WO2024114032A1 - 一种电解槽用密封垫片及电解槽 - Google Patents
一种电解槽用密封垫片及电解槽 Download PDFInfo
- Publication number
- WO2024114032A1 WO2024114032A1 PCT/CN2023/118066 CN2023118066W WO2024114032A1 WO 2024114032 A1 WO2024114032 A1 WO 2024114032A1 CN 2023118066 W CN2023118066 W CN 2023118066W WO 2024114032 A1 WO2024114032 A1 WO 2024114032A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- electrolytic cell
- sealing gasket
- rubber
- gasket
- sealing
- Prior art date
Links
- 238000007789 sealing Methods 0.000 title claims abstract description 80
- 229920001971 elastomer Polymers 0.000 claims abstract description 45
- 239000005060 rubber Substances 0.000 claims abstract description 45
- 229920002313 fluoropolymer Polymers 0.000 claims abstract description 25
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 18
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000008961 swelling Effects 0.000 claims abstract description 5
- 229920002943 EPDM rubber Polymers 0.000 claims description 13
- -1 polytetrafluoroethylene Polymers 0.000 claims description 10
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 7
- 230000000996 additive effect Effects 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 6
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 claims description 5
- 239000012784 inorganic fiber Substances 0.000 claims description 5
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 claims description 5
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 claims description 5
- 244000043261 Hevea brasiliensis Species 0.000 claims description 4
- 229920006235 chlorinated polyethylene elastomer Polymers 0.000 claims description 4
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 4
- 229920003052 natural elastomer Polymers 0.000 claims description 4
- 229920001194 natural rubber Polymers 0.000 claims description 4
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 4
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 claims description 3
- 229920001780 ECTFE Polymers 0.000 claims description 3
- 229920000459 Nitrile rubber Polymers 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 3
- 229920001973 fluoroelastomer Polymers 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 13
- 239000003513 alkali Substances 0.000 abstract description 12
- 230000035882 stress Effects 0.000 abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- 239000001301 oxygen Substances 0.000 abstract description 7
- 230000032683 aging Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 4
- 239000003792 electrolyte Substances 0.000 abstract description 4
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 39
- 238000000034 method Methods 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 101001121408 Homo sapiens L-amino-acid oxidase Proteins 0.000 description 2
- 102100026388 L-amino-acid oxidase Human genes 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- FGZBFIYFJUAETR-UHFFFAOYSA-N calcium;magnesium;silicate Chemical compound [Mg+2].[Ca+2].[O-][Si]([O-])([O-])[O-] FGZBFIYFJUAETR-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001739 rebound effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/60—Constructional parts of cells
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/70—Assemblies comprising two or more cells
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16J—PISTONS; CYLINDERS; SEALINGS
- F16J15/00—Sealings
- F16J15/02—Sealings between relatively-stationary surfaces
- F16J15/06—Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces
- F16J15/10—Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces with non-metallic packing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Definitions
- the present application belongs to the field of hydrogen production by alkaline water electrolysis, and specifically relates to a sealing gasket for an electrolytic cell and an electrolytic cell.
- the electrolytic cell for producing hydrogen by electrolysis of water is usually composed of several or even hundreds of electrolytic chambers, among which the sealing gaskets between the chambers and between the diaphragm and the pole frame play a core role.
- the gaskets are deformed by the compression force transmitted by the fastening bolts and disc springs at both ends of the electrolytic cell, and rely on the rebound effect to generate contact stress on the contact surface to achieve elastic compensation for sealing.
- PTFE polytetrafluoroethylene
- the tightening cycle is difficult to determine, and the PTFE creep will be further accelerated during the tightening process, affecting the service life of the gasket; during equipment start-up and shutdown or high and low temperature environment conversion conditions, PTFE has a low rebound rate and a slow rebound rate, and the gasket cannot rebound in time, posing a risk of sealing failure.
- the present application provides a sealing gasket for an electrolytic cell.
- the technical solution of the present application is as follows:
- a sealing gasket for an electrolytic cell comprising:
- a gasket body wherein an opening is provided in the gasket body, and a flow channel hole is provided on the gasket body;
- An outer ring fixedly arranged on the outer side wall of the gasket body
- the outer ring is made of water-swellable rubber.
- the gasket body is made of fluoroplastic or ethylene-propylene rubber.
- the outer ring is fixedly arranged on the outer side wall of the gasket body by bonding.
- the water-swellable rubber comprises one or a combination of two or more of ethylene-propylene rubber, EVA rubber, natural rubber, chloroprene rubber, ethylene-vinyl acetate rubber, chlorinated polyethylene rubber, polyacrylate rubber, ethylene acrylate rubber, nitrile rubber, and fluororubber.
- the maximum water-swelling rate of the water-swellable rubber is greater than or equal to 1000%.
