CN113186555A - High-current-density alkaline water electrolysis cell structure and device - Google Patents
High-current-density alkaline water electrolysis cell structure and device Download PDFInfo
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Abstract
The invention provides a high-current-density alkaline water electrolyzer structure and a high-current-density alkaline water electrolyzer device, which comprise a left end plate, a cathode collector plate, a plurality of small electrolysis chamber units, an anode collector plate and a right end plate which are sequentially stacked, and are fastened by a plurality of groups of bolts. Wherein, the electrolysis cell unit consists of a cathode unipolar plate, an insulating film, an anode unipolar plate and a sealing gasket arranged in the middle; the surfaces of the cathode single-pole plate and the anode single-pole plate are respectively provided with completely symmetrical flow fields, the flow field of the cathode single-pole plate is coated with a hydrogen evolution catalyst to form a cathode electrode, and the flow field of the anode single-pole plate is coated with nickel hydroxide to form an anode electrodeThe cathode and the anode are insulated and separated by an insulating film; the electrolysis device has the characteristics of large electrode surface area, large electrolysis current density and the like, and simultaneously, OH in the electrolyte is not required to be provided with a diaphragm‑Ions can rapidly migrate to the anode, so that the resistance voltage drop is effectively reduced, the electrolytic potential is reduced, the electrolytic efficiency of the electrolytic cell and the hydrogen production rate are increased, and the cost is greatly reduced.
Description
Technical Field
The invention relates to the technical field of electrolyzed water, in particular to a high-current-density alkaline water electrolyzer structure and a device.
Background
With the development of socio-economy, energy and environmental problems have become a worldwide problem. The fossil energy sources used at present, such as coal, petroleum and the like, belong to non-renewable energy sources, and meanwhile, the problem of environmental pollution caused by burning fossil fuels has gradually attracted attention of people. The problem of environmental pollution caused by energy shortage and energy consumption is two of the most serious problems facing mankind in this century, and the human society is also eagerly searching and developing renewable green alternative energy.
Among clean and renewable green alternative energy sources, hydrogen energy is one of effective ways to replace traditional energy sources. The existing hydrogen production technology is the most mature technology with commercialized water electrolysis hydrogen production technology, wherein the low-temperature water electrolysis hydrogen production mainly comprises alkaline water electrolysis and Proton Exchange Membrane (PEM) water electrolysis; the alkaline water electrolysis hydrogen production is an important technology for realizing large-scale hydrogen production and is one of the most mature hydrogen production technologies at present.
The main feature of PEM water electrolysis technology is to replace the traditional caustic solution electrolyte with solid polymer electrolyte. The so-called solid polymer is generally a perfluorosulfonic acid proton exchange membrane, and the sulfonic group has the property of transferring hydronium ions, which also causes a strong acid working environment inside PEM water electrolysis, thus requiring a catalyst material with high corrosion resistance. Meanwhile, because the energy consumption of the anode water electrolysis oxygen evolution process is high, a catalyst material with high activity represented by noble metal needs to be adopted, so that the water electrolysis cost is high, and the practical application of the catalyst is limited.
The proton exchange membrane in the PEM electrolytic cell has the excellent properties of high proton conductivity, small gas penetration rate, high compressive strength, thin thickness and the like, so that the proton exchange membrane electrolysis technology has the advantages of high current density and high electrolysis efficiency compared with other electrolysis technologies, and can be more suitable for hydrogen production by water electrolysis of renewable energy sources.
In the alkaline water electrolysis industry, hydrogen production by alkaline water electrolysis is one of important technologies for realizing large-scale hydrogen production, and an electrolytic cell of the alkaline water electrolysis industry generally adopts a bipolar electrolytic cell at present, wherein the electrolytic cell is a cell body of the electrolytic cell formed by regularly laminating a plurality of unit cells, and each electrolytic cell mainly comprises a polar frame, a bipolar main polar plate, a diaphragm, a cathode and an anode and a sealing gasket. One side of the bipolar main polar plate is a cathode, and the other side of the bipolar main polar plate is an anode, and the bipolar main polar plate is welded into a polar frame to form a whole. Each chamber is divided into a cathode chamber and an anode chamber, and a diaphragm is positioned between the cathode and the anode and mainly used for preventing oxyhydrogen gas from mixing.
