CN1471188A - Method for preparing intermediate-tmeperature solid oxide electrolyte superfine powder for fuel cell - Google Patents

Method for preparing intermediate-tmeperature solid oxide electrolyte superfine powder for fuel cell Download PDF

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CN1471188A
CN1471188A CNA021265569A CN02126556A CN1471188A CN 1471188 A CN1471188 A CN 1471188A CN A021265569 A CNA021265569 A CN A021265569A CN 02126556 A CN02126556 A CN 02126556A CN 1471188 A CN1471188 A CN 1471188A
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powder
agent
electrolyte
fuel cell
complexing
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阎景旺
程谟杰
董永来
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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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
    • 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

First, complexing metal ion by complexing agent, then adding organic gel-forming agent also as auxiliary complexing agent and fuel, and finally adding proper amount of NH4NO3. With being concentrated under 40-100 DEG C, the glue is heated till drastic combustion reaction similar to explode happens so as to generate superfine precursory powder of composite oxides. The method can synthesize electrolytical micropowder material possessing favorable sintering character with granularity in tens nano for solid oxide fuel cell. The method makes phasing temperature(superfine LSGM powder with granularity less then 100 nano is obtained) of La0.9 Sr0.1 Ca0.8 Mg0.2O[3-delta](LSGM9182) reduce to 1120 DEG C from 1500 DEG C by using solid state reaction method.

Description

A kind of method for preparing the intermediate temperature solid oxide fuel cell electrolyte superfine powder
Technical field
The present invention relates to a kind of preparation method of electrolyte superfine powder for fuel cell material, relate in particular to a kind of method for preparing the intermediate temperature solid oxide fuel cell electrolyte superfine powder.
Technical background
Solid Oxide Fuel Cell (SOFC) is the rapid novel green generation technology of coming of initiating of the eighties in last century.SOFC directly is transformed into electric energy with the chemical energy of fuel, have the Carnot cycle of not being subjected to and limit, other generation technologies such as the high and environmental friendliness of capacity usage ratio incomparable advantage.Exploitation simultaneously also is that to study the most deep system of SOFC widely be to be electrolytical high-temperature fuel cell system with yttrium stable zirconium oxide (YSZ) the earliest.Ionic conductivity is very low at low temperatures owing to YSZ, obtain commercial significant output power density, and battery must be worked under very high operating temperature.When the Solid Oxide Fuel Cell operating temperature was too high, the many interfacial reactions that taken place and the sintering degeneration of electrode etc. can reduce the efficient and the stability of battery, also make the selection of electrode critical material be subjected to bigger restriction simultaneously.If the working temperature of battery is reduced to below 800 ℃, just can avoid the sintering of interaction between battery component and electrode to degenerate, enlarge the range of choice of battery structure material, reduce manufacturing cost and the operating cost of SOFC.
The method that reduction SOFC operating temperature generally adopts comprises the novel electrolytes material that replaces having under the temperature in traditional electrolyte membrance support type structure and the research and development high ionic conductivity with electrode supporting electrolyte thin membrane structure.No matter adopt the sort of battery structure, the fine and close electrolytic thin-membrane of preparation all is one of key technologies in the SOFC development process.Adopt ultra-fine electrolyte powder, can under lower temperature, realize the densification of electrolyte membrance, thereby avoid the interaction between the various battery materials of battery three-in-one component preparation process effectively.
The method of synthetic SOFC electrolyte powder commonly used comprises solid reaction process, sol-gel process, citric acid method and firing method etc.The whole bag of tricks all respectively has its characteristics, particularly has bigger difference at the aspects of preparing such as electrolytical one-tenth phase temperature, powder granularity and sintering activity.Will be incubated the sufficiently long time with solid reaction process synthesis of solid electrolyte under very high sintering temperature and could become phase fully, the powder particles that synthesizes is big, specific surface is low, be difficult to shortcomings such as sintering densification.Methods such as employing sol-gel, citric acid, burning can effectively reduce the one-tenth phase temperature of electrolyte, prepare the oxide electrolyte powder of high-specific surface area.But these preparation method's ubiquity preparation conditions are difficult to control, be prone to metal ion segregation, the finished product powder problem such as serious of reuniting.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing the intermediate temperature solid oxide fuel cell electrolyte superfine powder, this method can prepare the solid oxide electrolyte superfine powder for fuel cell of high-specific surface area, high sintering activity.
