CN103224394A - Lithium carbonate modified cerium barium zirconate proton conductor material and preparation method thereof - Google Patents
Lithium carbonate modified cerium barium zirconate proton conductor material and preparation method thereof Download PDFInfo
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- CN103224394A CN103224394A CN2013101379557A CN201310137955A CN103224394A CN 103224394 A CN103224394 A CN 103224394A CN 2013101379557 A CN2013101379557 A CN 2013101379557A CN 201310137955 A CN201310137955 A CN 201310137955A CN 103224394 A CN103224394 A CN 103224394A
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Abstract
The invention discloses a lithium carbonate modified cerium barium zirconate proton conductor material. Raw material components and molar ratio percentage content thereof are BaCe0.7Zr0.1Y0.2O3-delta, and on the basis, 0%-7.5% by mass of lithium carbonate and 0%-4% by mole of zinc oxide are added. BaCe0.7Zr0.1Y0.2O3-delta powder is synthesized by a nitrate-citric acid gel auto-combustion method; then an inorganic salt sintering aid lithium carbonate zinc oxide are added in the power; the powder is shaped by dry pressing and sintered at a temperature of 1,150-1,300 DEG C. The raw materials of the lithium carbonate modified cerium barium zirconate proton conductor material are low in cost; the preparation process is simple and time-saving; relatively high conductivity can be obtained under the premise of increasing sintering performance of the materials; and the lithium carbonate modified cerium barium zirconate proton conductor material provides a foundation for low temperature development of solid oxide fuel cells.
Description
Technical field
The invention belongs to a kind of is the ceramic composition of feature with the composition, relates in particular to a kind of Quilonum Retard modification cerium barium zirconate proton conductor material and preparation method thereof.
Background technology
Fuel cell since have energy dress change the efficient height, pollution-free, the fuel suitability is strong, in light weight and advantage such as logical sequence solid-state structure, has development potentiality and application prospect, is called as 21 century most promising new generation of green Chemically generation device.One of development trend of Solid Oxide Fuel Cell (SOFC) is to reduce battery operated temperature.Calcium hematite structure proton conductor has higher specific conductivity and proton shifting number and lower electricity and leads activation energy (Iwallara H, OnoK.Proton conduction insintered oxides based on BaCeO
3[J] .J.Electrochem.Soc., 1988,135 (2): 529 ~ 533), be one of intermediate temperature solid oxide fuel cell (IT-SOFC) electrolyte optimal selection.Simple calcium hematite structure proton conductor can be divided into the decorations hydrochlorate and zirconate two classes of ion doping at a low price.Decorations hydrochlorate proton conductor mainly comprises the BaCeO of various low price ion dopings
3, SrCeO
3Deng, such material electric conductivity is higher, its monocrystal material specific conductivity at high temperature can reach the S/cln order of magnitude, multiphase ceramic one 10
-2Between～the lS/cln, but chemical stability is relatively poor, at CO
2And H
2React easily in the S atmosphere and generate CeO
2With corresponding carbonic acid thing, thereby cause the decline of specific conductivity, reduce the work-ing life of fuel cell, perhaps the atmosphere in combustion gas purity and the reaction process is had relatively high expectations, thereby cause higher use cost and maintenance cost.The zirconate proton conductor comprises BaZrO
3And SrZrO
3Deng, such material is almost pure proton electricity and leads, and chemical property is stable, and mechanical property is superior, but it prepares difficulty, need higher sintering temperature, and the crystal boundary specific conductivity is lower, the ionogen internal resistance of the battery that acts as a fuel is bigger, influence efficient (the Lguchi F of battery, Tsurui T, SataN, etalTherelationship between chemical composition distributions and specific grain boundary conductivity in Y-doped BaZrO
3Pfoton conductors[J] .Solid State Ionics, 2009,180 (6-8): 563～568).For single zirconium base and cerium base oxide, high-quality