The traditional alkaline water electrolysis technology has high energy consumption and low efficiency, and in the water electrolysis process, the cathode and the anode of the electrolysis electrode simultaneously generate hydrogen and oxygen, and an ion selective membrane is required to separate the oxygen from the hydrogen, so that the cost of hydrogen production is increased to a certain extent.
Disclosure of Invention
In order to better solve the problems of high energy consumption and low efficiency of the alkaline water electrolysis technology, and simultaneously, combine the characteristics and advantages of the PEM electrolysis technology, effectively reduce the cost and improve the electrolysis efficiency, the invention provides a high-current-density alkaline water electrolysis tank structure and a device, wherein the structure comprises a left end plate, a cathode collector plate, a plurality of electrolysis small chamber units, an anode collector plate and a right end plate which are sequentially overlapped. Wherein, the electrolysis cell unit consists of a cathode unipolar plate, an insulating film, an anode unipolar plate and a sealing gasket arranged in the middle; and sequentially fastening the left end plate, the cathode collector plate, the plurality of small electrolysis chamber units, the anode collector plate and the right end plate through a plurality of groups of bolts to form the electrolytic tank device.
Particularly preferably, the surfaces of the cathode unipolar plate and the anode unipolar plate of the electrolysis cell unit are respectively provided with completely symmetrical flow fields, the flow field of the cathode unipolar plate is coated with a hydrogen evolution catalyst to form a cathode electrode, and the flow field of the anode unipolar plate is coated with nickel hydroxide to form an anode electrode.
Further, the electrolytic cell units are sequentially connected in an overlapping manner, wherein the cathode unipolar plate coated with the hydrogen evolution catalyst of the previous electrolytic cell unit and the anode unipolar plate coated with the nickel hydroxide of the next electrolytic cell unit which are adjacently connected together can be combined into a whole in the actual production process or manufactured by adopting the same material with good electrical conductivity to form the bipolar plate with the bipolar function.
Particularly preferably, the cathode unipolar plate and the anode unipolar plate of the electrolysis cell unit are insulated by an insulating film, and the cathode electrode and the anode electrode are separated; the completely symmetrical flow fields form an electrolysis chamber cavity after being superposed, and a diaphragm, a cathode chamber and an anode chamber are not required to be arranged.
Particularly preferably, the hydrogen evolution catalysis cathode electrode of the electrolysis cell unit cathode unipolar plate has a catalysis effect on the generation of hydrogen by electrolyzing water, and the electrode material can be selected from binary Ni-Mo alloy, Ni-Son alloy, Ni-Co alloy or ternary Ni-Fe-Mo alloy and the like of metal Ni with higher electrocatalytic activity.
Particularly preferably, the electrode material of the anode unipolar plate of the electrolysis cell unit is selected from Ni (OH) doped with conductive metal Co or carbon-coated with spherical or flaky crystal structure2。
Further, the hydrogen evolution catalyst coated in the cathode unipolar plate flow field is characterized in that the catalyst coating process method comprises but is not limited to an electrodeposition method, a PTFE bonding method, a chemical reduction method, an ion spraying method, a high-temperature sintering method and the like.
Further, the nickel hydroxide electrode coated in the anode monopolar plate flow field is characterized in that the process method for coating the nickel hydroxide comprises but is not limited to a chemical (water-jet) bath, an electrodeposition method, an oxidation treatment method, an electrochemical dealloying method, an anodic oxidation method, an anode voltage oscillation method and the like.
Particularly preferably, the bipolar plate with bipolar property may be made of a material such as a carbon plate, a titanium metal plate, a nickel metal plate or a stainless steel plate; the processing method of the flow field channels on both sides of the bipolar plate includes but is not limited to carving, stamping, chemical corrosion, etc.