For achieving the above object, the metal nitrate that the present invention at first will prepare the electrolyte powder is dissolved in the deionized water, then corresponding solution is mixed, or metal oxide is dissolved in red fuming nitric acid (RFNA), makes the mixed solution of metal nitrate; In mixed solution, add the complexing agent (NH of b diammonium edta then 3H 2O solution), be incubated certain hour after being heated to 80 ℃, make the abundant complexing of metal ion; Add an amount of gelatinizing agent again (as the NH of citric acid 3H 2O solution), adjust the pH of solution between 6-7 with nitric acid or ammoniacal liquor; Another key character of this method is to add the NH of capacity at last 4NO 3Its effect is after the colloid that continues slowly to be heated to thickness forms, part is decomposed the effect of playing blowing agent, major part be after the colloid spontaneous combustion with colloid in organic substance the explosive combustion reaction of similar ammonium nitrate explosive takes place, form the equally distributed complex solid oxide electrolyte of unbodied component forerunner powder.This forerunner's powder can become phase at lower roasting temperature, make high-specific surface area, high sintering active solid oxide electrolyte superfine powder for fuel cell, be used for electrolyte membrance, the particularly preparation of electrode load type electrolyte ultrathin membrane, also can be directly used in the preparation of electrolytic thin-membrane, and roasting does not in advance become phase.
The present invention can be used to prepare the electrolyte of Solid Oxide Fuel Cell, as Y 2O 3Stable ZrO 2(YSZ); The LaGaO that SrO, MgO mix 3(LSGM); Sm 2O 3The CeO that mixes 2(SDC) or Gd 2O 3The CeO that mixes 2(GDC) etc., also can be used for preparing the synthetic of Ca-Ti ore type hybrid conductive composite oxides superfine powder.
The raw material that is used for the synthesis of solid oxide electrolyte among the present invention can be the nitrate of respective metal element, the oxide that also can be these metallic elements (only can be dissolved in the metallic element of red fuming nitric acid (RFNA) or rare nitric acid for those oxides, can replace nitrate with its oxide), but to oxide, must be respectively with mixing again behind red fuming nitric acid (RFNA) or the dilute nitric acid dissolution.
Adopting complexing agent can be various organic complexing agents commonly used, but can not contain the most nonmetalloid that can not volatilize under other metallic elements and the high temperature in the complexing agent, in order to avoid introduce other impurity elements in the electrolyte powder that synthesizes.The most frequently used complexing agent b diammonium disodium edta can not be directly used in this method, must make complexing agent with the ammonium salt of b diammonium edta.The ammonium salt of b diammonium edta is dissolved in ammoniacal liquor with b diammonium edta and makes.
The NH that adds b diammonium edta 3H 2Behind the O solution, adjust the pH value of mixed liquor with nitric acid or ammoniacal liquor, and suitably heating, so that metal ion is by fully complexing.The PH control range is 6-8, and temperature is controlled at 70-90 ℃.The ratio of total metal ion molal quantity is in b diammonium edta and the solution: 0.8-1.5: 1.
Gelatinizing agent comprises citric acid, polyvinyl alcohol, celluloid, polyvinyl alcohol uncle butyraldehyde etc.Gelatinizing agent (wherein citric acid ammoniacal liquor) dissolving back adds in the mixed solution, continues heating then, maintains the temperature at 40-100 ℃, and gelatinizing agent is 0.8-1.5 with metal ion total mole number ratio: 1.
NH 4NO 3Can the crystalline solid form directly add in the mixed solution, also dissolve in deionized water and make behind the solution and add again.Add NH 4NO 3The ratio of molal quantity and metal ion total mole number be 0.6-1.5: 1.
