CN101560668A - Electrochemical zinc-water hydrogen production and storage system and applications thereof - Google Patents
Electrochemical zinc-water hydrogen production and storage system and applications thereof Download PDFInfo
- Publication number
- CN101560668A CN101560668A CNA2008100110487A CN200810011048A CN101560668A CN 101560668 A CN101560668 A CN 101560668A CN A2008100110487 A CNA2008100110487 A CN A2008100110487A CN 200810011048 A CN200810011048 A CN 200810011048A CN 101560668 A CN101560668 A CN 101560668A
- Authority
- CN
- China
- Prior art keywords
- hydrogen
- zinc
- electrode
- electrochemical
- storage system
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention relates to an electrochemical zinc-water hydrogen production and storage system which adopts an electrodeposited zinc electrode. The electrochemical zinc-water hydrogen production and storage system is characterized in that a zinc electrode current collector and a gas-separating electrode are separated and put in an electrolyte, and a positive-divalent zinc compound exists in an aqueous solution of the electrolyte to be a zinc source substance so as to form a unit of the electrochemical zinc-water hydrogen production and storage system which comprises the electrodeposited zinc electrode, the electrolyte and the gas-separating electrode and is mounted in a sealing container to form hydrogen production and storage units; the units or a unit group is connected with an electrolyte storage container and a pump to form the system, and the electrolyte storage container is provided with a water-supplementing passage and connected with a gas-liquid separating device. When hydrogen is produced by electric discharge, the gas-separating electrode is connected with a negative electrode of an external power supply, the zinc electrode is connected with a positive electrode of the external power supply, and a direct current is switched on so that an external voltage of each electrodeposited system unit is smaller than 500 millivolts. The system can circularly produce a great amount of hydrogen at low cost, has prolonged service life, is convenient to linearly amplify and can be used for matching with the oil saving and the emission reduction of internal-combustion engines and other oil-storing and combustion-promoting fields.
Description
Technical field
The present invention relates to a kind of hydrogen production and storing technology, electrochemical zinc-water hydrogen production and storage system and the application that cooperates with oil engine thereof.
Background technology
The applicant in first to file, electrochemical zinc-water hydrogen production and storage method (200510046374.8, publication number CN1854063A), a kind of cheapness, convenience, reusable hydrogen-preparing hydrogen-storing method have been introduced, this method realizes by the electrochemical system that zinc electrode-electrolytic solution-gassing electrode constitutes, when needing storage hydrogen, the external power negative pole is connected on zinc electrode, the external power positive pole is connected on the gassing electrode, pass to direct current, the reduction reaction of zinc takes place, on the gassing electrode on the zinc electrode, the oxidizing reaction that relates to water generates oxygen and discharges; During hydrogen, connect gassing electrode and zinc electrode, on the zinc electrode, the oxidizing reaction of zinc takes place, on the gassing electrode, the reduction reaction of water takes place, generate hydrogen and discharge at external circuit.If zinc electrode is the powder porous electrode in the industry of employing conventional batteries, perhaps the metallic zinc galvanic deposit is flattened the fixed electrodeposited electrode again on the collector of zinc electrode, very big energy density is arranged, can be for fuel cell provide hydrogen source, but technical indicators such as its life-span, cost and hydrogen output distance still has bigger gap with needed hydrogen sources in energy storage field such as oil engine cooperate.
Oil engine is the fuel economy difference under different load rate operating mode, and in general, equal fuel is burnt more abundant when High Load Rate, sends more mechanical energy.Adopt accumulator system to cooperate with oil engine, can be when the working load demand be low, allow oil engine drive accumulator system simultaneously, improve the rate of load condensate of oil engine, store utilization with satisfying mechanical energy unnecessary outside the working load demand, in addition, the excess energies such as descending of the braking of the vehicles, deceleration, vehicle also can be recycled by accumulator system.As the oil electric mixed dynamic technology, unnecessary mechanical energy is converted into electrical power storage in secondary battery, suitably situation promotes vehicle with the electric energy that stores, but fuel-economizing 7%-40%; But secondary battery, high-power electric device cost an arm and a leg, and make it to popularize difficulty.During actual road surface sport car, adding massfraction to oil engine is about 4% hydrogen, and fuel-economizing 30-40% pollutes significantly and reduces; But present traditional hydrogen storage technology can not mix the hydrogen source that combustion is provided convenience for the oil engine hydrogenation.
Summary of the invention
The purpose of this invention is to provide a kind of electrochemical zinc-water hydrogen production and storage system, the big volume production hydrogen that can circulate inexpensively, long service life, easy linear amplification can be realized the application that cooperates with oil engine.
Electrochemical zinc-water hydrogen production and storage system of the present invention, it is characterized in that: a zinc electrode collector and a gassing electrode separation are opened in the electrolytic solution, it is zinc source material that positive divalent zinc compound is present in the aqueous electrolysis liquid, constitutes a unit of electrochemical zinc-water hydrogen production and storage system; At least one electrochemical zinc-water hydrogen production and storage system unit is installed in the sealed vessel of reserving fluid input channel, fluid output channel, electrode channel, or, constitute a hydrogen-preparing hydrogen-storing unit through a plurality of units that electrode serial or parallel connection or series-parallel connection are connected; Again with each unitary fluid input channel, fluid output channel, electrode channel respectively serial or parallel connection or series-parallel connection be connected, constitute hydrogen-preparing hydrogen-storing unit group; The fluid input channel of hydrogen-preparing hydrogen-storing unit or unit group, fluid output channel and the moisturizing passage is installed, the electrolytic solution storage vessel and the pump that are connected gas-liquid separation device connect and compose system; According to the interval of capacity requirement setting zinc electrode and gassing electrode, set hydrogen-preparing hydrogen-storing unit number according to unit time hydrogen manufacturing amount; During discharge hydrogen manufacturing, the gassing electrode is connected the external power negative pole, zinc electrode connects the positive pole of external power, and logical direct current is within 500 millivolts at the external voltage in each electrochemical system unit.