Particularly preferably, the bipolar plate with bipolar two-sided flow fields include, but are not limited to, parallel flow fields, multi-channel serpentine flow fields, herringbone flow fields, etc.
Particularly preferably, the bipolar plate can also be manufactured by welding a plate frame and a thin plate with a wave-shaped or corrugated flow field.
In the designed structure, the hydrogen evolution catalysis negative electrode and the hydrogen evolution catalysis anode electrode are respectively composed of a leftmost cathode electrode plate, a rightmost anode electrode plate, a bipolar plate and nickel hydroxide doped with conductive metal, insulating films are arranged in the middle of the negative electrode and the anode electrode plates, an electrolysis chamber cavity is formed after superposition, a diaphragm, a cathode chamber and an anode chamber are not required to be arranged, the hydrogen production step and the oxygen production step based on water electrolysis are carried out step by step and time by time, and oxygen and hydrogen can be produced in different time periods in the same cavity respectively.
The method for realizing the time-interval preparation of the hydrogen and the oxygen is based on that in the device, the anode electrode material selects Ni (OH)2The material has special chemical properties: as the positive electrode material Ni (OH) widely applied to the Cd-Ni and MH-Ni batteries2The NiOOH has a very classical Bode cycle, as shown in figure 3, according to the traditional crystallography theory, the active substance NiOOH in a charging state is divided into two crystal forms of beta-NiOOH and gamma-NiOOH, and the active substance in a discharging state corresponding to the beta-NiOOH and the gamma-NiOOH is beta-Ni (OH)2 With alpha-Ni (OH)2And a cyclic relationship is formed among the four. In the above Bode cycle, Ni (OH)2the/NiOOH showed better electrode reversibility. In the presence of Ni (OH)2When NiOOH is used as an anode material for water electrolysis, nickel oxyhydroxide (NiOOH) spontaneously undergoes an oxygen evolution reaction due to thermodynamic instability when an anode electrode (in the form of NiOOH) is in an aqueous solution environment at a relatively high temperature, and the chemical reaction equation shows that:
4NiOOH+2H2O→ 4 Ni(OH)2+ O2↑。
by using Ni (OH)2As anode electrode material, in the process of electrolyzing water in the electrolytic tank, under the action of hydrogen evolution catalyst, water molecules in the alkaline electrolyte are electrochemically reduced on the surface of the hydrogen evolution catalytic cathode electrode to generate a large amount of hydrogen, and simultaneously Ni (OH)2 The anode electrode is electrochemically oxidized into a NiOOH anode electrode, and oxygen is not released, and the chemical reaction equation is as follows:
cathode electrode reaction: h2O + e- → 1/2H2↑ +OH-；
Anode electrode reaction: ni (OH)2 + OH-－e- → NiOOH + H2O；
The general reaction formula is as follows: ni (OH)2 → NiOOH + 1/2H2↑。
When the external direct current power supply of the electrolytic cell is cut off and high-temperature saturated steam or high-temperature aqueous solution is introduced into the electrolyte of the electrolytic cell, the anode electrode (in the NiOOH form) is decomposed and reduced into Ni (OH) due to the thermodynamic instability of NiOOH2The electrode and the oxygen generated around the electrode have the following chemical reaction equation:
4NiOOH +2H2O → 4Ni(OH)2 + O2↑。
in conclusion [0020] to [0022], the hydrogen and oxygen can be prepared by electrolyzing water step by step and in different periods.
