WO2006114034A1

WO2006114034A1 - An electrochemical method for producing and storing hydrogen by the redox of zinc and water

Info

Publication number: WO2006114034A1
Application number: PCT/CN2006/000090
Authority: WO
Inventors: Chao Huang
Original assignee: Huang, Hao
Priority date: 2005-04-28
Filing date: 2006-01-20
Publication date: 2006-11-02
Also published as: US20080190781A1; JP2008539328A; CN1854063A

Abstract

The present invention provides an electrochemical method for producing and storing hydrogen by the redox of zinc and water. The method comprises a closed system consisted of gas-generating electrode-electrolyte-zinc electrode, the gas-generating electrode and zinc electrode are respectively connected to external circuits, it is characterized in that, when hydrogen is to be produced, the external circuits are connected, water is reduced into hydrogen on the gas-generating electrode, and zinc is oxidized into zinc oxide on the zinc electrode; when hydrogen is to be stored, enough water is applied to the closed system, and the negative pole of power source is connected to the external circuit of zinc electrode, and the positive pole of power source is connected to the external circuit of gas-generating electrode, then current is applied, zinc oxide is reduced into zinc on the zinc electrode, and water is oxidized into oxygen on the gas-generating electrode, and then the oxygen is released. The method is widely used, and the operation thereof is simple, it is especially suitable for applying hydrogen source for hydrogen fuel cell, and the electric power generated thereof also can be utilized for generating electricity together with fuel cell.

Description

Electrochemical zinc-water hydrogen production, hydrogen storage method

I. Technical field

The invention belongs to the technology of storing and manufacturing hydrogen energy, and particularly relates to a method for hydrogen production and hydrogen storage by electrochemical zinc-water.

Second, the background technology

With the gradual increase of petrochemical fuel consumption and the depletion of its storage, as well as the increasing emphasis on environmental protection, primary energy represented by oil, coal and natural gas will eventually be solar energy, wind energy, ocean energy, bioenergy, etc. Replaced by clean renewable energy. As a non-polluting secondary energy source, hydrogen energy has many outstanding advantages such as abundant resources, high combustion heat and water, and does not cause environmental pollution. It is widely recognized by countries all over the world. In particular, the hydrogen-oxygen (air) fuel cell that uses hydrogen as a fuel in recent years is an efficient, clean, long-life power generation device that will soon become an ideal power source for mobile electronic products and electric vehicles, hindering its popularity. One of the main reasons is the lack of a suitable source of hydrogen. At present, there are four main ways to supply hydrogen to fuel cells: 1. High pressure gas cylinder method; 2. Low temperature liquefaction method; 3. Hydrocarbon fuel reforming method; 4. Metal hydride hydrogen storage method. Among them, the gas cylinder method and the low temperature method all have major defects such as high cost and poor safety. The reforming process requires a higher temperature, a larger equipment, and a lower hydrogen purity. The metal hydride method has good safety and has become the focus of research on hydrogen storage technology research. However, the hydrogen storage alloy is relatively expensive, and the alloy is easily pulverized during the process of charging and discharging hydrogen, and the hydrogen charging process is complicated. · At present, it is a patented technology with the patent name "Electrochemical Aluminum-Hydrogen, Hydrogen Production and Design" (Application No.: 0214885.0.9). This technology is made of aluminum alloy. Two-phase circulating filtration closed structure composed of active-hydrogen catalytic catalytic plates Cheng, it has the advantages of high efficiency, safety, environmental protection, etc. The disadvantage is that the aluminum alloy electrode is a disposable consumable, which cannot be reused. The aluminum alloy electrode needs to be replaced after each hydrogen production, and the consumption is large. And the generated aluminum oxide needs to be removed by pump circulation filtration, and the hydrogen production process is complicated, which increases the cost.

Third, the content of the invention '

The object of the present invention is to provide an electrochemical zinc-water hydrogen production and hydrogen storage method which is safe, convenient, and low in cost, and can be repeatedly used by a zinc electrode. ·

In order to achieve the above object, the method adopted by the present invention is:

- A closed system consisting of a gassing electrode, an electrolyte and a zinc electrode, and the gassing electrode and the zinc electrode are connected to an external circuit. When the hydrogen gas is released, the gas-discharging electrode and the external circuit of the zinc electrode are turned on, and a water reduction reaction occurs on the gas-sparing electrode to release hydrogen gas, and zinc oxidation reaction occurs on the zinc electrode to form an oxidation product of zinc. Disconnect the external circuit, that is, stop releasing hydrogen; when storing hydrogen '' gas, first add water to the closed system, connect the negative pole of the external power supply to the external circuit of the zinc electrode, and connect the positive pole of the external power supply to the external circuit of the gas-dissolving electrode, with DC The zinc electrode is reduced on the zinc electrode, the zinc oxide is reduced to zinc, the zinc electrode is restored, and the water is oxidized by the gassing electrode to generate oxygen. .

The gassing electrode used in the present invention is composed of a hydrogen evolution electrode and an oxygen evolution electrode, or a hydrogen evolution electrode and an oxygen evolution electrode. The former uses an oxygen evolution electrode-electrolyte-zinc electrode-electricity-hydrogen evolution electrode system. When hydrogen is released, the hydrogen evolution electrode and the zinc electrode external circuit are connected. When the hydrogen gas is stored, the negative electrode of the external power source is connected to the external circuit of the zinc electrode. The positive electrode is connected to the external circuit of the electrode. The latter uses a zinc electrode, an electrolyte, a hydrogen evolution electrode, and a system for oxygen gas formation. When hydrogen is released, the zinc electrode and the hydrogen evolution electrode are combined with the oxygen electrode. Road, when storing hydrogen, connect the negative electrode of the power supply to the external electrode of the zinc electrode. 3⁄4± "The positive electrode is connected to the external circuit of the hydrogen evolution electrode and the oxygen evolution electrode."

The electrolyte of the present invention generally employs a strong alkaline electrolyte aqueous solution because the zinc electrode has good reversibility and strong current discharge capability under a strong alkaline aqueous solution. The following is an example of a strong alkaline electrolyte, illustrating the principle of electrochemical reaction occurring in the hydrogen-and hydrogen storage system of the zinc-water system of the present invention:

1. When hydrogen is released, the reaction occurs as follows: ' .

Zinc electrode:

Zn+20H"-2e→Zn(OH) ₂ (Ε.=-1.249 volts)

Or Z11+20H-— 2e— ΖηΟ+Η ₂ 0 (Ε°=-1.260 volts)

Gassing electrode:

2H ₂ 0+2e-20H H ₂ † (E°=-0.828 volts)

The total reaction is: Zn+2 0— Zn(OH) ₂ +H ₂ † (AE ^Q =0.421 volts)

Or Zn+23⁄4〇-Zn〇+ 3⁄4 t (ΔΕ°=0.432 volts) is essentially a process in which zinc reduced water forms ∑11 (0!3⁄4 ₂ or ΖηΟ, releasing hydrogen and electric energy. A certain voltage can be obtained in the external circuit. The current, the theoretical potential is 0.42-0.43 volts, and the current that is controlled by the external circuit can be easily controlled to control the amount of hydrogen released.

2. When storing hydrogen, the reaction occurs as follows:

f i pole: · .

Zn(〇H) ₂ +2e—Zn÷20H" (E ⁰ =− 1.249 volts)

Or Zn〇÷ H ₂ 0+2e→Zn+20H" (E°= -1.260 volts)

Gassing bungee: 2〇i- Γ— 2e— H ₂ 0+ l/20 ₂ † (E°=0.401 volts)

The total reaction is: Zn(〇H) ₂ — Zn+H ₂ 0 t + l/20 ₂ t (ΔΕ°=1.650 volts) or ZnO — Zii+ l/2〇 ₂ † (ΔΕ ⁰ = 1.661 volts) Ζη(ΟΗ) ₂ or ΖηΟ is electrolyzed and reduced to produce a process in which Zii emits oxygen. Because the overpotential is large, the actual decomposition voltage is higher than the theoretical potential of 1.65-1.66 volts, which can reach about 2 volts.

In the case of other electrolytes, or in the initial stage of discharge under strong alkaline electrolyte conditions, zinc discharge can produce a zinc oxidation product different from ∑11 (0 ₂ or 2110, but the charge and discharge process of hydrogen production and hydrogen storage is Principle, consistent with the above example:

The zinc electrode used in the hydrogen storage and hydrogen production method of the present invention is composed of a zinc active material, a binder, an additive, a current collector, a paste, a paste, a sintering, a box (tube), a foaming, an electrodeposition technique, and the like. Chemically processed, wherein the zinc active material may be composed of zinc alloy powder, zinc oxide, zinc hydroxide, zincate or the like or a combination thereof; the binder may be carboxymethyl cellulose (CMC), Polyhexafluoroethylene (PTFE) emulsion, polyvinyl alcohol (FVA), propylmethylcellulose (HPMC), polyethylene oxide (PEO), polyacrylic acid (PAA), polyvinylidene fluoride (PVDF:), six a mixture of one or more of the above binders such as fluoropropene; additives such as zinc oxide, calcium oxide, magnesium oxide, cadmium oxide, aluminum oxide, steel compounds, antimony compounds, lead compounds, calcium hydroxide, graphite Powder, acetylene black, carbon powder, - ^ black, activated carbon powder, chopped fiber, carbon fiber, etc., or a mixture of the above; the current collector can be made of foam metal, metal mesh, metal pedicle ( metal Be a ¹ Ah 'or alloy), and plated metal surface, or a composite plating method for treating physical science ¾; such as: foams brass, lead or tin-plated brass strip punching, the network brass. The above zinc electricity A structure such as a sheet shape, a porous powder or the like is preferably used, and a powder porous structure is preferable.

The electrolyte used in the hydrogen storage and hydrogen production method of the present invention is an aqueous solution of an aqueous solution, and is impregnated with a battery separator. The aqueous solution electrolyte is a solution having a pH of more than 4 and a concentration of 0.05 Mol/L-15Mo]/L, and an alkali metal or alkaline earth metal hydroxide aqueous solution or a mixture thereof may be used, preferably KOH, NaOH aqueous solution or a mixture thereof; or alkali is used. An aqueous solution of a metal or alkaline earth metal carbonate, a sulfate, a fluoride salt, or a mixture thereof, or a mixture thereof with an aqueous solution of an oxide; the separator may be: a hydrated cellulose film, a polyethylene graft film, a cellophane, a nylon cloth. , one of hydrated cellulose paper, cotton paper, potassium titanate paper, polyethylene felt, zirconia fiber paper, vinylon non-woven fabric, or the like, or a composite film made of one or more materials.

The hydrogen evolution electrode used in the present invention can be produced by a variety of methods using an active hydrogen evolution electrode having a very low hydrogen evolution overpotential. Active hydrogen evolution electrode is a composite material of pure metal, metal oxide, alloy or metal and alloy and oxide. It is electroplated, composite plating, thermal decomposition, ion plating, ion implantation, ion sputtering, electroless plating, metal foam technology. It can be made by a variety of chemical methods, or it can be made by combining the above two or three technologies. The 3⁄41 can be various forms of pure metals such as Ni, Co, Fe, Mo, 3⁄4\ pt, Pd, Ru and other low hydrogen over potential of the metal; may be an oxide, such as Ru0 _{_{_2,}} Ti0 _2, Zr0 _2, etc. '; may also be an alloy, such as Ni- Mo, Ni- B, Ni- P , Ni - NiS, Ni-Pt, Ni-Ru, Co-Mo, i-Wo, i--Sn, Mo-W, Co-W, Ni-hydrogen storage alloy, and Ni-P-Co-Mo-W, Ni-Co - Mo, \ i - o-.Vlo-H\ Ni P-Mo - Co, Ni- P- W, Ni- P- Co- Mo- W, Ni- B- Co, Ni- B - Mo , \ i -H-Co-\lo, Ni B- Co- .Mo- «', Ni- B- W, Ni- Co-hydrogen storage alloy, etc.; may also be -: fe or alloy and oxide Composite material, used in Ru0 ₂ , Zr0 ₂ , carbon particles The other supporting various composite materials made of pure metals and alloys contained more or mixed, such as _{Ni- Ru0 2, Ni-iVlo- u0} 2, Ni- NiS, Ni-Mo- W- Ru0 2 and the like;. Oxygen evolution The electrode is made of metal steel, iron, nickel mesh, belt, sheet, sheet, foam metal, 镀 is coated with Ni or sulfur-plated Ni, or it has special catalytic effect on oxygen evolution. A titanium-based platinum group compound electrode, a lanthanide-coated titanium electrode, a manganese dioxide-coated titanium electrode, a perovskite-type oxide electrode, or the like.

The hydrogen evolution electrode and oxygen evolution electrode used in the present invention can be formed on a metal steel, iron, nickel mesh, belt, sheet, sheet, or foam metal structure by Ni plating or sulfur plating Ni physical chemical treatment. . · '

The hydrogen evolution electrode, the oxygen evolution electrode, and the hydrogen evolution and oxygen evolution electrode may have various structures such as a sheet shape, a mesh shape, and a porous shape, and a gas diffusion electrode structure similar to a fuel cell electrode may be selected.

According to the present invention, the following two devices can be manufactured:

1. It consists of a liquid storage tank, a liquid control valve, a liquid injection port, a hydrogen collecting chamber, a hydrogen outlet, an oxygen outlet, a zinc electrode, a compartment partition, a hydrogen evolution electrode, an oxygen evolution electrode, a buffer tank, etc.; Above the hydrogen collecting chamber, there is an electrolytic cell system under the hydrogen collecting chamber, which is composed of a plurality of polar chambers, and the number of poles is determined according to the amount of hydrogen required and the rate of hydrogen release, and each row is arranged in each pole chamber. A hydrogen evolution electrode, a zinc electrode, and an oxygen evolution electrode are disposed, and each of the pole chambers is filled with a suction/dip separator, and the electrodes are separated, and an external circuit is connected outside each electrode, and a liquid injection port is provided on the liquid storage tank for supplementing the electrolyte In the aqueous solution or water, the hydrogen collecting chamber is provided with a hydrogen outlet, and a buffer tank is arranged under the electrolytic cell system to ensure the liquid level of the electrolyte in the electrolytic cell system is uniform. 3⁄4 When you need to release hydrogen, first open the liquid control valve so that the electrolyte in the reservoir is located. The diversion tube at the bottom of the sump flows into each of the pole chambers and the buffer tank in the electrolytic cell system, and the external circuit of the zinc electrode and the hydrogen evolution electrode is turned on and formed, and a large amount of hydrogen gas is generated on the hydrogen evolution electrode, and the hydrogen gas is collected in the hydrogen collection chamber. It gathers and flows out through the hydrogen outlet. With the outflow of hydrogen, in the electrochemical zinc-water hydrogen storage, the external positive and negative ends of the hydrogen production system will simultaneously output electrical energy, and the external circuit of the zinc electrode and the hydrogen evolution electrode will be disconnected, and the system stops hydrogen production; when hydrogen is required to be stored, First, sufficient water is supplied to the electrolytic cell system through the liquid injection port, and then the positive electrode of the external power source is connected to the external circuit of the oxygen evolution electrode, the negative electrode is connected to the external circuit of the zinc electrode, and the direct current is applied to the zinc electrode, and the zinc electrode starts to reduce and form zinc, and the oxygen evolution electrode starts to be large. Oxygen is produced, and oxygen is discharged through the oxygen outlet.

- 2, consisting of a liquid storage tank, a liquid control valve, a liquid injection port, a hydrogen collecting chamber, a hydrogen outlet, an oxygen outlet, a zinc electrode, a compartment partition, a hydrogen evolution electrode, an oxygen evolution electrode, a buffer tank, and the like; Located above the hydrogen collecting chamber, an electrolytic cell system is arranged under the hydrogen collecting chamber, which is composed of a plurality of polar chambers, and the number of the polar chambers is determined according to the amount of hydrogen generated and the rate of hydrogen release, and each of the polar chambers is The zinc electrode, the hydrogen evolution electrode and the oxygen evolution electrode are arranged, and they are not connected to each other, and each electrode is connected with an external circuit. Each of the pole chambers is filled with a suction membrane, and the electrodes are separated, and the electrodes are external. An external circuit is connected to the liquid storage tank for filling the electrolyte or water, and the hydrogen collecting chamber is provided with a hydrogen outlet port, and a buffer tank is arranged under the electrolytic cell system for ensuring the discharge of the electricity system. The liquid level is the same. When it is necessary to release hydrogen, first open the liquid control valve, so that the electrolyte in the liquid storage tank flows into the electrode chambers of the electrolytic cell-system through the diversion tube at the bottom of the liquid storage tank, and turns on the zinc electrode. And the hydrogen evolution and the external circuit of the oxygen electrode form a loop, and a large amount of hydrogen gas is generated on the hydrogen evolution and oxygen evolution electrode. The hydrogen gas is collected in the hydrogen collection chamber and flows out through the hydrogen outlet. With the outflow of hydrogen, in the electrochemical zinc-water hydrogen storage, the external positive and negative ends of the hydrogen production system will simultaneously output electrical energy, and only need to disconnect the zinc electrode and the hydrogen evolution electrode. In the external circuit, the system stops hydrogen production; when it is necessary to store hydrogen, 'first fill the electrolyte through the liquid injection port. The system is filled with sufficient water, then the positive electrode of the external power supply is connected to the external circuit of the oxygen evolution electrode, and the negative electrode is connected to the external electrode of the zinc electrode. On the road, through the direct current, the zinc electrode begins to reduce and form zinc. The hydrogen evolution and oxygen evolution electrode begins to generate a large amount of oxygen, and the oxygen is directly discharged through the oxygen outlet.

The invention adopts electrochemical technology, and adopts a hydrogen-making and hydrogen storage system formed by a combination of a zinc electrode and a gassing electrode in the electrolyte, and develops a new concept of efficient, safe and inexpensive reusable electricity. The chemical zinc-hydrogen production and hydrogen storage system is obviously different from the traditional hydrogen sources, and it is manifested in the following aspects:

1. Safe, convenient and controllable, the body can be large or small.

The hydrogen storage hydrogen production can be carried out at normal temperature and pressure, and belongs to the electric 'pool' reaction. It is only necessary to control the current to control the amount of hydrogen produced, and it is extremely quick and convenient to start and shut down. The system of the invention can be modularized, convenient to disassemble and assemble. Can be made into a miniature, small hydrogen source. It can also be combined into a large mobile or stationary hydrogen source.

2. High energy storage density, good hydrogen purity and wide working range.

Zinc itself has a high energy storage density, and the hydrogen produced under the condition of strong alkali electrolyte has high purity and can work under low temperature conditions, and is widely used.

3. Low cost, abundant raw materials, environmental protection and no pollution.

Since the system is essentially an electrochemical reaction between zinc and water, the system stores water and zinc, which is much less expensive than hydrogen storage alloys, and has a rich zinc resource. Due to the use of flawless raw materials, it is safe and reliable and will not cause environmental pollution. '

4, convenient and rechargeable, can be used repeatedly.

iL] can store hydrogen energy in this system by charging method, no need to set up hydrogen refueling station, gas cylinder Inconvenient hydrogen source. At the same time, only electricity and water are needed to store hydrogen. And can be used multiple times in a loop.

5. Hydrogen and electric energy are produced together.

When hydrogen is produced, not only does it require external power supply, but it also generates electricity.

The above advantages determine that the present invention has excellent application value in mobile and portable hydrogen sources. It is especially suitable for supplying hydrogen to hydrogen fuel cells. It can also use its by-produced electric energy to supply electricity together with fuel cells.

The invention is also suitable for the following technical fields: providing a convenient mobile hydrogen source for laboratories, welding equipment, etc.; for heat source, field lighting, etc. under the conditions of electricity, hydrogen sharing or single use. The invention can also be applied to energy storage, for example: storage of excess power during low peak period and power storage of solar power generation, and energy storage mode is hydrogen and electric energy storage.

Fourth, the specific implementation

Example I:

Take conductive carbon black 1.5g, zinc oxide 6.0g, mercury-free zinc powder 1.5g, polyvinyl alcohol 3% aqueous solution 3.3ml, sodium carboxymethyl cellulose 2% aqueous solution 25ml, polytetrafluoroethylene (PTFE) emulsion 4ml (10% mass concentration), stir well, heat into a mass, and roll into a sheet. Pressed on a 60 mesh brass wire for the zinc electrode, . Shanghai Shilong Company? The film is a separator, the foamed nickel sheet is an oxygen evolution electrode, and the Pt/C (platinum supported on conductive carbon black) catalyst foamed nickel sheet is a hydrogen evolution electrode, 5Mol/LK〇 The H aqueous solution is an electrolyte, and the electrolyte floods most of the bungee.

The effective area of the electrode of the single cell is 5 square centimeters.

Constant current charging: The zinc electrode is connected to the negative electrode, the foamed nickel piece is connected to the positive electrode, the current is 50 mA, charged for 3 hours, and allowed to stand for 15 minutes after charging. When charging, the positive gas is gas, and the two poles are not allowed to produce gas. Discharge gas production: The zinc electrode is the negative electrode, and the foamed nickel sheet coated with the Pt/C catalyst is the positive electrode. When the battery is discharged, the discharge current and voltage are measured by a multimeter. The circuit is turned on, and the current reaches 0.5 amps at the beginning of the discharge, accompanied by the sharp production of bubbles, and the gas production reaches 3.3 ml per minute. The current is reduced and the gas production is reduced. Turn off the circuit in the middle, stop the gas production, and turn on the circuit, that is, restore the gas production. When the charge and discharge are repeated three times, the current and voltage do not change much, and the phenomenon does not change.

Example . 2:

Take 2.5 g of mercury-free zinc powder, 7.5 g of zinc oxide, 3 ml of 3% aqueous solution of polyvinyl alcohol, mix and mix into a slurry, apply it on the nickel foam, dry it, and then compress it into a zinc electrode. The EPAT-AS-SL8 film is The battery separator, the foamed nickel sheet is a hydrogen evolution and oxygen evolution electrode, and the 0.5 Mol/L NaOH aqueous solution is an electrolyte, and the electrolyte floods most of the electrodes. The effective area of the single cell electrode is 10 square centimeters. .

Constant current charging: The zinc electrode is connected to the negative electrode, the foamed nickel piece is connected to the positive electrode, the current is 60 mA, and it is charged for 5 hours. After charging, it is allowed to stand for 15 minutes. When charging, the positive gas is gas, and the two poles are not allowed to produce gas.

Discharge gas production: The zinc electrode is the negative electrode, and the foamed nickel plate is the positive electrode. When the battery is discharged, the discharge current and voltage are detected by a multimeter. The circuit is turned on, the discharge current is 70mA, and the voltage is 46mV. Soon, the positive bubble appeared and the discharge current was 36mA ιΗ after 2 hours of discharge, and the i ii pressure was still 65mV. .

Collect the produced gas and start the discharge to 0.5 ml per minute. The current is regulated and the amount of gas changes. Repeated charging, discharge three times, the current and voltage changes little, the phenomenon remains unchanged.

Example 3 '

Take conductive carbon black 0.5g, zinc oxide 7g, mercury-free zinc powder 1.5g, polyvinyl alcohol 3% aqueous solution 3.3ml, sodium carboxymethyl cellulose 2% aqueous solution 25ml, polytetrafluoroethylene (PTFE> Emulsion 4 ml (10% mass-concentration-), stir well, heat into agglomerate, roll into a sheet. Press on a 60 mesh brass wire for the zinc electrode, PPAT-AS-SL8 film for the diaphragm, bubble nickel For the hydrogen evolution and oxygen evolution electrode, the 5 Mol/L KOH aqueous solution is an electrolyte, and the electrolyte floods most of the electrodes.

The cell electrode has an effective area of 12 square centimeters.

"Constant current charging: The zinc electrode is connected to the negative electrode, the foamed nickel piece is connected to the positive electrode, the current is 100 mA, and it is charged for 5 hours. After charging, it is allowed to stand for 15 minutes. When charging, the positive electrode is gas-filled, and the two poles are not gas-producing.

Discharge gas production: The zinc electrode is the negative electrode and the foamed nickel plate is the positive electrode. When the battery is discharged, the discharge current and voltage are detected by a multimeter. At the beginning of the discharge, the current reaches 0.5 amps, and after 1 hour, it can reach 0.1 amps, and 3 hours and 30 minutes are 62 mA. The discharge started with the sharp production of bubbles, and the gas production reached 3.3 ml per minute. The current is reduced and the gas production is reduced. Turn off the circuit in the middle, stop the gas production, turn on the circuit, and resume the gas production on the nickel.

When the charge and discharge are repeated three times, the current and voltage do not change much, and the phenomenon does not change.

The present invention has been disclosed and disclosed in the present disclosure, although they have been described by way of example, those skilled in the art Modifications, splicing or additions and subtractions are apparent to those skilled in the art, but their modifications are included in the scope and content of the present invention.

Claims

Rights request

1. An electrochemical zinc-water hydrogen production and hydrogen storage method, which is a closed system composed of a gassing electrode, an electrolyte and a zinc electrode. The gassing electrode and the zinc electrode are connected to an external circuit, and the characteristics are: When hydrogen is released, the gas-discharging electrode and the external circuit of the zinc electrode are turned on, and a water reduction reaction occurs on the gas-sparing electrode to release hydrogen gas; a zinc electrode undergoes oxidation reaction of zinc to form an oxidation product of zinc. When hydrogen storage is required, Make up the water in the closed system, connect the negative pole of the power supply to the external circuit of the zinc electrode, connect the positive pole of the power supply to the external circuit of the gas-dissolving 3⁄4 pole, and then pass the direct current, the zinc electrode is on the reduction reaction of zinc, and the oxidation product of zinc is It is reduced to zinc, the zinc electrode is restored, and the oxidation reaction of water occurs at the gassing electrode to generate oxygen.

2. The method for producing hydrogen and hydrogen storage by electrochemical zinc-water according to claim 1, wherein: said gas separation electrode is composed of a hydrogen evolution electrode and an oxygen evolution electrode; or a hydrogen evolution electrode and an oxygen evolution electrode are formed. . ,

3. The method for producing hydrogen and hydrogen storage by electrochemical zinc-water according to claim 1, wherein: the zinc electrode is pressed, smeared by a zinc active material, a binder, an additive, a current collector, Sintered, box (tube), foaming, electrodeposition technology and other various methods; its composition is: zinc active material from zinc alloy powder, zinc oxide, zinc hydroxide, zincate and other zinc a compound or a combination thereof; a binder consisting of carboxymethylcellulose <CMC), a polytetramethylene (PTFE) emulsion, polyvinyl alcohol (PVA), hydroxymethylcellulose

C HP C ) , a mixture of one or more of polyethylene oxide (PEO polyacrylic acid (PTFE), · or polyvinylidene fluoride (PVDF), hexafluoropropylene, etc.): composition; Zinc, calcium oxide, magnesium oxide, cadmium oxide, aluminum oxide, indium compound, antimony a compound, a lead compound, a calcium arsenate, a 'stone 3' powder acetylene black, a powder, a conductive carbon black, an activated carbon powder, a chopped fiber, a carbon fiber, or the like; the current collector is It is made of foam metal, metal mesh, metal strip (metal can be elemental or alloy), and is treated by physical and chemical methods such as electroplating and composite plating on the metal surface; preferably: foamed brass, lead-plated or tin-plated punched Brass belt, brass mesh.

4. The method for producing hydrogen and hydrogen storage by electrochemical zinc-water according to claim 1 or 3, wherein: the zinc electrode is in the form of a sheet or a powdery porous structure, preferably: a powder porous structure.

5. The method for producing hydrogen and hydrogen storage by electrochemical zinc-water according to claim 1, wherein: the electrolyte is an aqueous solution electrolyte, and is immersed in a battery separator, and the aqueous electrolyte is ρ Η greater than 4 , a solution having a concentration of 0.05 Mol / L - 15 Mol / L, an alkali metal or alkaline earth metal hydroxide aqueous solution or a mixture thereof, preferably KOH, NaOH aqueous solution or a mixture thereof; or an alkali metal or alkaline earth metal carbonate, An aqueous solution of a sulfate, a fluoride salt, or a mixture thereof, or a mixture thereof with an aqueous solution of a hydroxide; a separator: a hydrated cellulose film, a polyethylene graft film, a cellophane, a nylon cloth, a hydrated cellulose' paper, a cotton paper , one of materials such as potassium titanate paper, polyethylene felt, zirconia fiber paper, vinylon non-woven fabric, or the like, or a composite film made of one or more materials.

The method for producing hydrogen and hydrogen storage by electrochemical zinc-water according to claim 1 or 2, wherein the hydrogen evolution electrode is formed by forming a pure metal, a metal oxide, an alloy or a metal and an alloy with an oxide. Composite materials are made by electroplating, composite plating, thermal decomposition, ion plating, 3⁄4 sub-injection, ion sputtering, electroless plating, metal foam technology, etc., or a combination of the above two or three technologies. Made; the composition of the hydrogen evolution electrode is: Pure metal 3⁄4 selection: Co, Fe, Mo, W, Ρΐ, Pd, Ru; oxides are preferably: Ru0 ₂ , Ti0 ₂ , ZrO / etc.; alloys preferably: Ni - Mo, Ni - B, Ni - P, Ni - NiS, Ni-Pt, >!i-Ru, Co-Mo, X-Bu, Ni-Sn, Mo-W, Co-W', Ni-hydrogen storage alloy, and Ni-P-Co-Mo-W, Ni-Co- Mo, \' i -Co-Mo-W, Ni-P-Mo- Co, Ni-PW, Ni-P-Co-Mo-H', Ni-B-Co, Ni-B-Mo , .. B, Co-Mo, Ni-B-Co-Mo-W, Ni-B-\V, Ni-Co-hydrogen storage alloy; composite of metal or alloy and oxide: Ni- Ru0 ₂ , Ni - Mo Ru0 ₂ , Ni- iS, Ni-Mo-W- RuO, _c

The method for producing hydrogen and hydrogen storage by electrochemical zinc-water according to claim 1 or 2, wherein: the oxygen evolution electrode is a mesh, a strip or a plate made of steel, iron or nickel. On the structure of sheet, foam metal, etc., 釆 is made of Ni-plated or sulphur-plated Ni; or titanium-based platinum group electrode, lanthanide-coated titanium electrode, manganese dioxide-coated titanium electrode, perovskite Type oxide electrode. ·

.

The method for producing hydrogen and hydrogen storage by electrochemical zinc-water according to claim 1 or 2, wherein: the hydrogen evolution electrode and the oxygen evolution electrode are meshes of steel, iron and nickel. , the structure of sheet metal, sheet metal, foam metal, 釆 is made by Ni plating or sulfur plating Xi method. .

The method for hydrogen production and hydrogen storage of electrochemical zinc-water according to claim 1 or 2, wherein: the hydrogen evolution electrode, the oxygen evolution electrode, the hydrogen evolution electrode and the oxygen evolution electrode can be collected. Structures such as a mesh, a mesh, a gas diffusion electrode, and the like.