- the fluoroplastic comprises one or a combination of two or more of polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), polyethylene fluoride (PVDF), ethylene tetrafluoroethylene copolymer (ETFE), polychlorotrifluoroethylene (PCTFE), or chlorotrifluoroethylene-ethylene copolymer.
- PTFE polytetrafluoroethylene
- PFA tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer
- FEP tetrafluoroethylene-hexafluoropropylene copolymer
- PVDF polyethylene fluoride
- ETFE ethylene tetrafluoroethylene copolymer
- PCTFE polychlorotrifluoroethylene
- the fluoroplastic contains an inorganic additive, and the inorganic additive is selected from one or a combination of two or more of SiO 2 , inorganic fiber, and molybdenum disulfide.
- the EPDM rubber is selected from EPDM dipolymer rubber, EPDM terpolymer rubber or a combination of both.
- the width of the sealing gasket for the electrolytic cell is 1 mm to 500 mm, preferably 5 mm to 150 mm; and/or the thickness of the sealing gasket for the electrolytic cell is 0.1 mm to 300 mm; and/or the equivalent inner diameter of the sealing gasket for the electrolytic cell is 0.1 mm to 5000 mm; and/or the width of the outer ring accounts for 5% to 80% of the width of the sealing gasket for the electrolytic cell.
- the sealing gasket for the electrolytic cell is a polygonal frame or a ring.
- the flow channel hole is a round hole or a waist-shaped hole; and/or the cross-sectional area of the flow channel hole is 1 mm 2 to 100000 mm 2 .
- the present application also provides an electrolytic cell, which is provided with the above-mentioned sealing gasket for the electrolytic cell.
- the electrolytic cell further comprises a cathode chamber and an anode chamber, and a sealing gasket for the electrolytic cell is arranged between the cathode chamber and the anode chamber.
- the present application provides a sealing gasket for an electrolytic cell, which is formed by a gasket body and an outer ring made of water-swelling rubber.
- the gasket body is used to isolate the water-swelling rubber material from the alkali solution and oxygen inside the electrolytic cell, thereby increasing the gasket service life; and the water-swelling rubber material is used to compensate for the rebound defects of PTFE by using its excellent properties such as high resilience, good stress compensation, and low creep.
- Water-swellable rubber can rebound quickly and play a sealing role.
- water-swellable rubber has the function of stopping water with water. It can expand rapidly in volume when it comes into contact with a small amount of electrolyte. After expansion, it can fill the gap in the sealing interface, increase the contact stress, further improve the sealing effect, and reduce the risk of sealing failure.
- FIG1 is a schematic structural diagram of a sealing gasket for an electrolytic cell according to an embodiment
- Figure 2 Schematic diagram of the A-A’ section in Figure 1.
- a sealing gasket for an electrolytic cell comprising:
- the outer ring 4 is fixedly arranged on the outer side wall of the gasket body 1 .
- the outer ring 4 is made of water-swellable rubber.
- the gasket body is made of fluoroplastic or ethylene propylene rubber.
- Fluoroplastic refers to plastics made of fluorine resin. Because fluorine plastics contain fluorine atoms in their molecular structure, they have many excellent properties, such as excellent high temperature resistance, outstanding oil resistance, solvent resistance and wear resistance, good moisture resistance and low temperature resistance, heat and oxygen aging resistance, and strong alkali resistance.
- the present embodiment further limits the gasket body 1.
- the gasket body 1 is made of fluoroplastic (such as PTFE, etc.) or EPDM rubber material
- the fluoroplastic's high temperature resistance, heat-oxidation aging resistance, strong alkali resistance and other properties or the EPDM rubber's good alkali resistance, weather resistance, good resilience, low temperature resistance and other properties are utilized to isolate the water-swellable rubber material from the alkali solution and oxygen inside the electrolytic cell, thereby further improving the service life of the gasket.
- This embodiment provides a method of fixing the outer ring 4 on the outer side wall of the gasket body 1 by bonding.
- bonding existing methods can be used, such as first sandblasting the bonding surface or removing oil by solvent washing, and then bonding with adhesive.
- the gasket body 1 and the outer ring 4 are provided with teeth grooves that cooperate with each other.
- the outer wall of the gasket body 1 and the inner wall of the outer ring 4 are provided with tooth grooves in this embodiment, so that the two The teeth and grooves cooperate with each other.
- the contact surface can be increased (such as increasing the bonding area when adhesive is used for bonding), thereby increasing the connection strength between the gasket body 1 and the inner ring 2 in the tensile direction (such as the left and right direction in Figure 2).
- the teeth and grooves of the gasket body 1 and the outer ring 4 can also interact with each other, thereby increasing the connection strength in the shear direction (such as the up and down direction in Figure 2) when under pressure, thereby preventing the two from being misaligned and separated due to pressure.