Mixed solution will make moisture evaporation 70-90 ℃ of continuous stirring, forms the colloidal liquid of thickness clarification.Attention will remain the clarification of solution in heating process, promptly can not have precipitation to separate out.
When adding the thermal ignition colloid, note controlling each colloid amount.Otherwise before the combustion reaction of blasting, colloid can cause bursting of container because of caloric value is excessive simultaneously because of the rapid expansion of volume overflow container.
Description of drawings
Fig. 1 is La 0.9Sr 0.1Ga 0.8Mg 0.2O 3-δDifferential thermal-thermogravimetry (TG-DTA) analysis result of (LSGM 9182) forerunner's powder;
Fig. 2 is X-ray diffraction method (XRD) analysis result of LSGM 9182 forerunner's powder of treatment of different temperature;
Fig. 3 is transmission electron microscope (TEM) photo of LSGM 9182 superfine powders made of 1200 ℃ of roastings;
Fig. 4 is this synthetic temperature variant situation of LSGM 9182 electrolyte conductivity;
Fig. 5 is the situation that these synthetic LSGM 9182 electrolyte conductivity change with partial pressure of oxygen;
Fig. 6 is Sm 0.5Sr 0.5CoO 3-δ(SSC) differential thermal-thermogravimetry of forerunner's powder (TG-DTA) analysis result.
Embodiment
Example 1, La 0.9Sr 0.1Ga 0.8Mg 0.2O 3-δSynthesizing of (LSGM 9182) superfine powder
Calculate the synthetic required La (NO of certain mass LSGM9182 according to stoichiometric proportion 3) 36H 2O, Sr (NO 3) 2, Mg (NO 3) 26H 2O and Ga 2O 3Amount of reagent, more than several reagent all select analytical reagent for use.With excessive La (NO 3) 36H 2O, Sr (NO 3) 2, Mg (NO 3) 26H 2O is dissolved in the deionized water, (accurately calibrates the molar concentration of the metal ion of each nitrate solution as the EDTA compleximetry, and calculates the volume of required each nitrate solution in view of the above with chemical analysis.Press the accurate weighing Ga of amount of calculation with assay balance 2O 3, then with the red fuming nitric acid (RFNA) dissolving, because Ga 2O 3Relatively indissoluble so must heat while stirring the sufficiently long time, dissolves fully to guarantee it.Accurately measure La (NO by amount of calculation 3) 36H 2O, Sr (NO 3) 2, Mg (NO 3) 26H 2O solution is with Ga 2O 3Being dissolved in the solution that nitric acid obtains mixes.Take by weighing EDTA acid in 1.2: 1 ratios, add ammoniacal liquor to dissolving fully.This solution is joined in the mixed solution, and the pH value of adjusting solution with ammoniacal liquor or nitric acid is heated to 80 ℃ then to 6-7, and continuous stirring makes each metal ion species obtain abundant complexing.Take by weighing citric acid in 1.2: 1 ratio again, add after ammoniacal liquor makes it dissolving, add in the mixed solution, continue heating and stir.Add ammonium nitrate solid in 1: 1 ratio in mixed liquor at last, stirring makes it to dissolve fully.After this, with mixed liquor heating while stirring on magnetic stirring apparatus, at 80 ℃ moisture is evaporated gradually, to the colloid that forms thickness.The a small amount of colloid of each transfer continues to be heated to the violent combustion reaction of generation to ceramic vessel, generate ultra-fine solid oxide electrolyte forerunner powder.LSGM 9182 forerunner's powder can be made the LSGM superfine powder at 1200 ℃ of roasting 180min.
Example 2, La 0.9Sr 0.1Ga 0.8Mg 0.2O 3-δ(LSGM9182) detection of the determining of superfine powder sintering temperature, composite powder material granularity and electric conductivity
Be determined at mass change (weightlessness) in forerunner's powder roasting process and heat absorption, heat release situation with differential thermal-thermogravimetric (TG-DTA) method, the variation that preliminary judgement is taken place at the temperature-rise period predecessor, as shown in Figure 1.With forerunner's powder roasting 180min under different temperatures (290 ℃, 390 ℃, 590 ℃, 740 ℃, 950 ℃, 1120 ℃, 1320 ℃, 1450 ℃), with the phase structure of X-ray diffraction method mensuration product, the result as shown in Figure 2 then.At last with forerunner's powder at 1200 ℃ and 1300 ℃ of following roasting 180min, observe the pattern of LSGM finished product powder and the size of particle diameter with projection electron microscope (TEM), as shown in Figure 3.As can be seen from Figure 2, adopting LSGM9182 forerunner's powder of the inventive method preparation is being amorphous state below 590 ℃, and no characteristic X-ray diffraction maximum occurs; As can be seen from Figure 1, produce significantly weightlessness below the temperature at this, corresponding to remaining organic burning and volatilization in the presoma.The more more weak assorted peak of intensity on the XRD spectral line of 740 ℃ and 950 ℃, occurs,, flat rare thermal spike on the DTA curve, occurred corresponding to the oxide of some segregations or the carbonate of generation.In fact, just begun to occur the characteristic diffraction peak of perovskite phase on 740 ℃ XRD spectral line, during to 950 ℃, the perovskite structure characteristic peak is very obvious.To 1120 ℃, assorted peak disappears substantially, has generated LSGM 9182 powders of comparatively pure perovskite structure.From the tem observation result of Fig. 3 as can be known, the powder particle of 1200 ℃ of formation is spherical substantially, and particle diameter is about 50nm; 1300 ℃ of particle diameters that form powder are between 50-100nm.
Forerunner's powder at 1000 ℃ of pre-burning 120min, is pressed into the disk that thickness is 1mm then under the axial compressive force of 17.76MPa,, makes fine and close electrolyte membrane at 1450 ℃ of following roasting 360min.Diaphragm is cut into bar shaped, and electrode is made with platinum black in two ends, measures the conductivity of material under different temperatures and different partial with AC impedence method, respectively as shown in Figure 4 and Figure 5.As can be seen from Figure 4, ln (σ T) becomes linear dependence with 1/T, and it is 87.21KJ/mol that the electricity that can calculate LSGM 9182 is led activation energy.As can be seen from Figure 5, the conductivity of 800 ℃ of following LSGM 9182 does not change with the partial pressure of oxygen variation in very wide partial pressure of oxygen scope, shows the conduction property of pure oxygen ion conductor.
This embodiment shows, adopt method of the present invention the one-tenth phase temperature of LSGM9182 can be reduced to 1120 ℃ from 1500 ℃ of solid reaction process, and the powder particles that generates can reach densification under 1450 ℃ on the magnitude of tens nanometer, have very high sintering activity.
Example 3, Sm 0.5Sr 0.5CoO 3-δ(SSC) superfine powder is synthetic
Calculate the synthetic required Sr (NO of certain mass SSC according to stoichiometric proportion 3) 2, Co (NO 3) 36H 2O and Sm 2O 3Amount of reagent, more than several reagent all select analytical reagent for use.With Co (NO 3) 36H 2O, Sr (NO 3) 2, be dissolved in the deionized water, use chemical analysis, accurately calibrate the molar concentration of the metal ion of each nitrate solution as the EDTA compleximetry, and calculate the volume of required each nitrate solution in view of the above.Press the accurate weighing Sm of amount of calculation with assay balance 2O 3, dissolve with red fuming nitric acid (RFNA) then.Accurately measure Co (NO by amount of calculation 3) 36H 2O, Sr (NO 3) 2Solution is with Sm 2O 3Being dissolved in the solution that nitric acid obtains mixes.Take by weighing EDTA acid in 1.2: 1 ratios, add ammoniacal liquor to dissolving fully.This solution is joined in the mixed solution, and the pH value of adjusting solution with ammoniacal liquor or nitric acid is heated to 80 ℃ then to 6-7, and continuous stirring makes each metal ion species obtain abundant complexing.Take by weighing citric acid in 1.2: 1 ratio again, add after ammoniacal liquor makes it dissolving, add in the mixed solution, continue heating and stir.Add ammonium nitrate solid in 1: 1 ratio in mixed liquor at last, stirring makes it to dissolve fully.After this, with mixed liquor heating while stirring on magnetic stirring apparatus, at 80 ℃ moisture is evaporated gradually, to the colloid that forms thickness.Each shift a small amount of colloid and continue to be heated to the ceramic vessel violent combustion reaction takes place, generate fluffy ultra-fine, SSC forerunner's powder of being gathered into the coral reef shape.SSC forerunner's powder can be made the SDC superfine powder at 1000 ℃ of roasting 180min.Figure 6 shows that the TG-DTA analysis result of SSC forerunner's powder.As can be seen, SSC can become phase under 830 ℃.TEM result shows that the SSC superfine powder granularity of generation is about 50-100nm.
Example 4, Sm 2O 3The CeO that mixes 2(SDC) superfine powder is synthetic
Calculate the synthetic required Sm of certain mass SDC according to stoichiometric proportion 2O 3, Ce (NO 3) 2XH 2O, two kinds of reagent are all selected analytical reagent for use.Ce (NO 3) 2Be dissolved in the deionized water Sm 2O 3Dissolve with red fuming nitric acid (RFNA).Accurately calibrate the metal ion molar concentration of each solution with the EDTA compleximetry, and calculate the volume of required each nitrate solution in view of the above.Three kinds of nitrate are mixed in glass container.Take by weighing EDTA acid in 1.2: 1 ratios, add ammoniacal liquor to dissolving fully.This solution is joined in the mixed solution, and the pH value of adjusting solution with ammoniacal liquor or nitric acid is heated to 80 ℃ then to 6-7, and continuous stirring makes each metal ion species obtain abundant complexing.Press 1.2: 1 molar ratio weighing polyvinyl alcohol again, after making it to dissolve with deionized water, add in the mixed solution, continue heating and stirring.Add ammonium nitrate solid in 1: 1 ratio in mixed liquor at last, stirring makes it to dissolve fully.After this with mixed liquor heating while stirring on magnetic stirring apparatus, make moisture be evaporated to the colloid that forms thickness gradually at 80 ℃.The a small amount of colloid of each transfer continues to be heated to the violent combustion reaction of generation to pottery, generate fluffy ultra-fine SDC forerunner's powder.Forerunner's powder can be made the SDC superfine powder at 800 ℃ of roasting 180min.TEM result shows that the SDC superfine powder granularity of generation is below 50nm.

Claims (4)

1, a kind of method for preparing the intermediate temperature solid oxide fuel cell electrolyte superfine powder, its key step is:
(a) metal nitrate is dissolved in deionized water and makes the metallic ion mixed liquor that meets stoichiometric proportion;
(b) ammonia spirit of adding organic complexing agent in metallic ion mixed liquor, adjusting the pH value is 6-7,70-90 ℃ stirs;
(c) add auxiliary complexing and gelatinizing agent solution, 40-100 ℃ stirs;
(d) add blowing agent, 70-90 ℃ stirs, and violent combustion reaction takes place when colloid is ignited, and generates unbodied forerunner's powder;
(e) forerunner's powder obtained solid oxide electrolyte superfine powder for fuel cell at 600-1200 ℃ of following roasting 2-5 hour;
Electrolyte is Y 2O 3Stable ZrO 2The LaGaO that SrO, MgO mix 3Sm 2O 3The CeO that mixes 2Or Gd 2O 3The CeO that mixes 2
Described organic complexing agent is ethylenediamine tetra-acetic acid, amine triacetic acid, and organic complexing agent is 0.8-1.5 with the ratio of metal ion total mole number: 1;
Described auxiliary complexing and gelatinizing agent are citric acid, polyvinyl alcohol, celluloid or polyvinyl alcohol uncle butyraldehyde, and auxiliary complexing and gelatinizing agent are 0.8-1.5 with the ratio of metal ion total mole number: 1;
Described blowing agent is an ammonium nitrate, and incorporation is the ammonium nitrate molal quantity: metal ion total mole number=0.6-1.5: 1.
2, preparation method as claimed in claim 1 is characterized in that, described metal nitrate is that metal oxide is dissolved in the nitric acid and makes.
3, preparation method as claimed in claim 1 is characterized in that, the pH value of described mixed solution is with ammoniacal liquor or nitric acid adjustment.
4, preparation method according to claim 1 is characterized in that, citric acid adds in the mixed solution after with ammonia solvent in described auxiliary complexing and the gelatinizing agent.
CNA021265569A 2002-07-24 2002-07-24 Method for preparing intermediate-tmeperature solid oxide electrolyte superfine powder for fuel cell Pending CN1471188A (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1315211C (en) * 2005-11-30 2007-05-09 浙江大学 Process for preparing fuel battery powder of solid oxide and application
CN100449835C (en) * 2006-12-22 2009-01-07 清华大学 Composite doped cerium oxide electrolyte and preparation method thereof
CN100449834C (en) * 2006-12-22 2009-01-07 清华大学 Anode-electrolyte-cathode assembly of middly temp SOFC and preparation method thereof
CN100488915C (en) * 2005-11-10 2009-05-20 中国科学院合肥物质科学研究院 Lanthanum molybdate (La2Mo2O9) moderate temperature conductor material and its preparation method
CN103935961A (en) * 2014-04-21 2014-07-23 华侨大学 Metallic oxide nano-powder preparation method capable of achieving large-scale production
CN109742431A (en) * 2019-01-11 2019-05-10 内蒙古科技大学 A kind of cerium oxide body dopant dysprosia compound electrolyte material and preparation method thereof
CN112563546A (en) * 2020-12-29 2021-03-26 福州大学 Oxygen ion conductive medium-temperature solid oxide fuel cell electrolyte and preparation method thereof
CN112928317A (en) * 2019-12-05 2021-06-08 宁波行殊新能源科技有限公司 Preparation method of cerium oxide-based electrolyte material
CN116969506A (en) * 2023-09-25 2023-10-31 中石油深圳新能源研究院有限公司 Electrolyte material for solid oxide fuel cell and preparation method thereof

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100488915C (en) * 2005-11-10 2009-05-20 中国科学院合肥物质科学研究院 Lanthanum molybdate (La2Mo2O9) moderate temperature conductor material and its preparation method
CN1315211C (en) * 2005-11-30 2007-05-09 浙江大学 Process for preparing fuel battery powder of solid oxide and application
CN100449835C (en) * 2006-12-22 2009-01-07 清华大学 Composite doped cerium oxide electrolyte and preparation method thereof
CN100449834C (en) * 2006-12-22 2009-01-07 清华大学 Anode-electrolyte-cathode assembly of middly temp SOFC and preparation method thereof
CN103935961A (en) * 2014-04-21 2014-07-23 华侨大学 Metallic oxide nano-powder preparation method capable of achieving large-scale production
CN103935961B (en) * 2014-04-21 2017-01-25 华侨大学 Metallic oxide nano-powder preparation method capable of achieving large-scale production
CN109742431A (en) * 2019-01-11 2019-05-10 内蒙古科技大学 A kind of cerium oxide body dopant dysprosia compound electrolyte material and preparation method thereof
CN112928317A (en) * 2019-12-05 2021-06-08 宁波行殊新能源科技有限公司 Preparation method of cerium oxide-based electrolyte material
CN112563546A (en) * 2020-12-29 2021-03-26 福州大学 Oxygen ion conductive medium-temperature solid oxide fuel cell electrolyte and preparation method thereof
CN116969506A (en) * 2023-09-25 2023-10-31 中石油深圳新能源研究院有限公司 Electrolyte material for solid oxide fuel cell and preparation method thereof

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