CN102336453A - Device for decomposing water to produce hydrogen based on optical electrolytic bath - Google Patents
Device for decomposing water to produce hydrogen based on optical electrolytic bath Download PDFInfo
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- CN102336453A CN102336453A CN2010102387379A CN201010238737A CN102336453A CN 102336453 A CN102336453 A CN 102336453A CN 2010102387379 A CN2010102387379 A CN 2010102387379A CN 201010238737 A CN201010238737 A CN 201010238737A CN 102336453 A CN102336453 A CN 102336453A
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- water
- end plate
- hydrogen
- catalyzer
- electrode
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention relates to a novel optical electrolytic bath structure and particularly relates to a device for decomposing water into hydrogen and oxygen in an alkaline solution by virtue of the excitation action of light at a theoretical decomposition voltage lower than that of the water. The device is improved on the basis of a conventional alkaline water electrolytic bath, a membrane electrode structure is applied to the inside, zero distance between an electrode and a membrane electrode is ensured effectively, electrolytic efficiency is improved and energy consumption is lowered, and furthermore, the device has favorable stability.
Description
Technical field
The present invention relates to light assisted electrolysis water generates hydrogen device, specifically impressed voltage and to be aided with illumination be the constructional device of hydrogen, oxygen and ON-LINE SEPARATION with water decomposition in the basic soln system.
Background technology
In recent years, along with the continuous development of world economy, the acceleration consumption of non-renewable fossil oils such as coal, oil, Sweet natural gas, traditional energy system changes just step by step, the exploitation of new forms of energy, development work is extremely urgent.In numerous sustainable energies, sun power is that unique ability substitutes the energy that fossil oil also can satisfy human large-scale application.Yet, owing to there is areal variation property, and characteristic round the clock, sun power must be converted into other energy, could solve to store transportation problem.
In addition, in the energy system of 21st century, hydrogen is a kind of ideal secondhand energy, compares with other energy, and hydrogen energy source is efficient, environmental protection, its energy density (140MJ kg
-2) be solid fuel (50MJkg
-2) twice many, and its products of combustion is water, environmentally safe is considered to one of the most potential energy.Now a lot of scientific research institutions all are devoted to new technologies such as the production, storage, utilization, transportation of Hydrogen Energy.Inspired by this kind viewpoint, is the Hydrogen Energy of high-energy-density with conversion of solar energy, has caused scientific research personnel's extensive interest.And the occurring in nature hydrogenous material mainly is a water, is a direct way that obtains Hydrogen Energy through water electrolysis.
It is alkaline water electrolytic that water electrolysis commonly used is gone up in industry at present, and the electrode reaction formula is:
Negative electrode: 4H
2O+4e → 2H
2+ 4OH
-φ
0=-0.83V
Anode: 4OH
-→ 2H
2O+O
2+ 4e φ
0=+0.40V
Except that alkaline water electrolytic, when electrolytic reaction was in acid system or neutral system, its electrode reaction formula was:
Negative electrode: 4H
++ 4e → 2H
2φ
0=0V
Anode: 2H
2O → O
2+ 4H
++ 4e φ
0=1.23V
Can find out that from following formula the theoretical decomposition voltage of water and the pH value of solution are irrelevant, its essence all is the decomposition reaction of water, but owing to various metallic substance corrode in acidic solution more easily, so many employing basic solns are gone up in industry at present.
In the electrolytic reaction of water, it is a very complicated electrode process that the anode of oxygen is separated out, and relates to an electrochemical reaction that has the quadrielectron to participate in; Be accompanied by bigger overpotential in the process, so the anode evolution reaction of oxygen need could take place under the current potential than the corrigendum of the equilibrium potential of oxygen, particularly in acidic medium; Can as electrode can only be precious metals such as Au, Pt, or in acidic solution, can form the various metals of steady oxide, and when in alkaline system, carrying out the brine electrolysis reaction; Anode potential is lower; Can effectively prevent the corrosion of metal problem, therefore, alkaline water electrolytic is a kind of means of recent industrial hydrogen production.
