CN1966777A - Water electrolysis device with proton exchange membrane - Google Patents
Water electrolysis device with proton exchange membrane Download PDFInfo
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- CN1966777A CN1966777A CNA2005101104210A CN200510110421A CN1966777A CN 1966777 A CN1966777 A CN 1966777A CN A2005101104210 A CNA2005101104210 A CN A2005101104210A CN 200510110421 A CN200510110421 A CN 200510110421A CN 1966777 A CN1966777 A CN 1966777A
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- 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
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Abstract
The invention discloses a device for electrolyzing water with proton exchange membrane and providing highly pure hydrogen and oxygen for fuel cell. The device sequentially contains front side plate, diffuse plate, electric conduction plate, front special plate, H/O flow field plate, membrane electrode, and back special plate, baffle plat and rear side plate. Each of the units is round pressure-proof structure. Water, gas flow field and electric conduction plate adopts Ti alloy and other corrosion resistant alloy. Membrane electrode diffusion layer adopts carbon paper or cloth. The membrane electrode is high active 0 pole pitch electrode prepared by hot briquetting proton exchange membrane and composite Pt catalyst. The working medium of the invention is pure water, has no pollution to the environment, and can be recycled. The hydrogen and oxygen obtained from the invention has high purity and do not need complex purification treatment. Regenerative fuel cell energy storing system with high specific energy prepared by combining the invention and fuel cell can be used in various kinds of main power source and dynamical systems in spaceflight and aerobat.
Description
Technical Field
The invention relates to an electrolysis device, in particular to a water electrolysis device with a proton exchange membrane.
Background
A fuel cell is an electrochemical reaction device that directly converts chemical energy of hydrogen and oxygen into electric energy, and a power generation system can continuously supply electric energy as long as hydrogen and oxygen are continuously supplied, and the reaction product thereof is only purified water. On spacecraft with low flight times, the hydrogen and oxygen source can be provided by liquid hydrogen and liquid oxygen gasification. However, for spacecraft to perform long-term tasks, it is not possible to carry large quantities of liquid hydrogen and liquid oxygen due to volume and weight limitations. The hydrogen and oxygen can be repeatedly supplied for a long time by adopting the solar cell to electrolyze water generated by the fuel cell to generate electricity to prepare the hydrogen and the oxygen. The closed cycle system which utilizes solar energy to electrolyze water to produce hydrogen and oxygen and then generates electric energy through the electrochemical reaction of the fuel cell is called as a renewable fuel cell power generation system. The solar cell array has the advantages of high specific energy, long cycle life, continuous heavy current discharge and the like, and a power supply system formed by the solar cell array can ensure that the spacecraft can obtain electric energy without limit whether in the sun irradiation period or the earth shadow period. Therefore, the renewable fuel cell power generation system generated by combining the hydrogen fuel cell technology and the water electrolysis technology is the first choice of the main power system or the power system of various novel aerospace aircrafts at present.
The prior known water electrolysis technology adopts an alkaline asbestos membrane water electrolyzer, which has the defects that the electrolysis efficiency is low, the environment is polluted due to strong corrosivity of electrolyte of the electrolyzer, and the generated hydrogen has low purity and can be applied only through a complicated purification treatment process.
Disclosure of Invention
In order to overcome the defects of the prior known alkaline asbestos membrane water electrolyzer, the invention provides a proton exchange membrane water electrolyzer, which can prepare hydrogen and oxygen through water electrolysis to provide reaction gas for a fuel cell, and has the characteristics of low electrolysis power consumption, high purity of the prepared hydrogen and oxygen, and direct application without complicated subsequent purification treatment technology, thereby achieving the purpose of forming a renewable fuel cell power generation system with high specific energy characteristic by combination.
In order to solve the technical problems, the invention adopts the technical scheme that a proton exchange membrane water electrolysis device is provided, and the device comprises: the front end plate is used for positioning; then arranging diffusion plates in sequence, and uniformly distributing the electrolyzed water to each flow field plate flow channel; the front conductive plate is used forsupplying electric energy required by water electrolysis through an external power supply; a front special plate providing a passage for water and gas to be uniformly distributed; the membrane electrode is a place for generating hydrogen and oxygen through electrochemical reaction in the water electrolysis device; the hydrogen-oxygen flow field plate provides channels for electrolyzing water and generating gas distribution, the water is uniformly distributed to the membrane electrode diffusion layer through the flow field plate flow channels, and the water is electrolyzed on the anode catalyst layer; a rear special plate providing a channel for uniform distribution of water and gas; a rear conductive plate through which an external power supply supplies electric energy required for electrolyzing water; the buffer plate plays roles of insulation, pressure buffering and supporting; finally, positioning by using a rear end plate; the positioning holes ensure the orderly correspondence of each unit during integration, and high-elasticity silicon rubber is adopted for integral line sealing during integration of each unit, and finally, the metal screw is used for locking and fixing.