System of the present invention cooperates the application of oil engine: the outlet passageway of system is joined with oil engine by the road, and be connected with generator as power supply; Fashionable with the internal combustion engine generator assembly, oil engine directly is connected with generator, and the oil engine of the vehicles needs generator to be connected with oil engine and transmission system by clutch coupling or to disconnect; Unnecessary mechanical energy when utilizing internal combustion engine is converted into electric energy storage hydrogen, the hydrogen manufacturing of discharging again, and the hydrogen that feeds massfraction 0.1%-5% to oil engine cooperates hydrocarbon fuel combustion; The oxygen that produces during rechargeable hydrogen storage also can feed the further short combustion of oil engine.
Advantage of the present invention:
System of the present invention adopts galvanic deposit formula zinc electrode, only needs to install the collector of zinc electrode, and processing is simple, and is with low cost, do not have the deformation and the capacity attenuation problem of conventional batteries electrode, and lifetime of system is longer than conventional secondary battery far away.The easy linear amplification of native system can be with tens, up to a hundred hydrogen-preparing hydrogen-storing unit connect through series and parallel or series-parallel connection array configuration, partly constitute the hydrogen-preparing hydrogen-storing system with circulation of elecrolyte, and product hydrogen in a large number can circulate; Dismounting, combined and instant can be made into small-sized hydrogen source, and one-tenth also capable of being combined is large-scale moves or fixing hydrogen source.The water indirect electrolytic successively can be produced oxygen and hydrogen, feed oil engine respectively, than the direct electrolysis of water is produced oxygen and hydrogen, it is safer that logical knallgas is gone into oil engine, and can feed more substantial oxygen and hydrogen; Do not need expensive secondary battery, power electronic device and electric motor, just can reach the similar energy-saving and pollution-reducing effect of hybrid power, cost reduces greatly, and convenient the installation is easy to popularize.Can also be applied to other power storage, promote burning, the water indirect electrolytic produces oxygen and field such as hydrogen.
Description of drawings
Fig. 1 a is that the unitary electrode of hydrogen-preparing hydrogen-storing is vertically placed mounting means;
Fig. 1 b is the unitary electrode horizontal positioned of a hydrogen-preparing hydrogen-storing mounting means;
Fig. 2 a is the part combination synoptic diagram of press filter type sealed structure hydrogen-preparing hydrogen-storing unit group;
Fig. 2 b is the cell schematics of press filter type sealed structure among Fig. 2 a;
Fig. 3 is the electrochemical zinc-water hydrogen production and storage system exemplary plot;
Embodiment
Electrochemical zinc-water hydrogen production and storage system of the present invention, it is characterized in that the electrochemical zinc-water hydrogen production and storage system that galvanic deposit formula zinc electrode-electrolytic solution-gassing electrode is formed is installed in the container of reserving fluid input channel, fluid output channel, electrode channel, constitute the hydrogen-preparing hydrogen-storing unit, each unitary fluid channel, electrode channel are connected respectively, constitute hydrogen-preparing hydrogen-storing unit group, unit or unit group with the moisturizing passage is installed, the electrolytic solution storage vessel and the pump that connect gas-liquid separation device connect and compose system; During discharge hydrogen manufacturing, the gassing electrode is connected the external power negative pole, zinc electrode connects the positive pole of external power, logical direct current, and the external voltage in the electrochemical system unit that each galvanic deposit formula zinc electrode-electrolytic solution-gassing electrode is formed is less than 500 millivolts.Specify as follows:
(1) hydrogen-preparing hydrogen-storing unit a: zinc electrode and a gassing electrode separation are opened in the electrolytic solution, just constitute a unit of electrochemical zinc-water hydrogen production and storage system.System of the present invention adopts galvanic deposit formula zinc electrode, the collector of zinc electrode only is installed, it is zinc source material that positive divalent zinc compound is present in the aqueous electrolysis liquid, during rechargeable hydrogen storage zinc electrode connected direct current external power negative pole, the gassing electrode connects anodal, pass to direct current, positive divalent zinc obtains electronics and becomes on the collector that metallic zinc is deposited on zinc electrode; During discharge hydrogen manufacturing, metallic zinc loses electronics by external circuit, is converted into positive divalent zinc compound and gets back in the electrolytic solution, so circulation.
Unit of the electrochemical zinc-water hydrogen production and storage system that galvanic deposit formula zinc electrode-electrolytic solution-gassing electrode is formed or a plurality of units that are connected through electrode serial or parallel connection or series-parallel connection, be installed in the sealed vessel of reserving fluid input channel, fluid output channel, electrode channel, constitute a hydrogen-preparing hydrogen-storing unit.
The electrode mounting means has two kinds in the unit, and a kind of is vertically to place electrode, and as Fig. 1 a, a kind of is the horizontal positioned electrode, as Fig. 1 b.