But in alkaline water electrolytic, by the conversion of electric energy to the secondhand energy Hydrogen Energy, power consumption is higher.If can effectively utilize the luminous energy of occurring in nature, utilize the photoelectric conversion process of semiconductor material, directly accomplish the conversion of " photochemical energy ", can prevent the corrosion of metal problem, can improve energy utilization efficiency fully again.
Summary of the invention
The object of the present invention is to provide a kind of new type light electrolysis pool structure, can be being lower than under the theoretical decomposition voltage of water, by the excitation of light, in basic soln, be hydrogen and oxygen with water decomposition.The present invention improves on the basis in traditional alkaline water electrolytic pond, and the inner film electrode structure that adopts has effectively guaranteed the zero spacing between electrode and the barrier film, has improved electrolytic efficiency, reduced energy consumption, and this device has satisfactory stability property.
For realizing above-mentioned purpose, the technical scheme that the present invention adopts is:
A kind of photoelectrolytic cell water of decomposition hydrogen production bioreactor, it is successively by metal end plate, negative electrode, asbestos film, anode, conductive metal mesh, and rigidity printing opacity end plate is formed by stacking;
Metal end plate is provided with water flow field near cathode side and metal end plate is provided with water-in and water outlet, and water-in and water outlet are connected with water flow field; Negative electrode is a carbon paper electrode, and carbon paper electrode has supported the liberation of hydrogen catalyzer near asbestos film one side; The asbestos film is alkaline asbestos film;
Anode is a carbon paper electrode, and carbon paper electrode supports carbon paper electrode, the rigidity printing opacity end plate that oxygen-separating catalyst, opposite side support photocatalyst near asbestos film one side and is provided with water-in and the water outlet that runs through end plate;
Metal end plate is connected with positive pole with the negative pole of direct supply through lead respectively with conductive metal mesh; Be provided with the light source of irradiation rigidity printing opacity end plate in the rigidity printing opacity end plate outside.
Water-in and water outlet respectively through pipeline with mass concentration 5-30% Pottasium Hydroxide is housed or the sodium hydroxide solution storage tank links to each other, on the pipeline of water-in and/or water outlet, be provided with liquid pump.
Said liberation of hydrogen catalyzer is Pt/C, Pt-Ni/C or Pt-Pd/C catalyzer; Oxygen-separating catalyst is Pt, Ir, RuO
2Or IrO
2Catalyzer; Photocatalyst is P25TiO
2, ZnO
2, Fe
2O
3Or WO
3Catalyzer.
Said metal end plate is nickel plate, titanium plate or stainless steel plate; Conductive metal mesh is nickel screen, titanium net or stainless (steel) wire; Rigidity printing opacity end plate is quartz glass plate or the annular metal sheet that is inlaid with quartz glass plate for the middle part.Said light source is simulated solar irradiation radiating xenon lamp or other continuous tunable light source.
The present invention can be hydrogen, oxygen with water decomposition when impressed voltage is lower than the theoretical decomposition voltage of water, and can carry out ON-LINE SEPARATION to it under the booster action of light.
Operating process is following:
1) the anode end plate place leaves photic zone, and external light source can see through silica glass and shine anode surface.
2) in the middle of two stainless steel end plates, add film electrode structure, compress the assembling photoelectrolytic cell by mechanical force.
3) stainless steel end plate both sides have water-in and water outlet, and water-in gets into electrolyzer to solution from the bottom, and the gas-liquid two-phase of generation is the water outlet discharge from the top.
4) on photoelectrolytic cell inner anode surface oxygen evolution reaction takes place, cathode surface generation evolving hydrogen reaction produces gas and is separated by intermediate coat, collects respectively.
The present invention directly supports anode surface with photocatalyst, rather than is scattered in the cavity of cathode side, anode side, and the volume of photoelectrolytic cell is further compressed, and one-piece construction is compact more, is different from the photoelectrolytic cell of people's design such as Robert.
The present invention is through optimizing the internal structure of photoelectrolytic cell, by light be used for reduce the required impressed voltage of electrolytic process, directly convert part luminous energy into Hydrogen Energy, increase the energy utilization efficiency of system; And a kind of gas ON-LINE SEPARATION method is provided, and with hydrogen, the oxygen direct separation that the photoelectrolytic cell brine electrolysis produces, required energy consumption problem in security of system problem of avoiding gas to mix producing and the last handling process.
