CN103531833A - Proton conductor material in lithium/yttrium carbonate doped cerium barium zirconium complex phase structure - Google Patents

Proton conductor material in lithium/yttrium carbonate doped cerium barium zirconium complex phase structure Download PDF

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CN103531833A
CN103531833A CN201310499655.3A CN201310499655A CN103531833A CN 103531833 A CN103531833 A CN 103531833A CN 201310499655 A CN201310499655 A CN 201310499655A CN 103531833 A CN103531833 A CN 103531833A
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proton conductor
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lithium carbonate
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郭瑞松
王超
许雯雯
刘丽
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Tianjin University
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    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
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    • H01M8/1253—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides the electrolyte containing zirconium oxide
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    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract

The invention discloses a proton conductor material in a lithium/yttrium carbonate doped cerium barium zirconium complex phase structure, wherein the proton conductor material is prepared by adopting a soft chemical method by taking BaCe0.7Zr0.1Y0.2O3-delta (BCZY) as a matrix and further 2.5wt% of lithium carbonate as a liquid phase sintering agent. The method comprises the following steps: (1) obtaining light yellow BCZY powder by a nitrate-citric acid gel self-combustion method; (2) by taking BCZY powder as a matrix material, adding lithium carbonate, ball-milling and mixing, and dry pressing to mould at 150MPa after drying, grinding and sieving; then, burying and sintering at 1200-1300 DEG C, insulating for 5 hours to prepare the proton conductor material in the BCZY-2.5% Li2CO3 complex phase structure. The proton conductor material in the complex phase structure disclosed by the invention has good sinterability and conductivity, and the conductivity at 700 DEG C reaches 10-2S/cm, thereby laying a foundation for developing solid oxide fuel cells.

Description

Lithium carbonate/yttrium doped with cerium barium zirconate multiphase structure proton conductor material
Technical field
The invention belongs to a kind of the take ceramic composition that composition is feature, particularly lithium carbonate/yttrium doped with cerium barium zirconate multiphase structure proton conductor material and preparation method thereof.
Background technology
Fuel cell is a kind ofly will to be stored in chemical energy in fuel and to be converted into the electrochemical appliance of electric energy.Fuel cell is without overheated and mechanical switch process, so total energy efficiency is not limited by Carnot's cycle efficiency, is that a kind of energy dress changes that efficiency is high, pollution-free, fuel suitability is strong, lightweight and the new generation of green chemical generated device of structure of whole solid state.Cerate from people such as Iwahara in report perovskite in 1981 has (Iwahara H after proton conductive; Esaka T; Uchida H, Maeda N.Proton conduction in sintered oxides and its application to steam electrolytes for hydrogen production.Solid State Ionics1981; 3/4:359-63), proton conductor material has received increasing concern.When the cerate of perovskite structure adulterates through B position, just can produce the oxygen room for proton conduction, if electrolyte is placed in humidity or hydrogen atmosphere, proton will enter in lattice by oxygen room.Mainly by the mode of doping, this class cerium acid barium sill is studied at present, doped chemical is mainly Gd, Sm, Y, Tm, Yb, Lu and Sc etc., and wherein the cerium acid barium of Y doping has best ionic conductance.As the electrolyte of Solid Oxide Fuel Cell, must existing higher conductivity