CN111424286B - SO (SO)2Depolarized electrolytic cell - Google Patents

SO (SO)2Depolarized electrolytic cell Download PDF

Info

Publication number
CN111424286B
CN111424286B CN202010128777.1A CN202010128777A CN111424286B CN 111424286 B CN111424286 B CN 111424286B CN 202010128777 A CN202010128777 A CN 202010128777A CN 111424286 B CN111424286 B CN 111424286B
Authority
CN
China
Prior art keywords
electrolytic cell
polar plate
cathode
anode
graphite felt
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202010128777.1A
Other languages
Chinese (zh)
Other versions
CN111424286A (en
Inventor
陈崧哲
张平
王来军
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tsinghua University
Original Assignee
Tsinghua University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tsinghua University filed Critical Tsinghua University
Priority to CN202010128777.1A priority Critical patent/CN111424286B/en
Publication of CN111424286A publication Critical patent/CN111424286A/en
Application granted granted Critical
Publication of CN111424286B publication Critical patent/CN111424286B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • C25B9/70—Assemblies comprising two or more cells
    • C25B9/73—Assemblies comprising two or more cells of the filter-press type
    • 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
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • 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
    • C25B9/23—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms comprising ion-exchange membranes in or on which electrode material is embedded
    • 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
    • C25B9/65—Means for supplying current; Electrode connections; Electric inter-cell connections
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)

Abstract

SO (SO)2A depolarized electrolytic cell belongs to the technical field of electrochemistry. The electrolytic cell comprises one or more single cells which are arranged in sequence, wherein each single cell comprises a membrane electrode assembly, a cathode side supporting body, an anode side supporting body, a sealing ring, an upper polar plate and a lower polar plate. The anode side support body is made of graphite felt with large porosity; the upper polar plate and the lower polar plate adopt flat plate structures. The graphite felt with large porosity can provide good filling and supporting functions, so that anode materials can uniformly and quickly pass through the graphite felt, and the graphite felt can be stably used for a long time under the conditions of feed liquid soaking and high-current electrochemical reaction. Meanwhile, the graphite felt is easy to carry a catalyst, so that the efficiency of the electrochemical reaction in the electrolytic cell can be further improved. The invention effectively avoids the problems of high processing difficulty, high processing cost and the like caused by the flow channel engraving of the upper and lower polar plates. By adopting the technical scheme of the invention, the SO with high efficiency, stability, compactness and low cost can be constructed2Depolarizing the electrolytic cell.