Electrode is vertically placed: among Fig. 1 a, be two units in parallel to be installed constitute the unitary example of hydrogen-preparing hydrogen-storing.Gassing electrode 1 is processed or is bent into each vertical plane and links to each other with the lower horizontal plane sealing, the shape of upper opening, the box of a picture upper opening, gassing electrode 1 adopts porous material, electrolytic solution is fed in the sealed vessel by the fluid input channel, can see through the micropore of gassing electrode 1, soak gassing electrode 1 and zinc electrode 2, zinc electrode generally adopts planeform, gassing electrode 1 surrounds zinc electrode 2 from lower horizontal surface and each vertical plane, make in charging, the zinc particle that drops on the zinc electrode 2 in the processes such as discharge, because of micropore greater than gassing electrode 1, can only drop on the gassing electrode 1, zinc particle contact gassing electrode 1 can lose electronics, and the oxidation products that is converted into zinc is got back in the electrolytic solution, and the gassing electrode 1 that surrounds zinc electrode 2 plays the zinc particulate effect of dropping of eliminating.This mode is convenient to that low capacity is shallow to fill shallow situation of putting.Electrolytic solution 6 is arranged in the sealed vessel 5, and fluid input channel 7, fluid output channel 8 are arranged, gassing electrode 1 inwall can be lined with barrier film 4, and filter or partition 3 are arranged between gassing electrode 1 and the zinc electrode 2, its end face and gassing electrode 1 inwall are fixed, and gassing electrode 1 upper end links to each other with container 5 external powers; Zinc electrode 2 upper ends link to each other with container 5 external powers.A plurality of units that at least one electrochemical system unit or process electrode series and parallel or series-parallel connection array configuration connect can be installed.
Electrode horizontal positioned: see Fig. 1 b, it is characterized in that establishing gassing electrode 1, zinc electrode 2 is established in the bottom, and an electrochemical system unit only is installed in each container, constitutes a hydrogen-preparing hydrogen-storing unit in each sealed vessel 5 inside.The zinc particle that drops in charging, discharge process can only drop on zinc electrode 2 places of bottom.This mode is convenient to the increase capacity, and the also convenient bipolar system rhythmo structure that adopts reduces volume.
(2) hydrogen-preparing hydrogen-storing unit group: by the fluid channel with each unit respectively serial or parallel connection or series-parallel connection be connected, electrode is connected through serial or parallel connection or series-parallel connection respectively by the electrode path, constitutes hydrogen-preparing hydrogen-storing unit group.
Different sealed structure methods of attachment is similar, and it is more simple that the press filter type sealed structure constitutes hydrogen-preparing hydrogen-storing unit group.Press filter type sealed structure hydrogen-preparing hydrogen-storing unit group, shown in Fig. 2 a: on sealing material, as rubber plate, central authorities prescind square or rectangle, wide around forming, centre is empty press filtration plate 9, processes groove or hole on press filtration plate 9, dividing plate 10, the end plate 11 respectively and forms fluid input channel 7, fluid output channel 8.A plurality of press filtration plates 9 and several dividing plates 10, two end plates 11 are alignd, and forcing together forms the hydrogen-preparing hydrogen-storing unit group that a plurality of sealed vessels that the fluid channel communicates are formed.
The vertically electrochemical system unit of galvanic deposit formula zinc electrode 2-electrolytic solution 6-gassing electrode 1 composition of placement of one or more electrodes can be installed in each container, the electrochemical system unit of an electrode horizontal positioned perhaps is installed.
An electrochemical system unit is installed in each container among exemplary plot 2a, the 2b, do not add barrier film 4, gassing electrode 1 and zinc electrode 2 collectors are separated with the partition 12 that filter 3 and rubber or plastics are cut into M shape, and there are three lamination filter plates 9 every unit, and practical application can increase and decrease.Two electrodes stretch out respectively on top among Fig. 2 a, are used to connect external circuit, constitute a hydrogen-preparing hydrogen-storing unit; Several unit are twisted and are compressed with screw rod 13, nut 14, separate with dividing plate 10 between the unit, form fluid channel in parallel, of the electrode array parallel connection of each electrochemistry unit by stretching out respectively on top by figure, form the passage of electricity, promptly constitute the hydrogen-preparing hydrogen-storing unit group of press filter type sealed structure.
Set zinc electrode 2 and the interval of gassing electrode 1 and the number of plies of press filtration plate 9 according to capacity requirement, set hydrogen-preparing hydrogen-storing unit number according to unit time required hydrogen production amount; According to the gassing electrode total area, can approximately calculate unit time unit hydrogen manufacturing amount: when external power drags discharge, hydrogen manufacturing electric current on every square centimeter of gassing electrode 1 is at 10 milliamperes to 200 milliamperes, corresponding at normal temperatures and pressures about 0.07 ml/min is to the hydrogen manufacturing tolerance of 1.4 ml/min, general by the corresponding about 0.35 ml/min calculating of 50 milliamperes of hydrogen manufacturing electric currents of every square centimeter of gassing electrode, after determining unit time unit hydrogen manufacturing amount, total hydrogen manufacturing amount of unit time is the unit number divided by unit time unit hydrogen manufacturing amount.
