CN105576252A - Solid oxide fuel cell based on semiconductor junction effect and preparation method of solid oxide fuel cell - Google Patents

Solid oxide fuel cell based on semiconductor junction effect and preparation method of solid oxide fuel cell Download PDF

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CN105576252A
CN105576252A CN201610160492.XA CN201610160492A CN105576252A CN 105576252 A CN105576252 A CN 105576252A CN 201610160492 A CN201610160492 A CN 201610160492A CN 105576252 A CN105576252 A CN 105576252A
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fuel cell
anode
solid oxide
oxide fuel
negative electrode
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CN105576252B (en
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王广军
龙国徽
吴香英
纪媛
徐付占
孟元靖
梁旭
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Jilin University
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Jilin University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • H01M4/9025—Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
    • H01M4/9033—Complex oxides, optionally doped, of the type M1MeO3, M1 being an alkaline earth metal or a rare earth, Me being a metal, e.g. perovskites
    • 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
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • 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
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M2008/1293—Fuel cells with solid oxide electrolytes
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Fuel Cell (AREA)
  • Inert Electrodes (AREA)

Abstract

The invention relates to a solid oxide fuel cell based on a semiconductor junction effect and a preparation method of the solid oxide fuel cell. The solid oxide fuel cell structurally comprises a cathode, an anode and current collectors, wherein the current collectors are arranged on outer sides of the cathode and the anode. The solid oxide fuel cell is characterized in that the cathode is a proton/oxygen ion conductor material with properties of an n-type semiconductor, the anode is a proton/oxygen ion conductor material with properties of a p-type semiconductor, and a current carrier depletion layer is at the interface between the cathode and the anode. The solid oxide fuel cell is not equipped with a solid electrolyte layer, so that the ohmic loss caused by electrolyte is decreased to zero; and meanwhile, the solid oxide fuel cell further has the advantages of low interface transportation loss, production cost and working temperature and the like.

