CN113322483B - Novel renewable energy storage reactor and application thereof - Google Patents
Novel renewable energy storage reactor and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of solid oxide electrolytic cells, and particularly relates to a novel renewable energy storage reactor and application thereof. The renewable energy reactor is suitable for solid oxide cells with a cathode-supported or anode-supported structure; the solid oxide cell can utilize biomass-based micromolecules to assist in electrolyzing water, so that high-efficiency storage of renewable energy sources is realized. According to the renewable energy storage reactor developed by the invention, the supporting anode has a micro-channel structure, so that an effective way is provided for rapid gas diffusion; the catalyst is arranged in the micro-channel and used as a high-efficiency biomass catalytic reforming reactor, so that the carbon deposition resistance and the electrolytic stability of the battery are improved. Compared with the conventional process for preparing hydrogen by catalyzing biomass water reforming, the invention can utilize renewable electric energy to drive electrolysis, realize the synchronous and efficient storage of the biomass and the renewable electric energy, and obtain pure hydrogen in the cathode chamber, thereby omitting the hydrogen separation process.
Description
Technical Field
The invention belongs to the technical field of solid oxide electrolytic cells, and particularly relates to a novel renewable energy storage reactor and application thereof.
Background
The Solid Oxide Electrolytic Cell (SOEC) technology has the advantages of high energy conversion, flexible fuel and the like, and can be combined with renewable energy sources such as solar energy, wind energy and the like to convert the renewable energy sources into clean fuel hydrogen (H) 2 ) The renewable energy source structure solves the problems of intermittency, fluctuation and the like of renewable energy sources, and is an indispensable important component in a novel energy source structure in the future. The operation cost of high-temperature electrolysis is evaluated from the aspects of equipment, raw materials, energy power cost and the like, the energy power cost accounts for about 60 percent of the total operation cost, and the reduction of the electric energy consumption becomes the key for the commercial application of the high-temperature electrolysis technology. At present, the subject groups at home and abroad try to introduce hydrogen (H) into the anode side of the SOEC 2 ) Carbon monoxide (CO), carbon (C) and methane (CH) 4 ) And the reductive fuel is coupled with the SOEC process to reduce the open-circuit voltage, reduce the electric energy consumption and improve the hydrogen production efficiency by electrolyzing water. CH in currently selected supplemental Fuel gas 4 The partial oxidation assisted electrolysis has the most application value, CH 4 The maximum efficiency of the system is improved to 70% from 32% of the traditional SOEC mode after the introduction. But CH 4 Still is fossil energy, can not solve the reliance to fossil energy fundamentally.
In the existing auxiliary fuel, biomass fuel is not introduced, and mainly because mass transfer and carbon deposition problems exist in the reaction of the biomass fuel on the anode side, how to effectively solve the problem of the application of the biomass fuel in the solid oxide electrolytic cell technology is to couple the biomass fuel with the SOEC process to reduce open-circuit voltage, reduce electric energy consumption and improve the hydrogen production efficiency by electrolyzing water, which is a problem to be solved urgently in the technical field of the solid oxide cell at present.
Disclosure of Invention
The invention aims to provide a novel renewable energy storage reactor, wherein the supporting electrode has a micro-channel structure.
The invention also aims to provide the application of the novel renewable energy storage reactor, the reactor is applied to the solid oxide battery, the electric energy consumption during electrolysis is reduced, the conversion of pure renewable energy is realized, and the reactor has strong carbon deposition resistance, good stability and very high conversion efficiency.
In order to achieve the purpose, the invention adopts the following technical scheme:
a novel renewable energy storage reactor, comprising: an anode support body with a micro-channel structure, an electrolyte thin layer and a porous cathode layer; wherein the inside of the micro-channel structure is loaded with a catalyst for reforming biomass micromolecules, one end of the micro-channel structure starts from the surface of the anode and penetrates through the support body to reach the anode/electrolyte interface.