(3) hydrogen-preparing hydrogen-storing system: the fluid input channel of above-mentioned hydrogen-preparing hydrogen-storing unit or unit group, the fluid output channel with the moisturizing passage is installed, the electrolytic solution storage vessel and the pump that connect gas-liquid separation device connect and compose system.
As shown in Figure 3, hydrogen-preparing hydrogen-storing unit or unit group 15 are sealed vessel, there is fluid input channel 7 its upper end, fluid output channel 8 links to each other with electrolytic solution storage vessel 16 respectively, settling pump 19 between electrolytic solution storage vessel 16 and fluid input channel 7 is power, constitutes the electrolytic solution closed circulation system.Moisturizing passage 17, gas-liquid separation device 18 are installed respectively on the electrolytic solution storage vessel 16.Liberation of hydrogen wire netting or sheet 21 are established in electrolytic solution storage vessel 16 bottoms, are used to eliminate the zinc particle that round-robin electrolytic solution 6 is taken out of, and wire netting or sheet 21 that the zinc particle that drops contact has the liberation of hydrogen function can lose electronics, and the oxidation products that is converted into zinc is got back in the electrolytic solution.Before the pump strainer 23 can be installed.Electrolytic solution 6 can make electrolytic solution 6 concentration homogeneous, and weaken the polarization resistance of electrode reaction in total system discontinuous or circulation continuously, makes zinc deposit more evenly, the increase capacity.
Parts preparation and performance: gassing electrode 1 adopts the double electrode of analysing the oxygen function of liberation of hydrogen, can adopt nickel foam to flatten sheet, nickel porous sheet or on structures such as the net of metallic steel, iron, nickel material, porous belt, porous sheet material, porous sheet, foamed metal nickel plating etc. have the double composition of analysing the oxygen function of stronger liberation of hydrogen and constitute, combine by monolithic or multi-disc.Liberation of hydrogen wire netting or sheet 21 can adopt nickel foam to flatten sheet, nickel porous sheet or on structures such as the net of metallic steel, iron, nickel material, porous belt, foamed metal nickel plating etc. have stronger liberation of hydrogen materials with function and constitute.
Filter or partition 3 adopt electrolyte resistance corrosive non-conductor cheap material, as plastic wire or sheets such as tetrafluoroethylene, polyethylene, polypropylene, or the rubber of alkali resistance electrolytic solution etc.Barrier film 4 materials need have good ionic conductivity and lyophily.Barrier film 4 can be selected various battery diaphragms or other cheap material alkaline-resisting, that the life-span is long, as polyethylene felt, Zirconium oxide fibre paper, vinylon non-woven fabrics, nylon cloth etc., or its combination.
Native system uses: open the water compensating valve 20 of electrolytic solution storage vessel 16 earlier, from 17 moisturizings of moisturizing passage, cold conditions such as winter can directly be replenished trash ice, close water compensating valve 20 after the moisturizing.Drive circular electrolyte 6 with pump 19.When needing storage of hydrogen, the external source negative pole is connected on the zinc electrode 2, the external source positive pole is connected on the gassing electrode 1, pass to direct current, make the voltage of the electrochemical system unit that each zinc electrode-electrolytic solution-gassing electrode forms be greater than 1.66 volts theoretical voltage, be generally less than 3.00 volts, positive divalent zinc compound in the solution obtains electronics on zinc electrode 2 collectors, be reduced into zinc, galvanic deposit takes place, the zinc layer increases gradually; On gassing electrode 1, generation and the oxidizing reaction that water closes generate oxygen, discharge through fluid output channel 8, gas-liquid separation device 18 and outlet passageway 22.
During hydrogen, the reduction reaction at gassing electrode 1 generation water discharges hydrogen, and the oxidizing reaction of zinc takes place on the zinc electrode 2.The oxidation products of zinc is got back to again in the electrolyte solution 6, and hydrogen is discharged through fluid output channel 8, gas-liquid separation device 18 and air outlet valve 22.Electronic component such as available variable resistor or device are regulated discharge hydrogen manufacturing electric current in the external circuit, and the utmost point is controlled hydrogen output easily.Can also obtain bigger hydrogen manufacturing electric current by the method for intermittent discharge, promptly discharge the several seconds, the rest several seconds, so repeatedly, make the polarization of discharge generation weaken.
When needing bigger unit time hydrogen manufacturing amount, can adopt external power to drag the method for discharge, the electrode connection is opposite during promptly with charging, zinc electrode 2 is connected on the positive pole of external power, and gassing electrode 1 is connected on the negative pole of external power, pass to direct current, the external voltage in the electrochemical system unit that each galvanic deposit formula zinc electrode-electrolytic solution-gassing electrode is formed is within 500 millivolts, and dragging system produces bigger hydrogen manufacturing electric current.Drag hydrogen manufacturing institute consuming electric power, be equivalent to about 1/20th to 1/5th of the energy that charges, unit time hydrogen manufacturing amount can increase about ten times.
Unit time hydrogen manufacturing amount hour, amounts of hydrogen and hydrogen manufacturing electric current have good corresponding relation, the corresponding about 7 ml/min hydrogen manufacturing tolerance of the every at normal temperatures and pressures ampere electric current of each electrochemical system unit.
The control of charging capacity: can adopt various ways such as control duration of charging, electric weight, voltage and electric current.
When electric current and heat dissipation capacity are big, continuous circular electrolyte, and can locate to install scatterer at fluid input channel 7, fluid output channel 8, electrolytic solution storage vessel 16 etc.; In electric current and heat dissipation capacity hour, but intermittent cyclic.