Description

Solid Oxide Fuel Cell of based semiconductor knot effect and preparation method thereof
Technical field
The invention belongs to fuel cell field, especially relate to a kind of p-n junction Solid Oxide Fuel Cell.
Background technology
Fuel cell technology is considered to one of 21 century most promising clean energy technology.Usual fuel cell is divided into 5 classes: Proton Exchange Membrane Fuel Cells, Solid Oxide Fuel Cell, molten carbonate fuel cell, phosphoric acid fuel cell and alkaline fuel cell.But in fact, the emphasis of research at present mainly concentrates in Proton Exchange Membrane Fuel Cells and Solid Oxide Fuel Cell.Proton Exchange Membrane Fuel Cells has the advantages such as working temperature is low, easy to maintenance, toggle speed is fast, has had a lot of successfully demonstrative project at present, but has not also reached the requirement of commercial applications far away.First, the use of noble metal platinum causes product price to remain high on the one hand, has high requirement on the other hand, because extremely the foreign gas of trace can cause catalyst poisoning, thus make battery failure to hydrogen purity; Secondly, cold operation makes the product generated be aqueous water, easily causes the problems such as gas circuit embolism, so proton membrane fuel battery needs to design well water management, heat management etc., thus makes system complex.Can not directly use fossil combustion gas, be also the defect that of Proton Exchange Membrane Fuel Cells is very large.Solid Oxide Fuel Cell is compared, and has many good qualities: 1. hot operation ensure that sufficiently rapid dynamic process, thus noble metal can not be used as catalyst; 2. product is gaseous material, easily discharges battery pile, can not cause airway blockage; 3. can adapt to various fuel; 4. can carry out cogeneration, greatly improve fuel utilization efficiency.
Although Solid Oxide Fuel Cell possesses lot of advantages, some shortcomings of itself make it be difficult to enter practical stage.Usual Solid Oxide Fuel Cell is all three-decker: negative electrode, anode and electrolyte.Although this structure ensure that fuel cell can realize the conversion of chemical energy to electric energy, structure there are some birth defects.Three-decker makes fuel cell complex process in preparation, brings higher process costs; Three-decker must comprise two interfaces: electrolyte anodic interface and electrolyte cathode interface, and these two interfaces can cause very large electrical interface to transport loss, cause fuel battery power and efficiency losses; Can spread each other between interface and even react, thus directly have influence on the service life of battery; Intermediate layer electrolyte can bring very large ohmic loss, and this is also the main cause that Solid Oxide Fuel Cell needs at high temperature to operate.Electrolyte only has just can have good ionic conductivity at sufficiently high temperature.
Summary of the invention
Main purpose of the present invention is to overcome the deficiencies in the prior art, provides a kind of brand-new Solid Oxide Fuel Cell configuration.
For achieving the above object, the present invention is by the following technical solutions:
A kind of Solid Oxide Fuel Cell of based semiconductor knot effect, its structure comprises negative electrode and anode and is positioned at the cathode current collector of cathode outer side and the anode collector be positioned at outside anode, it is characterized in that, described negative electrode is the proton/oxygen ion conductor material with n-type semiconductor characteristic, described anode is the proton/oxygen ion conductor material with p-type semiconductor characteristic, in the interface of negative electrode and anode, there is the carrier depletion layer that negative electrode and anode are formed jointly.
In the Solid Oxide Fuel Cell of a kind of based semiconductor knot effect of the present invention, the preferred Tb of described negative electrode 0.2ce 0.4o 2-x(being designated as TDC) and cobalt oxide are the binary composite (being designated as TDC+Co) of 1:0.02 formation in molar ratio; Described anode preferred lithium cell positive material LiNi 0.8co 0.15al 0.05o 2-y(being designated as LNCA) or hydrogen separation membrane ceramic material BaZr 0.3ce 0.6y 0.1zn 0.05o 3-z, wherein x, y, z is non-stoichiometric number, and x, y, z is all greater than-1 and is less than 1.
In the Solid Oxide Fuel Cell of a kind of based semiconductor knot effect of the present invention, described anode collector preferred foams nickel or foam copper, described cathode current collector is preferred foams nickel or foam copper also.
In the Solid Oxide Fuel Cell of a kind of based semiconductor knot effect of the present invention, in order to obtain better performance, between negative electrode and cathode current collector or/and between anode and anode collector, also has decorative layer, the material identical with corresponding negative electrode or anode that described decorative layer is loose structure.