- the water-swellable rubber comprises one or a combination of two or more of ethylene-propylene rubber, EVA rubber, natural rubber, chloroprene rubber, ethylene-vinyl acetate rubber, chlorinated polyethylene rubber, polyacrylate rubber, ethylene acrylate rubber, nitrile rubber, and fluororubber, preferably one or a combination of two or more of ethylene-propylene rubber, chloroprene rubber, natural rubber, butadiene rubber, styrene-butadiene rubber, and chlorinated polyethylene rubber.
- the gasket body 1 is made of fluoroplastic or EPDM
- the fluoroplastic contains an inorganic additive, and the inorganic additive is selected from one or a combination of two or more of SiO 2 , inorganic fiber, and molybdenum disulfide.
- the inorganic fiber is selected from one or a combination of two or more of carbon fiber, calcium magnesium silicate, and glass fiber.
- the width w2 of the outer ring accounts for 5%-80% of the width w1 of the sealing gasket for the electrolytic cell.
- the sealing gasket for the electrolytic cell is a polygonal (such as a triangle, rectangle, rhombus, pentagon, etc.) frame or a ring.
- sealing gasket for the electrolytic cell preferably a rectangular frame or a ring.
- the length of its outer side is preferably 100 to 2500 mm.
- the specific sealing width (the width of one side of the sealing gasket squeezed by the electrode plate) is preferably 3 to 200 mm.
- the flow channel hole 3 is a round hole or a waist-shaped hole; and/or,
- the cross-sectional area of the flow channel hole 3 is 1 mm 2 to 100000 mm 2 .
- the shapes and sizes of the flow channel holes 3 are given above, and those skilled in the art can make specific selections according to the flow channel requirements of the specific electrolyzer. For example, in an alkaline water electrolyzer, several flow channel holes for alkali solution input are set below the sealing gasket, and several flow channel holes for hydrogen output and several flow channel holes for oxygen output are set above, and the number of the set flow channel holes is consistent with the number of the flow channel holes set on the corresponding plate frames of the cathode chamber and the anode chamber, and the shape and size of the set flow channel holes match the flow channel holes set on the corresponding plate frames of the cathode chamber and the anode chamber.
- the gasket body can be made of fluoroplastic (such as PTFE material) first.
- the gasket body made of fluoroplastic (such as PTFE material) adopts modified fluoroplastic material.
- the formula can select modifiers such as SiO2 , inorganic fiber (such as carbon fiber, calcium magnesium silicate, glass fiber), molybdenum disulfide, barium sulfate, one or more of them according to needs, and is prepared through processes such as mixing, molding, sintering, etc.
- the fluoroplastic gasket body After the fluoroplastic gasket body is made, it is sandblasted or cleaned, and after the treatment, it is sprayed with adhesive; finally, the fluoroplastic gasket body sprayed with adhesive is placed in the mold and meets the The water-swellable rubber is co-vulcanized using a vulcanizing device to prepare sealing gaskets for electrolytic cells.
- electrolyzer sealing gasket is used together with other accessories to assemble an electrolyzer, which is particularly suitable for filter press electrolyzer.
- the electrolyzer also includes a cathode chamber and an anode chamber, and the electrolyzer sealing gasket is arranged between the cathode chamber and the anode chamber.
- an alkaline water electrolyzer it is composed of an electrode plate, a diaphragm, a sealing gasket and a clamping device (including an end pressure plate) and other accessories, wherein the two sides of the electrode plate respectively constitute the cathode surface of the cathode chamber and the anode surface of the anode chamber, and the periphery of the electrode plate has a pole frame, and the sealing gasket is pressed on the pole frames of the two pole plates, thereby achieving insulation between the two pole plates.
- the present application provides a sealing gasket for an electrolytic cell, which is formed by a gasket body made of fluoroplastics and an outer ring made of water-swelling rubber.
- the sealing gasket for an electrolytic cell utilizes the high temperature resistance, heat-oxidation aging resistance, and strong alkali resistance of fluoroplastics to isolate the water-swelling rubber material from the alkali solution and oxygen inside the electrolytic cell, thereby increasing the service life of the gasket; and utilizes the excellent properties of the water-swelling rubber material, such as high resilience, good stress compensation, and low creep, to compensate for the rebound defects of PTFE.
- the water-swelling rubber has the function of stopping water with water, and can rapidly expand in volume when in contact with a small amount of electrolyte. After expansion, it can fill the gap in the sealing interface, increase the contact stress, further improve the sealing effect, and reduce the risk of sealing failure.
- one embodiment means that a particular feature, structure or characteristic described in conjunction with the embodiment is included in at least one embodiment of the present application.