The thickness of the electrode support body with the microchannel structure is 0.3 mm-1.5 mm, and the thickness of the thin electrolyte layer is 0.4 mu m-30 mu m; the diameter of the electrode/thin electrolyte interface microchannel is 0.5-5 μm, the microchannel of the electrode support body is a dendritic microchannel and penetrates through the support electrode, and the diameter of the microchannel is gradually combined and increased to 10-100 μm.
The renewable energy reactor is suitable for a solid oxide cell with a cathode-supported structure or an anode-supported structure; the solid oxide cell can utilize biomass-based small molecule energy storage.
Preferably, the biomass-based small molecule is one or more of ethanol, acetic acid and biodiesel.
Preferably, the anode of the renewable energy storage reactor is assisted by the electrolysis of water using biomass-based small molecules or using a mixture of biomass-based small molecules and water.
Preferably, the method for electrolyzing water by using biomass-based small molecules as an auxiliary anode of the renewable energy storage reactor comprises the following steps: (1) Sealing the renewable energy reactor in a ceramic tube, firstly heating to 260 ℃ at the speed of 2 ℃/min, preserving the temperature of 1h, and then heating to the operation temperature of 650-1050 ℃ at the speed of 4 ℃/min; (2) The cathode and the anode are evacuated by introducing inert gas, and then H is introduced 2 Reducing, introducing inert gas and H into cathode 2 O (10% -40%) and H 2 (2-15%) of mixed gas, and introducing mixed gas of inert gas and biomass-based micromolecules (5% -30%) into the anode. (3) And applying a potential to the reactor by using an external power supply, electrolyzing water at a cathode, and electrochemically oxidizing the biomass-based micromolecules at an anode.
Preferably, the method for electrolyzing water by using the mixture of biomass-based small molecules and water as the anode of the renewable energy storage reactor in an auxiliary manner comprises the following steps: (1) Sealing the renewable energy reactor in a ceramic tube, firstly heating to 260 ℃ at the speed of 2 ℃/min, preserving the temperature of 1h, and then heating to the operation temperature of 650-1050 ℃ at the speed of 4 ℃/min; (2) The cathode and the anode are evacuated by introducing inert gas, and then H is introduced 2 Reducing, introducing inert gas and H into cathode 2 O (10% -40%) and H 2 (2-15%) mixed gas and inert gas and H are introduced into anode 2 O and biomass-based small molecules. Wherein the gas introduced into the cathode in the step (2) can also be inert gas or H 2 O and H 2 The mixed gas of (1).
Preferably, the preparation method of the renewable energy reactor comprises the following steps: the electrode support body is prepared by a phase inversion method, and the catalyst of the reactor is loaded to the micro-channel through negative pressure assistance to prepare the renewable energy reactor electrode.
Preferably, the preparation method of the renewable energy reactor specifically adopts the following steps:
(1) Mixing the support body powder, the phase inversion solvent and the dispersing agent in a ball milling tank, and fully ball milling to obtain initial slurry;
(2) Carrying out negative pressure stirring on the initial slurry prepared in the step (1) in a vacuum stirrer to discharge gas in the slurry, so as to obtain the slurry meeting the phase inversion state;
(3) Pouring a layer of slurry prepared in the step (2) into a lower grinding tool, covering a stainless steel net, pouring a layer of slurry into an upper layer mold, pouring water into the mold at a constant speed after the slurry is filled in the mold, taking the water as a flocculating agent, then performing a phase inversion process, and taking down the stainless steel net after the phase inversion is finished to obtain an electrode blank;
(4) Soaking, drying and pre-sintering the electrode blank obtained in the step (3) to obtain a solid oxide cell electrode support body framework;
(5) Depositing and preparing a thin electrolyte layer on the surface of the electrode support body subjected to the pre-sintering through a Dip-coating method, then sintering to obtain a half cell, and finally spraying an electrode material and sintering to obtain a full cell;
(6) Loading a catalyst under negative pressure: and loading a catalyst into the dendritic micro-channel in a negative pressure auxiliary loading mode, and uniformly filling the micro-channel with the catalyst to obtain the renewable energy storage reactor.