SonElectricity is led with the high stable performance and is difficult to satisfy simultaneously, and the battery electrolyte that acts as a fuel separately is all not satisfactory.It is reported BaCeO
3With BaZrO
3Can form unlimited solid solution BaZr
xCe
1-xO
3, replace part BaZrO by Ce
3In Zr, can improve conductivity of electrolyte materials guaranteeing that material has under the prerequisite of higher chemical stability.In more than ten years in the past, the investigator passs zirconium cerium based solid solution material and has gone extensive studies.The character of solid-solution material changes along with the variation of zirconium cerium ratio, and the raising of zirconium content helps the stability of material, and the raising of cerium content then helps the conductivity of material.People such as Liu adopt the citric acid auto-combustion method to synthesize BaZf
0.1Ce
0.7Y
0.2O
3-δPowder is an anode with the Ni base, and having prepared thickness is the BaZf of 20 μ m
0.1Ce
0.7Y
0.2O
3-δZirconium cerium solid solution thin-film electrolyte adopts Sln
0.5Sr
0.5CoO
3-δ-BaZr
0.1Ce
0.7Y
0.2O
3-δAs composite cathode, the output rating of fuel battery assembled when 700 ° of C can reach 650mW/cm
2Test has good chemical stability under 600 ° of C, 0.5V constant voltage simultaneously, do not influence the normal operation of battery, the achievement in research before has than quantum jump (Mhgfei L, Jianfeng G. High performance of anode supported BaZr
0.1Ce
0.7Y
0.2O
3-δ(BZCY) electrolyte cell for IT-SOFC[J] .Intemational Journal of Hydrogen Energy, 2011,36 (21) 13741 ~ 13745).But because BaZrO
3Existence, still there is certain difficulty in the sintering densification of material, thereby and high temperature sintering cause Ba to make the performance degradation of material easily from A position disappearance, therefore the sintering method that is more prone to of research is very important.
Summary of the invention
Purpose of the present invention, it is simple to provide a kind of preparation method, saves cost, and densified sintering product can obtain the proton conductor material of the novel solid oxide fuel cell of excellent conductivity again at a lower temperature.
The present invention adopts the citrate gel auto-combustion method to prepare cerium barium zirconate proton conductor powder wood, reduces sintering temperature by adding the Quilonum Retard sintering aid, improves density.Change the addition of Quilonum Retard, the research Quilonum Retard-every performance of zirconium cerium acid barium material is determined its optimum addition, thereby is prepared the anode supporting type solid oxide fuel cell of excellent property.
The present invention is achieved by following technical solution:
The blunt modification cerium of carbonic acid barium zirconate proton conductor material, its feed composition and molar content thereof are: BaCe
0.7Zr
0.1Y
0.2O
3-δ, on this basis, add the Quilonum Retard of mass percent 0%～7.5% and the zinc oxide of molar percentage 0%～4%;
The preparation method of this Quilonum Retard modification cerium barium zirconate proton conductor material, step is as follows:
(1) according to BaCe
0.7Zr
0.1Y
0.2O
3-δStoichiometric ratio takes by weighing raw material respectively: Ba (NO
3)
2, ZrWO
3)
45H
2O, Ce (NO
3)
36H
2O, Y (NO
3)
36H
2O; According to total ionizable metal salt:
Ethylenediamine tetraacetic acid (EDTA)Be EDTA: citric acid is 1:1.5:1～1:2:1 mixed in molar ratio, joins in the 500mL deionized water, and regulating the pH value with strong aqua is 6～8, and the heated and stirred transpiring moisture obtains thick colloid, reacts in the stainless steel reaction container; Pre-burning under 240 ° of C again is incubated 5 hours; Under 1000～1100 ° of C, calcine at last, be incubated 5 hours, obtain light yellow pure phase BaCe
0.7Zf
0.1Y
0.2O
3-δPowder;
(2) powder with step (1) preparation is a body material, adds the zinc oxide of mass percent 0%～7.5% Quilonum Retard and molar percentage 0%～4%, mixes for the medium ball milling with the dehydrated alcohol; Drying, powder is put into mould after grinding, sieving, dry-pressing formed under 100～200MPa is base substrate; With gained base substrate sintering in 1150～1300 ° of C air atmospheres, be incubated 4～6 hours again, naturally cool to room temperature, make Quilonum Retard modification cerium barium zirconate proton conductor material.
The sintering processing of described step (2) is for burying burning, 5 ° of temperature rise rates C/ minute.