- examples of the term “in one embodiment” here do not necessarily all refer to the same embodiment.
- any reference signs placed between brackets shall not be construed as limiting the claims.
- the word “comprising” does not exclude the presence of elements or steps not listed in the claims.
- the word “a” or “an” preceding an element does not exclude the presence of a plurality of such elements.
- the use of the words first, second, and third, etc. does not indicate any order. These words may be interpreted as names.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Gasket Seals (AREA)
Abstract
本申请提供了一种电解槽用密封垫片及电解槽，其中电解槽用密封垫片包括：垫片主体，所述垫片主体内设有开口，所述垫片主体上设置有流道孔；外圈，固定设置在所述垫片主体的外侧壁；其中，所述垫片主体由氟塑料制成，所述外圈由遇水膨胀橡胶制成。本申请提供的电解槽用密封垫片利用氟塑料耐高温、耐热氧老化、耐强碱等特性隔绝遇水膨胀橡胶材料与电解槽内部碱液和氧气，提高垫片使用寿命；并且利用遇水膨胀橡胶材料回弹性高、应力补偿性好、蠕变低等优异特性补偿PTFE回弹缺陷，同时，遇水膨胀橡胶具备以水止水功能，与少量电解液接触即能够迅速体积膨胀，膨胀后可填补密封界面缝隙，提高接触应力，进一步提高密封效果，降低密封失效风险。
Description
本申请要求在2022年11月30日提交中国专利局、申请号为202223189645.3、发明名称为“一种电解槽用密封垫片及电解槽”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
本申请属于碱性电解水制氢领域，具体涉及一种电解槽用密封垫片及电解槽。
电解水制氢电解槽，通常由数个乃至数百个电解小室构成，其中小室与小室间及隔膜与极框间的密封垫片起核心作用，垫片受到电解槽两端紧固螺栓及碟簧传递的压缩力引起形变，依靠回弹作用在接触面产生接触应力，实现弹性补偿来密封。
现有制氢电解槽极板密封一般采用PTFE(聚四氟乙烯)垫片来密封，尤其是在大电解槽领域。PTFE属于工程塑料，分子链为线型螺旋构象，分子链间相互作用力小，结晶度高，有易蠕变松弛、回弹率低、弹性补偿差等缺点。应用在电解槽密封领域，PTFE蠕变后，尺寸难以恢复，需定期锁紧螺栓，锁紧周期难以确定，在锁紧螺栓过程中又会进一步加速PTFE蠕变，影响垫片使用寿命；在设备启停或高低温环境转换工况中，PTFE回弹率低、回弹速率慢，垫片不能够及时回弹，有密封失效风险。
发明内容
为解决现有技术中的问题，本申请提供了一种电解槽用密封垫片。本申请技术方案如下：
一种电解槽用密封垫片，包括：
垫片主体，所述垫片主体内设有开口，所述垫片主体上设置有流道孔；
外圈，固定设置在所述垫片主体的外侧壁；
其中，所述外圈由遇水膨胀橡胶制成。
进一步地，所述垫片主体由氟塑料或乙丙橡胶制成。
进一步地，所述外圈通过黏结固定设置在所述垫片主体的外侧壁。
进一步地，沿所述电解槽用密封垫片的厚度方向，所述垫片主体与所述外圈设置有相互配合的齿槽。
进一步地，所述遇水膨胀橡胶包含乙丙橡胶、EVA橡胶、天然橡胶、氯丁橡胶、乙烯-醋酸乙烯酯橡胶、氯化聚乙烯橡胶、聚丙烯酸酯橡胶、乙烯丙烯酸酯橡胶、丁腈橡胶、氟橡胶中的一种或两种以上的组合。
进一步地，所述遇水膨胀橡胶的遇水最大膨胀率大于等于1000％。
进一步地，所述氟塑料包含聚四氟乙烯(PTFE)、四氟乙烯-全氟烷基乙烯醚共聚物(PFA)、四氟乙烯-六氟丙烯共聚物(FEP)、聚乙烯氟化物(PVDF)、乙烯四氟乙烯共聚物(ETFE)、聚氯三氟乙烯(PCTFE)、或三氟氯乙烯-乙烯共聚物中的一种或两种以上的组合。
进一步地，所述氟塑料中含有无机添加剂，所述无机添加剂选自SiO2、无机纤维、二硫化钼中的一种或两种以上的组合。