The present invention has the following advantages:
1. electrolytic cell anode material is made up of semi-conductor, fully reduces the required external voltage of water decomposition in conjunction with the interaction energy of light, thereby effectively avoids anode corrosive problem under noble potential.
2. can anode and cathode and film be grouped together, form membrane electrode assembly, reduce the ohmage loss in the electrolytic process.
3. the gas direct-on-line that produces in the photoelectrolysis process separates, and the hydrogen purity of generation is high, and inclusion-free gas exists, and saves the post-processing step of gas delivery.
4. structure design of the present invention has satisfactory stability property, and volume is little, can effectively utilize illuminating area.
Description of drawings
Fig. 1 is the synoptic diagram of project organization of the present invention: wherein 1 is stainless steel nickel plating end plate; 2 is water-in; 3 is water port; 4 is negative electrode; 5 is photo cathode; 6 is alkaline asbestos film; 7 is the metal titanium currect collecting net; 8 is silica glass.
Fig. 2 be photoelectrolytic cell at normal temperatures, have or not the voltage-to-current relation curve when adding illumination
Fig. 3 be photoelectrolytic cell at normal temperatures, 1.23V, the electric current-time curve that records under the 350W xenon lamp illumination condition.
Fig. 4 be photoelectrolytic cell under the 1.23V impressed voltage, water of decomposition in the basic soln system, negative electrode are discharged the result images of gas after stratographic analysis.
Embodiment
Below in conjunction with accompanying drawing the present invention is described further:
The present invention opens a 60mm*40mm mouth by means of the structure of SPE water electrolysis at anode end plate, and opening part is inlayed a pieces of quartz glass; Be beneficial to seeing through of light, in the middle of two electrodes, sandwich membrane electrode assembly, compress by mechanical force; Near the end plate opening part is photo cathode; The light transmission silica glass that external light source sends shines photo cathode, produces electronics-hole and separates, and causes entire reaction.Process is following:
Anode: 4h
++ 4OH
-→ O
2+ 2H
2O
Negative electrode: 2e
-+ 2H
2O → H
2+ 2OH
-
Hydrogen, oxygen that reaction produces separate through intermediate coat, discharge from both sides respectively, carry out separated and collected through the gas-liquid two-phase separating tank.
The present invention in conjunction with the opto-electronic conversion effect of sun power, is hydrogen, oxygen with water decomposition, and it is carried out ON-LINE SEPARATION on the basis of alkaline water electrolytic; Through the utilization of intermediate coat electrode structure, the volume of photoelectrolytic cell is further compressed, reduce its space occupancy.
As shown in Figure 1, each forms the photoelectrolytic cell apparatus structure synoptic diagram after splitting, and wherein 1 is stainless steel metal nickel plating end plate; 2 is water-in; 3 is water outlet; 4 is negative electrode, and loading is 0.4mg/cm
2The Pt/C electrode; 5 is anode, supports commercialization P25TiO
2And RuO
2The TGP-H-60 carbon paper; 6 alkaline asbestos films for full caustic dip liquid; 7 is the metal titanium currect collecting net of percentage of open area 0.7; 8 is silica glass.
Array mode: two electrodes place alkaline asbestos film both sides; Wherein anode support photocatalyst one side towards the end plate opening part; And contact with ti-alloy mesh, ti-alloy mesh places on the silica glass, and the edge contacts with metal end plate; Membrane electrode assembly places between the two end plates, is fixed by mechanical force.
Embodiment 1:
Its embodiment is following:
1) adopt among Fig. 1 structure assembling photoelectrolytic cell and placing on the test platform, both sides lead to 1M KOH solution, and it was stablized 30 minutes at normal temperatures.
2) will between 0-2V, carry out the polarization curve test after 30 minutes, test is opened light source after accomplishing, and stablizes 5 minutes, is adding test polarization curve under the illumination condition.
The photoelectrolytic cell of Fig. 2 after for assembling be the relation curve between electric current and the impressed voltage at normal temperatures.Result by Fig. 2 can see, weak current can occur when photoelectrolytic cell is at voltage 1v under the illumination condition adding.With the increase gradually of impressed voltage, electric current increases, and illumination effect raises more outstanding with voltage.
