CN1417880A - Electrochemical aluminium-water hydrogen storing and producing method and equipment - Google Patents

Electrochemical aluminium-water hydrogen storing and producing method and equipment Download PDF

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CN1417880A
CN1417880A CN02148850A CN02148850A CN1417880A CN 1417880 A CN1417880 A CN 1417880A CN 02148850 A CN02148850 A CN 02148850A CN 02148850 A CN02148850 A CN 02148850A CN 1417880 A CN1417880 A CN 1417880A
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CN1290220C (en
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李振亚
王为
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Tianjin University
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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
    • Y02E60/32—Hydrogen storage
    • 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
    • Y02E60/50—Fuel cells

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Abstract

The present invention relates to one kind of electrochemical aluminium-water hydrogen storing and producing method and equipment. The equipment is one enclosed two-phase circulating and filtering system comprising aluminium alloy plate, electrolyte and high-activity hydrogen-separating catalytic plate. In needing releasing hydrogen, the power switch of the system is turned on to obtain pure hydrogen. The system may be used as hydrogen source for fuel cell to provide hydrogen for the fuel cell while providing electric power outwards. The electrochemical aluminum-water hydrogen storing and producing equipment consists of liquid tank, control valve, liquid injecting port, hydrogen colleclting chamber, hydrogen outlet, T-valve, circular filtering pump, aluminum alloy plate, hydrogen separating plate, etc.

Description

Electrochemical method and equipment for storing hydrogen and producing hydrogen by using aluminium-water
Technical Field
The invention belongs to the technology of hydrogen energy storage and manufacture, and particularly relates to a method and equipment for storing hydrogen and producing hydrogen by electrochemical aluminum-water.
Background
With the gradual increase of fossil fuel consumption and the gradual exhaustion of storage capacity, and the increasing emphasis on environmental protection, primary energy represented by petroleum, coal and natural gas is finally replaced by clean and renewable energy sources such as solar energy, wind energy, ocean energy, biomass energy and the like. The hydrogen energy is taken as a pollution-free secondary energy source, and has a plurality of outstanding advantages of rich resources, large combustion heat of the hydrogen, water as a combustion product, no environmental pollution and the like, and is generally regarded by various countries in the world. Experts predict that hydrogen energy and electric power will become two major pillars of a new energy system in the 21 st century.
The storage, transportation and release of hydrogen gas are one of the prerequisites for the development and utilization of hydrogen energy. The conventional hydrogen storage and transportation methods mainly include high-pressure hydrogen storage and transportation and low-temperature liquid hydrogen storage and transportation. However, the two methods have the serious defects of high cost, poor safety and stability, low hydrogen storage capacity and the like. Therefore, the solid metal hydride hydrogen storage and release technology, which stores hydrogen in the alloy in an atomic state, has become a key point in research and development of hydrogen storage technology in recent years due to its significant advantages in safety, economy, etc. compared with the conventional gaseous and liquid hydrogen storage and release technologies. At present, three mature series of metal hydride hydrogen storage and release materials are formed, including LaNi5Rare earth hydrogen storage/release alloy series represented by the following formula, titanium hydrogen storage/release alloy represented by TiFe, and Mg2A magnesium-based hydrogen storage and release alloy represented by Ni. Although the solid metal hydride hydrogen storage and release technology is greatly advanced compared with the traditional gaseous and liquid hydrogen storage and release technology, a great deal of problems still remain to be solved, such as how to further improve the hydrogen storage density of the metal hydride hydrogen storage and release material and reduce the specific gravity thereof, improve the thermal conductivity of the metal hydride hydrogen storage and release material, solve the sealing, pressure resistance and hydrogen embrittlement resistance of the hydrogen storage and release device, and how to make the hydrogen storage and release cycle times of the hydrogen storage and release material exceed 5000 times.
Disclosure of Invention
The invention aims to provide a novel electrochemical method and equipment for storing hydrogen and producing hydrogen by using aluminum-water.
The invention is formed by a two-phase circulating filtration closed system consisting of an aluminum alloy polar plate, an electrolyte and a high-activity hydrogen evolution catalytic polar plate, and the cathode reduction reaction of water is carried out on a high-efficiency hydrogen evolution catalytic electrode: releasing hydrogen; an anodic oxidation reaction of aluminum occurs on the aluminum alloy electrode: generating aluminum hydroxide; when hydrogen is required to be released, an external circuit switch of the electrochemical aluminum-water hydrogen storage and production equipment is switched on at normal temperature and normal pressure, and the system can release pure hydrogen.
The invention relates to an aluminum-water hydrogen storage and production system which utilizes the electrochemical reaction principle of water and aluminum alloy to realize the storage and release of hydrogen and simultaneously generate electric energy. The system generates the following cathode reduction reaction on the high-efficiency hydrogen evolution catalytic polar plate: the following anodic oxidation reactions take place on the aluminum alloy plate: . The aluminum-water hydrogen storage and production system actually stores aluminum alloy and water.