进一步地，所述乙丙橡胶选自二元乙丙橡胶、三元乙丙橡胶中的一种或两种的组合。
进一步地，所述电解槽用密封垫片的宽度为1mm～500mm，优选为5mm-150mm；和/或，所述电解槽用密封垫片的厚度为0.1mm～300mm；和/或，所述电解槽用密封垫片的等效内径为0.1mm～5000mm；和/或，所述外圈的宽度占所述电解槽用密封垫片的宽度的5％～80％。
进一步地，所述电解槽用密封垫片为多边形框体或环形。
进一步地，所述流道孔为圆孔或腰形孔；和/或，所述流道孔横截面积为1mm2～100000mm2。
另外，本申请还提供了一种电解槽，其设置有上述电解槽用密封垫片。
进一步地，所述电解槽还包含阴极室和阳极室，在所述阴极室和阳极室之间设置所述电解槽用密封垫片。
本申请提供一种电解槽用密封垫片，由垫片主体和遇水膨胀橡胶制成的外圈形成。从而利用垫片主体隔绝遇水膨胀橡胶材料与电解槽内部碱液和氧气，提高垫片使用寿命；并且利用遇水膨胀橡胶材料回弹性高、应力补偿性好、蠕变低等优异特性补偿PTFE回弹缺陷，在设备启停或高低温转换过程，
遇水膨胀橡胶能够迅速回弹，起到密封作用，同时，遇水膨胀橡胶具备以水止水功能，与少量电解液接触即能够迅速体积膨胀，膨胀后可填补密封界面缝隙，提高接触应力，进一步提高密封效果，降低密封失效风险。
上述说明仅是本申请技术方案的概述，为了能够更清楚了解本申请的技术手段，而可依照说明书的内容予以实施，并且为了让本申请的上述和其它目的、特征和优点能够更明显易懂，以下特举本申请的具体实施方式。
为了更清楚地说明本申请实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作一简单地介绍，显而易见地，下面描述中的附图是本申请的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1：一个实施例中电解槽用密封垫片的结构示意图；
图2：图1中A-A’截面示意图。
附图标记说明：
1、垫片主体；2、开口；3、流道孔；4、外圈。
1、垫片主体；2、开口；3、流道孔；4、外圈。
为使本申请实施例的目的、技术方案和优点更加清楚，下面将结合本申请实施例中的附图，对本申请实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本申请保护的范围。
在一个实施例中，如图1所示，提供了一种电解槽用密封垫片，包括：
垫片主体1，所述垫片主体1内设有开口2，所述垫片主体1上设置有流道孔3；
外圈4，固定设置在所述垫片主体1的外侧壁侧。
其中，所述外圈4由遇水膨胀橡胶制成。
本实施方式对现有技术进行改进，提供了一种电解槽用密封垫片，主要用于电解水制氢领域所用的小室间极框之间密封。在垫片主体1的外侧壁
设置外圈4，外圈4的材料为遇水膨胀橡胶，利用遇水膨胀橡胶材料回弹性高、应力补偿性好、蠕变低等优异特性补偿PTFE回弹缺陷，在设备启停或高低温转换过程，遇水膨胀橡胶能够迅速回弹，起到密封作用，同时，遇水膨胀橡胶具备以水止水功能，与少量电解液接触即能够迅速体积膨胀，膨胀后可填补密封界面缝隙，提高接触应力，提高密封效果，降低密封失效风险。
在一个实施方式中，所述垫片主体由氟塑料或乙丙橡胶制成。
氟塑料指用氟树脂制成的塑料。由于氟塑料分子结构中含有氟原子，所以具有许多优异的性能，如优良的高度的耐高温、突出的耐油性、耐溶剂和耐磨性能，良好的耐湿性和耐低温性、耐热氧老化、耐强碱。
乙丙橡胶是以乙烯、丙烯为主要单体的合成橡胶。乙丙橡胶因其主链是由化学稳定的饱和烃组成，故其耐碱、耐臭氧、耐热、耐候等耐老化性能优异，具有良好的耐化学品、电绝缘性能、冲击弹性、低温性能、低密度和高填充性及耐热水性和耐水蒸气性、良好的回弹性等。
本实施方式对垫片主体1进行了进一步限定，当垫片主体1采用氟塑料(如PTFE等)或者乙丙橡胶材料时，利用氟塑料耐高温、耐热氧老化、耐强碱等特性或者利用乙丙橡胶具备良好耐碱、耐天候、回弹性好、耐低温等特性隔绝遇水膨胀橡胶材料与电解槽内部碱液和氧气，进一步提高垫片使用寿命。
在一个实施方式中，如图1所示，所述外圈4通过黏结固定设置在所述垫片主体1的外侧壁。
本实施方式给出了一种通过黏结来将所述外圈4固定设置在所述垫片主体1的外侧壁的方式。关于黏结，可以采用现有的方式进行，如首先在黏结面进行喷砂或者通过溶剂洗涤等方法除油污，然后采用胶黏剂进行黏合。
在一个实施方式中，如图2所示，沿所述电解槽用密封垫片的厚度方向(即图2中的上下方向)，所述垫片主体1与所述外圈4设置有相互配合的齿槽。