The preparation method of the Solid Oxide Fuel Cell of a kind of based semiconductor knot of the present invention effect, has following steps:
1) take 0.2gTDC+Co, then take 0.2gLNCA or BaZr 0.3ce 0.6y 0.1zn 0.05o 3-z;
2) nickel foam or the foam copper disk of two pieces of diameter 12.8 mm of thickness 1mm is prepared;
3) by nickel foam or foam copper disk, TDC+Co, LNCA or BaZr 0.3ce 0.6y 0.1zn 0.05o 3-z, nickel foam or foam copper disk order they are filled out in the stainless steel mould being put into diameter 13mm successively, ensure that sample spreading is even;
4) dry-pressing formed under the pressure of 200-300MPa, obtain a complete fuel cell;
Described TDC+Co is Tb 0.2ce 0.4o 2-xwith the binary composite that cobalt oxide is 1:0.02 formation in molar ratio, described LNCA is anode material of lithium battery LiNi 0.8co 0.15al 0.05o 2-y.
Described TDC+Co can be prepared with conventional coprecipitation or sol-gal process, specifically can see document Balaguer, M.a., C.Sol í s, andJ.M.Serra, StudyoftheTransportPropertiesoftheMixedIonicElectronicCo nductorCe 1-xtb xo 2-δ+ Co (x=0.1,0.2) andEvaluationAsOxygen-TransportMembrane.ChemistryofMater ials, 2011.23 (9): p.2333-2343.
The present invention's clear superiority is compared with prior art:
1, bi-level fuel battery of the present invention eliminates solid electrolyte layer, thus the ohmic loss that electrolyte causes is dropped to zero.
2, the present invention reduces to an interface two of conventional fuel cell interfaces, thus reduces interface and transport loss.
3, double-decker of the present invention greatly simplifies preparation technology thus reduces production cost.
4, the present invention adopts commercialization lithium battery material, Commercial Prospect is possessed in material, make use of the catalytic activity of transition metal oxide and the ionic transport properties of its layer structure in commercialization lithium battery material simultaneously dexterously, make the operating temperature of battery be reduced to less than 600 degrees Celsius.
Accompanying drawing explanation
Fig. 1 is the Electronic Speculum sectional view of the Solid Oxide Fuel Cell of the based semiconductor knot effect of an embodiment of the present invention;
Fig. 2 is the output characteristic curve of the Solid Oxide Fuel Cell of based semiconductor of the present invention knot effect;
Fig. 3 is junction characteristic test (rectification curve) of the Solid Oxide Fuel Cell of based semiconductor of the present invention knot effect;
Fig. 4 is the fundamental diagram of the Solid Oxide Fuel Cell of based semiconductor of the present invention knot effect;
Fig. 5 is that the Solid Oxide Fuel Cell of based semiconductor of the present invention knot effect adopts decorative layer structure chart;
Fig. 6 is the equivalent circuit diagram of the Solid Oxide Fuel Cell of based semiconductor of the present invention knot effect.
Embodiment
Feature of the present invention and advantage will be described in detail by reference to the accompanying drawings by embodiment.
The preparation of embodiment 1 fuel cell
For the preparation method adopting TDC+Co and LNCA that this battery is described.
Take 0.2gTDC+Co sample and 0.2gLNCA; Prepare the nickel foam disk of two pieces of diameter 12.8 mm of thickness 1mm; By the order of nickel foam disk, TDC+Co sample, LNCA, nickel foam disk, they are filled out in the stainless steel mould being put into diameter 13mm successively, ensure that sample spreading is even; Dry-pressing formed under the pressure of 200-300MPa, a complete fuel cell can be obtained.
Please refer to Fig. 1, the cross section Electronic Speculum figure of the Solid Oxide Fuel Cell that the present invention is based on semiconductor junction effect in Fig. 1, clearly can see in figure that battery is made up of two-layer, loose one deck (i.e. the left side) is LNCA layer, and one deck of densification is TDC+Co layer, between two-layer, interface is clear.The reason of two-layer morphogenesis is, the a small amount of Co comprised in TDC+Co layer plays the effect of sintering aid, under the effect of sintering aid, TDC+Co layer can form fine and close one deck, thus to save in conventional preparation techniques repeatedly sintering step, but by the disposable formation compacted zone of online sintering and weaker zone structure.
If LNCA to be replaced with hydrogen separation membrane ceramic material BaZr 0.3ce 0.6y 0.1zn 0.05o 3-z, wherein z is greater than-1 and is less than 1, and nickel foam is replaced with foam copper, also can implement the present invention by said process.
The performance test of embodiment 2 fuel cell