The relative density of this cerium barium zirconate proton conductor material is more than 90%.
Beneficial effect of the present invention: use BaCe
0.7Zr
0.1Y
0.2O
3-δAs electrolyte, add Li
2CO
3As the liquid phase sintering auxiliary agent, thereby make electrolyte be issued to densification in lower sintering temperature.Owing to added inorganic salts lithium, increased the number of proton conduction, improved the crystal boundary of material situation, the specific conductivity expection can reach 10 under 600 ° of C
-2Siemens/cm.The present invention has improved its electrical property and stability when improving its sintering character, be application, the exploitation Solid Oxide Fuel Cell based theoretical that constantly advances cerium barium zirconate proton conductor material.
Description of drawings
Fig. 1 is the XRD figure spectrum of BZCY2.5L and BZCY sample among the embodiment of the invention l;
Fig. 2 is the relative density curve that adds the Quilonum Retard sample in the wooden inventive embodiments 1;
Fig. 3 is the scanning electronic microscope of ionogen section (SEM) photo behind the sintering in the embodiment of the invention 1;
Fig. 4 is the electron scanning micrograph of BZCY-5L sample in the embodiment of the invention 2;
Fig. 5 adds Different L i in the embodiment of the invention 1,2 and 5
2CO
3The conductivity of electrolyte materials curve of doping content.
Embodiment
The raw materials used analytical reagent that is of the present invention adopts nitrate-citrate gel auto-combustion method to prepare BaCe
0.7Zr
0.1Y
0.2O
3-δPowder; Below in conjunction with specific embodiment the present invention is further described.
According to BaCe
0.7Zr
0.1Y
0.2O
3-δStoichiometric ratio, get 1 mole of Ba (NO
3)
2,
0.7Mole CeWO
3)
36H
2O, 0.1 mole of Zr (NO
3)
45H
2O, 0.2 mole of Y (NO
3)
36H
2O, according to total metal ion: EDTA: citric acid (mol ratio)=1:1.5:1 mixes, be dissolved in the 50OlnL deionized water, using ammoniacal liquor regulator solution pH value is 8, obtains thick lurid gel thereby heated and stirred is constantly evaporated moisture, thereby organic compound combustion obtains linen powder in the stainless steel reaction container, pre-burning under 240 ° of C again is incubated 5 hours, calcines under 1000 ° of C at last, be incubated 5 hours, prepare the BaCe of pure phase
0.7Zr
0.1Y
0.2O
3-δ(BZCY) light yellow powder.Adding mass percent in matrix powder is 2.5% Quilonum Retard, mixed 6 hours for the medium ball milling with the dehydrated alcohol, again through super-dry, grind, sieve after, blended ionogen powder weighing 0.7 gram poured into carry out dry-pressing formedly in the 12mm mould, pressure is 100MPa, imbeds Quilonum Retard doped with cerium barium zirconate powder, buries burning in 1250 ° of C in air atmosphere, 5 ° of temperature rise rates C/ minute, be incubated 5 hours, naturally cool to room temperature then, make BaCe
0.7Zr
0.1Y
0.2O
3-δ-2.5%Li
2CO
3(BZCY2.5L) composite electrolyte.Fig. 1 is the XIRD collection of illustrative plates of BZCY and BZCY2.5L, as can be seen from the figure two kinds of materials all present single calcium hematite structure, for sample B ZCY-2.5L, though Quilonum Retard is as independently being added to, but the Quilonum Retard peak does not appear in sintered specimen, Quilonum Retard and principal crystalline phase solid solution are described, thereby acceleration of sintering makes material fine and close more.
Adopt Archimedes's drainage to measure its density, the relative density of BZCY2.5L reaches 93% behind 1250 ° of C sintering as can be seen from Figure 2, from the electron scanning micrograph of this material of Fig. 3 as seen, crystal grain is arranged closely, and pore-free exists, this bill of material reveals sintering character preferably, illustrates that the interpolation of Quilonum Retard has improved the sintering character of material.