The polarization curve that obtains through the method that adds illumination in this test adds under the illumination with nothing and compares, and current value is obviously higher, explains that anode produces response to illumination, and the electronics after the transition can effectively be transferred to negative electrode, and the photoelectrolytic cell catchment effect is good.
Embodiment 2:
Fig. 3 be photoelectrolytic cell at normal temperature, the electric current-time curve under the 1.23V impressed voltage.
Can find out that from the result of Fig. 3 under the constant impressed voltage, current value can reach 12mA when adding illumination, and keep stable.When stopping illumination suddenly, the current value rapid drawdown is about about 1mA after stablizing, and tends towards stability gradually, treats to recover again illumination, and current value rises rapidly, increases to stationary value gradually.System moves 2h continuously, and current value is also undamped, proves that the photoelectrolytic cell performance of design is relatively stable voluntarily.
Fig. 4 is the stratographic analysis image that photoelectrolytic cell negative electrode under steady operational status produces gas.
Can be found out that by correlated results among Fig. 4 photoelectrolytic cell negative electrode institute aerogenesis body is a hydrogen, the appearance at nitrogen peak possibly be because in the process of carrying out stratographic analysis, and airborne nitrogen gets into little kind of syringe and brings chromatographic column into and cause.By the appearance that confirms the nitrogen peak is because little kind of syringe caused really; Extract pure hydrogen with same syringe and get into the chromatographic instrument analysis, the nitrogen peak can occur equally, explain that the appearance of micro-nitrogen derives from air really; It really is hydrogen that the photoelectrolytic cell negative electrode is discharged gas, and purity is high.
Above instance explanation; The hydrogen, the oxygen separation that adopt apparatus of the present invention effectively photoelectrolysis to be produced; The gained hydrogen purity is high, and in addition, the complete assembly volume is little; Middle MEA structure can effectively reduce the impedance loss that exists in the electrolytic process, and structure design also has satisfactory stability property.
Claims (5)
1. photoelectrolytic cell water of decomposition hydrogen production bioreactor is characterized in that:
It is successively by metal end plate, negative electrode, asbestos film, anode, conductive metal mesh, and rigidity printing opacity end plate is formed by stacking;
Metal end plate is provided with water flow field near cathode side and metal end plate is provided with water-in and water outlet, and water-in and water outlet are connected with water flow field; Negative electrode is a carbon paper electrode, and carbon paper electrode has supported the liberation of hydrogen catalyzer near asbestos film one side; The asbestos film is alkaline asbestos film;
Anode is a carbon paper electrode, and carbon paper electrode supports carbon paper electrode, the rigidity printing opacity end plate that oxygen-separating catalyst, opposite side support photocatalyst near asbestos film one side and is provided with water-in and the water outlet that runs through end plate;
Metal end plate is connected with positive pole with the negative pole of direct supply through lead respectively with conductive metal mesh; Be provided with the light source of irradiation rigidity printing opacity end plate in the rigidity printing opacity end plate outside.
2. according to claims 1 described device, it is characterized in that:
Water-in and water outlet respectively through pipeline with mass concentration 5-30% Pottasium Hydroxide is housed or the sodium hydroxide solution storage tank links to each other, on the pipeline of water-in and/or water outlet, be provided with liquid pump.
3. according to claims 1 described device, it is characterized in that:
Said liberation of hydrogen catalyzer is Pt/C, Pt-Ni/C or Pt-Pd/C catalyzer;
Oxygen-separating catalyst is Pt, Ir, RuO
2Or IrO
2Catalyzer;
Photocatalyst is P25TiO
2, ZnO
2, Fe
2O
3Or WO
3Catalyzer.
4. according to claims 1 described device, it is characterized in that:
Said metal end plate is nickel plate, titanium plate or stainless steel plate;
Conductive metal mesh is nickel screen, titanium net or stainless (steel) wire;
Rigidity printing opacity end plate is quartz glass plate or the annular metal sheet that is inlaid with quartz glass plate for the middle part.
5. according to claims 1 described device, it is characterized in that:
Said light source is simulated solar irradiation radiating xenon lamp or other continuous tunable light source.