Description

SO (SO)2Depolarized electrolytic cell
Technical Field
The invention relates to an electrochemical device, in particular to a device for SO2An electrolytic cell for depolarization electrolysis belongs to the technical field of electrochemistry.
Background
SO2Depolarizing electrolytic electrolysis, SDE, is one of the key steps in mixed sulfur cycle hydrogen production (HyS-cycle). The mixed sulfur cycle is the simplest one in the thermochemical water decomposition process, and only contains two reactions, wherein one reaction is a thermochemical reaction-a sulfuric acid decomposition reaction; while the other reaction is an electrochemical reaction-i.e. the SDE process. The reaction formulae of the above two reactions are as follows:
H2SO4→SO2+H2O+1/2O2
2H2O+SO2→H2SO4+H2
the two reactions combine to produce the net reaction of water splitting to produce hydrogen and oxygen.
It can be seen that SDE is a hydrogen production step of mixed sulfur cycle, and the corresponding half-cell reaction is:
anode: 2H2O(l)+SO2(aq.)→H2SO4(aq.)+2H++2e-
Cathode: 2H++2e-→H2(g)。
The standard potential of the electrolytic water reaction at 25 ℃ is 1.229V, while SO2The standard potential of the depolarization electrolysis reaction is only 0.158V, so that the introduction of SDE electrolysis is expected to greatly improve the electrolysis efficiency. Under the condition that the sulfuric acid decomposition reaction (which needs to be carried out at 850 ℃) of the mixed sulfur cycle is coupled with a high-temperature gas cooled reactor, the mixed sulfur cycle is expected to realize efficient and large-scale clean hydrogen production. In addition, in the presence of SO2Under the conditions supplied, the SDE electrolysis process can also be applied independently, i.e. from SO2Preparing sulfuric acid and electrolyzing water to prepare hydrogen.
SDE electrolysis has gained much research since the american westinghouse company proposed mixed sulfur cycles. In connection with the cell structure, there has been a transition from the original parallel plate structure of the westinghouse company to the current PEM (proton exchange membrane) type cell structure. The national laboratory of the Sevenna River (SRNL) in USA designs and uses a PEM-based liquid phase feed (i.e., SO dissolved in the anolyte)2Sulfuric acid) in the electrolytic cell. On this basis, University of South Carolina (USC) in the united states proposed PEM-based gas phase feed (i.e., anodic gaseous SO)2And the cathode is pure water).
In the SDE cell, a membrane electrode assembly composed of an anode catalyst layer, a PEM and a cathode catalyst layer is an important component thereof, and is also the research and development focus of researchers in various countries. In addition, some research progresses in aspects of SDE operation parameters, SDE electrolysis voltage composition, current efficiency, simulation of mixed sulfur cycle process and the like are reported.
To improve the compactness of the apparatus and to control the cost, it is required to operate at a higher current densitySDE operation with simultaneous sulfuric acid, SO2It is extremely corrosive, and therefore the structural design and material selection of the SDE cell are very important.
The SDE cell or cell stack currently available consists of a series of cells of the same structure, the basic structure of each cell being shown in fig. 1. In a typical SDE cell stack, both the cathode-side support and the anode-side support use good electrical conductors in order to reduce the internal resistance of the cell as much as possible, and function as current collectors (also referred to as current collectors) for the cathode and the anode in the cell. In addition, if there is no support, the membrane electrode assembly may oscillate in a direction perpendicular to the membrane surface during material flow, and such oscillation is particularly significant when the membrane area is large, which is very disadvantageous in terms of operational stability. The cathode side and the anode side supporting bodies can fill the space between the polar plate and the proton selective permeation membrane, and play a role in supporting and fixing the proton selective permeation membrane to avoid the swinging.
At present, the anode side support in the SDE cell can be made of graphite support, etc., see "Steimke J L, et al, Characterization and analysis of single cell SO2depolarised electrolyzer, WSRC-STI-2006-00120.2006 "; but most used is carbon paper. The carbon paper has the advantages of good conductivity and good material penetrability after specific surface treatment. However, carbon paper is expensive to manufacture, has high brittleness, and is easily brittle during assembly. In the practical use process, the carbon paper is taken as a thin layer material, and is easy to move under the condition of material flow, so that the performance of the battery is seriously influenced. The carbon paper is often assembled with the anode catalyst layer, PEM and cathode catalyst layer, i.e., membrane electrode assembly, for one purpose of ensuring that it is maintained in a predetermined position during assembly and use.
From the overall structure of the SDE cell, in a general SDE cell, both sides of the bipolar plate need to be grooved to form flow channels for optimizing the flow of the feed liquid, and especially when carbon paper is used as a support, the flow channels need to be prefabricated, because the carbon paper is very thin, if the plate pressed on the carbon paper has no flow channels, the anode material cannot flow or the fluid resistance is very large, the feed liquid cannot flow smoothly and uniformly in the space between the plate and the membrane electrode assembly, and particularly, the large-flow SDE operation cannot be performed. Under the condition of manufacturing a flow channel, the machining requirement is high, the manufacturing cost is high, particularly when a thin plate is grooved, the consistency of the groove depth and the yield and reliability of a bipolar plate are difficult to ensure due to deformation generated in the machining process, the problems of machining cost and machining difficulty are more prominent, the multi-cell stacking of an SDE cell is obviously restricted, and the light weight and the compactness of an SDE device are hindered.
Disclosure of Invention