During with the oil engine fit applications,, reach simple control device at other system of the present invention and the generator installed of oil engine; The outlet passageway 22 of system is joined with oil engine by the road; Unnecessary mechanical energy during with internal combustion engine is converted into electric energy behind the electrochemical zinc-water hydrogen production and storage system rechargeable hydrogen storage by generator, and discharge hydrogen manufacturing feeds oil engine and mixes combustion; The oxygen that produces during rechargeable hydrogen storage also can feed the further short combustion of oil engine.
When the operation workload demand is low, when comprising idling, allow the oil engine operation drive generator simultaneously, improve the rate of load condensate of oil engine, be converted into electric energy with satisfying mechanical energy unnecessary outside the working load demand, to the electrochemical zinc-water hydrogen production and storage system rechargeable hydrogen storage, the oxygen that produces during charging feeds the short combustion of oil engine, charges tens seconds like this to several minutes; Then, drag discharge hydrogen manufacturing and arrived several minutes in tens seconds, hydrogen feeds oil engine, cooperates fuel combustion; Shallowly like this fill shallow putting, circulation so repeatedly.
More than allow the oil engine operation drive generator simultaneously, under the internal combustion engine generator group situation, oil engine directly is connected with generator, under the combustion engine vehicles situation, needs generator is connected with oil engine by clutch coupling.
Under combustion engine vehicles braking, deceleration, descending situation, generator is disconnected by clutch coupling and oil engine, be connected with transmission system, unnecessary mechanical energy such as the braking of the vehicles, deceleration, descending are converted into electric energy storage hydrogen, the hydrogen manufacturing of discharging again feeds hydrogen to oil engine and cooperates hydrocarbon fuel combustion.
Can be to the uptake hydrogenation, simple but need the hydrogen amount bigger.Generally also backfire controller to be installed when the hydrogen amount is big; Also will use mixing tank under the petrol motor situation, be mixed into the part air, diesel engine can be without mixing tank because of air excess.Also can in cylinder, directly spray hydrogen, need the hydrogen amount seldom through special device, effective.Add oxygen-rich air to oil engine, general directly add at the uptake place.
Embodiment
Following examples all adopt the press filter type sealed structure, and press filtration plate 9 and the thick rubber plate of dividing plate 10 usefulness 3mm, the thick poly (methyl methacrylate) plate of end plate 11 usefulness 7mm are installed as Fig. 2 a.Gassing electrode 1 adopts and flattens the nickel foam sheet.An electrochemical system unit is only installed in each hydrogen-preparing hydrogen-storing unit of press filter type sealed structure.Unit or unit group are connected with 500 milliliters of electrolytic solution storage bottle, constant flow pumps, and the electrolytic solution storage bottle connects 250 milliliters of scrubbing bottles that are used for gas-liquid separation, and scrubbing bottle connects the gas output tube construction system.
Example 1 is vertically placed a hydrogen-preparing hydrogen-storing unit of electrode: adopting 80 order tin-plated brass nets is zinc electrode 2 collectors, 10 order polythene nets are filter 3, be separated out the wide space of 2mm, polycthylene grafted film is a barrier film 4, electrolytic solution 6 is for containing the aqueous solution (mass concentration) of 4% zinc oxide, 33% potassium hydroxide, and the gassing electrode area is 16cm
2, the electrolytic solution intermittent cyclic.
Test 1: continuous current 0.8 peace charging, duration of charging 5-6 minute, voltage 2.1-2.5 volt; Do not add external voltage, only gassing electrode and zincode are pacified current gears discharge hydrogen manufacturing at external circuit by volt ohm-milliammeter 20,30 minutes have put.So charging, discharge circulate ten times repeatedly.
Test 2: continuous current 0.8 peace charging, 8 minutes duration of charging, voltage 2.1-2.5 volt; Drag about discharge 0.8 peace, 6 minutes discharge times, every cell voltage is born the 50-180 millivolt, and negative voltage is represented to drag discharge with external power during discharge.So charging, discharge circulate ten times repeatedly, and it is less to put amount of oxygen during charging, goes out amounts of hydrogen during discharge and obviously increases.Hydrogen manufacturing tolerance can reach about 5 milliliters of per minutes.
A hydrogen-preparing hydrogen-storing unit of example 2 horizontal positioned electrodes: gassing electrode 1 adopts two layers of foam nickel sheet, gassing electrode 1 useful area 15cm
2, 80 order tin-plated brass nets are zinc electrode 2 collectors, and filter 3 usefulness 10 order polythene nets are provided with 6 layers, are separated out the wide space of 6mm, and barrier film 4 is not installed, and electrolytic solution 6 is for containing the aqueous solution (mass concentration) of 4% zinc oxide, 33% potassium hydroxide, and electrolytic solution circulates continuously.
With 0.5 ampere electric current constant current charge, 2 hours duration of charging, voltage 2.1-2.5 volt.Do not drag discharge, only with the gassing electrode with zincode at external circuit by volt ohm-milliammeter current gear discharge hydrogen manufacturing, end less than 1 millivolt to voltage, charging, discharge and circulate so repeatedly ten times.