相较于所述垫片主体1与所述外圈4之间通过断面连接，通过本实施方式的在所述垫片主体1的外侧壁与所述外圈4的内侧壁分别设置齿槽，二者
的齿槽间相互配合，首先，可以增加接触面(如采用胶黏剂粘合时，增加粘合面积)，从而增加所述垫片主体1与所述内圈2的拉伸方向(如图2中的左右方向)连接强度，其次，所述垫片主体1与所述外圈4的齿槽之间本身也可以相互作用，从而在受压时增加剪切方向(如图2中的上下方向)的连接强度，防止二者受压而错位分离。
在一个实施方式中，所述遇水膨胀橡胶包含乙丙橡胶、EVA橡胶、天然橡胶、氯丁橡胶、乙烯-醋酸乙烯酯橡胶、氯化聚乙烯橡胶、聚丙烯酸酯橡胶、乙烯丙烯酸酯橡胶、丁腈橡胶、氟橡胶中的一种或两种以上的组合，优选乙丙橡胶、氯丁橡胶、天然橡胶、顺丁橡胶、丁苯橡胶、氯化聚乙烯橡胶中的一种或两种以上的组合。
其中，优选遇水膨胀橡胶中还含有产生遇水膨胀效果的成分，例如膨润土、聚氨酯预聚体、吸水树脂中的一种或两种以上的组合；更优选遇水膨胀橡胶中还含有炭黑、白炭黑、增塑剂、硫化剂、促进剂，经炼胶做成混炼胶。
优选地，所述遇水膨胀橡胶的遇水最大膨胀率大于等于1000％。
在一个实施方式中，所述垫片主体1由氟塑料或乙丙橡胶制成；
其中，所述氟塑料包含聚四氟乙烯(PTFE)、四氟乙烯-全氟烷基乙烯醚共聚物(PFA)、四氟乙烯-六氟丙烯共聚物(FEP)、聚乙烯氟化物(PVDF)、乙烯四氟乙烯共聚物(ETFE)、聚氯三氟乙烯(PCTFE)或三氟氯乙烯-乙烯共聚物中的一种或两种以上的组合。
所述乙丙橡胶选自二元乙丙橡胶、三元乙丙橡胶中的一种或两种的组合。
优选地，所述氟塑料中含有无机添加剂，所述无机添加剂选自SiO2、无机纤维、二硫化钼中的一种或两种以上的组合。进一步地，无机纤维选自碳纤维、钙镁硅酸盐、玻璃纤维中的一种或两种以上的组合。
可以通过在氟塑料中添加以上无机添加剂来对氟塑料进行改性，以进一步提高氟塑料的耐高温、耐热氧老化、耐强碱等性能。
在一个实施方式中，所述电解槽用密封垫片的宽度w1(如图2中电解槽用密封垫片截面从左到右的宽度)为1mm～500mm；和/或，
所述电解槽用密封垫片的厚度t1(如图2中电解槽用密封垫片截面从上到下的厚度)为0.1mm～300mm；和/或，
所述电解槽用密封垫片的等效内径(即图1中垫片主体内部开口2的等效圆面积的直径)为0.1mm～5000mm；
和/或，所述外圈的宽度w2占所述电解槽用密封垫片的宽度w1的5％-80％。
以上给出电解槽用密封垫片的尺寸范围，本领域技术人员可以根据具体的电解槽部件的尺寸进行具体选择。
在一个实施方式中，所述电解槽用密封垫片为多边形(如三角形、矩形、菱形、五边形等)框体或环形。
以上给出电解槽用密封垫片的形状，本领域技术人员可以根据具体的电解槽进行具体选择。优选为矩形框体或环形。
当为矩形框体时，其外侧边长优选为100～2500mm，在进行密封时，具体的密封宽度(密封垫片单边被极板挤压的宽度)优选为3～200mm。
在一个实施方式中，所述流道孔3为圆孔或腰形孔；和/或，
所述流道孔3横截面积为1mm2～100000mm2。
以上给出流道孔3的形状、尺寸，本领域技术人员可以根据具体电解槽的流道要求进行具体选择。例如在碱性水电解槽中，在密封垫片的下方设置数个用于碱液输入流道孔，在上方设置数个用于氢气输出的流道孔和数个用于氧气输出的流道孔，所设置的数量与阴极室和阳极室相应的极板框上设置的流道孔数量一致，所设置的形状、尺寸与阴极室和阳极室相应的极板框上设置的流道孔相匹配。
关于以上电解槽用密封垫片的制备方法，可以根据现有的方案进行。如，可以先用氟塑料(如PTFE材料)制作垫片主体，氟塑料(如PTFE材料)制作的垫片主体采用改性氟塑料材料，配方除氟塑料粉料之外，可以根据需要选用改性剂如SiO2、无机纤维(例如碳纤维、钙镁硅酸盐、玻璃纤维)、二硫化钼、硫酸钡中的一种或两种以上，经过例如混料、模压、烧结等工艺来制备；氟塑料的垫片主体制作完成后做喷砂或清洗处理，处理完成后喷涂胶黏剂；最后将喷涂了胶黏剂的氟塑料垫片主体放入模具中与遇
水膨胀橡胶用硫化设备共硫化，以制备电解槽用密封垫片。
另外，本领域技术人员知晓使用上述的电解槽用密封垫片与其他配件一起组装成电解槽，特别适用于压滤式电解槽。电解槽还包含阴极室和阳极室，在所述阴极室和阳极室之间设置所述的电解槽用密封垫片。例如在碱性水电解槽中，由电极板、隔膜、密封垫和夹紧装置(包含端压板)以及其他附件组成，其中电极板的两面分别构成阴极室的阴极面和阳极室的阳极面，电极板的外周具有极框，密封垫片压设于两个极板的极框上，从而实现两个极板之间的绝缘。
