CN101847734A - Method for preparing tubular solid oxide fuel cell - Google Patents
Method for preparing tubular solid oxide fuel cell Download PDFInfo
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- CN101847734A CN101847734A CN201010186133A CN201010186133A CN101847734A CN 101847734 A CN101847734 A CN 101847734A CN 201010186133 A CN201010186133 A CN 201010186133A CN 201010186133 A CN201010186133 A CN 201010186133A CN 101847734 A CN101847734 A CN 101847734A
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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
- Y02E60/50—Fuel cells
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention provides a method for preparing a tubular solid oxide fuel cell by using macromolecular gluing molding technology, and belongs to the field of solid fuel cells. The method comprises the following process steps of: adding mixed powder, homogeneous phase bonding agent, pore-forming material and dispersant for a fuel cell anode into aqueous solution containing macromolecular monomer and cross linker respectively, adjusting the pH value of the solution, and fully grinding and dispersing the solution to obtain anode slurry; adding a curing agent into the slurry, stirring the slurry, then quickly pumping vacuum to exhaust air, and pouring the slurry into a tubular die to perform heating and curing; and after mould release, pre-sintering the slurry to obtain a tubular anode support material, finally spraying electrolyte slurry on the outer surfaces of matrixes respectively to form anode-electrolyte composite membranes, sintering the membranes together, spraying cathode slurry on the outer side of electrolyte, and secondarily sintering the slurry to obtain the tubular solid oxide fuel cell with a sandwich structure and any shape. The tubular solid oxide fuel cell prepared by the method has the advantages of enhanced cell efficiency and high utilization rate of raw materials; and the preparation method is simple and environment-friendly, has good repeatability, greatly reduces the production cost, and is easy for industrialized implementation and application.
Description
Technical field
The present invention relates to macromolecule glue and be linked to be the method that the type technology prepares tubular type abnormity solid oxide fuel tubular type battery, belong to the solid fuel cell field.
Background technology
Fuel cell is a kind of using gases fuel, the chemical energy of fuel directly be converted to low voltage and direct current can electrochemical generating unit, the chemical energy that is about to hydrogen and oxygen is directly changed into the device of electric energy by electrode reaction.The maximum characteristics of this device are owing to do not relate to burning in the course of reaction, so its energy conversion efficiency is not subjected to the restriction of " Carnot cycle ", and its theoretical energy conversion rate is up to 60%～80%, and actual service efficiency then is 2～3 times of ordinary internal combustion engine.
Solid Oxide Fuel Cell (SOFC) technology is as a kind of high-temperature fuel cell, except having general fuel cell high efficiency, oligosaprobic advantage, SOFC also has the following advantages: (1) is carried out focus via heat recovery technology and is merged generating, can obtain to surpass 80% focus combined efficiency, when mixing use with steam turbine, its generating efficiency can reach 70～75%; Therefore (2) electrolyte of SOFC is a solid, does not have the problem of electrolyte evaporation and leakage, and electrode do not have the problem of corroding yet, and running life is long; (3) SOFC need not to use precious metal catalyst, and itself has interior rearrangement capability, can directly adopt natural gas, coal gas or other hydrocarbons to act as a fuel, and has simplified battery system; (4) generating efficiency height can bear overload, low carrying, even short circuit.
The commercialization fuel cell pack is made up of a plurality of monocell connection in series-parallel.Classify on the solid oxide fuel single-cell structure, can be divided into: tubular type and flat two class formations.Comparatively speaking, the advantage of tubular type SOFC is simple in structure, and sealing is easy, and the anti-thermal shock ability is strong, and is rapid to load-reaction, and scale is amplified easily, is that a kind of fine energy is realized business-like version.At present; what tubular type SOFC development was leading in the world is Siemens-Westinghouse company; they adopt the extrusion molding moulding; with the negative electrode pottery as supporter; electrolyte and anode adopt the method moulding of EVD or plasma spraying (plasma spraying), the equipment complexity of its use, technological requirement height; so the manufacturing cost height, the more extensiveization use of restriction Solid Oxide Fuel Cell.