Compared with the prior alkaline water electrolysis technology, the technical scheme provided by the invention has the following obvious technical effects:
the structure of the water electrolysis device adopts a structure design similar to that of a PEM electrolytic tank, wherein a cathode electrode is prepared by coating a hydrogen evolution catalytic material on the surface of a flow field runner of a cathode unipolar plate; the anode electrode is made by coating nickel hydroxide or nickel oxyhydroxide material on the surface of a flow field flow channel of the anode unipolar plate, and has the characteristics of large electrode surface area, large electrolysis current density and the like; meanwhile, an electrolysis chamber cavity is formed in the electrolysis small chamber unit, and a diaphragm, a cathode chamber and an anode chamber are not required to be arranged, so that OH of electrolyte in the electrolysis cell is generated in the process of producing hydrogen by electrolyzing water-Ions can be rapidly transferred to the anode, so that the resistance voltage drop in the electrolytic cell is effectively reduced, the electrolytic potential is reduced, the electrolytic efficiency and the hydrogen production rate of the electrolytic cell are increased, and the cost is greatly reduced.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts. In the drawings:
FIG. 1 is a schematic diagram of an alkaline cell structure and apparatus comprising three electrolysis cells according to a preferred embodiment of the present invention;
FIG. 2 is a schematic diagram of the construction of a single electrolytic cell provided in accordance with a preferred embodiment of the present invention;
FIG. 3 shows a preferred embodiment of the present invention, which provides a charge-discharge active electrode material Ni (OH)2The Bode cycle diagrams of the four crystal forms are used for explaining the basis of the operation of the device;
description of reference numerals: 1-left endplate; 2-cathode collector plate; 3-an electrolysis cell; 301-a cathode electrode; 302-a cathode electrode plate; 303-a sealing gasket; 304-an insulating film; 305-an anode electrode plate; 306-an anode electrode; 4-a bipolar plate; (ii) a 5-anode current collector plate; 6-right end plate.
Detailed Description
The structure and device of an alkaline water electrolyzer with high current density according to the present invention will be further described with reference to fig. 1-2, and the present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed embodiment and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments, and those skilled in the art can modify and color the alkaline water electrolyzer without changing the spirit and content of the present invention.
Please refer to fig. 1 and 2: a high current density alkaline water electrolyzer structure and apparatus, its structure includes left end plate 1, negative pole current collector plate 2, a plurality of electrolytic cell units 3 that superpose sequentially, positive pole current collector plate 5 and right end plate 6; the electrolytic cell unit 3 is composed of a cathode unipolar plate 302, an insulating film 304, an anode unipolar plate 305, and a gasket 303, and the electrolytic cell device is configured by fastening a left end plate 1, a cathode current collecting plate 2, a plurality of electrolytic cell units 3, an anode current collecting plate 5, and a right end plate 6 in this order by a plurality of sets of bolts.
In the device, the surfaces of the cathode unipolar plate 302 and the anode unipolar plate 305 of the electrolysis cell unit 3 are respectively provided with completely symmetrical flow fields, the cathode unipolar plate 302 is coated with a hydrogen evolution catalyst in the flow field to form a cathode electrode 301, and the anode unipolar plate 305 is coated with nickel hydroxide in the flow field to form an anode electrode 306, so as to form two electrodes of the electrolysis bath.
In the device, the cathode unipolar plate 302 and the anode unipolar plate 305 of one electrolysis cell unit 3 are insulated by an insulating film 304, and the separation of the cathode electrode 301 and the anode electrode 306 in the electrolysis cell unit is ensured; meanwhile, the completely symmetrical flow fields form an integral electrolytic chamber cavity after being superposed, and a diaphragm, a cathode chamber and an anode chamber are not required to be arranged.
The plurality of groups of electrolytic cell units 3 are sequentially connected in an overlapping manner, and the cathode unipolar plate 302 of the previous electrolytic cell unit and the anode unipolar plate 305 of the next electrolytic cell unit which are adjacently connected together can be combined into a whole in the actual production process or made of the same material with good electrical conductivity to form the bipolar plate 4 with double polarities.
In order to ensure that the electrolytic cell has good electrolytic activity performance, the electrode material of the hydrogen evolution catalytic cathode electrode 301 coated on the cathode unipolar plate 302 of the electrolysis small chamber unit 3 is selected from binary Ni-Mo alloy, Ni-Sn alloy, Ni-Co alloy or ternary Ni-Fe-Mo alloy and the like of metal Ni with high electrocatalytic activity.
