha-PbO 2 Layer thickness of alpha-PbO 2 /β-PbO 2 Nano Ti 4 O 7 30% of the total thickness of the composite active layer II 33;
compared with the traditional titanium-based lead dioxide net plate, the titanium-based composite lead dioxide net plate in the embodiment has the advantages that the electrolytic zinc liquid is 50g/LCu 2+ +200g/LH 2 SO 4 +40mg/LC1 - In +20mg/L organic matter (calculated as TOC), under the same electrolysis condition, the service life is prolonged by 0.5 times, the cell voltage can be reduced by 10mV, the conducting current efficiency is improved by more than 0.5%, and the phenomenon of titanium mesh deformation caused by short circuit burning plate is avoided.
The specific embodiments of the present utility model have been described in detail with reference to the accompanying drawings, but the present utility model is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present utility model.
Claims (9)
1. A fence type titanium-based lead dioxide electrode plate is characterized in that: comprises an electrode plate main body,
the electrode plate main body comprises a fence-type titanium-based composite lead dioxide plate body (3) and conductive reinforcing ribs (4), the conductive reinforcing ribs (4) comprise two layers of transverse conductive reinforcing ribs, a longitudinal conductive reinforcing rib I and a longitudinal conductive reinforcing rib II, the two layers of transverse conductive reinforcing ribs are horizontally and fixedly arranged in the middle of the fence-type titanium-based composite lead dioxide plate body (3), the longitudinal conductive reinforcing ribs I and the longitudinal conductive reinforcing ribs II are respectively and fixedly arranged on two sides of the fence-type titanium-based composite lead dioxide plate body (3), and two ends of the transverse conductive reinforcing ribs are respectively and fixedly arranged on the longitudinal conductive reinforcing ribs I and the longitudinal conductive reinforcing ribs II;
the fence-type titanium-based composite lead dioxide plate body (3) comprises a plurality of vertical hollow titanium-based/lead dioxide composite pipes I, a plurality of horizontal hollow titanium-based/lead dioxide composite pipes II and a plurality of horizontal hollow titanium-based/lead dioxide composite pipes III, wherein the plurality of vertical hollow titanium-based/lead dioxide composite pipes I are equidistantly arranged, and the horizontal hollow titanium-based/lead dioxide composite pipes II and the horizontal hollow titanium-based/lead dioxide composite pipes III are respectively fixedly arranged at the top end and the bottom end of the hollow titanium-based/lead dioxide composite pipes I;
the top end of the transverse hollow titanium-based/lead dioxide composite pipe II is fixedly provided with a transition titanium plate (2), and the top end of the transition titanium plate (2) is fixedly provided with a titanium-coated copper conductive beam (1).
2. The barrier-type titanium-based lead dioxide electrode plate according to claim 1, wherein: the conductive reinforcing rib (4) sequentially comprises a titanium matrix I (41), a fluorine-doped tin metal oxide interlayer I (42) and alpha-PbO from inside to outside 2 /β-PbO 2 Nano Ti 4 O 7 Composite active layer I (43).
3. The barrier-type titanium-based lead dioxide electrode plate according to claim 2, wherein: the transverse conductive reinforcing ribs of the conductive reinforcing ribs (4) are vertical titanium-based/lead dioxide composite pipes IV, titanium-based/lead dioxide composite sheets or titanium-based/lead dioxide composite nets, and the longitudinal conductive reinforcing ribs I and the longitudinal conductive reinforcing ribs II are titanium-based/lead dioxide composite pipes V.
4. A fence-type titanium-based lead dioxide electrode plate according to claim 3, characterized in that: when the transverse conductive reinforcing ribs are vertical titanium-based/lead dioxide composite pipes IV, a plurality of vertical through holes are uniformly formed in the transverse conductive reinforcing ribs, and the vertical hollow titanium-based/lead dioxide composite pipes I of the fence-type titanium-based composite lead dioxide plate body (3) penetrate through the vertical through holes of the transverse conductive reinforcing ribs; when the transverse conductive reinforcing ribs are titanium-based/lead dioxide composite sheets or titanium-based/lead dioxide composite nets, the transverse conductive reinforcing ribs are horizontally attached and fixedly arranged in the middle of the fence-type titanium-based composite lead dioxide plate body (3).
5. The barrier-type titanium-based lead dioxide electrode plate according to claim 1, wherein: the fence-type titanium-based composite lead dioxide plate body (3) sequentially comprises a titanium tube substrate II (31), a fluorine-doped tin metal oxide intermediate layer II (32) and alpha-PbO from inside to outside 2 /β-PbO 2 Nano Ti 4 O 7 Composite active layer II (33).
6. The barrier-type titanium-based lead dioxide electrode plate according to claim 1, wherein: the titanium-coated copper conductive beam (1) sequentially comprises a copper core (11), a nickel transition layer (12) and a titanium outer layer (13) from inside to outside.
7. The barrier-type titanium-based lead dioxide electrode plate according to claim 6, wherein: the two ends of the titanium-coated copper conductive beam (1) are fixedly provided with conductive heads connected with a copper core (11).
8. The barrier-type titanium-based lead dioxide electrode plate according to claim 1, wherein: the hollow cavities of the fence-type titanium-based composite lead dioxide plate body (3) and the conductive reinforcing ribs (4) are filled with sodium sulfate solution, lead alloy, magnesium sulfate solution, potassium sulfate solution or calcium sulfate solution.
9. The barrier-type titanium-based lead dioxide electrode plate according to claim 1, wherein: rectangular openings I and II are symmetrically formed in two sides of the vertical central axis on the transition titanium plate (2).
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