there is again good operational stability.Yet the development of present proton conductor is existing a kind of relation of mutual restriction aspect stability and conductivity.Zirconates proton conductor comprises BaZrO 3and SrZrO 3deng, such material is almost pure proton electricity and leads, stable chemical nature, and mechanical performance is superior, but it prepares difficulty, need higher sintering temperature, and crystal boundary conductivity is lower, larger as the electrolyte internal resistance of fuel cell, affect efficiency (the Lguchi F of battery, Tsurui T, Sata N, et al.The relationship between chemical composition distributions and specific grain boundary conductivity in Y-doped BaZrO 3proton conductors[J] .Solid State Ionics, 2009,180 (6-8): 563～568).Cerate proton conductor mainly comprises the BaCeO of various low price ion dopings 3, SrCeO 3deng, such material electric conductivity is higher, and its multiphase ceramic is generally 10 -2between～1S/cm, but chemical stability is poor, at CO 2and H 2in S atmosphere, easily reaction generates CeO 2with corresponding carbonic acid thing, thereby cause the decline of conductivity, reduce the useful life of fuel cell, or the atmosphere in combustion gas purity and course of reaction is had relatively high expectations, thereby cause higher use cost and maintenance cost.For single zirconium base and cerium base oxide, high proton electricity is led with high stable performance and is difficult to meet simultaneously, all not satisfactory as fuel-cell electrolyte separately.(Zuo CD, Zha SW, Liu ML, Hatano M, the Uchiyama M.Ba (Zr such as Zuo 0.1ce 0.7y 0.2) O 3-δas an electrolyte for low-temperature solid-oxide fuel cells.Adv Mater2006; 18 (24): 3318-20) BaCe (Y) O 3in material, Ce element element doping, prepares Ba (Zr 0.1ce 0.7y 0.2) O 3-δelectrolyte, thus the electrochemical stability of this material can under the prerequisite that guarantees high conductivity, be improved.Through experimental results show that to there is the highest ionic conductivity in this series compound, in the time of 500 ℃, reach 0.009S/cm, and this electrolyte contains 15% volume H 500 2o or 2% volume CO 2reducing atmosphere under test kept stable in week age.But due to BaZrO 3existence, the sintering densification of material still needs higher temperature (1550 ℃), thereby and high temperature sintering easily cause Ba from A position disappearance, to make the performance degradation of material, the sintering method that therefore research is more prone to is very important.
The present invention uses BaCe 0.7zr 0.1y 0.2o 3-δ(BCZY) as electrolyte matrix material, additional Li 2cO 3as liquid-phase sintering auxiliary agent, thereby make electrolyte be issued to densification in lower temperature.Owing to having added a small amount of inorganic salts lithium, increased the number of proton conduction, improved the crystal boundary situation of material, when improving its sintering character, improved its chemical property and chemical stability, for constantly advancing the application of yttrium doped with cerium barium zirconate proton conductor material to lay the foundation.
Summary of the invention
The present invention adopts citrate gel auto-combustion method to prepare yttrium doped with cerium barium zirconate proton conductor powder, by BaZr 0.1ce 0.7y 0.2o 3-δ(BCZY) charge ratio of powder, pH value and calcining heat rationally determines, by adding lithium carbonate sintering aid, reduce sintering temperature again, improve density, thereby prepare the proton conductor material of the anode supporting type solid oxide fuel cell of function admirable.
The object of this invention is to provide a kind of cost-savingly, preparation method is simple, and densified sintering product can obtain again the proton conductor material of the novel solid oxide fuel cell of excellent conductivity and stability at a lower temperature.
The present invention is achieved by following technical solution.