Preferably, the step (5) may also be implemented by directly spraying the electrode material after the pre-fired electrode support is impregnated with the thin electrolyte layer, and then co-firing to directly obtain the full cell.
Preferably, the support material in step (1) may be Sm 0.2 Ce 0.8 O 2 、Gd 0.1 Ce 0.9 O 2 、(Sc 2 O 3 ) 0.10 (CeO 2 ) 0.01 (ZrO 2 ) 0.89 、(Y 2 O 3 ) 0.08 Zr 0.92 O 2 、La 0.9 Sr 0.1 Ga 0.8 Mg 0.2 O 3 、La 1.9 Ca 0.1 Zr 2 O 7 、La 0.9 Sr 0.1 ScO 3 、Ba 3 Ca 1.18 Nb 1.82 O 9 、BaCe 0.9 Y 0.1 O 3 、BaCe 0.6 Zr 0.3 Y 0.1 O 3 、BaZr 0.9 Y 0.1 O 3 、SrCe 0.95 Yb 0.05 O 3 Or BaCe 0.4 Zr 0.4 Y 0.2 O 3 The electrolyte is (Y) 2 O 3 ) 0.08 Zr 0.92 O 2 Or Gd 0.1 Ce 0.9 O 2 。
Preferably, the pre-sintering temperature in the step (4) is 1000-1100 ℃, and the sintering temperature in the step (5) is 1200-1500 ℃.
Preferably, the catalyst having reforming ability of step (1) is in the form of particles or fibers.
The invention provides a new auxiliary electrolysis fuel-biomass fuel, such as ethanol, acetic acid, biodiesel and the like, for auxiliary electrolysis, and the SOEC technology is utilized to carry out energy conversion by using the biomass fuel to assist electrolysis water, so that the problem of dependence on fossil energy can be fundamentally eliminated. The biomass is used for reaction on the anode side, the main problems of mass transfer and carbon deposition are solved, the problems of mass transfer and carbon deposition can be effectively solved based on a newly developed battery structure, namely a micro-channel support electrode, and a catalyst, and the biomass electrolysis system is high in electrolysis efficiency and stable in operation.
According to the invention, the catalyst is added into the dendritic micro-channel in a negative pressure auxiliary adding manner, so that the reactor with high-efficiency reforming capability and anti-carbon deposition capability is formed.
Advantageous effects
According to the renewable energy reactor developed by the invention, the support electrode has a micro-channel structure, so that an effective way is provided for rapid gas diffusion; when the electrolyte and the electrodes on two sides are co-fired, the bonding force between the electrodes and the electrolyte interface can be further increased; the catalyst is added into the micro-channel to form a reactor with high catalytic capability, so that the biomass reforming reaction or biomass oxidation reforming reaction can be efficiently catalyzed, and the carbon deposition resistance and stability of the battery are improved. Compared with other biomass hydrogen production and water electrolysis hydrogen production processes, the invention simultaneously considers two technical means, and is safe and efficient.
Drawings
FIG. 1 is a schematic diagram of biomass renewable energy assisted electrolysis;
FIG. 2 is a schematic diagram of a novel renewable energy reactor manufacturing process;
FIG. 3 is a reactor microstructure prepared by Process one in example 1 of the present invention;
FIG. 4 is an electrochemical impedance spectrum of the solid oxide electrolytic cell of application example 1 operating at 800 ℃;
FIG. 5 is a current density-voltage (C-V) curve of the solid oxide electrolytic cell described in application example 1 operating at 800 ℃;
FIG. 6 is a graph of the electrochemical stability test of the solid oxide cell of application example 1 operating at 800 ℃ at 1A cm -2 The current density is operated for 150h, and no obvious attenuation is caused. Simultaneous cathode and anode generation of large quantities of H 2 。
FIG. 7 is an electrochemical impedance spectrum of the solid oxide cell of application example 2, operating at 800 ℃;
FIG. 8 uses the solid oxide electrolytic cell described in example 2 with a current density-voltage (C-V) curve at 800 deg.C operation;
FIG. 9 is a graph of electrochemical stability of ethanol electrochemical oxidation assisted electrolysis at 800 deg.C operating temperature using the solid oxide cell described in 2 at 3A cm -2 The anode operates for 100 hours under the current density without obvious attenuation, and a large amount of synthesis gas (CO + H) is generated at the anode 2 ）。
FIG. 10 shows a solid oxide cell using the solid oxide cell described in FIG. 2, the cell being at 3A cm -2 SEM, EDS and soot analysis plots after 100h run at current density.