The anode electrode 306 material coated on the anode unipolar plate 305 of the electrolysis cell unit 3 is selected from conductive metal Co-doped or carbon-coated Ni (OH)2 with a spherical or flaky crystal structure, and has good electrode reversibility.
In the cathode unipolar plate 302, the cathode electrode 301 formed by coating the hydrogen evolution catalyst in the flow field may be coated by a catalyst coating process selected from, but not limited to, an electrodeposition method, a PTFE bonding method, a chemical reduction method, an ion spraying method, a high temperature sintering method, and the like.
The anode electrode 306 is formed by coating nickel hydroxide in the flow field of the anode unipolar plate 305, and the process method for coating nickel hydroxide can be selected from but not limited to a chemical (water-jet) bath, an electrodeposition method, an oxidation treatment method, an electrochemical dealloying method, an anodic oxidation method, an anode voltage oscillation method, and the like.
In the device, the bipolar plate 4 with bipolarity can be made of a material of a carbon plate, a titanium metal plate, a nickel metal plate or a stainless steel plate; the two-sided flow field channel processing of the bipolar plate 4 may include, but is not limited to, engraving, stamping, chemical etching, and the like.
In the device, the flow field structure of the bipolar plate 4 with two sides includes, but is not limited to, a parallel flow field, a multi-channel serpentine flow field, a herringbone flow field, etc.
Description of the Process for producing Hydrogen and oxygen by electrolyzing Water step by step and time
The structural design of the alkaline water electrolysis device is designed based on the difference from the traditional process method for producing hydrogen by alkaline water electrolysis, and the structural design is based on the following process method:
advanced hydrogen production method
1. Introducing a 10-30% potassium hydroxide or sodium hydroxide aqueous solution into flow field runners of each electrolysis cell unit 3 of the alkaline electrolysis cell by external power, wherein the flowing electrolyte solution is in full contact with a hydrogen evolution catalytic cathode electrode 301 of a cathode unipolar plate 302 and a nickel hydroxide anode electrode 306 of an anode electrode plate 305 of the electrolysis cell unit 3;
2. an external direct current power supply of the alkaline electrolytic cell is switched on, under the action of direct current electrolysis, water molecules in the electrolyte solution are electrochemically reduced on the surfaces of the hydrogen evolution catalytic cathode electrodes 301 of the electrolytic cells 3, so that hydrogen is generated, and the preparation of the hydrogen is completed;
at this time, nickel hydroxide (Ni (OH)) in each cell unit 32The anode electrode 306 is electrochemically oxidized to NiOOH anode electrode 306 without the generation of oxygen, and the chemical reaction equation is as follows:
cathode electrode reaction: h2O + e- → 1/2H2↑ +OH-；
Anode electrode reaction: ni (OH)2 + OH-－e- → NiOOH + H2O；
The general reaction formula is as follows: ni (OH)2 → NiOOH + 1/2H2↑；
(II) later-stage oxygen generation method
3. After hydrogen production is finished, an external direct-current power supply of the alkaline electrolytic cell is disconnected, and high-temperature saturated steam or high-temperature aqueous solution is introduced into the electrolyte in the flow field flow channel of each small electrolytic cell unit 3 of the alkaline electrolytic cell through external power, so that the temperature of the electrolyte reaches about 95 ℃; at this time, due to the thermodynamic instability of the anode electrode (in NiOOH form) 306 in each electrolytic cell unit 3, the anode electrode (in NiOOH form) 306 is decomposed and reduced to the ni (oh)2 anode electrode 306, and oxygen is generated around the anode electrode, completing the production of hydrogen, whose chemical reaction equation is as follows:
4NiOOH +2H2O → 4Ni(OH)2 + O2↑；
and (III) the steps of the method are implemented step by step, so that the step (I) and the step (II) are alternately and circularly carried out, and the preparation of the hydrogen and the oxygen in different time periods can be realized.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the embodiments. Even if various changes are made to the present invention, it is within the scope of the present invention if they fall within the scope of the claims of the present invention and their equivalents.