According to BaCe
0.7Zr
0.1Y
0.2O
3-δStoichiometric ratio, get 1 mole of Ba (NO
3)
2, 0.7 mole of CeWO
3)
36H
2O, 0.1 mole of Zf (NO
3)
45H
2O, 0.2 mole of Y (NO
3)
36H
2O, according to total metal ion: EDTA: citric acid (mol ratio)=1:2:1 mixes, be dissolved in the 500mL deionized water, using ammoniacal liquor regulator solution pH value is 6, thereby heated and stirred make moisture constantly evaporation obtain thick lurid gel, thereby organic compound combustion obtains linen powder in the stainless steel reaction container, pre-burning 5 hours under 240 ° of C again, under 1050 ° of C, calcined 5 hours at last, prepare the light yellow powder of BZCY of pure phase.The interpolation mass percent is 5% Quilonum Retard in matrix powder, with the dehydrated alcohol is medium mixing and ball milling 6 hours, again through super-dry, grind, sieve after, blended ionogen powder weighing 0.7 gram poured into carry out dry-pressing formedly in the 12mm mould, pressure is 150MPa, imbeds Quilonum Retard doped with cerium barium zirconate powder, buries burning in 1250 ° of C in air atmosphere, 5 ° of temperature rise rates C/ minute, be incubated 5 hours, naturally cool to room temperature then, make BaCe
0.7Zr
0.1Y
0.2O
3-δ-5%Li
2CO
3(BZCY-5L) composite electrolyte.
Adopt Archimedes's drainage to measure its density, relative density reaches more than 95%.Fig. 4 is the scanned photograph of sintered specimen, and sample crystal grain is closely arranged, and this bill of material reveals sintering character preferably.
According to BaCe
0.7Zr
0.1Y
0.2O
3-δStoichiometric ratio, get 1 mole of Ba (NO
3)
2, 0.7 mole of CeWO
3)
36H
2O, 0.1 mole of Zr (NO
3)
45H
2O, 0.2 mole of YWO
3)
36H
2O, according to total metal ion: EDTA: citric acid (mol ratio)=1:1.5:1 mixes, be dissolved in the 500mL deionized water, using ammoniacal liquor regulator solution pH value is 7, thereby heated and stirred make moisture constantly evaporation obtain thick lurid gel, thereby organic compound combustion obtains linen powder wood in the stainless steel reaction container, pre-burning 5 hours under 240 ° of C again, under 1100 ° of C, calcined 5 hours at last, prepare the light yellow powder of BZCY of pure phase.Adding mass percent in matrix powder is 7% Quilonum Retard, with the dehydrated alcohol is medium mixing and ball milling 6 hours, again through super-dry, grind, sieve after, blended ionogen powder weighing 0.7 gram poured into carry out dry-pressing formedly in the 15mm mould, pressure is 200MPa, imbeds Quilonum Retard doped with cerium barium zirconate powder, buries burning in 1150 ° of C in air atmosphere, 5 ° of temperature rise rates C/ minute, be incubated 6 hours, naturally cool to room temperature then, make BaCe
0.7Zr
0.1Y
0.2O
3-δ-7%Li
2CO
3(BZCY7L) composite electrolyte.
Adopt Archimedes's drainage to measure its density, relative density reaches 90%, and this bill of material reveals sintering character preferably.
Embodiment 4
According to BaCe
0.7Zr
0.1Y
0.2O
3-δStoichiometric ratio, get 1 mole of Ba (NO
3)
2, 0.7 mole of CeWO
3)
36H
2O, 0.1 mole of Zr (NO
3)
45H
2O, 0.2 mole of Y (NO
3)
36H
2O, according to total metal ion: EDTA: citric acid (mol ratio)=1:2:1 mixes, be dissolved in the 500mL deionized water, using ammoniacal liquor regulator solution pH value is 8, thereby heated and stirred make moisture constantly evaporation obtain thick lurid gel, thereby organic compound combustion obtains linen powder wood in the stainless steel reaction container, pre-burning 5 hours under 240 ° of C again, under 1100 ° of C, calcined 5 hours at last, prepare the light yellow powder of BZCY of pure phase.Adding mass percent in matrix powder is 7.5% Quilonum Retard, with the dehydrated alcohol is medium mixing and ball milling 6 hours, again through super-dry, grind, sieve after, blended ionogen powder weighing 0.7 gram poured into carry out dry-pressing formedly in the 12mm mould, pressure is 100MPa, imbeds Quilonum Retard doped with cerium barium zirconate powder, buries burning in 1150 ° of C in air atmosphere, 5 ° of temperature rise rates C/ minute, be incubated 5 hours, naturally cool to room temperature then, make BaCe
0.7Zr
0.1Y
0.2O
3-δ-7.5%Li
2CO
3(BZCY7.5L) composite electrolyte.