Comparatively speaking, battery adopts the structure of anode-supported mode, fuel cell can move in the mode of interior reformation, simplify outer reformer, structure is more succinct, anode material (as YSZ and NiO material) just can reach proper supporting intensity, thus adopted by many producers both at home and abroad and research institution in recent years, as the extrusion modling of U.S. Acumentrics company, Korea S energy research institute, Kyocera etc.
People such as the domestic Shanghai Li Lisong of silicate research institute have applied for patent " method of dip moulding pipe type solid oxide fuel battery ", publication number CN1700494A in 2005.This prior art has been introduced a kind of high-temperature tubular preparation of solid oxide fuel cell, by batching, ball milling, vacuumize, process such as dipping, the demoulding, pre-burning, sintering, heat treatment, based on tubular die, by control to the dipping number of times, the sandwich structure of the different electrodes of control tubular type SOFC that can be substantially, work simplification is easy to grasp.Owing to adopt organic solvent to prepare slurry, increase later stage efforts at environmental protection amount, to the environmental sensibility height, also be difficult to prepare the SOFC battery of the tubular structure of labyrinth simultaneously on the technology.
People such as the Meng Guang of China Science ﹠ Technology University credit have applied for patent " a kind of anode support tube type solid oxide fuel battery " in 2002, publication number CN 2547010Y, the special-shaped tubular anode support of seven arms is arranged in the employing extruder molds, prepare special-shaped perforated tubular battery at last.Its battery advantage has: 1) increase the effecting reaction area, improve power density and 2) the interior space utilization efficient of raising stay pipe.The extruder moulding all requires harshness for mold design and extrusion process during for labyrinth, is not easy the assurance success rate of preparing product, is unfavorable for industrialized production.
More satisfactory anode support need certain structure intensity, microcosmic evenly, the electricity behind the venting capability, work reduction leads greatly, and electrolyte matched coefficients of thermal expansion.On the fuel cell for Zirconia electrolytic, generally adopting zirconia and nickel oxide is backing material at present.
Foregoing invention prepares the anode-supported preparation method, owing to adopt solid phase extruding or the moulding of organic solvent powder, when guaranteeing matched coefficients of thermal expansion, the nickel oxide addition can not be too many, leads at venting capability and electricity to be difficult on the ability guarantee.As adopt part of nickel to add with the solution form, guaranteeing can effectively to improve nickel in other uniformity of supporter distribution molecular level and continuity under the nickel content condition.After powdery pore-creating material adds sintering at present, in supporter, form the part closed pore easily, be unfavorable for improving the diffuser efficiency of gas, increase the polarization resistance value in anode support.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of macromolecule glue that adopts and be linked to be the method that the type forming technique prepares tubular solid oxide fuel cell, simple and easy adjusting support body material composition, microstructure and material homogeneity strengthen battery efficiency.
The technical solution adopted in the present invention is:
A kind of method for preparing tubular solid oxide fuel cell is characterized in that may further comprise the steps:
(1) method that adopts macromolecule glue to be linked to be type prepares the tubular anode supporter, and described tubular anode supporter is the ceramic anode supporter, and its preparation method may further comprise the steps:
A) preparation contains the aqueous solution of high polymer monomer and crosslinking agent, ceramic powder raw material, homogeneous phase bridging agent, pore-creating material and dispersant is added in the described aqueous solution somaplasm that is supported material respectively again;
B) add alkali or acid in the supporter slurry of step a) gained, the acidity-basicity ph value of adjusting described supporter slurry is 6～12;
C) the supporter slurry with the step b) gained carries out planetary ball mill, obtains finely dispersed supporter slurry;
D) the supporter slurry with the step c) gained leaves standstill, vacuumizes processing, discharges the gas ingredients in the described supporter slurry;
E) the supporter slurry with the step d) gained adds the high molecular polymerization catalyst, pours into after stirring in the tubular mould, and insulation allows described supporter slurry solidify in mould, and body is supported;
F) remove mould, the supporter presintering with the step f) gained obtains the tubular anode supporter;
(2) evenly spray electrolyte at the supporter outer surface, obtain anode-electrolyte structure layer after the drying and sintering;
(3), obtain the tubular solid oxide fuel cell of anode-supported after the drying and sintering at the even sprayed cathode material of anode-electrolyte structure layer outer surface.