Example 3 is vertically placed 45 hydrogen-preparing hydrogen-storing unit of electrode: the copper sheet that adopts 0.1 mm thick is zinc electrode 2 collectors, and it is partition 12 that the thick rubber of 3mm is cut into M shape, and the aperture is that 1.5 centimetres tetrafluoroethylene net is a filter 3, is separated out the wide space of 4mm, does not add barrier film 4.Containing the full aqueous solution that closes zinc oxide, 40% potassium hydroxide, 1.5% lithium hydroxide (mass concentration) is electrolytic solution 6, and the gassing electrode area is every unit 60cm
2The hydrogen manufacturing electric current can reach 1.5 to 4.0 peaces.9 hydrogen-preparing hydrogen-storing element circuit series connection, adopt 8 dividing plates 10,2 end plates 11, the press filtration mode is assembled into one group, circuit is connected respectively with fluid passage between 5 groups, 2700 square centimeters of this system's gassing electrode total areas, electrolytic solution circulates continuously, and the hydrogen-preparing hydrogen-storing system adopts that low capacity is shallow to be filled the shallow mode of putting and work.
Rechargeable hydrogen storage, 110 volts to 130 volts of voltages continue 3 minutes; External power drags discharge hydrogen manufacturing, and 6 volts to negative 18 volts of voltage negative continue 2 minutes; Circulate so repeatedly ten times.Total unit time hydrogen manufacturing amount can reach 0.45 liter/minute to 1.22 liters/minute.
Example 4 systems cooperate the application of oil engine
The electrochemical zinc-water hydrogen production and storage system of use-case 3, the gasoline engine generator that cooperation rated output is 650 watts (Shanghai is raised engine company of section and produced):
Between the engine and carburetor of gasoline engine generator and inlet mouth threeway is installed, threeway connects backfire controller successively, air mixer, system's outlet passageway 22.The generator alternating current output terminal connects the voltate regulator input terminus, and output voltage regulator connects rectifier bridge, with the electrode of rectifier bridge connection hydrogen-preparing hydrogen-storing system, carries direct current to system.During running of an engine, inlet mouth produces negative pressure, oxygen and hydrogen that the hydrogen-preparing hydrogen-storing system produces, respectively by system's outlet passageway 22, the bubbling air mixing tank, with air mixed after backfire controller is inhaled into the gasoline engine inlet-air mouth.The oil mass device for accurately measuring is installed at the oil pipe place.
Test (1) starts gasoline engine generator, does not connect load earlier, does not connect the hydrogen-preparing hydrogen-storing system, makes it be in idling mode, measures its specific fuel oil consumption.
Test (2) starts gasoline engine generator, connects zinc-water hydrogen production and storage system, and system charges to hydrogen-preparing hydrogen-storing, regulates 110 to 130 volts of charging voltages with voltate regulator, and the oxygen of output feeds inlet mouth, measures its specific fuel oil consumption.Separately oxygenation is 3 to 6 minutes, and oil consumption lacks 5% to 20% during than idling.
Test (3), the test (2) that continues, the reversal connection output terminal changes the sense of current, reduces the voltate regulator output voltage, and 6 volts extremely negative 18 volts of voltage negative drag the hydrogen-preparing hydrogen-storing system discharge, and the hydrogen of generation also feeds inlet mouth, measures its specific fuel oil consumption.Separately hydrogenation is 2 to 4 minutes, and oil consumption lacks 6% to 22% during than idling.
Test (4) starts gasoline engine generator, connect zinc-water hydrogen production and storage system, earlier the hydrogen-preparing hydrogen-storing system is charged, regulate 110 volts to 130 volts of charging voltages with voltate regulator, the time that oxygen is produced in charging is 3 minutes, the oxygen of output feeds inlet mouth, then, the reversal connection output terminal changes the sense of current at once, reduce voltage, drag 6 volts of voltage negative extremely negative 18 volts (negative voltage represents to drag discharge), drag zinc-water hydrogen production and storage system discharge hydrogen manufacturing, hydrogen feeds inlet mouth, the time that hydrogen is produced in charging is 2 minutes, charge and discharge so repeatedly, alternately produce oxygen and hydrogen, feed engine intake respectively, measure its specific fuel oil consumption, the oil consumption the when result replaces the oxygenation hydrogenation lacks 6% to 15% during than idling.
The fuel that the hydrogen quality of the mixed combustion of hydrogenation accounts for oil engine consumption adds the hydrogen 0.1%-5% of quality altogether, can determine unit time need hydrogen quality according to oil engine unit time specific fuel consumption, converses total hydrogen manufacturing weight range of unit time; Again by estimation of each hydrogen-preparing hydrogen-storing unit gassing electrode area or experiment, determine a unit of cells time hydrogen manufacturing amount after, determine hydrogen-preparing hydrogen-storing system element number with total unit time hydrogen manufacturing amount divided by a unit of cells time hydrogen manufacturing amount.As example 4, the gasoline engine generator idling mode specific fuel oil consumption that rated output is 650 watts is determined as 5.55 gram/minute, calculate 0.056 gram hydrogen/minute for fuel add hydrogen altogether quality 1%, the unit time hydrogen manufacturing amount of corresponding at normal temperatures and pressures about 627 ml/min.Prepare to feed the hydrogen cooperation fuel combustion of massfraction 1.5%, need about 941 ml/min of hydrogen.Example 3 each hydrogen-preparing hydrogen-storing unit gassing electrode area 60cm
2,, be calculated as the unit time hydrogen manufacturing amount of about 21 ml/min generally by corresponding about 0.35 ml/min of 50 milliamperes of hydrogen manufacturing electric currents of every square centimeter of gassing electrode; 941 approximate 45 divided by 21, and estimation needs to install 45 hydrogen-preparing hydrogen-storing unit; It is 1 group that 9 hydrogen-preparing hydrogen-storing units in series are installed, 5 groups of totally 45 hydrogen-preparing hydrogen-storing unit of connecting, and total hydrogen manufacturing amount of measuring unit time can reach 0.45 liter/minute to 1.22 liters/minute.Gasoline engine generator in can usual practice 4 under the idling mode provides the hydrogen of the about 0.72%-1.95% of massfraction to cooperate fuel combustion.