Lithium carbonate/yttrium doped with cerium barium zirconate multiphase structure proton conductor material, its composition and molar content are as follows:
With BaCe 0.7zr 0.1y 0.2o 3-δabbreviation BCZY is matrix, and additional mass percent is that 2.5% lithium carbonate is as liquid-phase sintering auxiliary agent;
The preparation method of this lithium carbonate/yttrium doped with cerium barium zirconate multiphase structure proton conductor material, adopts softening method to prepare in two steps:
(1) adopt nitrate-citrate gel auto-combustion method, with Ba (NO 3) 2, Zr (NO 3) 45H 2o, Ce (NO 3) 36H 2o, Y (NO 3) 36H 2o, ethylenediamine tetra-acetic acid ethylenediaminetetraacetic acid, citric acid, ammoniacal liquor are raw material, according to total ionizable metal salt: EDTA: citric acid is 1:1.5:1/1:2:1 mixed in molar ratio, add in deionized water and heat, with ammoniacal liquor, regulating pH is 6～8, add thermal agitation transpiring moisture, obtain thick colloid; This gel is reacted in stainless steel reaction container again, in 240 ℃ of pre-burnings, be incubated 5 hours, finally calcining at 1000 ℃, is incubated 5 hours, obtains light yellow BCZY powder;
(2) by the BCZY powder of step (1), be basis material, additional mass percent is 2.5% lithium carbonate, take absolute ethyl alcohol as the mixing of medium ball milling; Drying, powder is put into mould after grinding, sieving, dry-pressing formed under 150MPa, afterwards the circular disc test specimen of gained is buried to burning in 1200～1300 ℃ of air atmospheres, be incubated 5 hours, making lithium carbonate/yttrium doped with cerium barium zirconate is BCZY-2.5%Li 2cO 3multiphase structure proton conductor material.
It is 1250 ℃ that described step (1) is buried burning temperature, 5 ℃/min of heating rates.
The present invention has prepared lithium carbonate/yttrium doped with cerium barium zirconate multiphase structure proton conductor material with good agglutinating property and conductivity.The yttrium of take doping is prepared cerium barium zirconate as basis material, introduces lithium carbonate sintering aid and reduces sintering temperature, and the introducing of inorganic salts simultaneously can increase proton conduction number, improves crystal boundary electricity and leads, and conductivity can reach 10 at 700 ℃ -2s/cm, for exploitation Solid Oxide Fuel Cell is laid a good foundation.
Accompanying drawing explanation
Fig. 1 is the XRD collection of illustrative plates of the BCZY powder after different temperatures calcining;
Fig. 2 is 1250 ℃ of BCZY-2.5%Li after sintering 2cO 3the electron scanning micrograph of sample;
Fig. 3 is with BCZY-2.5%Li 2cO 3for current-voltage and the electric current-power of electrolytical monocell at 600～700 ℃;
Fig. 4 is the electron scanning micrograph of 1250 ℃ of BCZY samples after sintering.
Embodiment
The present invention is raw materials used is: Ba (NO 3) 2, Zr (NO 3) 45H 2o, Ce (NO 3) 36H 2o, Y (NO 3) 36H 2o, ethylenediamine tetra-acetic acid ethylenediaminetetraacetic acid, citric acid, concentrated ammonia liquor, above reagent is all analytical reagent.
EDTA is that a kind of complexones can generate with the metallic ion coordination of multiple difficult complexing stable chelate, but only use EDTA to become colloidality bad, although being not so good as EDTA, citric acid complex become colloidality better, so be combined with the synthetic BZCY powder of two kinds of complexing agents.
According to object product B aCe 0.7zr 0.1y 0.2o 3-δthe metering score another name of chemical formula is got needed raw material, adopts nitrate-citrate gel auto-combustion method to prepare BaCe 0.7zr 0.1y 0.2o 3-δ(BCZY) powder, adds 0% or 2.5% quality lithium carbonate (Li 2cO 3) as sintering aid.First nitrate, EDTA and citric acid are according to 1:1.5:1/1:2:1(mol ratio) add in about 500mL deionized water and heat, use ammoniacal liquor to regulate pH value 6～8, add thermal agitation and constantly evaporate until finally obtain thick flaxen colloid.This gel is poured in stainless steel reaction container and continued heating, and along with the rising of temperature, the most of organic substance spontaneous combustion in container, discharges a large amount of heats, obtains fluffy pale powder.And then 240 ℃ of pre-burnings 5 hours, remaining organic compound combustion is fallen.At 900～1000 ℃, calcine subsequently and within 5 hours, obtain BCZY powder.On this basis material, add 2.5% quality lithium carbonate, ball milling mixes for 6 hours.Drying, grind, sieve after, the powder obtaining is poured in the mould of 12mm, at 150MPa forming under the pressure; Subsequently by the sample of gained in 1200～1300 ℃ of sintering 5 hours (burying burning) in air atmosphere, 5 ℃/min of heating rates, then naturally cool to room temperature, make lithium carbonate/yttrium doped with cerium barium zirconate (BCZY-2.5%Li 2cO 3) multiphase structure proton conductor material.