本申请提供一种电解槽用密封垫片，由氟塑料制成的垫片主体和遇水膨胀橡胶制成的外圈形成。电解槽用密封垫片利用氟塑料耐高温、耐热氧老化、耐强碱等特性隔绝遇水膨胀橡胶材料与电解槽内部碱液和氧气，提高垫片使用寿命；并且利用遇水膨胀橡胶材料回弹性高、应力补偿性好、蠕变低等优异特性补偿PTFE回弹缺陷，同时，遇水膨胀橡胶具备以水止水功能，与少量电解液接触即能够迅速体积膨胀，膨胀后可填补密封界面缝隙，提高接触应力，进一步提高密封效果，降低密封失效风险。
本文中所称的“一个实施例”、“实施例”或者“一个或者多个实施例”意味着，结合实施例描述的特定特征、结构或者特性包括在本申请的至少一个实施例中。此外，请注意，这里“在一个实施例中”的词语例子不一定全指同一个实施例。
在此处所提供的说明书中，说明了大量具体细节。然而，能够理解，本申请的实施例可以在没有这些具体细节的情况下被实践。在一些实例中，并未详细示出公知的方法、结构和技术，以便不模糊对本说明书的理解。
在权利要求中，不应将位于括号之间的任何参考符号构造成对权利要求的限制。单词“包含”不排除存在未列在权利要求中的元件或步骤。位于元件之前的单词“一”或“一个”不排除存在多个这样的元件。单词第一、第二、以及第三等的使用不表示任何顺序。可将这些单词解释为名称。
最后应说明的是：以上实施例仅用以说明本申请的技术方案，而非对其限制；尽管参照前述实施例对本申请进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或
者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本申请各实施例技术方案的精神和范围。
Claims (13)
- 一种电解槽用密封垫片，其特征在于，包括：垫片主体，所述垫片主体内设有开口，所述垫片主体上设置有流道孔；外圈，固定设置在所述垫片主体的外侧壁；其中，所述外圈由遇水膨胀橡胶制成。
- 如权利要求1所述的电解槽用密封垫片，其特征在于，所述垫片主体由氟塑料或乙丙橡胶制成。
- 如权利要求1所述的电解槽用密封垫片，其特征在于，所述外圈通过黏结固定设置在所述垫片主体的外侧壁。
- 如权利要求1所述的电解槽用密封垫片，其特征在于，沿所述电解槽用密封垫片的厚度方向，所述垫片主体与所述外圈设置有相互配合的齿槽。
- 如权利要求1所述的电解槽用密封垫片，其特征在于，所述遇水膨胀橡胶包含乙丙橡胶、EVA橡胶、天然橡胶、氯丁橡胶、乙烯-醋酸乙烯酯橡胶、氯化聚乙烯橡胶、聚丙烯酸酯橡胶、乙烯丙烯酸酯橡胶、丁腈橡胶、氟橡胶中的一种或两种以上的组合。
- 如权利要求1所述的电解槽用密封垫片，其特征在于，所述遇水膨胀橡胶的遇水最大膨胀率大于等于1000％。
- 如权利要求2所述的电解槽用密封垫片，其特征在于，所述氟塑料包含聚四氟乙烯、四氟乙烯-全氟烷基乙烯醚共聚物、四氟乙烯-六氟丙烯共聚物、聚乙烯氟化物、乙烯四氟乙烯共聚物、聚氯三氟乙烯或三氟氯乙烯-乙烯共聚物中的一种或两种以上的组合。
- 如权利要求2所述的电解槽用密封垫片，其特征在于，所述氟塑料中含有无机添加剂，所述无机添加剂选自SiO2、无机纤维、二硫化钼中的一种或两种以上的组合。
- 如权利要求2所述的电解槽用密封垫片，其特征在于，所述乙丙橡胶选自二元乙丙橡胶、三元乙丙橡胶中的一种或两种的组合。
- 如权利要求1所述的电解槽用密封垫片，其特征在于，所述电解槽用密封垫片的宽度为1mm～500mm；和/或，所述电解槽用密封垫片的厚度为0.1mm～300mm；和/或，所述电解槽用密封垫片的等效内径为0.1mm～5000mm；和/或，所述外圈的宽度占所述电解槽用密封垫片的宽度的5％～80％。
- 如权利要求1所述的电解槽用密封垫片，其特征在于，所述电解槽用密封垫片为多边形框体或环形；和/或，所述流道孔为圆孔或腰形孔；和/或，所述流道孔横截面积为1mm2～100000mm2。
- 一种电解槽，其特征在于，设置有权利要求1～11中任一项所述的电解槽用密封垫片。
- 如权利要求12所述的一种电解槽，其特征在于，还包含阴极室和阳极室，在所述阴极室和阳极室之间设置所述电解槽用密封垫片。
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| CN202223189645.3U CN219637358U (zh) | 2022-11-30 | 2022-11-30 | 一种电解槽用密封垫片及电解槽 |