Claims (6)
1, a kind of electrochemical zinc-water hydrogen production and storage system, adopt galvanic deposit formula zinc electrode, it is characterized in that: a zinc electrode collector and a gassing electrode separation are opened in the electrolytic solution, it is zinc source material that positive divalent zinc compound is present in the aqueous electrolysis liquid, constitutes a unit of electrochemical zinc-water hydrogen production and storage system; A unit of electrochemical zinc-water hydrogen production and storage system is installed in the sealed vessel of reserving fluid input channel, fluid output channel, electrode channel, or, constitute a hydrogen-preparing hydrogen-storing unit through a plurality of units that electrode serial or parallel connection or series-parallel connection are connected; Again with each unitary fluid input channel, fluid output channel, electrode channel respectively serial or parallel connection or series-parallel connection be connected, constitute hydrogen-preparing hydrogen-storing unit group; The fluid input channel of hydrogen-preparing hydrogen-storing unit or unit group, fluid output channel and the moisturizing passage is installed, the electrolytic solution storage vessel and the pump that are connected gas-liquid separation device connect and compose system; During discharge hydrogen manufacturing, the gassing electrode is connected the external power negative pole, zinc electrode connects the positive pole of external power, logical direct current, and the external voltage in each electrochemical system unit is less than 500 millivolts.
2, electrochemical zinc-water hydrogen production and storage system according to claim 1 is characterized in that the system job mode: positive divalent zinc obtains electronics and becomes on the collector that metallic zinc is deposited on zinc electrode during rechargeable hydrogen storage; During discharge hydrogen manufacturing, metallic zinc loses electronics by external circuit, is converted into positive divalent zinc compound and gets back in the electrolytic solution, so circulation.
3, electrochemical zinc-water hydrogen production and storage system according to claim 1 is characterized in that: during rechargeable hydrogen storage, external power gives the voltage of the electrochemical system unit that each zinc electrode-electrolytic solution-gassing electrode forms greater than 1.66 volts, less than 3.00 volts; During discharge hydrogen manufacturing, every square centimeter of gassing electrode pair is answered the hydrogen manufacturing tolerance of 0.07 ml/min to 1.4 ml/min.
4, electrochemical zinc-water hydrogen production and storage system according to claim 1, it is characterized in that the electrode in the hydrogen-preparing hydrogen-storing unit vertically places: porous gassing electrode (1) is processed into that each vertical plane links to each other with the lower horizontal plane sealing, the shape of upper opening, with zinc electrode (2) from lower horizontal surface and the encirclement of each vertical plane.
5, electrochemical zinc-water hydrogen production and storage system according to claim 1, it is characterized in that the electrode horizontal positioned in the hydrogen-preparing hydrogen-storing unit: in each sealed vessel (5), gassing electrode (1) is established on top, zinc electrode (2) is established in the bottom, and an electrochemical system unit is installed in each container.
6, the application of the described electrochemical zinc-water hydrogen production and storage system of a kind of claim 1 is characterized in that behind the electrochemical zinc-water hydrogen production and storage system rechargeable hydrogen storage, discharge hydrogen manufacturing, and the hydrogen that feeds massfraction 0.1%-5% to oil engine cooperates fuel combustion; The oil engine that the native system cooperation is arranged is when the operation workload demand is low, allow oil engine drive generator simultaneously, improve the rate of load condensate of oil engine, be converted into electric energy with satisfying mechanical energy unnecessary outside the working load, rechargeable hydrogen storage on electrochemical zinc-water hydrogen production and storage system, the oxygen that produces during charging also can feed the further short combustion of oil engine, charge tens seconds to several minutes, drag discharge hydrogen manufacturing then and arrived several minutes in tens seconds, hydrogen feeds oil engine, cooperates fuel combustion; Circulation so repeatedly.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100110487A CN101560668A (en) | 2008-04-17 | 2008-04-17 | Electrochemical zinc-water hydrogen production and storage system and applications thereof |
| PCT/CN2009/071251 WO2009127145A1 (en) | 2008-04-17 | 2009-04-13 | Electrochemical system comprising zinc and water for producing and storing hydrogen and the use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100110487A CN101560668A (en) | 2008-04-17 | 2008-04-17 | Electrochemical zinc-water hydrogen production and storage system and applications thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101560668A true CN101560668A (en) | 2009-10-21 |
Family
ID=41198785