The invention aims to provide SO2Depolarized electrolytic cell, intended to solve the existing SO2The following problems exist with depolarized cells: 1) the bipolar plate needs to be provided with flow passages carved on two sides, so that the processing difficulty is high and the processing cost is high; 2) the problems that the cost is high, the brittleness is high, the brittle fracture is easy to occur during assembly and the like caused by the fact that the anode side supporting body is made of carbon paper are solved, and in addition, the carbon paper is not easy to fix in the battery and is easy to move under the material flowing condition, so that the performance of the battery is seriously influenced.
The technical scheme of the invention is as follows:
SO (SO)2Depolarized electrolytic cell, this electrolytic cell include one or more monocells of arranging in proper order, every monocell contains membrane electrode assembly, cathode side supporter, anode side supporter, sealing washer to and upper plate and bottom plate, its characterized in that: the anode side support body adopts graphite felt; the upper polar plate and the lower polar plate adopt flat plate structures.
Preferably, a single-layer or multi-layer carbon fiber grid or metal grid is attached to the surface or the inner part of the graphite felt.
The porosity of the graphite felt in the anode side support body is preferably more than or equal to 70%, the carbon content is more than or equal to 98%, and the thickness of the graphite felt is 0.5 mm-10 cm.
In the above technical solution, the cathode side support and the anode side support both carry catalysts, or one of the supports carries a catalyst; the upper polar plate and the lower polar plate are made of corrosion-resistant metal plates, rigid graphite plates or flexible graphite plates. The membrane electrode assembly consists of an anode catalyst layer, a proton selective permeation membrane and a cathode catalyst layer, or consists of a proton selective permeation membrane and a cathode catalyst layer. The periphery of the cathode side supporting body is wrapped with a cathode sealing ring, and the periphery of the anode side supporting body is wrapped with an anode sealing ring.
Compared with the prior art, the invention has the following advantages and prominent technical effects:
the invention adopts the graphite felt with high porosity as the anode side support body, and fully utilizes the characteristics of porosity, high conductivity and electrochemical corrosion resistance of the graphite felt with high porosity, thereby achieving SO2The efficient and low-cost depolarized electrolytic cell. The concrete aspects are as follows: 1) the graphite felt with large porosity has compressibility, and can be firmly arranged in the battery under the auxiliary reinforcement of the carbon fiber grids or the metal grids, thereby not only providing good filling and supporting functions, but also realizing the uniform and rapid passing of materials in the battery; 2) graphite felt with its high conductivity enables SO2The depolarized electrolytic cell has smaller internal resistance and high chemical stability, and can be stably used for a long time under the conditions of feed liquid soaking and high-current electrochemical reaction. 3) The graphite felt has porosity and certain thickness, and is easy to load catalyst thereon, thereby further increasing SO2Efficiency of electrochemical reactions inside depolarized cells. 4) Because the graphite felt with large porosity solves the problem that the anode material flows uniformly in the polar region, SO2The depolarized electrolytic cell can adopt a flat plate/bipolar plate or a plate/bipolar plate with a flow channel carved on one side (namely, the flow channel is carved on the cathode side only), thereby avoiding the problems of high processing difficulty, high processing cost and the like caused by the fact that the flow channel is carved on the two sides. In summary, by adopting the technical scheme of the invention, the SO with high efficiency, stability, compactness and low cost can be constructed2Depolarizing the electrolytic cell. Is particularly suitable for the anode fluid (i.e. the anode electrolyte) containing SO2The sulfuric acid solution of (3) is a place where hydrogen gas is efficiently produced by electrolyzing water at a relatively low voltage.
Drawings
FIG. 1 isIn the prior art SO2Schematic diagram of typical structure of single cell of depolarized electrolytic cell.
FIG. 2 shows an SO according to the present invention2Schematic structure of single cell of depolarized electrolytic cell.
In the figure: 1-an upper polar plate; 2-cathode side support; 3-a cathode sealing ring; 4-a membrane electrode assembly; 5-anode side support; 6-anode sealing ring; 7-lower polar plate.
Detailed Description
The principles, construction and specific implementations of the present invention are further described with reference to the accompanying drawings and examples.
FIG. 1 is a diagram of SO in the prior art2The typical structure principle of the depolarized electrolytic cell is schematically shown, the electrolytic cell takes a membrane electrode assembly 4 as a center, and is distributed with a cathode side support body 2, an anode side support body 5, an upper polar plate 1 with a flow channel and a lower polar plate 7 with a flow channel, the periphery of the support body is sealed by a sealing ring 3 and a sealing ring 6, and the outer side of the sealing ring is flush with the outer edge of a bipolar plate. The seal ring 3 is positioned between the upper bipolar plate 1 and the membrane electrode assembly 4, the center of the seal ring is wrapped by the cathode side support body 2, the lower seal ring 6 is positioned between the lower bipolar plate 7 and the membrane electrode assembly 4, the center of the seal ring is wrapped by the anode side support body 5, the isolation between the cathode chamber and the anode chamber in the battery is realized, and the leakage of substances in the battery to the environment can be prevented.