Embodiment 1(comparative example)
Adopt nitrate-citrate gel auto-combustion method to prepare BCZY powder, according to BaCe 0.7zr 0.1y 0.2o 3-δstoichiometric proportion, 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, total metal ion: EDTA: citric acid (mol ratio)=1:1.5:1, be dissolved in 500mL deionized water, using ammoniacal liquor regulator solution pH value is 6, thereby add thermal agitation make moisture constantly evaporation obtain thick lurid gel, thereby in stainless steel reaction container, organic compound combustion obtains linen powder, then pre-burning 5 hours at 240 ℃, finally at 900 ℃, calcine 5 hours, prepare the light yellow powder of BCZY.Fig. 1 (a) is the X-ray diffractogram of this powder, and this figure shows can not prepare pure BCZY 900 ℃ of calcinings, need to further carry out the exploration of calcining heat.
Embodiment 2(comparative example)
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, total metal ion: EDTA: citric acid (mol ratio)=1:1.5:1, be dissolved in 500mL deionized water, using ammoniacal liquor regulator solution pH value is 6, thereby add thermal agitation make moisture constantly evaporation obtain thick lurid gel, thereby in stainless steel reaction container, organic compound combustion obtains linen powder, then pre-burning 5 hours at 240 ℃, finally at 950 ℃, calcine 5 hours, prepare the light yellow powder of BCZY.Fig. 1 (b) is the X-ray diffractogram of this powder, still has the diffraction maximum of brium carbonate to exist in the powder of the clear 950 ℃ of calcinings of this chart, and this powder does not still reach BCZY pure phase, illustrates that calcining heat need to continue to improve.
Embodiment 3
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, total metal ion: EDTA: citric acid (mol ratio)=1:1.5:1, be dissolved in 500mL deionized water, using ammoniacal liquor regulator solution pH value is 6, thereby add thermal agitation make moisture constantly evaporation obtain thick lurid gel, thereby in stainless steel reaction container, organic compound combustion obtains linen powder, then pre-burning 5 hours at 240 ℃, finally at 1000 ℃, calcine 5 hours, prepare the light yellow powder of BCZY of pure phase.Fig. 1 (c) is the X-ray diffractogram of this powder, diffraction maximum without brium carbonate and other impurity in the powder of the clear 1000 ℃ of calcinings of this chart exists, this powder is the BCZY of pure phase, illustrates that 1000 ℃ of insulations 5 hours are the calcine technologies of preparation pure phase BCZY powder the best.
Embodiment 4
Get the BCZY matrix powder that embodiment 3 obtains, additional 2.5% lithium carbonate, take absolute ethyl alcohol as medium mixing and ball milling 6 hours, through super-dry, grind, sieve after, the electrolyte powder of mixing is weighed to 0.7 gram to be poured into and in 12mm mould, carries out dry-pressing formed acquisition disc-shaped green compact, briquetting pressure is 150MPa, using lithium carbonate/yttrium doped with cerium barium zirconate powder as burying material, green compact sample is buried to burning in air atmosphere in 1250 ℃, 5 ℃/min of heating rates, be incubated 5 hours, then naturally cool to room temperature, make BCZY-2.5%Li 2cO 3multiphase structure proton conductor disc-shaped material, adopts Archimedes's drainage to measure its density, and its density reaches 95.2%, and material list reveals good sintering character.Fig. 2 is this proton conductor sample section stereoscan photograph, and in visible sample, almost pore-free exists, full densification.