The aluminum alloy polar plate in the aluminum-water hydrogen storage and production system is composed of aluminum and alloy elements, and is made into an aluminum alloy ingot by a metallurgy method and then made into the aluminum alloy polar plate. When the aluminum-water hydrogen storage and production system is in a hydrogen production state, the system has high electrochemical activity, and the oxidation of the atomic aluminum into + 3-valent aluminum ions is easily realized; and when the aluminum-water hydrogen storage and production system is in a hydrogen storage state, the aluminum alloy polar plate is in an inactive state. The high performance of such aluminum alloy plates is achieved by alloying pure aluminum. The adopted alloy elements mainly comprise: gallium, indium, lead, bismuth, tin, zinc, magnesium, cadmium, manganese, phosphorus, tellurium, iron, platinum, etc., can adopt Chinese invention patents: 91109160.2.
The high-activity hydrogen-evolution catalytic polar plate in the aluminium-water hydrogen storage and production system has high electrocatalytic activity for the reaction of hydrogen gas generated by reduction of water cathode, and can be made by various methods, and the high-activity hydrogen-evolution catalytic polar plate is made of oxide, pure metal, alloy or metal and oxideThe formed composite material and the like are manufactured into the high-activity hydrogen evolution catalytic polar plate by adopting a physical method such as an electroplating technology, a composite plating technology, a thermal decomposition technology, an ion plating technology, an ion implantation technology, an ion sputtering technology and the like, or a combination of two or three technologies. The composition of the high-activity hydrogen evolution catalytic plate can be oxides, such as: RuO2、TiO2、ZrO2(ii) a It may also be a pure metal, for example: pt, Pd, Ni, Mo, W, Co, Ru, Fe; alloys are also possible, for example: Ni-Pt, Ni-Ru, Ni-P, Ni-B, Ni-Mo, Co-Mo, Ni-Mo-W, Ni-Co-Mo-W Ni-P-Mo-Co, Ni-P-Co-Mo, Ni-P-W, Ni-P-Co-Mo-W, Ni-B-Co, Ni-B-Mo, Ni-B-Co-W, Ni-B-Co-Mo-W, Ni-B-W, Mo-W, Mo-Co, Co-W, etc.; it may also be a composite of a metal and an oxide, for example: Ni-RuO2、Ni-ZrO2、Ni-TiO2、Mo-RuO2、W-RuO2、Co-RuO2、Ni-P-RuO2、Ni-B-RuO2、Ni-Mo-RuO2、Co-Mo-RuO2、Ni-Co-Mo-RuO2、Ni-Mo-W-RuO2、Ni-Co-Mo-W-RuO2、Ni-P-Mo-Co-RuO2、Ni-P-Co-Mo-RuO2、Ni-P-W-RuO2、Ni-P-Co-Mo-W-RuO2、Ni-B-Co-RuO2、Ni-B-Mo-RuO2、Ni-B-Co-Mo-RuO2、Ni-B-Co-Mo-W-RuO2、Ni-B-W-RuO2、Mo-W-RuO2、Mo-Co-RuO2、Co-W-RuO2、Ni-P-TiO2、Ni-B-TiO2、Ni-Mo-TiO2、Co-Mo-TiO2、Ni-Co-Mo-TiO2、Ni-Mo-W-TiO2、Ni-Co-Mo-W-TiO2、Ni-P-Mo-Co-TiO2、Ni-P-Co-Mo-TiO2、Ni-P-W-TiO2、Ni-P-Co-Mo-W-TiO2、Ni-B-Co-TiO2、Ni-B-Mo-TiO2、Ni-B-Co-Mo-TiO2、Ni-B-Co-Mo-W-TiO2、Ni-B-W-TiO2、Mo-W-TiO2、Mo-Co-TiO2、Co-W-TiO2、Ni-P-ZrO2、Ni-B-ZrO2、Ni-Mo-ZrO2、Co-Mo-ZrO2、Ni-Co-Mo-ZrO2、Ni-Mo-W-ZrO2、Ni-Co-Mo-W-ZrO2、Ni-P-Mo-Co-ZrO2、Ni-P-Co-Mo-ZrO2、Ni-P-W-ZrO2、Ni-P-Co-Mo-W-ZrO2、Ni-B-Co-ZrO2、Ni-B-Mo-ZrO2、Ni-B-Co-Mo-ZrO2、Ni-B-Co-Mo-W-ZrO2、Ni-B-W-ZrO2、Mo-W-ZrO2、Mo-Co-ZrO2、Co-W-ZrO2And so on.
The electrolyte used in the aluminum-water hydrogen storage and production system is NaCl, KCl and AlCl with the pH value of 4-103、NH4Cl、K2CO3、Na2CO3、Na2SO4And an aqueous salt solution or a salt mixture solution, wherein the salt content in the solution is the weight percentage concentration (the same below), and the concentration range is 0.02-10%.