FIG. 2 shows an SO according to the present invention2The structural principle schematic diagram of the depolarized electrolytic cell comprises at least one single cell which is arranged in sequence, and each single cell comprises a membrane electrode assembly 4, a cathode side support body 2, an upper polar plate 1, an anode side support body 5 and a lower polar plate 7. The anode side support 5 is made of graphite felt, and a single-layer or multi-layer carbon fiber mesh or metal mesh can be attached to the surface or the inner part of the graphite felt, so that the shape keeping capacity of the graphite felt is enhanced. The porosity of the graphite felt in the anode side support body 5 is more than or equal to 70%, the carbon content is more than or equal to 98%, and the thickness of the graphite felt is preferably 0.5 mm-10 cm. The cathode side support 2 and the anode side support 5 each carry a catalyst, or one of the supports carries a catalyst. The periphery of the cathode side supporting body 2 is wrapped with a cathode sealing ring 3, and the anode side branchThe periphery of the support body 5 is wrapped with an anode sealing ring 6.
The upper polar plate 1 and the lower polar plate 7 of the invention adopt a flat plate-shaped structure. The upper polar plate 1 and the lower polar plate 7 are made of corrosion-resistant metal plates, rigid graphite plates or flexible graphite plates.
The membrane electrode assembly consists of an anode catalyst layer, a proton selective permeation membrane and a cathode catalyst layer, or consists of a proton selective permeation membrane and a cathode catalyst layer.
When the electrolytic cell is formed by stacking a plurality of single cells, the outer sides of the single cells positioned at two sides are provided with end plates, and the SO2The depolarized electrolytic cell is pressed to a set pressure by a press and then is fastened and formed, a pull rod penetrates through the end plates, and the pull rod is fastened through a nut.
In the following, specific examples are given to further understanding the present invention.
Example 1:
by adopting the scheme of the invention, the SO formed by 5 single cells which are sequentially stacked and arranged is manufactured2The depolarized electrolytic cell consists of membrane electrode assembly comprising anode catalyst layer, proton selective permeating membrane and cathode catalyst layer. Wherein the proton selective permeable membrane is Nafion 115 (DuPont) proton exchange membrane, both sides of the membrane are sprayed with Pt/C catalyst layers, and the effective membrane area of each single cell is 50cm2The amount of Pt used is 0.6mg/cm2The amount of Pt used in the cathode side and the anode side were the same and 0.3mg/cm, respectively2. A cathode side support body 2, an upper polar plate 1, an anode side support body 5 and a lower polar plate 7 are sequentially distributed on two sides of the membrane electrode assembly. The cathode side support was 0.3mm thick carbon paper and the anode side support was 0.5mm graphite felt (porosity 85%, carbon content 99.5%).
The upper polar plate and the lower polar plate are both titanium metal plates with the thickness of 1mm and anti-corrosion coatings. On the anode side, a carbon fiber grid is additionally paved between the polar plate and the graphite felt, so that the shape keeping capability of the graphite felt is enhanced. The cathode side supporting body and the anode side supporting body are wrapped by a cathode sealing ring and an anode sealing ring, and the materials of the cathode side supporting body and the anode side supporting body are Viton A fluororubber.
After the 5 single battery units are stacked and arranged, aluminum alloy end plates are arranged on the two outermost sides, pull rods penetrating through the end plates are arranged, and after the pressure is applied to the battery units and the end plates through a press machine, the whole electrolysis-electrodialysis cell is fastened by screwing pull rod nuts.
At 50 ℃ with the above SO2The depolarized electrolytic cell is used for electrolysis, and the anode material contains saturated SO230 wt.% sulfuric acid, the cathode material is pure water, the external direct current keeps the current constant at 25A, the total cell voltage is 4.97V, and the hydrogen production rate of the cathode region is measured to be 50L/h.
Example 2:
by adopting the scheme of the invention, the SO formed by 10 single cells which are sequentially stacked and arranged is manufactured2The depolarized electrolytic cell consists of membrane electrode assembly comprising anode catalyst layer, proton selective permeating membrane and cathode catalyst layer. Wherein the proton selective permeable membrane is Nafion 117 (DuPont) proton exchange membrane, Pt/C catalyst layers are sprayed on both sides of the membrane, and the effective membrane area of each single cell is 100cm2The amount of Pt used is 0.5mg/cm2The amount of Pt used was the same for the cathode and anode sides, and was 0.25mg/cm for each2. The two sides of the membrane electrode assembly are sequentially distributed with a cathode side support body, an upper polar plate, an anode side support body and a lower polar plate. The cathode side support and the anode side support were each a 4cm thick graphite felt (porosity 92%, carbon content 99.9%).
Both the upper and lower plates were hard graphite plates (available from POCO, USA) of 3mm thickness.
The cathode side supporting body and the anode side supporting body are wrapped by a cathode sealing ring and an anode sealing ring, and the materials of the cathode side supporting body and the anode side supporting body are Viton A fluororubber.
After the 10 battery units are stacked and arranged, aluminum alloy end plates are arranged on the two outermost sides, pull rods penetrating through the end plates are arranged, and after the battery units and the end plates are pressurized by a press machine, the whole electrolysis-electrodialysis cell is fastened by screwing pull rod nuts.
At 70 deg.C, with the above SO2The depolarized electrolytic cell is used for electrolysis, and the anode material contains saturated SO240 wt.% sulfuric acid, no material is introduced into the cathode region, external direct current keeps the current constant at 53A, and the total cell voltageThe hydrogen production rate in the cathode region is measured to be 200L/h at 8.5V.
Example 3:
by adopting the scheme of the invention, the SO formed by 10 single cells which are sequentially stacked and arranged is manufactured2The depolarized electrolytic cell consists of membrane electrode assembly comprising anode catalyst layer, proton selective permeating membrane and cathode catalyst layer. Wherein the proton selective permeable membrane is Nafion 117 (DuPont) proton exchange membrane, Pt/C catalyst layers are sprayed on both sides of the membrane, and the effective membrane area of each single cell is 100cm2The amount of Pt used is 0.5mg/cm2The amount of Pt used on the cathode side and the anode side is the same. The two sides of the membrane electrode assembly are sequentially distributed with a cathode side support body, an upper polar plate, an anode side support body and a lower polar plate. The anode side support was 2.5mm graphite felt (porosity 92%, carbon content 99.9%), the cathode side support was 3.5mm graphite felt (porosity 92%, carbon content 99.9%) and 0.3mm thick carbon paper, with the carbon paper between the graphite felt and the membrane electrode assembly.
Both the upper and lower plates were 1.5mm flexible graphite plates (available from siegri, germany).
On the anode side, a metal tantalum grid is additionally paved between the polar plate and the graphite felt, so that the shape keeping capability of the graphite felt is enhanced.
The cathode side supporting body and the anode side supporting body are wrapped by a cathode sealing ring and an anode sealing ring, and the materials of the cathode side supporting body and the anode side supporting body are Viton A fluororubber.
After the 10 battery units are stacked and arranged, aluminum alloy end plates are arranged on the two outermost sides, pull rods penetrating through the end plates are arranged, and after the battery units and the end plates are pressurized by a press machine, the whole electrolysis-electrodialysis cell is fastened by screwing pull rod nuts.
At 75 deg.C, with the above SO2The depolarized electrolytic cell is used for electrolysis, and the anode material contains saturated SO240 wt.% sulfuric acid, no material is introduced into the cathode region, the external direct current keeps the current constant at 65A, the total cell voltage is 9.5V, and the hydrogen production rate of the cathode region is measured to be 243L/h.
Example 4:
by adopting the scheme of the inventionAs SO composed of 20 single cells arranged one above the other2The depolarized electrolytic cell consists of membrane with selective proton permeability and cathode catalyst layer. Wherein the proton selective permeable membrane is Nafion 115 (DuPont) proton exchange membrane, a Pt/C catalyst layer is sprayed on one side of the cathode, and the effective membrane area of each single cell is 1000cm2The amount of Pt on the cathode side was 0.3mg/cm2The anode side was not sprayed with a catalyst layer. The two sides of the membrane electrode assembly are sequentially distributed with a cathode side support body, an upper polar plate, an anode side support body and a lower polar plate. Both the cathode side support and the anode side support were 3mm graphite felt (porosity 92%, carbon content 99.9%).
Wrapping a layer of carbon fiber grid in the graphite felt of the anode side support, spraying Pt/C catalyst dispersed in Nafion solution on one surface of the graphite felt facing a membrane electrode assembly before assembling, and drying at 110 ℃ for 6 hours to obtain the anode side support loaded with the Pt catalyst, wherein the use amount of Pt is 0.3mg/cm2。
Both the upper and lower plates were 1.5mm flexible graphite plates (available from siegri, germany).
The cathode side supporting body and the anode side supporting body are wrapped by a cathode sealing ring and an anode sealing ring, and the materials of the cathode side supporting body and the anode side supporting body are Viton A fluororubber.
After the 20 battery units are stacked and arranged, aluminum alloy end plates are arranged on the two outermost sides, pull rods penetrating through the end plates are arranged, and after the battery units and the end plates are pressurized by a press machine, the whole electrolysis-electrodialysis cell is fastened by tightening pull rod nuts.
At 80 ℃ with the above SO2The depolarized electrolytic cell is used for electrolysis, and the anode material contains saturated SO240 wt.% sulfuric acid, no material is introduced into the cathode region, the external direct current keeps the current constant at 500A, the total cell voltage is 0.87V, and the cathode region hydrogen production rate is measured to be 3.75m3/h。
Example 5:
by adopting the scheme of the invention, the SO formed by 10 single cells which are sequentially stacked and arranged is manufactured2Depolarized electrolytic cell, membrane electrode assemblyThe proton selective permeation membrane and the cathode catalysis layer. Wherein the proton selective permeable membrane is Nafion 115 (DuPont) proton exchange membrane, the anode side is not sprayed with catalyst layer, the cathode side is sprayed with Pt/C catalyst layer, and the effective membrane area of each single cell is 700cm2The amount of Pt used on the cathode side was 0.1mg/cm2. The two sides of the membrane electrode assembly are sequentially distributed with a cathode side support body, an upper polar plate, an anode side support body and a lower polar plate. The cathode side support and the anode side support were each a 5mm graphite felt (porosity 92%, carbon content 99.9%).
Before assembling a cathode side support body and an anode side support body, spraying Pt/C catalyst dispersed in Nafion solution on one surface of the support body facing to a membrane electrode assembly, and drying at 120 ℃ for 6h to obtain a graphite felt support body loaded with the Pt catalyst, wherein the use amount of Pt on the cathode side support body and the anode side support body is 0.3mg/cm2。
Both the upper and lower plates were 1.5mm flexible graphite plates (available from siegri, germany).
The cathode side supporting body and the anode side supporting body are wrapped by a cathode sealing ring and an anode sealing ring, and the materials of the cathode side supporting body and the anode side supporting body are Viton A fluororubber.
After the 10 battery units are stacked and arranged, aluminum alloy end plates are arranged on the two outermost sides, pull rods penetrating through the end plates are arranged, and after the battery units and the end plates are pressurized by a press machine, the whole electrolysis-electrodialysis cell is fastened by screwing pull rod nuts.
At 80 ℃ with the above SO2The depolarized electrolytic cell is used for electrolysis, and the anode material contains saturated SO247 wt.% sulfuric acid, no material is introduced into the cathode region, external direct current keeps the current constant at 480A, the total cell voltage is 9.5V, and the cathode region hydrogen production rate is measured to be 1.8m3/h。