The proton exchange membrane water electrolysis device is used as a key single machine of a renewable fuel cell space power supply system, and can produce hydrogen and oxygen through water electrolysis to provide reaction gas for a fuel cell. Compared with the prior known alkaline asbestos membrane water electrolyzer, the electrolyzer has the advantages that the working medium is pure water, the environment is not polluted, the electrolyzer can be recycled, the purity of the generated hydrogen and oxygen is high, and complicated purification treatment is not needed. The invention can be applied to the main power supply system or the power system of various aerospace and aviation aircrafts.
Drawings
FIG. 1 is a perspective view of a water electrolysis apparatus with proton exchange membrane according to the present invention.
FIG. 2 is a plan view of the water electrolyzing apparatus with proton exchange membrane of the present invention.
The method comprises the following steps: the device comprises a front end plate 1, a diffusion plate 2, a front conductive plate 3, a front special plate 4, a Membrane Electrode (MEA)5, an oxyhydrogen flow field plate 6, a rear special plate 7, a rear conductive plate 8, a buffer plate 9 and a rear end plate 10.
Fig. 3 is a schematic structural view of the front and rear end plates of fig. 2 according to the present invention.
Fig. 4 is a schematic structural view of the buffer plate of fig. 2 according to the present invention.
Fig. 5 is a schematic structural view of the front and rear conductive plates of fig. 2 according to the present invention.
FIG. 6 is a schematic structural view of the oxyhydrogen flow field plate in FIG. 2 according to the present invention.
Fig. 7 is a schematic structural view of front and rear special plates in fig. 2 according to the present invention.
FIG. 8 shows the performance test effect of the proton exchange membrane water electrolysis apparatus of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
FIG. 1 is a perspective view of a water electrolysis apparatus with proton exchange membrane according to the present invention.
FIG. 2 is a plan view of the water electrolyzing apparatus with proton exchange membrane of the present invention. The device consists of a front end plate 1, a diffusion plate 2, a front conductive plate 3, a front special plate 4, a membrane electrode 5, an oxyhydrogen flow field plate 6, a rear special plate 7, a rear conductive plate 8, a buffer plate 9 and a rear end plate 10 in sequence from front to back.
Each unit in the proton exchange membrane water electrolysis device is of a circular pressure-resistant structure and assembled by adopting a multipole integrated structure, and each unit part of the electrolytic cell adopts silicon rubber to realize integral line sealing. Firstly, a front end plate 1 is positioned, then all units are positioned in sequence as shown in figure 2, a diffusion plate 2, a front conductive plate 3, a front special plate 4, a membrane electrode 5, an oxyhydrogen flow field plate 6, a rear special plate 7, a rear conductive plate 8, a buffer plate 9 and a rear end plate 10 are positioned, wherein the positioning holes ensure the orderly correspondence of all units during integration, high-elasticity silicon rubber is adopted for integral line sealing during integration of all units, and finally the device is locked and fixed by metal screws as shown in figure 1.
In the proton exchange membrane water electrolysis device, the front special plate 4, the oxyhydrogen flow field plate 6, the rear special plate 7, the front conductive plate 3 and the rear conductive plate 8 are made of metal titanium alloy or other corrosion-resistant alloys. The front end plate (1) and the rear end plate (10) are made of aluminum alloy materials, and the diffusion plate 2 and the buffer plate 9 are made of electrically insulated polycarbonate materials.
The membrane electrode 5 is a typical porous gas diffusion electrode, is a high-activity zero-polar-distance electrode formed by hot pressing a diffusion layer, a catalyst layer and a PEM (proton exchange membrane), is a place for generating hydrogen and oxygen through electrochemical reaction in a water electrolysis device, and has high electrolysis efficiency. The diffusion layer of the membrane electrode is prepared from carbon paper and a water repellent polytetrafluoroethylene or vinylidene fluoride, and plays roles in supporting, diffusing gas and collecting current; the catalyst layer is prepared by an electrocatalyst (a hydrogen electrode is a platinum or carbon-supported platinum catalyst, an oxygen electrode is a multi-element alloy anti-oxygen corrosion catalyst), polytetrafluoroethylene or vinylidene fluoride and a proton conductor (perfluorinated sulfonic acid ion exchange resin); the Proton Exchange Membrane (PEM) is a perfluorosulfonic acid ion exchange membrane.