Ceramic powder raw material in the described step a) is: Zirconium powder and nickel oxide powder.
Homogeneous phase bridging agent in the described step a) is the nickel salt in the water soluble, is: nickel nitrate, nickel acetate, nickel formate, nickel chloride, the one or more combination in the nickelous sulfate.
Pore-creating material in the described step a) is the millimeter or the micron order fiber material of carbon or hydrocarbon organic material, is: the one or more combination in micron carbon fiber, graphite fibre, acrylic, polypropylene fibre, the polyamide fibre.
Dispersant in the described step a) is: the one or more combination in citric acid, ammonium polyacrylate, the di-2-ethylhexylphosphine oxide bitter edible plant sodium sulfonate (NNO).
High polymer monomer in the described step a) is: a kind of or both combinations in methoxy polyethylene glycol methacrylate-styrene polymer (MPEGMA), the dimethylaminoethyl methacrylate (DMAEMA).
Crosslinking agent in the described step a) is: a kind of or both combinations in hexadiene tartaric acid diamines (DATDA), polyethylene glycol (1500) dimethylacrylate (PEG (1500) DMA).
Adopt the method that adds acid or add ammoniacal liquor in the described step b), the acid-base value of regulating the supporter slurry.
High molecular polymerization catalyst in the described step d) is: 2,2 '-azo [2-(2-imidazoline-2-yl) propane] hydrochloride (AZIP).
By adjusting supporter moulding material and sprayed on material, can be worth the tubular solid oxide fuel cell of porous material support or cathode support.
The beneficial effect that the present invention produced is:
(1) macromolecule glue be linked to be the type technology can simple and easy adjusting support body material composition, microstructure and material homogeneity, by mold design, can prepare the tubular structure of all kinds of labyrinths;
(2) anode support microcosmic, machinery and electric property excellence strengthen battery efficiency;
(3) can repeat moulding, the utilization rate of raw materials height for crushing members, substandard of profile;
(4) the simple environmental protection of preparation method, good reproducibility are produced and are greatly reduced cost, are easy to realization of industrialization and application.
Description of drawings
Fig. 1 is the SOFC battery flat tube sectional view of 5 pore structure anode-supported of employing this method preparation.
Number in the figure is represented: 1-anode support, 2-through hole, 3-dielectric substrate, 4-cathode material layer.
Specific embodiments
Below in conjunction with Fig. 1 embodiments of the invention are elaborated:
The invention provides a kind of method for preparing tubular solid oxide fuel cell, the method that this method adopts macromolecule glue to be linked to be type prepares the tubular anode supporter, adopts the mode of spraying to make dielectric substrate and cathode layer in supporting body surface.Specifically may further comprise the steps:
(1) preparation contains the aqueous solution of high polymer monomer and crosslinking agent, ceramic powder raw material, homogeneous phase bridging agent, pore-creating material and dispersant is added in the described aqueous solution somaplasm that is supported material respectively again.Wherein: the ratio of monomer and crosslinking agent is 1: 15～15: 1, and concentration of aqueous solution is: between 10～25%; Homogeneous phase bridging agent and powder stock ratio are 1: 100～1: 5, and pore-creating material and powder stock ratio are 1: 100～1: 5, and dispersant and powder stock ratio are 1: 100～1: 20.The ceramic powder raw material is: Zirconium powder and nickel oxide powder.Zirconia material has high rigidity, high strength, and high tenacity, the physical and chemical performance that high resistance to wear and chemical resistance or the like are good, zirconia have been widely used in fields such as pottery and refractory material; Nickel oxide also is a raw material of making nickel salt and Raney nickel as the adhesive agent and the colouring agent of pottery.The homogeneous phase bridging agent is the nickel salt in the water soluble, comprising: nickel nitrate, nickel acetate, nickel formate, nickel chloride, nickelous sulfate etc.The pore-creating material is the millimeter or the micron order fiber material of carbon or hydrocarbon organic material, comprising: micron carbon fiber, graphite fibre, acrylic, polypropylene fibre, polyamide fibre etc.Dispersant comprises: citric acid, ammonium polyacrylate, di-2-ethylhexylphosphine oxide bitter edible plant sodium sulfonate (NNO) etc.High polymer monomer comprises: methoxy polyethylene glycol methacrylate-styrene polymer (MPEGMA), dimethylaminoethyl methacrylate (DMAEMA) etc.Crosslinking agent comprises: hexadiene tartaric acid diamines (DATDA), polyethylene glycol (1500) dimethylacrylate (PEG (1500) DMA) etc.