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008100110487A Pending CN101560668A (en) | 2008-04-17 | 2008-04-17 | Electrochemical zinc-water hydrogen production and storage system and applications thereof |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN101560668A (en) |
| WO (1) | WO2009127145A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103241710A (en) * | 2013-05-16 | 2013-08-14 | 桂林电子科技大学 | Integrated hydrogen supply device integrating hydrogen production and hydrogen storage |
| WO2020147635A1 (en) * | 2018-01-17 | 2020-07-23 | Chao Huang | Aqueous hybrid super capacitor |
| CN113737219A (en) * | 2021-08-31 | 2021-12-03 | 北京绿钛科技有限公司 | Device for electrolytic hydrogen production and preventing mixing |
| CN116161617A (en) * | 2023-02-21 | 2023-05-26 | 上海氢栖科技有限公司 | Hydrogen production device and hydrogen energy power supply |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB201710224D0 (en) | 2017-06-27 | 2017-08-09 | Univ Surrey | Hydrogen generator |
| FR3079530B1 (en) * | 2018-04-03 | 2024-04-26 | Ergosup | ELECTROCHEMICAL PROCESS FOR PRODUCING GASEOUS HYDROGEN UNDER PRESSURE BY ELECTROLYSIS THEN BY ELECTROCHEMICAL CONVERSION |
| NL2022332B1 (en) * | 2018-12-31 | 2020-07-23 | Univ Delft Tech | Electrolytic cell for H2 generation |
| FR3128589A1 (en) * | 2021-10-22 | 2023-04-28 | Ergosup | Electrochemical system and process for the production of hydrogen by electrolysis of decoupled water, comprising a stage of deoxygenation of the electrolyte |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6770186B2 (en) * | 2001-11-13 | 2004-08-03 | Eldat Communication Ltd. | Rechargeable hydrogen-fueled motor vehicle |
| CN1290220C (en) * | 2002-11-22 | 2006-12-13 | 天津大学 | Electrochemical aluminium-water hydrogen storing and producing method and equipment |
| US6991719B2 (en) * | 2003-05-13 | 2006-01-31 | Texaco Ovonic Fuel Cell Llc | Method for producing and transporting hydrogen |
| US7169497B2 (en) * | 2003-05-15 | 2007-01-30 | The Gillette Company | Electrochemical cells |
| CN1854063A (en) * | 2005-04-28 | 2006-11-01 | 黄潮 | Electrochemical zinc-water hydrogen making and storing method |
-
2008
- 2008-04-17 CN CNA2008100110487A patent/CN101560668A/en active Pending
-
2009
- 2009-04-13 WO PCT/CN2009/071251 patent/WO2009127145A1/en active Application Filing
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103241710A (en) * | 2013-05-16 | 2013-08-14 | 桂林电子科技大学 | Integrated hydrogen supply device integrating hydrogen production and hydrogen storage |
| WO2020147635A1 (en) * | 2018-01-17 | 2020-07-23 | Chao Huang | Aqueous hybrid super capacitor |
| CN113678218A (en) * | 2018-01-17 | 2021-11-19 | 黄潮 | Water system hybrid super capacitor |
| JP2022517035A (en) * | 2018-01-17 | 2022-03-03 | チャオ フゥァン | Aqueous hybrid supercapacitor |
| CN113737219A (en) * | 2021-08-31 | 2021-12-03 | 北京绿钛科技有限公司 | Device for electrolytic hydrogen production and preventing mixing |
| CN116161617A (en) * | 2023-02-21 | 2023-05-26 | 上海氢栖科技有限公司 | Hydrogen production device and hydrogen energy power supply |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2009127145A1 (en) | 2009-10-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101560668A (en) | Electrochemical zinc-water hydrogen production and storage system and applications thereof | |
| CN102823046B (en) | Flow battery group | |
| EP0207122B1 (en) | Gas generator of an engine | |
| US4069371A (en) | Energy conversion | |
| US7021249B1 (en) | Hydrogen addition to hydrocarbon fuel for an internal combustion engine | |
| US5712054A (en) | Rechargeable hydrogen battery | |
| KR102609168B1 (en) | Hybrid battery and electrolyte device | |
| CN1854063A (en) | Electrochemical zinc-water hydrogen making and storing method | |
| CN102939455A (en) | Fuel enrichment method and device | |
| CN101949341B (en) | Electrochemical appliance used for energy conservation and emission reduction of automobile combustion engine and manufacturing method thereof | |
| CN111403778A (en) | Open type uninterrupted power supply metal air fuel cell system | |
| JP2019019379A (en) | Electro-chemical device | |
| CN101570865A (en) | Incessant hydrogen production generating device taking amphoteric metal as raw material | |
| CA2788601A1 (en) | Hydrogen generator | |
| WO2019184532A1 (en) | Bimetallic thermally regenerative amino battery system, flow battery system, and use method | |
| US10920717B1 (en) | Hydrogen producing system and device for improving fuel efficiency and reducing emissions of internal combustion and/or diesel engines | |
| CN201371738Y (en) | Fuel self-generating system of motor vehicle | |
| CN103993327A (en) | Oxyhydrogen gas generating device and car equipped with same | |
| CN200989264Y (en) | Environment protection fuel-economizer with hydroelectrolysate as energy | |
| CN101188299A (en) | Powdered fuel cell | |
| CN108808176B (en) | Oxygen dissolving type metal air battery with sub-cabin circulation and spraying | |
| CN216720003U (en) | Hydrogen power battery system | |
| CN110299582A (en) | A kind of aluminium air power generation module group unit | |
| CN205744194U (en) | Water fuel car | |
| CN1691384A (en) | Metal fuel generator (power plant) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20091021 |