Claims (5)

1. SO (SO)2The depolarized electrolytic cell comprises one or more single cells which are arranged in sequence, wherein each single cell comprises a membrane electrode assembly (4), a cathode side support body (2), an anode side support body (5), an upper polar plate (1) and a lower polar plate(7) The method is characterized in that: the anode side support body (5) adopts graphite felt; the upper polar plate (1) and the lower polar plate (7) adopt flat plate-shaped structures; a single-layer or multi-layer carbon fiber grid or metal grid is attached to the surface or the interior of the graphite felt;
the porosity of the graphite felt in the anode side support body (5) is more than or equal to 70%, the carbon content is more than or equal to 98%, and the thickness of the graphite felt is 0.5 mm-10 cm.
2. A SO according to claim 12Depolarized electrolytic cell, its characterized in that: the cathode side support body (2) and the anode side support body (5) are loaded with catalysts, or one of the support bodies is loaded with a catalyst.
3. A SO as claimed in claim 1 or 22Depolarized electrolytic cell, its characterized in that: the upper polar plate (1) and the lower polar plate (7) are made of corrosion-resistant metal plates, rigid graphite plates or flexible graphite plates.
4. A SO according to claim 12Depolarized electrolytic cell, its characterized in that: the membrane electrode assembly (4) consists of an anode catalyst layer, a proton selective permeation membrane and a cathode catalyst layer, or consists of a proton selective permeation membrane and a cathode catalyst layer.
5. A SO according to claim 12Depolarized electrolytic cell, its characterized in that: the periphery of the cathode side supporting body (2) is wrapped with a cathode sealing ring (3), and the periphery of the anode side supporting body (5) is wrapped with an anode sealing ring (6).
CN202010128777.1A 2020-02-28 2020-02-28 SO (SO)2Depolarized electrolytic cell Active CN111424286B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010128777.1A CN111424286B (en) 2020-02-28 2020-02-28 SO (SO)2Depolarized electrolytic cell