Adopt Archimedes's drainage to measure its density, relative density reaches 89%, with BaCe
0.7Zr
0.1Y
0.2O
3-δMatrix is compared, and this bill of material reveals sintering character preferably.
Embodiment 5
According to BaCe
0.7Zr
0.1Y
0.2O
3-δStoichiometric ratio, get 1 mole of Ba (NO
3)
2, 0.7 mole of Ce (NO
3)
36H
2O, 0.1 mole of Zr (NO
3)
45H
2O, 0.2 mole of Y (NO
3)
36H
2O, according to total metal ion: EDTA: citric acid (mol ratio)=1:1.5:1 mixes, be dissolved in the 5OOmL deionized water, making and getting rid of ammoniacal liquor regulator solution pH value is 7, thereby heated and stirred make moisture constantly evaporation obtain thick lurid gel, thereby organic compound combustion obtains linen powder in the stainless steel reaction container, pre-burning 5 hours under 240 ° of C again, under 1100 ° of C, calcined 5 hours at last, prepare the light yellow powder of BZCY of pure phase.Adding mass percent in matrix powder is that 2.5% Quilonum Retard and molar percentage are 2.5% zinc oxide, with the dehydrated alcohol is medium mixing and ball milling 6 hours, again through super-dry, grind, sieve after, blended ionogen powder weighing 0.7 gram poured into carry out dry-pressing formedly in the 12mm mould, pressure is 100MPa, imbeds Quilonum Retard doped with cerium barium zirconate powder, buries burning in 1250 ° of C in air atmosphere, 5 ° of temperature rise rates C/ minute, be incubated 4 hours, naturally cool to room temperature then, make BaCe
0.7Zr
0.1Y
0.2O
3-δ-2.5%ZnO-2.5%Li
2CO
3(BZCY-2.5L-2.5Z) composite electrolyte.
Adopt Archimedes's drainage to measure its density, relative density reaches 90%, and this bill of material reveals sintering character preferably.
Embodiment 6
According to BaCe
0.7Zr
0.1Y
0.2O
3-δStoichiometric ratio, get 1 mole of Ba (NO
3)
2, 0.7 mole of Ce (NO
3)
36H
2O, 0.1 mole of Zr (NO
3)
45H
2O, 0.2 mole of Y (NO
3)
36H
2O, according to total metal ion: EDTA: citric acid (mol ratio)=1:1.5:1 mixes, be dissolved in the 50OmL deionized water, using ammoniacal liquor regulator solution pH value is 7, thereby heated and stirred make moisture constantly evaporation obtain thick lurid gel, thereby organic compound combustion obtains linen powder wood in the stainless steel reaction container, pre-burning 5 hours under 240 ° of C again, under 1100 ° of C, calcined 5 hours at last, prepare the light yellow powder of BZCY of pure phase.Adding molar percentage in matrix powder is 2.5% zinc oxide, with the dehydrated alcohol is medium mixing and ball milling 6 hours, again through super-dry, grind, sieve after, blended ionogen powder weighing 0.7 gram poured into carry out dry-pressing formedly in the 15mm mould, pressure is 150MPa, imbed Quilonum Retard mix the wrong sour barium powder of decorations, in air atmosphere, in 1200 ° of C, bury burning, 5 ° of temperature rise rates C/ minute, be incubated 5 hours, naturally cool to room temperature then, make BaCe
0.7Zr
0.1Y
0.2O
3-δ-2.5ZnO (BZCY-2.5Z) composite electrolyte.
Adopt Archimedes's drainage to measure its density, relative density reaches 90%, and this bill of material reveals sintering character preferably.