The monocell that embodiment 1 obtains is encapsulated on alumina tube, in the temperature range of 400-580 degree Celsius, to battery LNCA side and TDC+Co side logical fuel gas (as hydrogen) and air respectively, just can obtains stable electric energy and export.Battery specific works principle is as follows: LNCA is anode material of lithium battery, and in lithium battery, lithium ion can move freely in the layer structure of LNCA, thus ensures the free migration of lithium ion, realizes charging and discharging lithium battery process; In fuel cell of the present invention, nickel and cobalt component have extraordinary catalytic activity to fuel molecule (such as hydrogen), and the proton ratio lithium ion that catalysis produces is also little, so the proton produced can move freely equally in the layer structure of LNCA, thus realize anode of fuel cell half-reaction
H 2＝2H ++2e
And in TDC+Co side, oxygen molecule can the catalyzed reduction on surface, and oxonium ion can be transported to anode by Lacking oxygen thus realize negative electrode half-reaction inside TDC+Co
O 2＝2O 2-+4h
Finally, overall reaction is realized
O 2+2H 2＝2H 2O
Although there is no electrolyte as the electrical isolation layer of negative electrode and anode, but due to the material that TDC+Co is n-type semiconductor characteristic, and LNCA is p-type semiconductor elastomeric material, so can carrier depletion layer be formed at two-layer interface place, thus realize the electrical isolation of negative electrode and anode, guarantee from battery, to export electric energy smoothly.
Please refer to Fig. 2, Fig. 2 is the output characteristic of battery, and battery maximum power density in the interval of 500-580 degree Celsius reaches 230-300mWcm -2and traditional sandwich structure battery needs effectively to export electric energy 600-850 degree Celsius of ability, consider that the cell thickness prepared in the present embodiment is 1.2mm, so above-mentioned power density is also far from having given play to the maximum potential of this kind of configuration device, if adopt thin film technique to prepare the compacted zone of tens micron thickness to replace present compacted zone, under same operating temperature, the power density of battery may reach Wcm completely -2rank.
Please refer to Fig. 3, be the rectification curve of battery in Fig. 3, inside battery has a built-in p-n junction as can see from Figure 3, and this knot makes battery can not short circuit just.
Please refer to Fig. 4, Fig. 4 is the p-n junction operation of fuel cells schematic diagram prepared with TDC+Co and LNCA material, and cathode side oxygen molecule is embedded into inside intracell Lacking oxygen at TDC+Co layer catalyzed generation oxonium ion, anode side diffusion under the effect of concentration gradient; Another side anode side hydrogen molecule is catalyzed to be embedded in the layer structure of LNCA for hydrogen ion, and last hydrogen ion and oxonium ion water generation reaction discharge battery from anode-side.Because LNCA has p-type semiconductor characteristic, TDC+Co is n-type semiconductor, and both interfaces form planar p-n junction, have blocked electronics transmission channel between the two layers, thus can be obtained the electric energy of fuel cell reaction generation by external circuit.
In order to improve reaction interface area, improving catalytic activity, solve the problems such as Carbon deposition, the decorative layer that one deck is loose can be increased.Please refer to Fig. 5, Fig. 5 is the p-n junction fuel cell configuration picture with decorative layer, and decorative layer provides more reaction interface for loose and porous structure is easy to gas diffusion simultaneously.It should be noted that, although depict two decorative layers in figure, in practical application, only can use a decorative layer.Because in male or female can be made another layer of compacted zone in practical application and make porous layer, such porous layer side does not just need decorative layer, and only needs to be coated with corresponding decorative layer in the outside of compacted zone.Decorative layer preferably adopts with the identical material of counter electrode, thus avoids heat coupling and chemical matching problem, and can not introduce new biphase interface, makes only there is a kind of biphase interface in battery, ensures that the interface loss of battery drops to minimum.
Please refer to Fig. 6, Fig. 6 is the equivalent circuit diagram of fuel cell of the present invention.Because two electrodes adopt the material of N-shaped and p-type semiconductor characteristic respectively, p-n junction can be formed between two-layer, equivalent electric circuit can be regarded a voltage source as and follow a p-n junction diodes in parallel again with after internal resistance series connection, because diode is in reverse-bias state, so can not conducting, this guarantees battery can not internal short-circuit, thus can obtain energy from battery efficiently.
Above content is in conjunction with concrete execution mode further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, some simple deduction or replace can also be made, all should be considered as belonging to protection scope of the present invention.