The electrochemical aluminum-water hydrogen storage and production equipment mainly comprises a liquid storage tank 2, a liquid control valve 1, a liquid injection port 14, a hydrogen collection chamber 13, a hydrogen outlet 11, a three-way valve 12, a circulating filter pump 10, an electrolytic cell system 3, a buffer tank 9 and the like; wherein the liquid storage tank, the buffer tank and the electrolytic cell system are connected through pipelines; the electrolytic cell system is composed of a plurality of polar chambers 8, an aluminum alloy polar plate 5 and a hydrogen evolution polar plate 7 are arranged in each polar chamber, the aluminum alloy polar plates and the hydrogen evolution polar plates in the same polar chamber are not connected with each other, the aluminum alloy polar plates and the hydrogen evolution polar plates of adjacent polar chambers are connected on a compartment partition plate 6 to realize electric connection, the aluminum alloy polar plates and the hydrogen evolution polar plates of the two outermost polar chambers of the electrolytic system respectively form a positive output end and a negative output end of electrochemical aluminum-water hydrogen storage and production equipment, the positive output end and the negative output end are respectively connected with an external circuit by leads to form a loop, and each polar chamber is filled with electrolyte 4; the liquid storage tank is provided with a liquid injection port 14 for supplementing electrolyte; a hydrogen outlet 11 is arranged on the hydrogen collection chamber, and a buffer tank 9 is arranged below the electrolytic cell system and used for ensuring that the liquid level heights of the electrolyte in each pole chamber of the electrolytic cell system are the same; the circulation filter pump 10 is connected to the liquid storage tank and the buffer tank, and the three-way valve 12 is used for controlling the circulation filter of the electrolyte or guiding the electrolyte into the liquid storage tank for storage.
The purpose of arranging a circulating filtration system in the aluminum-water hydrogen storage and production system is to enhance the circulation of electrolyte between an aluminum alloy polar plate and a hydrogen evolution catalytic polar plate in the aluminum-water hydrogen storage and production system and improve the hydrogen production speed, and to remove aluminum hydroxide precipitate formed in the electrolyte along with the generation of hydrogen.
The invention adopts electrochemical technology, develops a brand new concept of high-efficiency, safe and cheap environment-friendly electrochemical aluminum-water hydrogen storage and production system by adopting a circulating closed system consisting of an aluminum alloy polar plate, a high-activity hydrogen evolution catalytic polar plate and electrolyte, is fundamentally different from various hydrogen storage and release technologies generally adopted at home and abroad or under development at present, and is mainly expressed in the following aspects:
1) the electrochemical aluminum-water hydrogen storage and production system is a two-phase circulating filtration closed system consisting of an aluminum alloy polar plate, an electrolyte and a high-activity hydrogen evolution catalytic polar plate, so that the system is safe and reliable, convenient to carry and low in price, and cannot cause any pollution to the environment.
2) The electrochemical aluminum-water hydrogen storage and hydrogen production system releases 100 percent of pure hydrogen, and the weight hydrogen storage efficiency and the volume hydrogen storage efficiency of the system exceed the most advanced hydrogen storage technology reported at present. If the aluminum oxide formed by dehydrating the only byproduct aluminum hydroxide of the aluminum-water hydrogen storage and hydrogen production system is widely applied to the industries of ceramics, medicines and the like, the aluminum-water hydrogen storage and hydrogen production system can provide electric energy to the outside while releasing hydrogen, and the price of hydrogen storage and hydrogen production is lower.
3) The electrochemical aluminum-water hydrogen storage and production system utilizes the electrochemical reaction principle of water and aluminum alloy to realize the storage and release of hydrogen and simultaneously generate electric energy, and the process generates the following cathode reduction reaction on a high-efficiency hydrogen evolution catalytic electrode: on the aluminum alloy electrode, the following anodic oxidation reaction occurs: . Therefore, the electrochemical aluminum-water hydrogen storage and production system actually stores aluminum alloy and water. When hydrogen is required to be released, the electrochemical aluminum is communicated at normal temperature and normal pressureA switch outside the water hydrogen storage and production system, and the system can release pure hydrogen with required quantity. The aluminum-water hydrogen storage and production system can output electric energy outwards while releasing hydrogen. Thus, it is actually a hydrogen and electricity cogeneration system. Because the purity of the hydrogen released by the aluminum-water hydrogen storage and production system is 100 percent, if the aluminum-water hydrogen storage and production system is matched with a fuel cell to form an aluminum-water hydrogen storage and production system and fuel cell integrated working power station, the aluminum-water hydrogen storage and production system can provide required hydrogen for the fuel cell and can also provide electric energy for the outside together with the fuel cell. The efficiency of the aluminum-water hydrogen storage and production system is maximized.