Embodiment 7
According to BaCe
0.7Zr
0.1Y
0.2O
3-δStoichiometric ratio, get 1 mole of Ba (NO
3)
2, 0.7 mole of Ce (NO
3)
36H
2O, 0.1 mole of ZfWO
3)
45H
2O, 0.2 mole of Y (NO
3)
36H
2O, according to total metal ion: EDTA: citric acid (mol ratio)=1:1.5:1 mixes, be dissolved in the 500mL deionized water, using ammoniacal liquor regulator solution pH value is 8, thereby heated and stirred make moisture constantly evaporation obtain thick lurid gel, thereby organic compound combustion obtains linen powder in the stainless steel reaction container, pre-burning 5 hours under 240 ° of C again, under 1100 ° of C, calcined 5 hours at last, prepare the light yellow powder of BZCY of pure phase.Adding mass percent in matrix powder is that 2.5% Quilonum Retard and molar percentage are 4% zinc oxide, with the dehydrated alcohol is medium mixing and ball milling 6 hours, again through super-dry, grind, sieve after, blended ionogen powder weighing 0.7 gram poured into carry out dry-pressing formedly in the 12mm mould, pressure is 100MPa, imbeds Quilonum Retard doped with cerium barium zirconate powder, buries burning in 1300 ° of C in air atmosphere, 5 ° of temperature rise rates C/ minute, be incubated 5 hours, naturally cool to room temperature then, make BaCe
0.7Zr
0.1Y
0.2O
3-δ-4%ZnO-2.5%Li
2CO
3(BZCY-2.5L-4Z) composite electrolyte.
Adopt Archimedes's drainage to measure its density, relative density reaches 96%, and this bill of material reveals sintering character preferably.
Application Example 1
With BaCe
0.7Zr
0.1Y
0.2O
3-δ-Li
2CO
3(25% mass percent) powder is an electrolyte, puts it into to carry out dry-pressing formedly in the 12mm diameter die, and pressure is 150MPa; Imbed the blunt doped with cerium barium zirconate of carbonic acid ionogen powder at 1250 ° of C sintering in air, 5 ° of temperature rise rates C/ minute are incubated 5 hours, naturally cool to room temperature then.The coupons that obtains is placed on the self-control specific conductivity test tube, filamentary silver is introduced as electrode in two ends, under wet hydrogen atmosphere, test, the sample testing temperature is 500 ~ 800 ° of C, the temperature interval is 50 ° of C, adopt the linear time base sweep volt-ampere to test with electrochemical workstation, utilize formula O=L/RA to calculate specific conductivity.As can be seen from Figure 5, when 600 ° of C, 650 ° of C, 700 ° of C, specific conductivity is respectively 7.27X10
-3S/cm, 9.81 * 10
-3S/cm, 1.11 * 10
-2S/cm.
Application Example 2
With BaCe
0.7Zr
0.1Y
0.2O
3-δLi
2CO
3(5% mass percent) powder is an electrolyte, uses distribution, drawing method, heat treatment technics and the specific conductivity testing method identical with Application Example 1.As can be seen from Figure 5, when 600 ° of C, 650 ° of C, 700 ° of C, the specific conductivity of electrolyte is respectively 8.58X10
-3S/cm, 1.39 * 10
-3S/cm, 1.6 * 10
-2S/cm.
Application Example 3
With BaCe
0.7Zr
0.1Y
0.2O
3-δZnO (2.5% quality)-Li
2CO
3(2.5% mass percent) powder is an electrolyte, uses distribution, drawing method, heat treatment technics and the specific conductivity testing method identical with Application Example 1.As can be seen from Figure 5, when 600 ° of C, 650 ° of C, 700 ° of C, specific conductivity is respectively 2.89 * 10
-3S/cm, 3.51 * 10
-3S/cm, 4.32X10
-3S/cm.
Quilonum Retard modification cerium barium zirconate proton conductor material that the present invention proposes and preparation method thereof, oneself is described by embodiment, person skilled obviously can be changed or suitably change and combination content as herein described in not breaking away from content of the present invention, spirit and scope, realizes the present invention.Special needs to be pointed out is, the replacement that all are similar and change apparent to those skilled in the artly, they are regarded as being included in spirit of the present invention, scope and the content.