Claims (5)

1. the Solid Oxide Fuel Cell of a based semiconductor knot effect, its structure comprises negative electrode and anode and is positioned at the cathode current collector of cathode outer side and the anode collector be positioned at outside anode, it is characterized in that, described negative electrode is the proton/oxygen ion conductor material with n-type semiconductor characteristic, described anode is the proton/oxygen ion conductor material with p-type semiconductor characteristic, in the interface of negative electrode and anode, there is the carrier depletion layer that negative electrode and anode are formed jointly.
2. the Solid Oxide Fuel Cell of a kind of based semiconductor knot effect according to claim 1, is characterized in that, described negative electrode is Tb0.2Ce0.4O2-x and cobalt oxide is the binary composite of 1:0.02 formation in molar ratio; Described anode is anode material of lithium battery LiNi0.8Co0.15Al0.05O2-y or hydrogen separation membrane ceramic material BaZr0.3Ce0.6Y0.1Zn0.05O3-z, and wherein x, y, z is non-stoichiometric number, and x, y, z is all greater than-1 and is less than 1.
3., according to the Solid Oxide Fuel Cell of a kind of based semiconductor knot effect of claim 1 art, it is characterized in that, described anode collector is nickel foam or foam copper; Described cathode current collector is nickel foam or foam copper.
4. according to the Solid Oxide Fuel Cell of the arbitrary described a kind of based semiconductor knot effect of claims 1 to 3, it is characterized in that, between negative electrode and cathode current collector or/and between anode and anode collector, there is decorative layer, the material identical with corresponding negative electrode or anode that described decorative layer is loose structure.
5. a preparation method for the Solid Oxide Fuel Cell of the based semiconductor knot effect of claim 1, has following steps:
1) take 0.2gTDC+Co, then take 0.2gLNCA or BaZr 0.3ce 0.6y 0.1zn 0.05o 3-z;
2) nickel foam or the foam copper disk of two pieces of diameter 12.8 mm of thickness 1mm is prepared;
3) by nickel foam or foam copper disk, TDC+Co, LNCA or BaZr 0.3ce 0.6y 0.1zn 0.05o 3-z, nickel foam or foam copper disk order they are filled out in the stainless steel mould being put into diameter 13mm successively, ensure that sample spreading is even;
4) dry-pressing formed under the pressure of 200-300MPa, obtain a complete fuel cell;
Described TDC+Co is Tb 0.2ce 0.4o 2-xwith the binary composite that cobalt oxide is 1:0.02 formation in molar ratio, described LNCA is anode material of lithium battery LiNi 0.8co 0.15al 0.05o 2-y.
CN201610160492.XA 2016-03-21 2016-03-21 SOFC based on semiconductor junction effect and preparation method thereof Expired - Fee Related CN105576252B (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106602114A (en) * 2017-01-22 2017-04-26 河北博威集成电路有限公司 Fuel cell electrolyte and PIN configuration solid oxide fuel cell
CN106848495A (en) * 2017-01-22 2017-06-13 河北博威集成电路有限公司 Solid oxide electrochemical energy device and preparation method thereof
CN107994234A (en) * 2017-11-06 2018-05-04 深圳大学 Ceramic fuel cell and preparation method thereof
CN110021771A (en) * 2019-04-23 2019-07-16 湖北大学 Based on SnO2The preparation method of-SDC semiconductor-ion conductor schottky junction fuel cell
CN112048735A (en) * 2020-09-14 2020-12-08 湖北大学 Solid oxide electrolytic cell and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
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CN101278428A (en) * 2005-09-29 2008-10-01 米克罗西利特龙公司 Fuel battery unit cell, fuel battery unit cell array, fuel battery module, and fuel battery system
CN103081197A (en) * 2010-08-02 2013-05-01 Gett燃料电池国际公司 Fuel cell

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101278428A (en) * 2005-09-29 2008-10-01 米克罗西利特龙公司 Fuel battery unit cell, fuel battery unit cell array, fuel battery module, and fuel battery system
CN103081197A (en) * 2010-08-02 2013-05-01 Gett燃料电池国际公司 Fuel cell

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106602114A (en) * 2017-01-22 2017-04-26 河北博威集成电路有限公司 Fuel cell electrolyte and PIN configuration solid oxide fuel cell
CN106848495A (en) * 2017-01-22 2017-06-13 河北博威集成电路有限公司 Solid oxide electrochemical energy device and preparation method thereof
CN106848495B (en) * 2017-01-22 2023-12-01 河北博威集成电路有限公司 Solid oxide electrochemical energy device and preparation method thereof
CN107994234A (en) * 2017-11-06 2018-05-04 深圳大学 Ceramic fuel cell and preparation method thereof
CN110021771A (en) * 2019-04-23 2019-07-16 湖北大学 Based on SnO2The preparation method of-SDC semiconductor-ion conductor schottky junction fuel cell
CN112048735A (en) * 2020-09-14 2020-12-08 湖北大学 Solid oxide electrolytic cell and preparation method thereof
US20220081790A1 (en) * 2020-09-14 2022-03-17 Hubei University Solid oxide electrolysis cell (soec) and preparation method thereof
CN112048735B (en) * 2020-09-14 2022-04-19 湖北大学 Solid oxide electrolytic cell and preparation method thereof

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