4) Because the electrochemical aluminum-water hydrogen storage and production system actually stores aluminum alloy and water, the hydrogen storage process is very convenient, only aluminum alloy and water are added, no special equipment and operation conditions are needed, and the problem of poor cycle life of the existing solid metal hydrogen storage material does not exist.
Drawings
FIG. 1: schematic diagram of electrochemical aluminum-water hydrogen storage and production equipment.
Detailed Description
The invention is described in further detail below with reference to the following figures and detailed description:
example 1;
the electrochemical aluminum-water hydrogen storage and production device is shown in figure 1. The device comprises a liquid storage tank 2, a liquid control valve 1, a liquid injection port 14, a hydrogen collection chamber 13, a hydrogen outlet 11, a three-way valve 12, a circulating filter pump 10, an aluminum alloy polar plate 5, a chamber partition plate 6, a hydrogen separation polar plate 7, a buffer tank 9 and the like. The liquid storage tank 2 is positioned above the hydrogen collection chamber 13 (or below the buffer tank); an electrolytic cell system 3 is arranged below the hydrogen collecting chamber and consists of a plurality of polar chambers 8, the number of the polar chambers is determined according to the size of hydrogen quantity required to be generated and the release rate of the hydrogen, an aluminum alloy polar plate 5 and a hydrogen evolution polar plate 7 are arranged in each polar chamber, the aluminum alloy polar plates and the hydrogen evolution polar plates in the same polar chamber are not connected with each other, the aluminum alloy polar plates and the hydrogen evolution polar plates of adjacent polar chambers are connected on a chamber partition plate 6 to realize electric connection, the aluminum alloy polar plates and the hydrogen evolution polar plates of the two outermost polar chambers of the electrolytic cell system respectively form a positive output end and a negative output end of electrochemical aluminum-water hydrogen storage and hydrogen production equipment, the positive output end and the negative output end are respectively connected with an external circuit by leads to form a loop, and each polar chamber is filled with electrolyte 4; the liquid storage tank is provided with a liquid injection port 14 for supplementing electrolyte; a hydrogen outlet 11 is arranged on the hydrogen collection chamber, and when an external circuit is connected, hydrogen generated by the aluminum-water hydrogen storage and production system flows out through the hydrogen outlet; a buffer tank 9 is arranged below the electrolytic cell system and used for ensuring that the liquid level heights of the electrolyte in each pole chamber of the electrolytic cell system are the same; the circulating filter pump 10 is connected with the liquid storage tank and the buffer tank, and when the aluminum-water hydrogen storage and production system works, the circulating filter pump continuously operates to realize the circulation of the electrolyte in the electrolytic cell system and continuously remove the aluminum oxide precipitate generated in the electrolytic process; the three-way valve 12 is used for controlling the electrolyte to be circularly filtered or to be guided into a liquid storage tank for storage, when the three-way valve 12 is in a working state of controlling the electrolyte to be circularly filtered, the electrolyte flows into each pole chamber in the electrolytic cell system through a conveying pipe which is positioned at the bottom of the liquid storage tank and is respectively connected with each pole chamber of the electrolytic cell system, then flows into a buffer tank through a micropore pipe which is positioned at the bottom of each pole chamber, and returns to the liquid storage tank again under the action of the circulating filter pump. The alumina precipitate in the electrolyte which has passed through the circulating filter pump and returned to the liquid sump again is substantially removed. Thereafter, the electrolyte solution is continuously circulated between the reservoir and the buffer tank.
The operation procedure of the electrochemical aluminum-water hydrogen storage and production system is as follows: firstly, opening a liquid control valve 1 to enable the electrolyte in a liquid storage tank 2 to flow into each pole chamber in an electrolytic cell system 3 and a buffer tank 9 through a guide pipe positioned at the bottom of the liquid storage tank, then enabling a three-way valve 12 to be in a state of controlling the electrolyte to carry out circulating filtration work, opening a circulating filtration pump 10 to realize the circulating filtration of the electrolyte in each pole chamber in the electrolytic cell system 3, and simultaneously switching on an external circuit switch of an electrochemical aluminum-water hydrogen storage and production system, at the moment, the whole electrochemical aluminum-water hydrogen storage and production system is in a work state, starting to produce a large amount of hydrogen on a hydrogen evolution polar plate 7, and gathering the hydrogen in a hydrogen collection chamber 13 and flowing out through a hydrogen outlet 11. Along with the outflow of hydrogen, electric energy is simultaneously output at the external positive and negative ends of the electrochemical aluminum-water hydrogen storage and hydrogen production system. When the electrochemical aluminum-water hydrogen storage and hydrogen production system is in a non-working state, the external circuit switch of the electrochemical aluminum-water hydrogen storage and hydrogen production system is only required to be switched off, the three-way valve 12 is placed in a state of guiding the electrolyte into the liquid storage tank, the circulating filter pump 10 is closed after the electrolyte is completely guided into the liquid storage tank, and the electrochemical aluminum-water hydrogen storage and hydrogen production system is in a hydrogen storage state.