Claims (3)
1. Quilonum Retard modification cerium barium zirconate proton conductor material, its feed composition and molar content thereof are: BaCe
0.7Zr
0.1Y
0.2O
3-δ, on this basis, add the Quilonum Retard of mass percent 0%～7.5% and the zinc oxide of molar percentage 0%～4%;
The preparation method of this Quilonum Retard modification cerium barium zirconate proton conductor material, step is as follows:
(1) according to BaCe
0.7Zr
0.1Y
0.2O
3-δStoichiometric ratio takes by weighing raw material respectively: Ba (NO
3)
2, Zr(NO
3)
45H
2O, Ce (NO
3)
36H
2O, Y (NO
3)
36H
2O; According to total metal-salt from: ethylenediamine tetraacetic acid (EDTA) is EDTA: citric acid is l:1.5:1～1:2:1 mixed in molar ratio, join 500mL and go from Yu Shuizhong, getting rid of strong aqua adjusting pH value is 6～8, the heated and stirred transpiring moisture, obtain thick colloid, in the stainless steel reaction container, react; Pre-burning under 240 ° of C again is incubated 5 hours; Under 1000～1100 ° of C, calcine at last, be incubated 5 hours, obtain light yellow pure phase BaCe
0.7Zr
0.1Y
0.2O
3-δPowder;
(2) powder with step (1) preparation is a body material, adds the zinc oxide of mass percent 0%～7.5% Quilonum Retard and molar percentage 0%～4%, mixes for the medium ball milling with the dehydrated alcohol; Drying, powder is put into mould after grinding, sieving, dry-pressing formed under 100～200MPa is base substrate; With gained base substrate sintering in 1150～1300 ° of C air atmospheres, be incubated 4～6 hours again, naturally cool to room temperature, make Quilonum Retard modification cerium barium zirconate proton conductor material.
2. according to the Quilonum Retard modification cerium barium zirconate proton conductor material of claim 1, it is characterized in that the sintering processing of described step (2) is for burying burning, 5 ° of temperature rise rates C/ minute.
3. according to the Quilonum Retard modification cerium barium zirconate proton conductor material of claim 1, it is characterized in that the relative density of this cerium barium zirconate proton conductor material is more than 90%.
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| CN103586014A (en) * | 2013-11-28 | 2014-02-19 | 南京工程学院 | Membrane capable of performing electrocatalysis degradation of tail gas nitrogen oxide with high selectivity under low temperature and its preparation method |
| CN105531860A (en) * | 2013-08-27 | 2016-04-27 | 住友电气工业株式会社 | Electrode material for fuel electrode, solid electrolyte-electrode laminate, method for producing solid electrolyte-electrode laminate, and fuel cell |
| CN107406332A (en) * | 2015-03-30 | 2017-11-28 | 住友电气工业株式会社 | Proton conductor, fuel cell solid electrolyte layer, battery structure and the fuel cell including battery structure |
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| CN105531860A (en) * | 2013-08-27 | 2016-04-27 | 住友电气工业株式会社 | Electrode material for fuel electrode, solid electrolyte-electrode laminate, method for producing solid electrolyte-electrode laminate, and fuel cell |
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| CN107406332B (en) * | 2015-03-30 | 2020-11-03 | 住友电气工业株式会社 | Proton conductor, solid electrolyte layer for fuel cell, cell structure, and fuel cell including cell structure |
| CN108232263A (en) * | 2018-01-02 | 2018-06-29 | 珠海光宇电池有限公司 | Composite solid electrolyte and preparation method thereof |
| CN110444796A (en) * | 2019-09-10 | 2019-11-12 | 东北大学 | A method of improving solid-oxide fuel battery electrolyte conductivity |
| CN110444796B (en) * | 2019-09-10 | 2022-05-17 | 东北大学 | Method for improving electrolyte conductivity of solid oxide fuel cell |
| CN112062567A (en) * | 2020-09-17 | 2020-12-11 | 中国科学院上海应用物理研究所 | Method for preparing zirconium-yttrium-doped barium cerate powder by using molten salt and powder obtained by method |
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