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| CN219637358U (zh) * | 2022-11-30 | 2023-09-05 | 无锡隆基氢能科技有限公司 | 一种电解槽用密封垫片及电解槽 |
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| JP2000178780A (ja) * | 1998-12-14 | 2000-06-27 | Asahi Chem Ind Co Ltd | 塩化アルカリ電解用ガスケット |
| EP1293709A1 (de) * | 2001-09-10 | 2003-03-19 | Frenzelit-Werke GmbH & Co. KG | Weichstoffdichtung |
| CN213574106U (zh) * | 2020-11-09 | 2021-06-29 | 山东龙祥新材料科技有限公司 | 一种弹性密封垫及管片 |
| CN113755855A (zh) * | 2021-09-09 | 2021-12-07 | 中国船舶重工集团公司第七一八研究所 | 一种电解槽极框及电解槽 |
| CN216200470U (zh) * | 2021-09-14 | 2022-04-05 | 麦得克密封科技(宁波)有限公司 | 一种高密封性的遇水膨胀式橡胶密封垫 |
| CN114934789A (zh) * | 2022-06-02 | 2022-08-23 | 中国建筑第二工程局有限公司 | 一种装配式车站复合式防水密封垫 |
| CN115287689A (zh) * | 2022-08-31 | 2022-11-04 | 陕西华秦新能源科技有限责任公司 | 一种唇形密封圈及电解槽密封结构 |
| CN219637358U (zh) * | 2022-11-30 | 2023-09-05 | 无锡隆基氢能科技有限公司 | 一种电解槽用密封垫片及电解槽 |
-
2022
- 2022-11-30 CN CN202223189645.3U patent/CN219637358U/zh active Active
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- 2023-09-11 WO PCT/CN2023/118066 patent/WO2024114032A1/zh unknown
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1109088A (zh) * | 1994-03-23 | 1995-09-27 | 中国船舶工业总公司第七研究院第七一八研究所 | 一种填充型氟塑料复合密封垫片和垫圈 |
| JP2000178780A (ja) * | 1998-12-14 | 2000-06-27 | Asahi Chem Ind Co Ltd | 塩化アルカリ電解用ガスケット |
| EP1293709A1 (de) * | 2001-09-10 | 2003-03-19 | Frenzelit-Werke GmbH & Co. KG | Weichstoffdichtung |
| CN213574106U (zh) * | 2020-11-09 | 2021-06-29 | 山东龙祥新材料科技有限公司 | 一种弹性密封垫及管片 |
| CN113755855A (zh) * | 2021-09-09 | 2021-12-07 | 中国船舶重工集团公司第七一八研究所 | 一种电解槽极框及电解槽 |
| CN216200470U (zh) * | 2021-09-14 | 2022-04-05 | 麦得克密封科技(宁波)有限公司 | 一种高密封性的遇水膨胀式橡胶密封垫 |
| CN114934789A (zh) * | 2022-06-02 | 2022-08-23 | 中国建筑第二工程局有限公司 | 一种装配式车站复合式防水密封垫 |
| CN115287689A (zh) * | 2022-08-31 | 2022-11-04 | 陕西华秦新能源科技有限责任公司 | 一种唇形密封圈及电解槽密封结构 |
| CN219637358U (zh) * | 2022-11-30 | 2023-09-05 | 无锡隆基氢能科技有限公司 | 一种电解槽用密封垫片及电解槽 |
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