Example 2:
in example 1, an aluminum alloy ingot made of aluminum, gallium, tin and bismuth was rolled and shearedThe cut aluminum alloy polar plate is used as an anode, Ni-S is plated on foamed nickel to be a high-activity hydrogen evolution catalytic polar plate, and AlCl with the concentration of 0.2 percent is used3The water solution is electrolyte, the electrolytic cell system adopts 10 electrode chambers, and the areas of the aluminum alloy electrode plate and the hydrogen evolution catalytic electrode plate are both 10 multiplied by 10cm2The hydrogen output rate of the electrochemical aluminum-water hydrogen storage and production equipment after the external circuit is connected is 1 L.min-1。
Example 3:
in example 1, an aluminum alloy ingot made of aluminum, gallium, tin and bismuth is used, a rolled and sheared aluminum alloy electrode plate is used as an anode, foamed nickel is used as an active hydrogen evolution catalytic electrode plate, and AlCl with the concentration of 0.5% is used3The water solution is electrolyte, the electrolytic cell system adopts 10 electrode chambers, and the areas of the aluminum alloy electrode plate and the hydrogen evolution catalytic electrode plate are both 10 multiplied by 10cm2The hydrogen output rate of the electrochemical aluminum-water hydrogen storage and production equipment after the external circuit is connected is 0.8 L.min-1。
Example 4:
in example 1, the alloy is prepared from aluminum, gallium, tin, bismuth and leadRolling and shearing to obtain Al-alloy plate as anode, electroplating Ni-Mo alloy on foamed Ni as high-activity hydrogen-separating catalytic plate, and collecting 0.1% of AlCl3Adding 4% NaCl mixed water solution as electrolyte, using 10-electrode chamber as electrolytic cell system, and making the areas of aluminium alloy polar plate and hydrogen evolution catalytic polar plate be 10X 10cm2The hydrogen output rate of the electrochemical aluminum-water hydrogen storage and production equipment after the external circuit is connected is 1.5 L.min-1。
Example 5:
in example 1, an aluminum alloy ingot prepared by smelting aluminum, gallium, tin, bismuth and lead is adopted, a rolled and sheared aluminum alloy polar plate is used as an anode, a foamed nickel composite electroplated Ni/Mo-W multiphase alloy is used as a high-activity hydrogen evolution catalytic polar plate, and AlCl with the concentration of 0.2% is adopted3Adding 9% NaCl mixed water solution as electrolyte, using 10-electrode chamber as electrolytic cell system, and making the areas of aluminium alloy polar plate and hydrogen-evolution catalytic polar plate be 10X 10cm2The hydrogen output rate of the electrochemical aluminum-water hydrogen storage and hydrogen production equipment after the external circuit is connected is 1.5 L.min-1。
While the combination and method of the present invention has been described in terms of preferred embodiments by reference to the present disclosure, it will be apparent to those skilled in the art that the method and apparatus described herein can be combined or modified or certain parts can be added or removed without departing from the spirit, scope and range of the invention, and more particularly, all such similar substitutes and modifications will be apparent to those skilled in the art and are intended to be included within the spirit, scope and range of the invention.

Claims (9)

1. A method for electrochemical aluminum-water hydrogen storage and hydrogen production is a two-phase circulating filtration closed system consisting of an aluminum alloy polar plate, an electrolyte and a high-activity hydrogen evolution catalytic polar plate; the method is characterized in that:
the cathodic reduction reaction of water takes place on a high-efficiency hydrogen evolution catalytic electrode: releasing hydrogen; an anodic oxidation reaction of aluminum occurs on the aluminum alloy electrode: generating aluminum hydroxide; when hydrogen is required to be released, an external circuit switch of the electrochemical aluminum-water hydrogen storage and production equipment is switched on at normal temperature and normal pressure, and the system can release pure hydrogen.
2. A method for electrochemical storage of hydrogen and hydrogen from aluminum-water as claimed in claim 1, wherein said aluminum alloy plate is composed of aluminum plus alloying elements, and the alloying elements used are mainly: gallium, indium, lead, bismuth, tin, zinc, magnesium, tellurium, phosphorus, cadmium, manganese, iron, platinum, and the like.
3. The method for electrochemical hydrogen storage and production of aluminum-water as claimed in claim 1, wherein the high-activity hydrogen-evolution catalytic plate is prepared by using oxide, pure metal, alloy or composite material formed by metal and oxide, etc. by electroplating or composite plating technology, or thermal decomposition technology, or ion plating technology, or ion implantation technology, or ion sputtering technology, or by using two or three technologies in combination.
4. A method for electrochemical aluminum-water hydrogen storage and production according to claim 1 or 3, wherein the high-activity hydrogen-evolution catalytic plate comprises: the oxides are preferably: RuO2、TiO2、ZrO2(ii) a The pure metals are preferably: pt, Ni, Mo, W, Co, Pd, Ru, Pt, Fe; the alloy is preferably: Ni-P, Ni-B, Ni-Mo, Co-Mo, Ni-Mo-W, Ni-Co-Mo-W Ni-P-Mo-Co, Ni-P-Co-Mo, Ni-P-W, Ni-P-Co-Mo-W, Ni-B-Co, Ni-B-Mo, Ni-B-Co-Mo-W, Ni-B-W, Mo-W, Mo-Co, Co-W; the composite of metal and oxide is preferably: Ni-RuO2、Ni-ZrO2、Ni-TiO2、Mo-RuO2、W-RuO2、Co-RuO2、Ni-P-RuO2、Ni-B-RuO2、Ni-Mo-RuO2、Co-Mo-RuO2、Ni-Co-Mo-RuO2、Ni-Mo-W-RuO2、Ni-Co-Mo-W-RuO2、Ni-P-Mo-Co-RuO2、Ni-P-Co-Mo-RuO2、Ni-P-W-RuO2、Ni-P-Co-Mo-W-RuO2、Ni-B-Co-RuO2、Ni-B-Mo-RuO2、Ni-B-Co-Mo-RuO2、Ni-B-Co-Mo-W-RuO2、Ni-B-W-RuO2、Mo-W-RuO2、Mo-Co-RuO2、Co-W-RuO2、Ni-P-TiO2、Ni-B-TiO2、Ni-Mo-TiO2、Co-Mo-TiO2、Ni-Co-Mo-TiO2、Ni-Mo-W-TiO2、Ni-Co-Mo-W-TiO2、Ni-P-Mo-Co-TiO2、Ni-P-Co-Mo-TiO2、Ni-P-W-TiO2、Ni-P-Co-Mo-W-TiO2、Ni-B-Co-TiO2、Ni-B-Mo-TiO2、Ni-B-Co-Mo-TiO2、Ni-B-Co-Mo-W-TiO2、Ni-B-W-TiO2、Mo-W-TiO2、Mo-Co-TiO2、Co-W-TiO2、Ni-P-ZrO2、Ni-B-ZrO2、Ni-Mo-ZrO2、Co-Mo-ZrO2、Ni-Co-Mo-ZrO2、Ni-Mo-W-ZrO2、Ni-Co-Mo-W-ZrO2、Ni-P-Mo-Co-ZrO2、Ni-P-Co-Mo-ZrO2、Ni-P-W-ZrO2、Ni-P-Co-Mo-W-ZrO2、Ni-B-Co-ZrO2、Ni-B-Mo-ZrO2、Ni-B-Co-Mo-ZrO2、Ni-B-Co-Mo-W-ZrO2、Ni-B-W-ZrO2、Mo-W-ZrO2、Mo-Co-ZrO2、Co-W-ZrO2。
5. An electrochemical method for storing hydrogen and producing hydrogen from aluminum and water as claimed in claim 1, wherein the electrolyte is a single salt aqueous solution or a mixture of multiple salts with a pH of 4-10.
6. The method for electrochemical aluminum-water hydrogen storage and production according to claim 1 or 5, wherein the electrolyte is NaCl, KCl or AlCl with pH value of 4-103、NH4Cl、K2CO3、Na2CO3、Na2SO4Etc. of a single kind of salt or a mixture of a plurality of salts, the salt content in the solution being the weight percentageThe concentration is 0.02-10%.
7. An electrochemical aluminum-water hydrogen storage and production device mainly comprises a liquid storage tank (2), a liquid control valve (1), a liquid injection port (14), a hydrogen collection chamber (13), a hydrogen outlet (11), a three-way valve (12), a circulating filter pump (10), an electrolytic cell system (3), a buffer tank (9) and the like; the method is characterized in that: the liquid storage tank, the buffer tank and the electrolytic cell system are connected through pipelines; the electrolytic cell system is composed of a plurality of polar chambers (8), an aluminum alloy polar plate (5) and a hydrogen evolution polar plate (7) are arranged in each polar chamber, the aluminum alloy polar plates and the hydrogen evolution polar plates in the same polar chamber are not connected with each other, the aluminum alloy polar plates and the hydrogen evolution polar plates of adjacent polar chambers are connected on a chamber partition plate (6) to realize electric connection, the aluminum alloy polar plates and the hydrogen evolution polar plates of the two outermost polar chambers of the electrolytic system respectively form a positive output end and a negative output end of electrochemical aluminum-water hydrogen storage and hydrogen production equipment, the positive output end and the negative output end are respectively connected with an external circuit by leads to form a loop, and each polar chamber is filled with electrolyte (4); the liquid storage tank is provided with a liquid injection port (14) for supplementing electrolyte; a hydrogen outlet (11) is arranged on the hydrogen collection chamber, and a buffer tank (9) is arranged below the electrolytic cell system and used for ensuring that the liquid level heights of the electrolyte in each pole chamber of the electrolytic cell system are the same; the circulating filter pump (10) is connected with the liquid storage tank and the buffer tank, and the three-way valve (12) is used for controlling the electrolyte to be circularly filtered or to be guided into the liquid storage tank for storage.