(2) add acid or add ammoniacal liquor in the supporter slurry of step (1) gained, the acidity-basicity ph value of adjusting described supporter slurry is 6～12.
(3) the supporter slurry with step (2) gained carries out planetary ball mill, obtains finely dispersed supporter slurry.
(4) the supporter slurry with step (3) gained leaves standstill, vacuumizes processing, discharges the gas ingredients in the described supporter slurry.
(5) the supporter slurry with step (4) gained adds the high molecular polymerization catalyst, pours into after stirring in the tubular mould, is incubated 0.5～2h under 40～80 ℃ temperature conditions, allows described supporter slurry solidify in mould, and body is supported.Wherein: the high molecular polymerization catalyst is: 2,2 '-azo [2-(2-imidazoline-2-yl) propane] hydrochloride (AZIP), the high polymer monomer that the corresponding aqueous solution adopted.
(6) remove mould, the supporter presintering with step (5) gained obtains the tubular anode supporter.
(7) at supporter outer surface spraying electrolyte, after the drying, sintering under 1200～1450 ℃ of temperature conditions obtains anode-electrolyte structure layer.
(8) at anode-electrolyte structure layer outer surface sprayed cathode material, after the drying, sintering under 1200～1350 ℃ of temperature conditions obtains the tubular solid oxide fuel cell of anode-supported.
Above step can add tacryl by adjusting supporter moulding material and sprayed on material in support body material, adopt macromolecule glue to be linked to be the method for type again, and the preparation sintering obtains the porous material supporter.This is because the pre-heat fusing of tacryl makes supporter inside form a plurality of cavitys, becomes the porous material supporter.Then, skin lamination spraying electrolyte and cathode material at the porous material supporter make the tubular solid oxide fuel cell that porous material supports.
Also can with Zirconium powder in the supporter moulding material and nickel oxide powder, replace with lanthana powder, strontium oxide strontia powder and manganese oxide powder by adjusting supporter moulding material and sprayed on material.The method that adopts macromolecule glue to be linked to be type prepares cathode support body earlier, at the skin lamination spraying electrolyte and the anode material of anode support, makes the tubular solid oxide fuel cell of cathode support.
Present embodiment has provided detailed execution mode being to implement under the prerequisite with the technical solution of the present invention, but protection scope of the present invention is not limited to following embodiment.
Preparation 100ml contains the aqueous solution of dimethylaminoethyl methacrylate (DMAEMA) and hexadiene tartaric acid diamines (DATDA) (ratio 1: 1) concentration 20% earlier.In the aqueous solution, add zirconia (3YSZ) powder 300g and nickel oxide powder 180g, nickel acetate 40g, carbon fiber 10g and citric acid 5g respectively.Add several 20% ammoniacal liquor adjustment aqueous ph values then and equal 12.