Fig. 3 shows the structure of the front and rear end plates (1, 10) of the water electrolysis device, wherein the electrolyzed water inlet and outlet and the gas outlet are all on the front end plate, the water enters the electrolytic cell from the anode chamber, the oxygen generated after electrolysis is brought out of the electrolytic cell along with the residual water, the outlet is connected to the water tank, the water is recycled, and the hydrogen and the oxygen are dehydrated and dried by the water-gas separation device and then are directly used by the fuel cell.
The left side of the figure 4 is the structure of the diffusion plate 2, which is a channel for diffusing the electrolyzed water to the anode chamber, and the water is uniformly distributed to each flow field plate flow channel by the diffusion plate and then flows through the diffusion layer anode reaction area of the membrane electrode to participate in the electrochemical reaction. Fig. 4 shows the structure of the rear cushion plate 10 for insulation, pressure buffering, and support.
Fig. 5 shows the structure of the front and rear conductive plates (3, 8) using titanium alloy or other corrosion-resistant highly conductive alloy through which an external power source supplies electric power required for water electrolysis.
FIG. 6 shows a structure of an oxyhydrogen flow field plate 6, wherein the water-oxygen surface is an anode plate, the hydrogen surface is a cathode plate, and the anode plate and the cathode plate are made of titanium alloy or other corrosion-resistant alloy plates with the thickness of 1-4 mm, so as to provide channels for electrolyzing water and generating gas distribution. The two sides of the anode plate and the cathode plate are both provided with flow channel grooves, the flow channels, the diversion trenches and the sealing grooves are firstly processed on the metal plate in the processing process, and then square through holes for the electrolytic water and the gas to enter and exit are processed. The oxyhydrogen flow field plate 6 of the device is designed into a linear flow channel, the depth of the flow channel is 0.3-0.6 mm, and the width of the flow channel is 0.5-1.0 mm. Under the condition of electrifying, water is uniformly distributed to the membrane electrode diffusion layer through flow field plate flow channels, and electrolysis is carried out on the anode catalyst layer.
Fig. 7 shows the structure of the front and rear special plates (4, 7) which also function as the anode and cathode plates, except that there are flow channel grooves on one side and a planar structure on the other side, which also provides channels for uniform distribution of water and gas.
The working principle of the proton exchange membrane water electrolysis device of the invention is as follows: the method comprises the steps of firstly, sending ultrapure water (deionized water, the resistivity is more than 1M omega cm) intoa water storage tank, conveying the ultrapure water into an anode of an electrolytic tank through a water pump or automatically feeding the ultrapure water into the anode of the electrolytic tank under the action of pressure difference, feeding the ultrapure water into a membrane electrode carbon paper or a carbon cloth diffusion layer through a flow field plate under the external power-on condition, decomposing the ultrapure water in an anode catalyst layer, releasing electrons at the anode by using negative oxygen ions formed by electrolysis to form oxygen, discharging the oxygen from an anode chamber, carrying partial water to circulate back to a water tank again, and directly using the oxygen. The ultrapure water decomposes protons generated at the anode to hydrate ions (H)3O+) In the form of the method, electrons are obtained through reaching the cathode through a proton exchange membrane to form hydrogen, and the hydrogen is discharged from the cathode chamber and can be directly used after water-gas separation and drying.
The reactions that occur in the electrolyzer are as follows:
anode:
cathode:
and (3) integration:
the invention has the characteristics that: the proton exchange membrane is used as solid electrolyte to directly electrolyze pure water, the membrane electrode preparation adopts a forming process similar to that of a fuel cell membrane electrode, and the sealing structure adopts high-elasticity silicon rubber sealing material to realize integral line sealing. The flow channel design of the flow field plate fully ensures that water required by electrolysis is uniformly distributed on the surface of the whole membrane electrode, and is beneficial to discharging reaction products of hydrogen and oxygen, and the generated hydrogen and oxygen have higher working pressure (0.3-0.4 Mpa) and can be directly supplied to a fuel cell for working. The flow field plate material has strong corrosion resistance and long service life, and can ensure the long-term stable work of the water electrolysis device.
The invention has the advantages that: the water electrolyzer adopts a proton exchange membrane as a solid electrolyte, directly uses high-purity water for electrolysis, has no corrosion problem of the traditional alkaline electrolyte, has no pollution to the environment, and can be recycled. The purity of the hydrogen generated by pure water is high, and the hydrogen can be directly applied without complicated purification treatment technology. The membrane electrode is formed by hot-pressing proton exchange membrane and platinum or metal oxide composite catalyst, can effectively reduce electrode polarization overpotential, realize low electrolysis voltage under high current density, improve electrolysis efficiency, and is a high-efficiency catalytic electrode. The combination of the proton exchange membrane water electrolysis device and the fuel cell forms a renewable fuel cell system which is the chemical energy storage power supply system with the highest specific energy at present.