Claims (8)
1. A high current density alkaline water electrolyzer structure and device, characterized by that to include left end plate, negative pole current collector plate, a plurality of electrolytic cell units, positive pole current collector plate and right end plate that superpose sequentially; the electrolysis cell unit is composed of a cathode unipolar plate, an insulating film, an anode unipolar plate and a sealing gasket, and the left end plate, the right end plate, the current collecting plate and the plurality of electrolysis cells are fastened through a plurality of groups of bolts to form the electrolysis bath device.
2. The high current density alkaline water electrolyser structure and apparatus of claim 1 wherein said cathode and anode unipolar plates are provided with substantially symmetrical flow fields on their surfaces, respectively, said cathode unipolar plate flow fields being coated with a hydrogen evolution catalyst to form a cathode electrode and said anode unipolar plate flow fields being coated with nickel hydroxide to form an anode electrode.
3. The high current density alkaline water electrolyser structure and apparatus of claim 1 wherein the sequentially stacked intermediate cell units are joined together adjacent the cathode monopolar plate of the preceding cell unit and the anode monopolar plate of the succeeding cell unit and are technically combined into one piece to form a bipolar plate.
4. The electrolysis cell unit of claim 1, wherein the cathode and anode unipolar plates are insulated by an insulating film and separate the cathode and anode electrodes; the completely symmetrical flow fields form an electrolysis chamber cavity after being superposed, and a diaphragm, a cathode chamber and an anode chamber are not required to be arranged.
5. The bipolar plate of claim 3, wherein the bipolar plate is made of a material selected from the group consisting of a carbon plate, a titanium metal plate, a nickel metal plate, and a stainless steel plate.
6. The bipolar plate of claim 3 wherein the two-sided flow field flow channel processing of the bipolar plate includes but is not limited to engraving, stamping, and chemical etching.
7. The bipolar plate of claim 3 wherein the flow channels of the bipolar plate include, but are not limited to, parallel flow fields, multi-channel serpentine flow fields, herringbone flow fields, and the like.
8. The bipolar plate of claim 3, wherein the bipolar plate is further fabricated by welding a frame to a sheet having a corrugated or corrugated flow field.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115216782A (en) * | 2022-06-28 | 2022-10-21 | 中国华能集团清洁能源技术研究院有限公司 | Alkaline water electrolysis tank voltage monitoring and ultrasonic wave strengthening device and control method thereof |
| WO2023103812A1 (en) * | 2021-12-08 | 2023-06-15 | 嘉庚创新实验室 | Electrochemical reaction device, and method for producing oxygen |
| CN117248230A (en) * | 2023-11-16 | 2023-12-19 | 上海治臻新能源股份有限公司 | Electrolytic tank |
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2021
- 2021-05-04 CN CN202110487078.0A patent/CN113186555A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023103812A1 (en) * | 2021-12-08 | 2023-06-15 | 嘉庚创新实验室 | Electrochemical reaction device, and method for producing oxygen |
| CN115216782A (en) * | 2022-06-28 | 2022-10-21 | 中国华能集团清洁能源技术研究院有限公司 | Alkaline water electrolysis tank voltage monitoring and ultrasonic wave strengthening device and control method thereof |
| CN115216782B (en) * | 2022-06-28 | 2024-05-14 | 中国华能集团清洁能源技术研究院有限公司 | Alkaline water electrolysis cell voltage monitoring and ultrasonic strengthening device and control method thereof |
| CN117248230A (en) * | 2023-11-16 | 2023-12-19 | 上海治臻新能源股份有限公司 | Electrolytic tank |
| CN117248230B (en) * | 2023-11-16 | 2024-03-01 | 上海治臻新能源股份有限公司 | Electrolytic tank |
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