The mixture that configures is carried out planetary ball mill 2 hours, obtain finely dispersed backing material slurry.Leave standstill a moment, discharge gas in the slurry by the mode of vacuumizing, add 2,2 then '-azo [2-(2-imidazoline-2-yl) propane] hydrochloride (AZIP) 0.2g, pour into after stirring in the flat tube mould, allow slurry in mould, solidify in 60 ℃ of insulation 1h.After removing mould, 1000 ℃ of sintering 2h obtain the tubular anode supporter.Behind spraying 8YSZ slurry on the supporter outer surface, 1400 ℃, obtain anode-electrolyte structure layer behind the 2h sintering; Evenly spray the LSM slurry again at anode-electrolyte structure layer outer surface at last, 1250 ℃ of sintering 2h obtain the pipe type solid oxide individual fuel cell.
Shown in Figure 1 is the SOFC battery flat tube sectional view that adopts 5 pore structure anode-supported of this method preparation.In the middle of being arranged in is anode support 1, and the method that is linked to be type by above-mentioned macromolecule glue is prepared from, and mainly may further comprise the steps: prepare burden, disperse, regulate slurry pH-value, vacuum exhaust, pour mould, heating cure, the demoulding and presintering into.It solidifies the mould that adopts and has central support, makes the internal placement of the anode support 1 that sintering forms that 5 through holes 2 be arranged, and through hole 2 feeds fuel gas when generating, thereby makes SOFC battery reflection generating.The outer surface of anode support 1 is followed successively by dielectric substrate 3 and cathode material layer 4, and they adopt the method for layering spraying successively and drying and sintering, obtains the SOFC battery flat tube of 5 pore structure anode-supported.
Adopt this method, can not be subjected to the constraint of original product structure fully, tubular solid oxide fuel cell is designed to arbitrary shape, to be adapted to the design and use of the tubular solid oxide fuel cell under different occasions, the different demand by mold design.
Claims (10)
1. method for preparing tubular solid oxide fuel cell is characterized in that may further comprise the steps:
(1) method that adopts macromolecule glue to be linked to be type prepares the tubular anode supporter, and described tubular anode supporter is the ceramic anode supporter, and its preparation method may further comprise the steps:
A) preparation contains the aqueous solution of high polymer monomer and crosslinking agent, ceramic powder raw material, homogeneous phase bridging agent, pore-creating material and dispersant is added in the described aqueous solution somaplasm that is supported material respectively again;
B) add alkali or acid in the supporter slurry of step a) gained, the acidity-basicity ph value of adjusting described supporter slurry is 6～12;
C) the supporter slurry with the step b) gained carries out planetary ball mill, obtains finely dispersed supporter slurry;
D) the supporter slurry with the step c) gained leaves standstill, vacuumizes processing, discharges the gas ingredients in the described supporter slurry;
E) the supporter slurry with the step d) gained adds the high molecular polymerization catalyst, pours into after stirring in the tubular mould, and insulation allows described supporter slurry solidify in mould, and body is supported;
F) remove mould, the supporter presintering with the step f) gained obtains the tubular anode supporter;
(2) evenly spray electrolyte at the supporter outer surface, obtain anode-electrolyte structure layer after the drying and sintering;
(3), obtain the tubular solid oxide fuel cell of anode-supported after the drying and sintering at the even sprayed cathode material of anode-electrolyte structure layer outer surface.
2. the method for preparing tubular solid oxide fuel cell according to claim 1 is characterized in that: the ceramic powder raw material in the described step a) is: Zirconium powder and nickel oxide powder.
3. the method for preparing tubular solid oxide fuel cell according to claim 1 is characterized in that: the homogeneous phase bridging agent in the described step a) is the nickel salt in the water soluble, is: nickel nitrate, nickel acetate, nickel formate, nickel chloride, the one or more combination in the nickelous sulfate.
4. the method for preparing tubular solid oxide fuel cell according to claim 1, it is characterized in that: the pore-creating material in the described step a) is the millimeter or the micron order fiber material of carbon or hydrocarbon organic material, is: the one or more combination in micron carbon fiber, graphite fibre, acrylic, polypropylene fibre, the polyamide fibre.
5. the method for preparing tubular solid oxide fuel cell according to claim 1 is characterized in that: the dispersant in the described step a) is: the one or more combination in citric acid, ammonium polyacrylate, the di-2-ethylhexylphosphine oxide bitter edible plant sodium sulfonate.