Detailed Description
The foregoing invention will be described in further detail with reference to the following examples and accompanying drawings in order to provide a further understanding of the nature and technical means of the invention, and the objects and functions attained thereby. However, it should not be understood that the scope of the present invention as defined above is limited to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention.
Example 1
36.99 gNiO, 24.66 g (Y) 2 O 3 ) 0.08 Zr 0.92 O 2 The powder, 4.3 g polyethersulfone, 24 g of N-methyl pyrrolidone and 0.43 g polyvinylpyrrolidone were weighed and placed in a ball mill jar and ball milled using a planetary ball mill 48 h to form a premix. And filtering the premixed slurry, placing the filtered premixed slurry in a vacuum stirring device, stirring and exhausting, wherein the vacuum degree is set to be minus 0.08 to minus 0.1 MPa, and stirring and exhausting for 20 min to obtain the electrode slurry which does not contain bubbles and is uniformly mixed. Pouring the slurry into a lower mold, placing a stainless steel screen with 70 mu m screen holes on the surface of the slurry to enable the slurry to slightly penetrate through the stainless steel screen, pressing an upper mold with openings at the upper end and the lower end on the screen, and injecting the slurry with the thickness of 10 mm to 15 mm. Water was used as flocculant and poured from the top of the slurry to initiate the phase inversion process. And (3) carrying out phase inversion for 1.5 h, then demoulding, tearing off the screen, placing the formed microchannel electrode blank in a beaker filled with water, soaking for 6 h, and replacing the residual solvent. Then, the green body is placed in an oven to be dried, the drying temperature is 50-60 ℃, and the drying time is 5-12 h. And (3) sintering the dried blank at high temperature, heating to 400 ℃ at the speed of 1 ℃/min, preserving the heat of 1h, removing volatile substances, heating to 1050 ℃ at the speed of 2 ℃/min, preserving the heat of 2h, finally cooling to 500 ℃ at the speed of 5 ℃/min, and naturally cooling to obtain the Ni/YSZ pre-sintered blank.
Mixing 3 g (Y) 2 O 3 ) 0.08 Zr 0.92 O 2 Electrolyte powder and 0.1 g of PVP-40000 are weighed and poured into a ball milling tank, 30 ml ethanol is added, and the electrolyte is prepared by ball milling 12 h. And then, dipping a layer of electrolyte thin layer on the smooth surface of the Ni/YSZ pre-sintered blank by using a dip-coating method, and finally, drying the blank in an oven at the drying temperature of 50-60 ℃ for more than 30 min until the blank is completely dried to obtain the YSZ electrolyte dipped support electrode blank.
Cathode preparation
Process one
Impregnating YSZ electrolyte into the support electrode blank with 1Raising the temperature to 400 ℃ per min, preserving the heat at 1h, removing volatile substances, raising the temperature to 1380 ℃ at 2 ℃ per min, preserving the heat at 5 h, finally cooling to 500 ℃ at 2 ℃ per min, and naturally cooling to prepare the half cell. 3.6 g of NiO and 2.4 g of Gd were weighed 0.1 Ce 0.9 O 2 Putting the powder and 0.1 g of PVP-40000 into a ball milling tank, adding 30 ml ethanol, and carrying out ball milling on 12 h to prepare electrolyte slurry. Holes were punched in the label paper with a 10 mm diameter punch, aligned to the middle of the half cell and attached to the evaporation dish. And (3) placing the evaporating dish on a heating table, setting the temperature of the heating table to be 120 ℃, and then uniformly spraying the electrode slurry on the surface of the electrolyte by using a spray gun, wherein the thickness of the electrode is 20-30 micrometers. And (3) heating the sprayed half cell to 400 ℃ at the speed of 1 ℃/min, preserving the heat of the half cell for 1h, removing volatile substances, heating to 1280 ℃ at the speed of 2 ℃/min, preserving the heat of the half cell for 2h, finally cooling to 500 ℃ at the speed of 2 ℃/min, and naturally cooling to prepare the full cell.