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010128777.1A CN111424286B (en) 2020-02-28 2020-02-28 SO (SO)2Depolarized electrolytic cell

Publications (2)

Publication Number Publication Date
CN111424286A CN111424286A (en) 2020-07-17
CN111424286B true CN111424286B (en) 2021-06-08

Family

ID=71547255

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010128777.1A Active CN111424286B (en) 2020-02-28 2020-02-28 SO (SO)2Depolarized electrolytic cell

Country Status (1)

Country Link
CN (1) CN111424286B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113151853B (en) * 2021-03-08 2024-02-06 清华大学 SO (SO) device 2 Depolarized electrolytic cell and method of operating same
CN113611873B (en) * 2021-07-29 2022-09-27 清华大学 SO (SO) 2 Preparation and laying method of anode support body of depolarized electrolytic cell

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4443316A (en) * 1980-11-06 1984-04-17 Kernforschungsanlage Julich Gesellschaft Mit Beschrankter Haftung Electrolysis cell with intermediate chamber for electrolyte flow

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4443316A (en) * 1980-11-06 1984-04-17 Kernforschungsanlage Julich Gesellschaft Mit Beschrankter Haftung Electrolysis cell with intermediate chamber for electrolyte flow

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Characterization Testing and Analysis of Single Cell SO2 Depolarized Electrolyzer;J. L. Steimke;《WSRC-STI-2006-00120.2006》;20060915;第13页 *

Also Published As

Publication number Publication date
CN111424286A (en) 2020-07-17

Similar Documents

Publication Publication Date Title
CA2966834C (en) Oxygen-generating anode
US11035045B2 (en) Apparatus for producing organic hydride and method for producing organic hydride using same
Huskinson et al. A high power density, high efficiency hydrogen–chlorine regenerative fuel cell with a low precious metal content catalyst
CN113373462A (en) For electrochemical reduction of CO2Membrane type liquid flow electrolytic cell and testing process
CN1966777A (en) Water electrolysis device with proton exchange membrane
JP2010535942A (en) Electrolyzer with anode depolarized by sulfur dioxide and method of using the same in hydrogen production
Nagasawa et al. The effect of flow-field structure in toluene hydrogenation electrolyzer for energy carrier synthesis system
CN111424286B (en) SO (SO)2Depolarized electrolytic cell
Aziznia et al. A Swiss-roll liquid–gas mixed-reactant fuel cell
CA2989151A1 (en) Water treatment system using alkaline water electrolysis device and alkaline fuel cell
Prabhuram et al. Methanol adsorbates on the DMFC cathode and their effect on the cell performance
Nagasawa et al. Chemical-hydrogenation functionalized flow-field in toluene direct electro-hydrogenation electrolyzer for energy-carrier synthesis system
KR20190083546A (en) Electrochemical hydrogenation reactor and method of hydrogenation using the same
Huang et al. Effects of Nafion content in membrane electrode assembly on electrochemical Bunsen reaction in high electrolyte acidity
Ravichandran et al. Platinum deposition on the nafion membrane by impregnation reduction using nonionic surfactant for water electrolysis–An alternate approach
CN217628644U (en) Three-electrode system-based electrolytic tank for two-step method water electrolysis hydrogen production
Mondal et al. A spontaneous hydrogen fuel purifier under truly ambient weather conditions
CN113151853B (en) SO (SO) device 2 Depolarized electrolytic cell and method of operating same
CN111424287B (en) Electrolysis-electrodialysis cell for hydrogen iodide concentration
Fujita et al. An electrochemical oxygen separator using an ion-exchange membrane as the electrolyte
CN216237301U (en) Efficient proton exchange membrane electrolytic cell
Zhang et al. Design of gas diffusion electrode electrolyzer for CO2 reduction to CO with Cl2 and Na2CO3 produced as by-products
CN113611873B (en) SO (SO) 2 Preparation and laying method of anode support body of depolarized electrolytic cell
RU2656219C1 (en) Coaxial electrochemical compressor of hydrogen
CN211665190U (en) Electrolytic cell structure and electrolytic device

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant