WO2009127145A1 - Système électrochimique comprenant du zinc et de l'eau pour produire et stocker de l'hydrogène, et son utilisation - Google Patents

Système électrochimique comprenant du zinc et de l'eau pour produire et stocker de l'hydrogène, et son utilisation Download PDF

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WO2009127145A1
WO2009127145A1 PCT/CN2009/071251 CN2009071251W WO2009127145A1 WO 2009127145 A1 WO2009127145 A1 WO 2009127145A1 CN 2009071251 W CN2009071251 W CN 2009071251W WO 2009127145 A1 WO2009127145 A1 WO 2009127145A1
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electrode
zinc
hydrogen storage
hydrogen
electrochemical
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黄潮
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04201—Reactant storage and supply, e.g. means for feeding, pipes
    • H01M8/04216—Reactant storage and supply, e.g. means for feeding, pipes characterised by the choice for a specific material, e.g. carbon, hydride, absorbent
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B5/00—Electrogenerative processes, i.e. processes for producing compounds in which electricity is generated simultaneously
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04201—Reactant storage and supply, e.g. means for feeding, pipes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • H01M8/065—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants by dissolution of metals or alloys; by dehydriding metallic substances
    • 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

Definitions

  • Electrochemical zinc-water hydrogen storage system and application thereof
  • the invention relates to a hydrogen production and storage technology, in particular to an electrochemical zinc-water hydrogen storage system and its application to an internal combustion engine. Background technique
  • Electrochemical Zinc-Water Hydrogen Storage Method (200510046374.8, Publication No. CN1854063A), describes an inexpensive, convenient, and reusable hydrogen storage method for hydrogen production by a zinc electrode.
  • Electrolyte system formed by electrolyte-dissolving electrode.
  • the negative electrode of the external power supply is connected to the zinc electrode
  • the positive electrode of the external power source is connected to the gas-dissolving electrode
  • the direct current is applied, and the zinc reduction reaction occurs on the zinc electrode.
  • an oxidation reaction involving water occurs to generate oxygen gas.
  • an external electrode is connected to the gas-sparing electrode and the zinc electrode, and zinc oxidation occurs on the zinc electrode, and water is generated on the gas-sparing electrode.
  • the reduction reaction generates hydrogen gas to be discharged.
  • the zinc electrode adopts the powder porous electrode in the traditional battery industry, or the metal zinc is electrodeposited on the current collector of the zinc electrode and then flattened and fixed to the electrodeposition electrode, the energy density can provide a hydrogen source for the fuel cell.
  • the technical indicators such as life, cost and hydrogen production are still far from the hydrogen sources required for energy storage in conjunction with internal combustion engines.
  • the internal combustion engine has different fuel economy under different load rate conditions. Generally speaking, the same amount of fuel burns more fully at high load rate and emits more mechanical energy.
  • the energy storage system is matched with the internal combustion engine, so that when the workload demand is low, the internal combustion engine can simultaneously drive the energy storage system, increase the load rate of the internal combustion engine, and store and utilize excess mechanical energy beyond the workload demand.
  • the brake of the vehicle Excess energy such as deceleration, downhill of the vehicle, etc. can also be recycled through the energy storage system.
  • the hybrid electric power technology converts excess mechanical energy into electrical energy and stores it in the battery pack. When appropriate, the stored electric energy is used to propel the vehicle, which can save 7%-40% of fuel.
  • the object of the present invention is to provide an electrochemical zinc-water hydrogen storage system and an application thereof, which can continuously produce a large amount of hydrogen at a low cost, has a long service life, is easy to linearly amplify, and can be used in cooperation with an internal combustion engine.
  • Electrochemical zinc-water hydrogen storage system Using an electrodeposited zinc electrode, the zinc electrode current collector and the gassing electrode are arranged in an aqueous solution electrolyte containing a positive divalent zinc compound to form an electrochemical zinc-water system. a unit of a hydrogen hydrogen storage system; wherein a distance between the zinc electrode and the gassing electrode is in a range of 1 mm to 30 mm; and the electricity is installed in a sealed container leaving a fluid input channel, a fluid output channel, and an electrode channel Chemistry a unit of a zinc-water hydrogen storage system, wherein the fluid input channel and the fluid output channel are connected to an electrolyte storage container and a pump connected with a water supply passage, a gas-liquid separation device, and a pump;
  • the structure of the hydrogen-storing hydrogen storage unit is placed vertically in the sealed container: the gas-dissolving electrode has a shape in which the vertical surface is closed to the lower horizontal plane and the upper opening is open, and the zinc electrode is disposed in the lower horizontal plane and each vertical plane;
  • the gas-dissolving electrode adopts a porous gas-discharging electrode; a gap is left between the gas-sparing electrode and the zinc electrode;
  • the structure of the electrode for hydrogen storage hydrogen storage unit is placed horizontally in a sealed container: a gassing electrode is arranged on the upper part and a zinc electrode is arranged on the lower part; a porous gassing electrode is used for the gas separation electrode; a space is left between the gas separation electrode and the zinc electrode;
  • the number of units of the electrochemical zinc-water hydrogen storage system is at least one; when the number of units of the electrochemical zinc-water hydrogen storage system is two or more, the connection between the plurality of units
  • the electrodes are connected in series or in parallel, or in series and parallel; the fluid input channel, the fluid output channel and the electrode channel of each of the units are respectively connected in series or in parallel, or in series and parallel to form a hydrogen storage hydrogen storage unit group;
  • the gas-sparing electrode is externally connected to the negative electrode of the DC power source, and the zinc electrode is externally connected to the positive electrode of the DC power source, and the applied voltage in each electrochemical system unit is less than 500 mV;
  • the zinc electrode uses a normal divalent zinc compound as a zinc source material in the electrolyte
  • the application of the electrochemical zinc-water hydrogen storage hydrogen storage system when the electrochemical zinc-water hydrogen storage system is charged and stored for hydrogen, the hydrogen is discharged, and the hydrogen fuel is supplied to the internal combustion engine with a mass fraction of 0.1%-5%. Combustion; When the operating load of the internal combustion engine with this system is less than 50%, let the internal combustion engine drive the generator at the same time, increase the load rate of the internal combustion engine, convert the excess mechanical energy beyond the working load into electric energy, and use the converted electric energy.
  • the electrochemical zinc-water hydrogen storage system is charged and stored in hydrogen, and the oxygen generated during charging can also be ignited into the internal combustion engine for further combustion, charging for several tens of seconds to several minutes, and then dragging and discharging hydrogen for several tens of seconds to several minutes. Hydrogen is introduced into the internal combustion engine to burn with the fuel; this cycle is repeated.
  • the system of the invention adopts an electrodeposited zinc electrode, and only needs to install a current collector of a zinc electrode, which is simple in processing and low in cost, and has no deformation and capacity attenuation of the conventional battery electrode, and the system life is much longer than that of the conventional battery pack.
  • the system of the invention is linearly enlarged in structure, and can connect tens of hundreds of hydrogen-producing hydrogen storage units through series, parallel or series-parallel combination, and form a hydrogen storage hydrogen storage system with the circulating portion of the electrolyte, which can be large Cycle hydrogen production; easy to assemble and disassemble, can be made into a small hydrogen source, or combined into a large mobile or fixed hydrogen source.
  • the invention can indirectly electrolyze water, successively generate oxygen and hydrogen, and respectively pass into the internal combustion engine, and directly electrolyze oxygen to generate oxygen and hydrogen.
  • the hydrogen-oxygen mixed gas is safer into the internal combustion engine, and can pass a larger amount of oxygen. With hydrogen.
  • the invention can achieve the energy-saving and pollution-reducing effect similar to the hybrid power without the expensive battery pack, the power electronic device and the electric motor, and the cost is greatly reduced, the installation is convenient, and the popularization is easy.
  • the invention is particularly applicable to internal combustion engines, and can also be applied to other fields such as electric energy storage, combustion promotion, and water-to-electrolysis to produce oxygen and hydrogen.
  • Figure la is a vertical placement and installation method of the hydrogen storage hydrogen storage unit
  • Figure lb shows the electrode horizontal placement and installation method of the hydrogen storage hydrogen storage unit
  • 2a is a schematic view showing the assembly of components of a hydrogen filter hydrogen storage unit group of a pressure filter type sealing structure
  • Figure 2b is a schematic view of the unit of the pressure filter sealing structure of Figure 2a;
  • FIG. 3 is a diagram showing an example of an electrochemical zinc-water hydrogen storage system. detailed description
  • the electrochemical zinc-water hydrogen hydrogen storage system of the invention installs an electrochemical zinc-water hydrogen storage system composed of an electrodeposited zinc electrode-electrolyte-gassing electrode in a fluid input channel and a fluid output channel.
  • a hydrogen storage hydrogen storage unit is formed, and the fluid passage and the electrode passage of each unit are respectively combined and connected to form a hydrogen storage hydrogen storage unit group, the unit or the unit group is installed with a water supply passage, and the gas-liquid separation device is connected.
  • the electrolyte storage container and the pump are connected to form a system; when discharging hydrogen, the gassing electrode is connected to the negative electrode of the external power source, the zinc electrode is connected to the positive electrode of the external power source, and the direct current is applied, and each electrodeposited zinc electrode-electrolyte-gassing
  • the external voltage on the electrochemical system of the electrode composition is less than 500 millivolts.
  • a hydrogen storage hydrogen storage unit a zinc electrode and a gas separation electrode are separated into an electrolyte to form a unit of an electrochemical zinc-water hydrogen storage system.
  • the system of the present invention employs an electrodeposited zinc electrode, and only a current collector of a zinc electrode is installed, and a divalent zinc compound is provided as a zinc source substance in an aqueous solution electrolyte, and can be dissolved or partially dissolved.
  • When charging hydrogen storage connect the zinc electrode to the negative electrode of the DC external power supply, connect the gas electrode to the positive electrode, and pass the direct current.
  • the positive divalent zinc gets the electrons into the current collector of the zinc electrode deposited on the zinc electrode.
  • the metal zinc passes through the outside. The circuit loses electrons and is converted to a positive divalent zinc compound back into the electrolyte, thus circulating.
  • One unit of an electrochemical zinc-water hydrogen storage system composed of an electrodeposited zinc electrode-electrolyte-gassing electrode or a plurality of units connected in series or in parallel or series-parallel connection through electrodes, installed in a fluid input channel
  • the fluid output channel and the sealed container of the electrode channel constitute a hydrogen storage hydrogen storage unit.
  • the electrode is placed vertically: In Figure la, an example is shown in which two units connected in parallel form a hydrogen production unit.
  • the gas-dissolving electrode 1 is processed (for example, bent) such that each vertical surface is closed to the lower horizontal plane, and the upper opening is shaped like an upper open box.
  • the gas-dissolving electrode 1 is made of a porous material, and the electrolyte is poured through the fluid input channel 7. In the sealed container, the gassing electrode 1 and the zinc electrode 2 can be immersed through the micropores of the gassing electrode 1.
  • the gas-dissipating electrode 1 surrounds the zinc electrode 2 from the lower horizontal plane and each vertical surface, so that the zinc particles falling on the zinc electrode 2 during charging, discharging, and the like are larger than the micropores of the gas-sparing electrode 1. , can only fall on the gassing electrode 1, the zinc particles contact the gassing electrode 1 will react to lose electrons, and the oxidation product converted into zinc returns to the electrolyte, and the gassing electrode 1 surrounding the zinc electrode 2 is thus eliminated. The role of falling zinc particles. This way, it is convenient for small capacity shallow filling and shallow.
  • the sealed container 5 has an electrolyte 6 , a fluid input channel 7 , and a fluid output channel 8 .
  • the inner wall of the gassing electrode 1 may be lined with a membrane 4 , and a gas barrier or separator 3 is disposed between the gas separation electrode 1 and the zinc electrode 2 . It is fixed to the inner wall of the gas-dissipating electrode 1, and the upper end of the gas-sparing electrode 1 is connected to the external power source of the container 5; the upper end of the zinc electrode 2 is connected to the external power source of the container 5. At least one unit of electrochemical system or a plurality of units connected by a combination of electrode strings, parallel or series-parallel connection may be installed.
  • a gas-dissolving electrode 1 is arranged on the upper part and a zinc electrode 2 is arranged in the lower part, and only one electrochemical system unit is installed in each container to form a hydrogen-storing hydrogen storage unit.
  • the zinc particles dropped during charging and discharging can only fall on the lower zinc electrode 2. In this way, it is convenient to increase the capacity, and it is also convenient to adopt a bipolar laminated structure to reduce the volume.
  • Hydrogen storage hydrogen storage unit group Each unit is connected in series or in parallel or in series and parallel by a fluid passage, and the electrodes are connected by series or parallel or series and parallel connection of the electrode passages to form a hydrogen storage hydrogen storage unit group.
  • the structure of the different sealed containers 5 is similarly connected, and the filter-type sealing structure constitutes a hydrogen storage hydrogen storage unit group.
  • the hydrogen storage hydrogen storage unit group is a pressure filter type sealing structure, as shown in Fig. 2a: On the sealing material, such as a rubber sheet, the center is cut square (or rectangular) to form an intermediate transparent filter plate 9, the pressure filter plate 9 A groove or a hole is formed in the partition plate 10 and the end plate 11 to form a fluid input passage 7 and a fluid output passage 8. A plurality of filter plates 9 and a plurality of separators 10 are sandwiched between the two end plates 11 and aligned, and pressed together to form a hydrogen storage hydrogen storage unit group composed of a plurality of sealed containers in which fluid passages communicate.
  • Each container may be equipped with one or more electrodeposited zinc electrodes placed vertically with the electrode 2 - electrolyte 6 - gassing electrode 1 composed of electrochemical system units, or an electrochemical system unit with an electrode placed horizontally.
  • Example 2a, 2b is installed in each container with an electrochemical system unit, without the diaphragm 4, the gassing electrode 1 and the zinc electrode 2 current collector are cut into an E shape by a spacer or a spacer 3 and rubber or plastic (clockwise) The spacers 12 of the 90 degree corner are separated. Only three hydrogen-making hydrogen storage units are drawn, and each unit has three laminated filter plates 9, which can be increased or decreased in practical applications.
  • the gas-dissolving electrode and the zinc electrode respectively protrude from the upper part, and are used for connecting an external circuit to form a hydrogen-storing hydrogen storage unit; a plurality of units are screwed with a screw 13 and a nut 14, and a partition 10 is used between the units.
  • a parallel fluid channel is formed, and each electrochemical unit forms an electric passage through the parallel connection of the electrodes extending in the upper part, that is, the hydrogen-making hydrogen storage unit group constituting the pressure filter type sealing structure.
  • the spacing between the zinc electrode 2 and the gassing electrode 1 is set according to the capacity requirement (generally in the range of 1 mm to 30 mm; this embodiment can be respectively: lmm, 5 mm, 10 mm, 15 mm, 20 mm, 25 mm, 30 mm (here is an example) To support the protection range)) and the number of layers of the filter plate 9, the number of hydrogen storage units is set according to the amount of hydrogen required per unit time; according to the total area of the gas separation electrode, one unit of hydrogen can be calculated per unit time. Quantity, such as: When the external power source is dragged and discharged, the hydrogen production current on the gassing electrode 1 per square centimeter is between 10 mA and 200 mA.
  • the amount of hydrogen produced is about 0.07 ml/min to 1.4 ml/min.
  • the hydrogen production current is 50 mA per square centimeter of the gassing electrode corresponding to about 0.35 ml/min to calculate the hydrogen production amount, and one unit time is determined. After the unit produces hydrogen, the total hydrogen production per unit time is divided by the unit hydrogen production per unit time.
  • Hydrogen storage hydrogen storage system The fluid input channel of the above hydrogen production hydrogen storage unit or unit group, and the fluid output passage is connected with an electrolyte storage container and a pump connected with a water supply passage, a gas-liquid separation device, and a pump.
  • the hydrogen storage hydrogen storage unit or unit group 15 is a sealed structure having a fluid input passage 7 at its upper end, and a fluid output passage 8 connected to the electrolyte storage container 16, respectively, in the electrolyte storage container 16 and the fluid input.
  • the pump 19 is placed between the passages 7 to be powered, and constitutes an electrolyte closed circulation system.
  • a water supply passage 17 and a gas-liquid separation device 18 are respectively mounted on the electrolyte storage container 16.
  • a hydrogen absorbing metal mesh or sheet 21 is disposed at the bottom of the electrolyte storage container 16 for eliminating zinc particles carried by the circulating electrolyte 6. The dropped zinc particles contact the metal mesh or sheet 21 having a hydrogen evolution function to lose electrons and convert to zinc.
  • the oxidation product is returned to the electrolyte.
  • a filter 23 can be installed in front of the pump.
  • the electrolyte 6 is intermittently or continuously circulated throughout the system, so that the concentration of the electrolyte 6 is uniform, and the polarization resistance of the electrode reaction is weakened, so that the zinc deposition is more uniform and the capacity is increased.
  • the gas-dissolving electrode 1 adopts an electrode for hydrogen evolution and oxygen evolution, and a nickel foam flat sheet, a porous nickel sheet or a metal steel which is coated with a nickel or the like having a strong hydrogen evolution and oxygen evolution function may be used. , iron, nickel mesh, porous tape, porous sheet, porous sheet, metal foam, made of a single or multiple pieces.
  • the hydrogen evolution metal mesh or sheet 21 may be a nickel foam flat sheet coated with a nickel or the like having a strong hydrogen evolution and oxygen evolution function, a porous nickel sheet or a mesh made of metal steel, iron or nickel, a porous belt, or a metal foam. Wait.
  • the zinc electrode 2 current collector is made of a metal mesh or a metal strip or the like, such as a copper mesh or a belt; it can be formed by electroplating or composite plating on the surface of the conductor, such as a lead-plated or tin-plated punched brass strip, brass. Net, foam brass, etc.
  • Separate mesh or spacer 3 non-conductor cheap materials resistant to electrolyte corrosion, such as plastic mesh or sheet of polytetrafluoroethylene, polyethylene, polypropylene, or rubber with alkali-resistant electrolyte.
  • the separator 4 material needs good ionic conductivity and lyophilicity.
  • Various battery separators or other alkali-resistant, long-life and inexpensive materials such as polyethylene felt, zirconia fiber paper, vinylon non-woven fabric, nylon cloth, etc. can be selected. , or a combination thereof (eg: cascading combination).
  • the electrolyte 6 is an alkaline aqueous solution having a pH of more than 4 and a concentration of 0.05 Mol/L to 15 Mol/L, preferably an aqueous solution of potassium hydroxide or sodium hydroxide or a mixture thereof, or an alkali metal or alkaline earth metal carbonate.
  • An aqueous solution of a sulfate or a fluoride salt or a mixture thereof, and a positive divalent zinc compound is added to the electrolyte 6 as a zinc source material, and the zinc compound is generally a solution having a concentration greater than 0.1 mol/L or a supersaturated solution with a precipitate.
  • the fluid input channel 7, the fluid output channel 8, and the sealed container 5 can be made of materials resistant to electrolyte corrosion, such as plastics such as polyethylene and polypropylene, or rubber materials resistant to alkaline electrolytes.
  • the end plate 11 is made of a hard plate such as a metal plate or a glass plate.
  • the separator 10 may be a hard plate such as a glass plate or a rubber or plastic material.
  • the sealing container 5 can be prepared by a sealing structure in the form of plastic welding or the like, or a pressure filter type sealing structure commonly used in the chemical industry, that is, a space is processed in the middle of the sealing material, and a sealed container is formed by pressing with a hard plate. Easy to assemble and disassemble.
  • the system uses: first open the water supply valve 20 of the electrolyte storage container 16, replenish water from the water supply channel 17, winter The cold weather can be directly supplemented with crushed ice, and the water replenishing valve 20 is closed after the water is replenished.
  • the pump 19 is used to circulate the electrolyte 6.
  • the negative electrode of the external power supply is connected to the zinc electrode 2
  • the positive electrode of the external power source is connected to the gas-dissolving electrode 1, and the direct current is applied to the voltage of the electrochemical system unit composed of each zinc electrode-electrolyte-gassing electrode.
  • the positive divalent zinc compound in the solution obtains electrons on the zinc electrode 2 current collector, is reduced to zinc, undergoes electrodeposition, and the zinc layer gradually grows; on the gassing electrode 1 A water-related oxidation reaction occurs, generating oxygen, which is discharged through the fluid output passage 8, the gas-liquid separation device 18, and the outlet passage 22.
  • the zinc electrode and the gas-sparing electrode can be connected to each other through an external circuit to produce hydrogen.
  • an external power source can be used to discharge and discharge, that is, opposite to the electrode connection during charging.
  • the zinc electrode 2 is connected to the positive electrode of the external power source, and the gassing electrode 1 is connected to the negative electrode of the external power source, and the direct current is applied, and the electrochemical system unit composed of each electrodeposited zinc electrode-electrolyte-evaporation electrode is used.
  • the external voltage is within 500 millivolts (eg, 450 millivolts, or 300 millivolts), and the drag system produces a larger hydrogen production current.
  • the power consumed by hydrogen production is equivalent to about one-twentieth to one-fifth of the charging energy, and the hydrogen production per unit time can be increased by about ten times.
  • the hydrogen production per unit time has a good correspondence with the hydrogen production current.
  • the unit current per ampere of each electrochemical system unit corresponds to about 7 ml/min of hydrogen production at normal temperature and pressure.
  • Charge capacity control It can be used to control charging time, power, voltage and current.
  • the electrolyte is continuously circulated, and a radiator can be installed in the fluid input channel 7, the fluid output channel 8, the electrolyte storage container 16, etc.; when the current and heat dissipation are small, the cycle can be intermittently performed.
  • the system and the generator of the present invention When used in conjunction with an internal combustion engine, the system and the generator of the present invention are installed beside the internal combustion engine, and a simple control device; the outlet passage 22 of the system is connected to the internal combustion engine via the pipeline; and the excess mechanical energy of the internal combustion engine is converted into electric energy by the generator.
  • the converted electric energy is used to charge the hydrogen storage system of the electrochemical zinc-water hydrogen storage system, and then the hydrogen is discharged into the internal combustion engine for co-firing; the oxygen generated during the hydrogen storage can also be further ignited into the internal combustion engine.
  • the internal combustion engine When the workload demand is low (such as less than 50%), including idle speed, let the internal combustion engine work to drive the generator at the same time, increase the load rate of the internal combustion engine, convert the excess mechanical energy beyond the workload requirement into electrical energy, and then use the converted
  • the electric energy is charged to the electrochemical zinc-water hydrogen storage hydrogen storage system, and the oxygen generated during charging is introduced into the internal combustion engine to ignite, so that the charging is performed for several tens of seconds to several minutes; then, the discharge hydrogen is produced by the discharge for several tens of seconds to several minutes.
  • Hydrogen is introduced into the internal combustion engine to cooperate with the fuel combustion; such shallow filling and shallow release, so repeated cycles.
  • the above operation allows the internal combustion engine to drive the generator at the same time.
  • the internal combustion engine is directly connected to the generator.
  • the generator needs to be connected to the internal combustion engine through the clutch.
  • the generator is disconnected from the internal combustion engine through the clutch, and is connected with the transmission system to convert excess mechanical energy such as braking, deceleration, and downhill of the vehicle into electric energy storage, and then Hydrogen is produced by electric discharge, and hydrogen is supplied to the internal combustion engine to be combusted with hydrocarbon fuel.
  • the following examples all employ a pressure filter type sealing structure, as shown in Fig. 2a, a 3 mm thick rubber plate for the filter plate 9 and the separator 10, and a 7 mm thick plexiglass plate for the end plate 11.
  • the gassing electrode 1 is a flattened foamed nickel sheet.
  • Each hydrogen production hydrogen storage unit of the filter-type sealing structure is installed with only one electrochemical system unit.
  • the unit or unit group is connected to a 500 ml electrolyte storage bottle and a constant flow pump.
  • the electrolyte storage bottle is connected to a 250 ml gas wash bottle for gas-liquid separation, and the gas cylinder is connected to a gas output tube to form a system.
  • Example 1 A hydrogen-making hydrogen storage unit with electrodes placed vertically: an 80-mesh tin-plated brass mesh is used as a zinc electrode 2 current collector, and a 10-mesh polyethylene mesh is a mesh net 3, which is separated by a space of 2 mm, and is grafted with polyethylene.
  • the membrane was a membrane 4, and the electrolytic solution 6 was an aqueous solution (mass concentration) containing 4% zinc oxide and 33% potassium hydroxide, and the gassing electrode area was 16 cm 2 , and the electrolytic solution was intermittently circulated.
  • Test 1 Constant current 0.8A charging, charging time 5-6 minutes, voltage 2.1-2.5 volts; no external voltage, only the gassing electrode and zinc electrode in the external circuit through the multimeter 20 current discharge discharge hydrogen, 30 minutes Finish. Such charging and discharging are repeated ten times repeatedly.
  • Test 2 Constant current 0.8 A charging, charging time 8 minutes, voltage 2.1-2.5 volts; drag discharge 0.8 amps, discharge time 6 minutes, each cell voltage minus 50-180 mV, negative voltage during discharge means external power supply Drag and discharge.
  • the amount of oxygen released during charging is small, and the amount of hydrogen discharged during discharge is significantly increased.
  • the amount of hydrogen produced can reach about 5 ml per minute.
  • Example 2 A hydrogen storage hydrogen storage unit in which the electrode is placed horizontally:
  • the gas separation electrode 1 uses two layers of foamed nickel sheets, the gassing electrode 1 has an effective area of 15 cm 2 , and the 80 mesh tinned brass net is a zinc electrode 2 current collector, and the grid 3
  • An aqueous solution containing saturated zinc oxide, 40% potassium hydroxide, and 1.5% lithium hydroxide (mass concentration) is the electrolyte 6, and the gassing electrode area is per single Yuan 60cm 2 .
  • the hydrogen production current can reach 1.5 to 4.0 amps.
  • the nine hydrogen-storing hydrogen storage unit circuits are connected in series, and eight separators 10 and two end plates 11 are assembled into a unit group by pressure filtration.
  • the circuit between the five unit groups and the fluid passage are connected in series, and the system has a total of gas-dissolving electrodes. With an area of 2,700 square centimeters, the electrolyte is continuously circulated, and the hydrogen storage system uses a small capacity shallow charging method.
  • the total hydrogen production per unit time can reach 0.45 L / min to 1.22 L / min.
  • Example 3 Use the electrochemical zinc-water hydrogen storage system of Example 3 with a gasoline generator with a rated power of 650 watts (commercially available from Shanghai Yanke Engine Company):
  • a tee is installed between the engine carburetor of the gasoline generator and the air inlet, and the three-way is sequentially connected with an anti-tempering device, an air mixer, and a system air outlet passage 22.
  • the AC output end of the generator is connected to the input end of the voltage regulator, and the output end of the voltage regulator is connected to the rectifier bridge.
  • the rectifier bridge is used to connect the electrodes of the hydrogen storage system to deliver DC power to the system.
  • the intake port When the engine is running, the intake port generates a negative pressure, and the oxygen and hydrogen generated by the hydrogen storage hydrogen storage system pass through the system outlet passage 22, respectively, to the air mixer, mix with the air, and are sucked into the gasoline engine intake port through the anti-tempering device. .
  • Test (1) Start the gasoline generator, do not connect the load, do not connect the hydrogen storage system of the present invention, and let it be in an idle state, and measure the fuel consumption rate.
  • Test (2) start the gasoline generator, connect the zinc-water hydrogen storage system of the invention, charge the hydrogen hydrogen storage system, adjust the charging voltage by 110 to 130 volts with a voltage regulator, and generate oxygen into the intake air. Port, measure its fuel consumption rate. Adding oxygen for 3 to 6 minutes alone, the fuel consumption is 5 % to 20 % less than the idle speed.
  • Test (3) follow the test (2), reverse the output, change the current direction, reduce the regulator output voltage, the voltage is negative 6 volts to minus 18 volts, drag the hydrogen storage system to discharge, the generated hydrogen is also passed Enter the air inlet and measure the fuel consumption rate. Hydrogenation alone for 2 to 4 minutes, fuel consumption is 6 to 22% less than idling.
  • Test (4) Start the gasoline generator, connect the zinc-water hydrogen storage system, first charge the hydrogen storage system, adjust the charging voltage from 110 volts to 130 volts with a voltage regulator, and charge the oxygen for 3 minutes.
  • the produced oxygen is introduced into the air inlet, and then immediately reverses the output end, changes the current direction, lowers the voltage, and drags the voltage minus 6 volts to minus 18 volts (negative voltage indicates drag discharge), dragging zinc-water
  • the hydrogen production hydrogen storage system discharges hydrogen, and the hydrogen gas is introduced into the air inlet.
  • the time for charging hydrogen production is 2 minutes. This is repeated charging and discharging, alternately generating oxygen and hydrogen, respectively, and passing into the engine air inlet to measure the fuel consumption rate. As a result, the fuel consumption during alternating oxygenation is 6% to 15% lower than that at idle.
  • the hydrogen quality of the hydro-combustion co-firing accounts for 0.1%-5% of the total mass of the fuel consumed by the internal combustion engine.
  • the hydrogen consumption per unit time can be determined according to the fuel consumption rate per unit time of the internal combustion engine, and the total hydrogen production range per unit time can be converted. Through the estimation or experiment of the gas-dissolving electrode area of each hydrogen-storing hydrogen storage unit, after determining the hydrogen production amount per unit time, the total hydrogen production per unit time is divided by the hydrogen production amount per unit time to determine the hydrogen storage hydrogen storage system unit. number. As shown in Example 4, the fuel consumption rate of the gasoline generator with rated power of 650 watts is determined to be 5.55 g/min.
  • the calculation of 0.056 g of hydrogen per minute is 1% of the total mass of the fuel plus hydrogen, and the amount of hydrogen produced per unit time at a normal temperature and pressure of about 627 ml/min.
  • Example 3 The gas-discharging electrode area of each hydrogen-storing hydrogen storage unit is 60 cm 2 , and the hydrogen current is generally about 0.35 ml/min per 50 cm of the gas-dissolving electrode per square centimeter, which is calculated as a hydrogen production amount per unit time of about 21 ml/min.
  • 941 divided by 21 is equal to 45, it is estimated that 45 hydrogen storage units need to be installed; 9 hydrogen storage units are installed in series, and 5 groups are connected in series with 45 hydrogen storage units.
  • the amount of hydrogen produced can reach 0.45 liters / minute to 1.22 liters / minute.
  • the gasoline generator in the idle state in Example 4 can be supplied with a mass fraction of about 0.72% to 1.95% of hydrogen-combusted fuel.

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Abstract

L'invention porte sur un système électrochimique comprenant Zn et H2O pour produire et stocker de l'hydrogène, dans lequel système une électrode, obtenue par électrodéposition de Zn sur le collecteur de courant, est utilisée comme collecteur de courant de l'électrode de Zn. Le collecteur de courant de l'électrode de Zn et une électrode de libération de gaz sont disposés de façon séparée dans un électrolyte aqueux contenant un composé de zinc, ce par quoi une unité de système électrochimique pour produire et stocker de l'hydrogène peut être construite. L'unité de système électrochimique pour produire et stocker de l'hydrogène peut être disposée dans un récipient hermétiquement scellé dans lequel un passage d'entrée de liquide, un passage de sortie de liquide et un passage pour supporter une électrode peuvent être réservés. Dans le système, le passage d'entrée de liquide et le passage de sortie de liquide sont reliés à une protubérance et au récipient d'électrolyte, dans lequel un passage de remplissage en eau est disposé, et un séparateur gaz-liquide est relié. La plage de la distance entre ledit collecteur de courant de l'électrode de Zn et l'électrode de libération de gaz est de 1 mm à 30 mm. Le système peut être utilisé pour produire de façon considérable et périodique de l'hydrogène à moindre coût, et il a une longue durée de vie. Le système peut être réalisé sous une plus grande taille de façon commode, et utilisé dans un moteur à gaz pour économiser de l'essence et diminuer la décharge, et il peut également être utilisé dans l'autre domaine de stockage d'énergie et de facilitation de combustion.
PCT/CN2009/071251 2008-04-17 2009-04-13 Système électrochimique comprenant du zinc et de l'eau pour produire et stocker de l'hydrogène, et son utilisation Ceased WO2009127145A1 (fr)

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FR3079530A1 (fr) * 2018-04-03 2019-10-04 Ergosup Procede electrochimique de production d'hydrogene gazeux sous pression par electrolyse puis par conversion electrochimique
WO2020141975A1 (fr) 2018-12-31 2020-07-09 Technische Universiteit Delft Cellule électrolytique pour la génération de h2
US20230126106A1 (en) * 2021-10-21 2023-04-27 BST Systems, Inc. Electrolyzer for spontaneously generating hydrogen and a method for implementing same
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US20230366106A1 (en) * 2022-05-11 2023-11-16 Nooter/Eriksen, Inc. Hydrogen generation and chemical energy storage

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US11031189B2 (en) * 2018-01-17 2021-06-08 Chao Huang Aqueous hybrid super capacitor
WO2021173079A1 (fr) * 2020-02-25 2021-09-02 Nanyang Technological University Batterie pneumatique électrochimique
CN113737219B (zh) * 2021-08-31 2024-06-21 王国经 用于电解制氢防混合的装置
CN116161617A (zh) * 2023-02-21 2023-05-26 上海氢栖科技有限公司 一种制氢装置及氢能电源

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CN111108061B (zh) * 2017-06-27 2023-04-04 萨里大学 氢气发生器
WO2019002841A1 (fr) * 2017-06-27 2019-01-03 University Of Surrey Générateur d'hydrogène
CN111108061A (zh) * 2017-06-27 2020-05-05 萨里大学 氢气发生器
US11447879B2 (en) 2017-06-27 2022-09-20 University Of Surrey Hydrogen generator
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FR3079530A1 (fr) * 2018-04-03 2019-10-04 Ergosup Procede electrochimique de production d'hydrogene gazeux sous pression par electrolyse puis par conversion electrochimique
WO2020141975A1 (fr) 2018-12-31 2020-07-09 Technische Universiteit Delft Cellule électrolytique pour la génération de h2
CN113454268A (zh) * 2018-12-31 2021-09-28 巴托莱瑟私人公司 用于h2产生的电解池
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US20230126106A1 (en) * 2021-10-21 2023-04-27 BST Systems, Inc. Electrolyzer for spontaneously generating hydrogen and a method for implementing same
US12492481B2 (en) * 2021-10-21 2025-12-09 BST Systems, Inc. Electrolyzer for spontaneously generating hydrogen and a method for implementing same
WO2023067164A1 (fr) * 2021-10-22 2023-04-27 Ergosup Systeme electrochimique et procede de production d'hydrogene par electrolyse de l'eau decouplee, comportant une etape de desoxygenation de l'electrolyte
FR3128589A1 (fr) * 2021-10-22 2023-04-28 Ergosup Système électrochimique et procédé de production d’hydrogène par électrolyse de l’eau découplée, comportant une étape de désoxygénation de l’électrolyte
US20230366106A1 (en) * 2022-05-11 2023-11-16 Nooter/Eriksen, Inc. Hydrogen generation and chemical energy storage

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