Process two
3.6 g of NiO and 2.4 g of Gd were weighed 0.1 Ce 0.9 O 2 Putting the powder and 0.1 g of PVP-40000 into a ball milling tank, adding 30 ml ethanol, and carrying out ball milling on 12 h. Holes were punched in the weighing paper with a 12 mm diameter punch, aligned right in the middle of the YSZ electrolyte impregnated support electrode blank, and pressed into the evaporation dish. And (3) placing the evaporating dish on a heating table, setting the temperature of the heating table to be 120 ℃, and then uniformly spraying the electrode slurry on the surface of the electrolyte by using a spray gun, wherein the thickness of the electrode is 20-30 micrometers. And (3) heating the sprayed pre-sintered battery to 400 ℃ at the speed of 1 ℃/min, preserving the heat of the pre-sintered battery for 1h, removing volatile substances, heating to 1280 ℃ at the speed of 2 ℃/min, preserving the heat of the pre-sintered battery for 2h, finally cooling to 500 ℃ at the speed of 2 ℃/min, and naturally cooling. And directly sintering the mixture in one step to prepare the full cell.
Preparation of ethanol reforming assisted water electrolysis catalyst
CeO 2 Catalyst precursor: measuring 5 ml nano-scale CeO 2 And (3) measuring 10 ml acetic acid to dilute the solution, adding the diluted solution into the full-battery support electrode microchannel prepared by the first process in a negative pressure auxiliary impregnation mode, and sintering the solution for 2 hours at 750 ℃.
Ni/CeO 2 -Al 2 O 3 Fiber catalyst: weigh 0.4308 gNi (NO) 3 ) 2 ·6H 2 O（≥98%），1.084 gAl(NO 3 ) 3 ·9H 2 O（≥99%），0.2008 g Ce(NO 3 ) 3 ·6H 2 O (more than or equal to 99 percent), 8 g distilled water, 2 g absolute ethyl alcohol (more than or equal to 99 percent), 1 g polyvinylpyrrolidone (PVP, molecular weight of 1300000) are placed in a beaker, and added with magnetons to stir more than 5 h until clear, transparent and bubble-free. Then preparing a fiber catalyst by using an electrostatic spinning machine, and sintering the fiber catalyst at 800 ℃ to obtain 2 h. Grinding the phase-formed fiber catalyst, placing a certain mass into a glass vial, adding ethanol, sufficiently crushing in ultrasonic wave, adding into a support electrode microchannel by using a negative pressure (-2-1 bar) auxiliary adding mode, drying, and repeatedly operating to ensure 241mm 3 The mass of the fiber catalyst in the support body is from 3mg to 10mg, and the novel renewable energy storage reactor for ethanol reforming auxiliary electrolytic water is prepared.
Example 2
The preparation process of the full cell is the same as the second process in the embodiment 1, the full cell is prepared by co-sintering the electrode and the electrolyte, and the pure ethanol is used for assisting in electrolyzing water through electrochemical oxidation.
Preparing an ethanol electrochemical oxidation auxiliary electrolytic water catalyst:
PD-Gd 0.1 Ce 0.9 O 2 catalyst precursor: 0.0444 g of Gd (NO) was weighed 3 ) 3 ·6H 2 O（≥99%），0.3936 g Ce(NO 3 ) 3 ·6H 2 O (. Gtoreq.99%), 4.72 g N, N-dimethylformamide, 0.102 g polyvinylpyrrolidone (PVP, molecular weight 1300000) were placed in a beaker and dissolved thoroughly. Weigh 0.0533 g Pd (NO) 3 ) 3 ·2H 2 O (more than or equal to 99 percent) is dissolved in the prepared solution of 1 g. Then dipped into the support electrode microchannel, and sintered for 750 hours, repeated 2 times.