8. The electrochemical aluminum-water hydrogen storage and production device as claimed in claim 7, wherein the operation method comprises: firstly, opening a liquid control valve (1) to enable electrolyte in a liquid storage tank (2) to flow into each pole chamber in an electrolytic cell system (3) and a buffer tank (9) through a guide pipe positioned at the bottom of the liquid storage tank, then enabling a three-way valve (12) to be in a working state of controlling the electrolyte to carry out circulating filtration, opening a circulating filter pump (10) to realize the circulating filtration of the electrolyte in each pole chamber in the electrolytic cell system (3), and simultaneously switching on an external circuit switch of an electrochemical aluminum-water hydrogen storage and hydrogen production system, wherein the whole electrochemical aluminum-water hydrogen storage and hydrogen production system is in a working state, a large amount of hydrogen begins to be generated on a hydrogen plate (7), and the hydrogen is accumulated in a hydrogen collection chamber (13) and flows out through a hydrogen outlet (11); along with the outflow of hydrogen, electric energy is simultaneously output at the external positive and negative ends of the electrochemical aluminum-water hydrogen storage and production system; when the electrochemical aluminum-water hydrogen storage and hydrogen production system is in a non-working state, the external circuit switch of the electrochemical aluminum-water hydrogen storage and hydrogen production system is only required to be switched off, the three-way valve (12) is placed in a state of leading the electrolyte into the liquid storage tank, and the circulating filter pump (10) is closed after the electrolyte is completely led into the liquid storage tank, so that the electrochemical aluminum-water hydrogen storage and hydrogen production system is in a hydrogen storage state.
9. An electrochemical apparatus for storing hydrogen and producing hydrogen from aluminum-water as claimed in claim 8, wherein if it is used with fuel cell, it forms an integrated working power station of aluminum-water hydrogen storage and production system and fuel cell, and can provide the required amount of hydrogen for fuel cell and provide electric energy for outside together with fuel cell.
CNB021488509A 2002-11-22 2002-11-22 Electrochemical aluminium-water hydrogen storing and producing method and equipment Expired - Fee Related CN1290220C (en)

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WO2006114034A1 (en) * 2005-04-28 2006-11-02 Huang, Hao An electrochemical method for producing and storing hydrogen by the redox of zinc and water
CN100350670C (en) * 2004-12-25 2007-11-21 中国科学技术大学 Liquid controlled open aluminum-air battery device
WO2009127145A1 (en) * 2008-04-17 2009-10-22 Huang Chao Electrochemical system comprising zinc and water for producing and storing hydrogen and the use thereof
CN1924100B (en) * 2006-08-29 2010-12-29 华北电力大学 Thermoelectricity united supplying method for simultaneous preparing H2 and FeCO3 and apparatus thereof
CN101289163B (en) * 2007-04-20 2011-04-06 中国科学院大连化学物理研究所 Aluminum alloy for preparing hydrogen by hydrolytic decomposition and preparation thereof
CN101284646B (en) * 2008-02-29 2011-07-20 上海大学 Hydrogen preparing process by reacting pure alminuim powder with water
CN102560521A (en) * 2012-01-14 2012-07-11 新疆哥兰德新能源有限公司 Method for electrochemically preparing high-purity aluminum oxide
CN102943280A (en) * 2012-10-18 2013-02-27 成都华泽晶体材料有限公司 Method for preparing high-purity aluminium hydroxide powder by electrochemical method
CN103361668A (en) * 2012-04-10 2013-10-23 天津大学 Device for producing hydrogen/storing hydrogen by using aluminum-water and liquid flow way of device
CN103469288A (en) * 2013-09-02 2013-12-25 陈文智 Electroplating bath provided with circulating filtration device
CN103515638A (en) * 2012-06-28 2014-01-15 上海绿丽工贸有限公司 Integrated hydrogen production-hydrogen storage power generation system
CN103633397A (en) * 2012-08-02 2014-03-12 瓦尔达微电池有限责任公司 Hydrogen evolution cell having a cathode pocket
CN104577164A (en) * 2015-01-07 2015-04-29 浙江大学 Single-stage turbine cogeneration system and single-stage turbine cogeneration method based on aluminum-water reaction