6. the method for preparing tubular solid oxide fuel cell according to claim 1 is characterized in that: the high polymer monomer in the described step a) is: a kind of or both combinations in methoxy polyethylene glycol methacrylate-styrene polymer, the dimethylaminoethyl methacrylate.
7. the method for preparing tubular solid oxide fuel cell according to claim 1 is characterized in that: the crosslinking agent in the described step a) is: a kind of or both combinations in hexadiene tartaric acid diamines, the polyethylene glycol dimethacrylate.
8. the method for preparing tubular solid oxide fuel cell according to claim 1 is characterized in that: adopt the method that adds acid or add ammoniacal liquor, the acid-base value of regulating the supporter slurry in the described step b).
9. the method for preparing tubular solid oxide fuel cell according to claim 1 is characterized in that: the high molecular polymerization catalyst in the described step d) is: 2,2 '-azo [2-(2-imidazoline-2-yl) propane] hydrochloride.
10. according to each described method for preparing tubular solid oxide fuel cell in the claim 1～9, it is characterized in that:, can make the tubular solid oxide fuel cell of porous material support or cathode support by adjusting supporter moulding material and sprayed on material.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111416134A (en) * | 2020-03-31 | 2020-07-14 | 西安交通大学 | Metal flat tube support, battery/electrolytic cell and battery stack structure |
| CN113381047A (en) * | 2021-05-25 | 2021-09-10 | 湖北赛傲氢能科技有限公司 | High-temperature oxide ion conductor battery and preparation method thereof |
| CN114824346A (en) * | 2022-05-26 | 2022-07-29 | 西安交通大学 | One-end-sealed conductive flat tube support type solid oxide fuel cell/electrolytic cell and cell stack structure |
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| CN1700494A (en) * | 2005-05-30 | 2005-11-23 | 中国科学院上海硅酸盐研究所 | Method for dip moulding pipe type solid oxide fuel battery |
| CN1233057C (en) * | 2003-04-09 | 2005-12-21 | 中国科学院过程工程研究所 | Method for preparing strontium lanthanum manganate self-supporting tube of solid oxide fuel cell by utiling slip-casting process |
| CN101162779A (en) * | 2007-10-26 | 2008-04-16 | 华南理工大学 | Preparation method of anode supporter of tube-type solid-oxide fuel battery |
| CN101295792A (en) * | 2007-04-24 | 2008-10-29 | 中国科学院大连化学物理研究所 | Compound anode of solid-oxide fuel battery and method for producing the same |
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| CN1233057C (en) * | 2003-04-09 | 2005-12-21 | 中国科学院过程工程研究所 | Method for preparing strontium lanthanum manganate self-supporting tube of solid oxide fuel cell by utiling slip-casting process |
| CN1700494A (en) * | 2005-05-30 | 2005-11-23 | 中国科学院上海硅酸盐研究所 | Method for dip moulding pipe type solid oxide fuel battery |
| CN101295792A (en) * | 2007-04-24 | 2008-10-29 | 中国科学院大连化学物理研究所 | Compound anode of solid-oxide fuel battery and method for producing the same |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111416134A (en) * | 2020-03-31 | 2020-07-14 | 西安交通大学 | Metal flat tube support, battery/electrolytic cell and battery stack structure |
| CN111416134B (en) * | 2020-03-31 | 2021-03-26 | 西安交通大学 | Metal flat tube support, battery/electrolytic cell and battery stack structure |
| CN113381047A (en) * | 2021-05-25 | 2021-09-10 | 湖北赛傲氢能科技有限公司 | High-temperature oxide ion conductor battery and preparation method thereof |
| CN113381047B (en) * | 2021-05-25 | 2023-12-15 | 湖北赛傲氢能科技有限公司 | High-temperature oxide ion conductor battery and preparation method thereof |
| CN114824346A (en) * | 2022-05-26 | 2022-07-29 | 西安交通大学 | One-end-sealed conductive flat tube support type solid oxide fuel cell/electrolytic cell and cell stack structure |
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