Ru-Gd 0.1 Ce 0.9 O 2 Fiber catalyst: 0.3173 g Gd (NO) was weighed 3 ) 3 ·6H 2 O（≥99%），0.1313 g RuCl 3 ，2.7475 g Ce(NO 3 ) 3 ·6H 2 O (more than or equal to 99 percent), 8 g distilled water, 2 g absolute ethyl alcohol (more than or equal to 99 percent), 0.8 g polyvinylpyrrolidone (P)VP, molecular weight 1300000) was placed in a beaker and added with magnetic stirring 10 h above until clear and transparent without bubbles. Then preparing a fiber catalyst by using an electrostatic spinning machine, and sintering the fiber catalyst at 800 ℃ to obtain 2 h. Grinding the phase-formed fiber catalyst, placing a certain mass into a glass vial, adding ethanol, sufficiently crushing in ultrasonic wave, adding into a support electrode microchannel by using a negative pressure (-2-1 bar) auxiliary adding mode, drying, and repeatedly operating to ensure 241mm 3 And (3) the mass of the fiber catalyst in the support body is 3mg to 10mg, and the novel renewable energy storage reactor for the ethanol electrochemical oxidation auxiliary electrolytic water is prepared.
The reactor is used for storing pure renewable energy sources
Application example 1
Ethanol reforming assisted electrolysis: and (3) testing the electrochemical stability at the operation temperature of 800 ℃, sealing the electrolytic cell of the reactor for the efficient catalytic ethanol reforming reaction prepared by the first process in the embodiment 1 in an alumina ceramic tube by using a ceramic high-temperature sealing adhesive, raising the temperature to 260 ℃ at the speed of 2 ℃/min, preserving the heat for 1h, and raising the temperature to 800 ℃ at the speed of 4 ℃/min. Ar is introduced into the cathode and the anode to be exhausted, and then H is introduced 2 Reduction, then cathodic addition of 30% Ar +60% CO 2 +10%H 2 And anode introduction of 77% Ar +20% H 2 O+3%C 2 H 5 OH gas or cathodic 50% Ar +40% H 2 O+10%H 2 And anode introduction of 77% Ar +20% H 2 O+3%C 2 H 5 OH gas. The cells were first tested for ac impedance using an electrochemical workstation with a high frequency setting of 100000HZ and a low frequency setting of 0.1HZ, the results of which are shown in figure 4. The cells were then tested for current density-voltage (C-V) curves using an electrochemical workstation with a cut-off voltage of no more than 1.5V, and the results are shown in fig. 5. Finally, stability test is carried out, and the battery is 1A cm -2 The current density was run at 150h with no significant attenuation, and the results are shown in fig. 6. Simultaneous cathode and anode generation of large quantities of H 2 。
Application example 2
Ethanol electrochemical oxidation assisted electrolysis: electrochemical stability test at 800 deg.C operating temperature, the reactor for high efficiency catalytic ethanol oxidation reforming reaction prepared in example 2 was sealed and bonded with ceramic at high temperatureThe agent is sealed in an alumina ceramic tube, the temperature rises to 260 ℃ at the rate of 2 ℃/min, the temperature is kept for 1h, and the temperature rises to 800 ℃ at the rate of 4 ℃/min. Ar is introduced into the cathode and the anode to be exhausted, and then H is introduced 2 Reduction, then cathodic addition of 60% Ar +30% H 2 And anode was purged with 92.5% Ar +7.5% C2H5OH gas. The cells were first tested for ac impedance using an electrochemical workstation with a high frequency setting of 100000HZ and a low frequency setting of 0.1HZ, the results of which are shown in figure 7. The cells were then tested for current density-voltage (C-V) curves using an electrochemical workstation with a cut-off voltage of no more than 1.5V, and the results are shown in fig. 8. Finally, stability test is carried out, and the battery is at 3A cm -2 The current density is 100H, no obvious attenuation is generated, see figure 9, a large amount of H is generated at the cathode 2 Simultaneous anodic production of large quantities of synthesis gas (CO + H) 2 ) (ii) a Fig. 10 is a cross section SEM of the reactor after stability test by introducing ethanol for electrochemical oxidation assisted electrolysis, and it can be seen that there is no significant carbon deposition inside the reactor after reaction, and EDS further proves that only a very small proportion of carbon is generated.