CN105417495A (en) * 2015-12-29 2016-03-23 杜善骥 Underwater-type magnesium-gallium-alloy hydrogen production device working method
CN108649240A (en) * 2018-05-15 2018-10-12 常州大学 A kind of fuel cell
CN109093129A (en) * 2018-07-10 2018-12-28 氢电中科（广州）新能源设备有限公司 A kind of the hydrogen manufacturing alloy and intelligent road-lamp of alumal dopen Nano Zero-valent Iron
CN111224172A (en) * 2020-01-16 2020-06-02 荆门市探梦科技有限公司 Aqueous battery system
CN113690469A (en) * 2021-08-25 2021-11-23 浙江大学 Aluminum-water electrochemical cell system
CN115818568A (en) * 2022-11-25 2023-03-21 王凯 Cracking agent for cracking water vapor to produce hydrogen, preparation, use and reactivation method thereof

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CN100350670C (en) * 2004-12-25 2007-11-21 中国科学技术大学 Liquid controlled open aluminum-air battery device
WO2006114034A1 (en) * 2005-04-28 2006-11-02 Huang, Hao An electrochemical method for producing and storing hydrogen by the redox of zinc and water
CN1924100B (en) * 2006-08-29 2010-12-29 华北电力大学 Thermoelectricity united supplying method for simultaneous preparing H2 and FeCO3 and apparatus thereof
CN101289163B (en) * 2007-04-20 2011-04-06 中国科学院大连化学物理研究所 Aluminum alloy for preparing hydrogen by hydrolytic decomposition and preparation thereof
CN101284646B (en) * 2008-02-29 2011-07-20 上海大学 Hydrogen preparing process by reacting pure alminuim powder with water
WO2009127145A1 (en) * 2008-04-17 2009-10-22 Huang Chao Electrochemical system comprising zinc and water for producing and storing hydrogen and the use thereof
CN102560521A (en) * 2012-01-14 2012-07-11 新疆哥兰德新能源有限公司 Method for electrochemically preparing high-purity aluminum oxide
CN103361668B (en) * 2012-04-10 2015-09-16 天津大学 With device and the flow regime thereof of aluminium-water hydrogen manufacturing/Chu Qing
CN103361668A (en) * 2012-04-10 2013-10-23 天津大学 Device for producing hydrogen/storing hydrogen by using aluminum-water and liquid flow way of device
CN103515638B (en) * 2012-06-28 2016-03-02 上海绿丽工程技术有限公司 A kind of hydrogen manufacturing-storage hydrogen power generation integrated system
CN103515638A (en) * 2012-06-28 2014-01-15 上海绿丽工贸有限公司 Integrated hydrogen production-hydrogen storage power generation system
CN103633397B (en) * 2012-08-02 2017-06-20 瓦尔达微电池有限责任公司 Liberation of hydrogen battery with negative electrode bag
CN103633397A (en) * 2012-08-02 2014-03-12 瓦尔达微电池有限责任公司 Hydrogen evolution cell having a cathode pocket
CN102943280A (en) * 2012-10-18 2013-02-27 成都华泽晶体材料有限公司 Method for preparing high-purity aluminium hydroxide powder by electrochemical method
CN102943280B (en) * 2012-10-18 2016-01-06 成都华泽晶体材料有限公司 A kind of method of electrochemical production Two-step purifying body
CN103469288A (en) * 2013-09-02 2013-12-25 陈文智 Electroplating bath provided with circulating filtration device
CN104577164B (en) * 2015-01-07 2017-01-04 浙江大学 Single turbine co-generation unit based on aluminum-water reaction and method
CN104577164A (en) * 2015-01-07 2015-04-29 浙江大学 Single-stage turbine cogeneration system and single-stage turbine cogeneration method based on aluminum-water reaction
CN105417495A (en) * 2015-12-29 2016-03-23 杜善骥 Underwater-type magnesium-gallium-alloy hydrogen production device working method
CN108649240A (en) * 2018-05-15 2018-10-12 常州大学 A kind of fuel cell
CN108649240B (en) * 2018-05-15 2021-06-22 常州大学 Fuel cell
CN109093129A (en) * 2018-07-10 2018-12-28 氢电中科（广州）新能源设备有限公司 A kind of the hydrogen manufacturing alloy and intelligent road-lamp of alumal dopen Nano Zero-valent Iron
CN111224172A (en) * 2020-01-16 2020-06-02 荆门市探梦科技有限公司 Aqueous battery system
CN113690469A (en) * 2021-08-25 2021-11-23 浙江大学 Aluminum-water electrochemical cell system
CN113690469B (en) * 2021-08-25 2022-12-06 浙江大学 Aluminum-water electrochemical cell system
CN115818568A (en) * 2022-11-25 2023-03-21 王凯 Cracking agent for cracking water vapor to produce hydrogen, preparation, use and reactivation method thereof
CN115818568B (en) * 2022-11-25 2024-04-09 王凯 Cracking agent for hydrogen production by cracking water vapor, preparation, use and reviving method thereof

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