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|---|---|---|---|
| CN2010102387379A CN102336453B (en) | 2010-07-28 | 2010-07-28 | Device for decomposing water to produce hydrogen based on optical electrolytic bath |
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|---|---|---|---|
| CN2010102387379A CN102336453B (en) | 2010-07-28 | 2010-07-28 | Device for decomposing water to produce hydrogen based on optical electrolytic bath |
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|---|---|
| CN102336453A true CN102336453A (en) | 2012-02-01 |
| CN102336453B CN102336453B (en) | 2013-06-19 |
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ID=45512461
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103952717A (en) * | 2014-05-07 | 2014-07-30 | 北京化工大学 | Photoelectrochemical decomposition water and organic synthesis coupled cascade reaction design method |
| CN109115935A (en) * | 2018-09-06 | 2019-01-01 | 江苏大学 | The detection device and method of loaded catalyst different parts Hydrogen Evolution Performance |
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| US4472260A (en) * | 1982-12-23 | 1984-09-18 | Neefe Charles W | Light driven hydrogen oxygen generator |
| WO2001002624A1 (en) * | 1999-07-05 | 2001-01-11 | Ecole Polytechnique Federale De Lausanne (Epfl) | Tandem cell for water cleavage by visible light |
| JP2006265697A (en) * | 2005-03-25 | 2006-10-05 | Sharp Corp | Semiconductor light electrode for water electrolysis |
| CN101275236A (en) * | 2007-03-27 | 2008-10-01 | 通用汽车环球科技运作公司 | Apparatus to reduce the cost of renewable hydrogen fuel generation by electrolysis using combined solar and grid power |
| CN101307458A (en) * | 2008-01-21 | 2008-11-19 | 大庆石油学院 | High-efficiency self-coupling solar hydrogen-system making |
| CN101376987A (en) * | 2008-09-28 | 2009-03-04 | 大连理工大学 | Photoelectrochemistry composite or coupled hydrogen making and oxygen making apparatus and method |
| CN101629300A (en) * | 2009-05-21 | 2010-01-20 | 中国科学院广州能源研究所 | Method for separating and preparing hydrogen by decomposing water in fuel cell through photocatalysis |
-
2010
- 2010-07-28 CN CN2010102387379A patent/CN102336453B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4472260A (en) * | 1982-12-23 | 1984-09-18 | Neefe Charles W | Light driven hydrogen oxygen generator |
| WO2001002624A1 (en) * | 1999-07-05 | 2001-01-11 | Ecole Polytechnique Federale De Lausanne (Epfl) | Tandem cell for water cleavage by visible light |
| US6936143B1 (en) * | 1999-07-05 | 2005-08-30 | Ecole Polytechnique Federale De Lausanne | Tandem cell for water cleavage by visible light |
| JP2006265697A (en) * | 2005-03-25 | 2006-10-05 | Sharp Corp | Semiconductor light electrode for water electrolysis |
| CN101275236A (en) * | 2007-03-27 | 2008-10-01 | 通用汽车环球科技运作公司 | Apparatus to reduce the cost of renewable hydrogen fuel generation by electrolysis using combined solar and grid power |
| CN101307458A (en) * | 2008-01-21 | 2008-11-19 | 大庆石油学院 | High-efficiency self-coupling solar hydrogen-system making |
| CN101376987A (en) * | 2008-09-28 | 2009-03-04 | 大连理工大学 | Photoelectrochemistry composite or coupled hydrogen making and oxygen making apparatus and method |
| CN101629300A (en) * | 2009-05-21 | 2010-01-20 | 中国科学院广州能源研究所 | Method for separating and preparing hydrogen by decomposing water in fuel cell through photocatalysis |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103952717A (en) * | 2014-05-07 | 2014-07-30 | 北京化工大学 | Photoelectrochemical decomposition water and organic synthesis coupled cascade reaction design method |
| CN109115935A (en) * | 2018-09-06 | 2019-01-01 | 江苏大学 | The detection device and method of loaded catalyst different parts Hydrogen Evolution Performance |
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| Publication number | Publication date |
|---|---|
| CN102336453B (en) | 2013-06-19 |
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