The renewable energy storage reactor is also suitable for acetic acid and biodiesel biomass materials, and has high electrolysis efficiency and stable operation.
Claims (5)
1. Use of a novel renewable energy storage reactor, characterized in that it comprises: an anode support body with a micro-channel structure, an electrolyte thin layer and a porous cathode layer; wherein the inside of the micro-channel structure is loaded with a catalyst for reforming biomass micromolecules, one end of the micro-channel structure starts from the surface of the anode and penetrates through the support body to reach the anode/electrolyte interface;
the thickness of the electrode support body with the microchannel structure is 0.3mm to 1.5mm, and the thickness of the thin electrolyte layer is 0.4 mu m to 30 mu m; the diameter of the electrode/thin electrolyte interface microchannel is 0.5-5 μm, the microchannel of the electrode support body is a dendritic microchannel and penetrates through the support electrode, and the diameter of the microchannel is gradually combined and increased to 10-100 μm;
the support material is Sm 0.2 Ce 0.8 O 2 、Gd 0.1 Ce 0.9 O 2 、(Sc 2 O 3 ) 0.10 (CeO 2 ) 0.01 (ZrO 2 ) 0.89 、(Y 2 O 3 ) 0.08 Zr 0.92 O 2 、La 0.9 Sr 0.1 Ga 0.8 Mg 0.2 O 3 、La 1.9 Ca 0.1 Zr 2 O 7 、La 0.9 S r0.1 ScO 3 、Ba 3 Ca 1.18 Nb 1.82 O 9 、BaCe 0.9 Y 0.1 O 3 、BaCe 0.6 Zr 0.3 Y 0.1 O 3 、BaZr 0.9 Y 0.1 O 3 、SrCe 0.95 Yb 0.05 O 3 Or BaCe 0.4 Zr 0.4 Y 0.2 O 3 The electrolyte is (Y) 2 O 3 ) 0.08 Zr 0.92 O 2 Or Gd 0.1 Ce 0.9 O 2；
The renewable energy reactor is suitable for solid oxide cells with a cathode-supported or anode-supported structure; the solid oxide cell utilizes biomass-based micromolecules to assist in electrolyzing water, so that energy storage is realized;
the method for electrolyzing water by using biomass-based micromolecules as an anode of the renewable energy storage reactor comprises the following steps:
(1) Sealing the renewable energy reactor in a ceramic tube, firstly heating to 260 ℃ at the speed of 2 ℃/min, preserving the temperature of 1h, and then heating to the operation temperature of 650-1050 ℃ at the speed of 4 ℃/min;
(2) The cathode and the anode are evacuated by introducing inert gas, and then H is introduced 2 Reducing, introducing inert gas and H into cathode 2 O and H 2 The anode is filled with inert gas and mixed gas of biomass-based micromolecules;
(3) An external power supply is used for applying electric potential to the reactor, water is electrolyzed at the cathode, and biomass-based micromolecules are oxidized electrochemically at the anode.
2. The use of claim 1, wherein the biomass-based small molecule is one or a mixture of ethanol, acetic acid and biodiesel.
3. Use according to claim 1 or 2, wherein the anode of the renewable energy storage reactor is used for assisted electrolysis of water with biomass-based small molecules or with a mixture of biomass-based small molecules and water.
4. The use according to claim 3, wherein the renewable energy reactor is used for carrying out a biomass-based small molecule reaction by an anode production method comprising:
(1) Firstly, preparing a catalyst with reforming capacity;
(2) And (2) uniformly filling the catalyst prepared in the step (1) into the micro-channel of the anode support body to obtain the anode for carrying out the biomass-based small molecule reforming reaction.
5. The use according to claim 4, wherein the catalyst having reforming ability of step (1) is in the form of particles or fibers.
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