The main performance indexes are as follows: the water electrolysis device is quickly started at room temperature, the proton exchange membrane water electrolysis device can generate high-purity hydrogen and oxygen with the pressure of 0.3-0.4 MPa within 30s, the current efficiency is more than 90%, the single cell electrolysis voltage is less than 2.0V under the working current density of 300-400 mA/cm2, and no fault occurs after 1000 hours of accumulated operation.
Fig. 8 shows a test performance diagram ofthe device of the present invention, which integrates three pairs of electrolyzers by assembling the proton exchange membrane water electrolysis device and the membrane electrode, wherein the test conditions are as follows: supplying power by a steady-flow voltage-stabilizing source, automatically and circularly supplying water by a water tank, and operating at room temperature by using ultra-pure water (deionized water with the resistivity of 1M omega. cm). When the water electrolysis device with the proton exchange membrane works, the flow rate of hydrogen produced is 2.45-2.8L/min, the flow rate of oxygen is 1.2-1.4L/min, the gas pressure is 0.3-0.4 MPa, the current density is 350-400 mA/cm2, and the single-chip electrolysis voltage is less than 2.0V.
Claims (6)
1. A proton exchange membrane water electrolysis apparatus, comprising: the front end plate is used for positioning; diffusion plates are sequentially arranged to provide electrolyzed water to be distributed to flow channels of each flow field plate; the front conductive plate is connected with an external power supply and provides electric energy required by water electrolysis; a front special plate providing a passage for water and gas to be uniformly distributed; the membrane electrode is a place for generating hydrogen and oxygen through electrochemical reaction in the water electrolysis device; the hydrogen-oxygen flow field plate provides channels for electrolyzing water and generating gas distribution; a rear special plate providing a channel for uniform distribution of water and gas; the rear conductive plate is connected with an external power supply and provides electric energy required by water electrolysis; the buffer plate is used for insulating, buffering pressure and supporting; and the rear end plate is used for final positioning, is provided with a positioning hole and is used for locking and fixing each unit by a metal screw rod.
2. The proton exchange membrane electrolytic water device according to claim 1, wherein: each unit in the device is of a circular pressure-resistant structure, a bipolar integrated structure is adopted for assembly, and each unit part of the electrolytic cell is sealed integrally by silicon rubber.
3. The proton exchange membrane electrolytic water device according to claim 1, wherein: the front special plate, the oxyhydrogen flow field plate, the rear special plate, the front conductive plate and the rear conductive plate are made of metal titanium alloy or other corrosion-resistant alloys; the front end plate and the rear end plate are made of aluminum alloy materials; the diffusion plate and the buffer plate are made of electrically insulating polycarbonate materials.
4. The proton exchange membrane electrolytic water device according to claim 1 or 3, characterized in that: the double-sided flow channel groove, the flow channel, the diversion trench and the sealing groove of the oxyhydrogen flow field plate are arranged on the two sides of the oxyhydrogen flow field plate, the square through holes for the electrolytic water and the gas to enter and exit are formed, the thickness of the flow field plate is 1-4 mm, the depth of the flow channel is 0.3-0.6 mm, and the width of the flow channel is 0.5-1.0 mm.
5. The proton exchange membrane electrolytic water device according to claim 1 or 3, characterized in that: the front end plate is simultaneously provided with an electrolyzed water inlet and an electrolyzed water outlet and a gas outlet, water enters the electrolytic cell from the anode chamber, oxygen generated after electrolysis is taken out of the electrolytic cell along with the residual water, and the outlet is connected to the water tank.
6. The proton exchange membrane electrolytic water device according to claim 1, wherein: the membrane electrode is a zero-polar-distance electrode formed by hot-pressing a diffusion layer, a catalyst layer and a proton exchange membrane; the diffusion layer is prepared from carbon paper and a water repellent polytetrafluoroethylene or vinylidene fluoride; the catalyst layer is prepared from a platinum or carbon-supported platinum catalyst or a multi-element alloy anti-oxygen corrosion catalyst, polytetrafluoroethylene or vinylidene fluoride and proton conductor perfluorinated sulfonic acid ion exchange resin; the proton exchange membrane is a perfluorinated sulfonic acid ion exchange membrane.
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