Application Example 1, the resulting proton conductor circular disc test specimen of embodiment 4 is placed on testing tube, filamentary silver is introduced as electrode in two ends, under wet hydrogen atmosphere, carry out conductivity test, probe temperature is 500～800 ℃, temperature interval is 50 ℃, with electrochemical workstation, adopts linear sweep voltammetry to test, and utilizes formula σ=L/RA to calculate this material electric conductivity.When 600 ℃, 650 ℃ and 700 ℃, conductivity is respectively 7.27 * 10 -3s/cm, 9.81 * 10 -3s/cm and 1.11 * 10 -2s/cm.The conductivity of 650 ℃ approaches Expected Results substantially, and in the time of 700 ℃, conductivity has reached Expected Results completely.
Application Example 2, is placed on the resulting proton conductor circular disc test specimen of embodiment 4 in boiling water and boils 10 hours, observes the face shaping variation of boiling rear sample.Boiling water water-bath after 10 hours sample face shaping be not any change, this sample is carried out to X-ray diffraction analysis, in the sample after water-bath, there is not the diffraction maximum of any impurity, show that its chemical stability is good.
Application Example 3, with the resulting BCZY-2.5%Li of embodiment 3 2cO 3powder, as electrolyte, is prepared anode support type monocell.Adopt lamination to press altogether technology, it is that 15mm mould is dry-pressing formed that anode layer powder and a small amount of electrolyte powder are put into diameter successively.Then this disk is obtained to anode-supported electrolyte part at 1250 ℃ of sintering.At this parts electrolyte one, survey and apply LSrCoMnO 5+ δcathode slurry, 1000 ℃ of insulations 2 hours, making anode support type lithium carbonate/yttrium doped with cerium barium zirconate multiphase structure proton conductor material was electrolytical monocell.The two poles of the earth of fuel cell after assembling with filamentary silver, are placed in hydrogen atmosphere by one end of battery, and the other end is placed in oxygen atmosphere, utilize electrochemical workstation test battery performance.Fig. 3 is the performance chart of this anode support type monocell, and when 600 ℃, 650 ℃ and 700 ℃, the power density of battery has reached respectively 56mW/cm 2, 243mW/cm 2and 427mW/cm 2.
Embodiment 5(comparative example)
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, total metal ion: EDTA: citric acid (mol ratio)=1:2:1, be dissolved in 500mL deionized water, using ammoniacal liquor regulator solution pH value is 8, thereby add thermal agitation make moisture constantly evaporation obtain thick lurid gel, thereby in stainless steel reaction container, organic compound combustion obtains linen powder, then pre-burning 5 hours at 240 ℃, finally at 1000 ℃, calcine 5 hours, prepare the light yellow powder of BCZY.This powder body material is carried out to X-ray diffractogram analysis of spectrum, and the diffraction maximum without brium carbonate and other magazine in the powder under this temperature calcining exists, the BCZY that this powder is pure phase.This powder be take ethanol as medium mixing and ball milling 6 hours, through super-dry, grind, sieve after, electrolyte powder is weighed to 0.7 gram and pours into and in 12mm mould, carry out dry-pressing formedly, pressure is 150MPa, in yttrium doped with cerium barium zirconate powder, in air atmosphere, in 1250 ℃, bury burning, 5 ℃/min of heating rates, are incubated 5 hours, then naturally cool to room temperature, make BCZY electrolyte, adopt Archimedes's drainage to measure its density, its density reaches 74.9%.This embodiment does not add lithium carbonate, is to study as a comparison use.Fig. 4 is this BCZY bath sample profile scanning electromicroscopic photograph, in visible sample, has a large amount of pores, and density is poor.
Embodiment 6
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, total metal ion: EDTA: citric acid (mol ratio)=1:1.5:1, be dissolved in 500mL deionized water, using ammoniacal liquor regulator solution pH value is 7, thereby add thermal agitation make moisture constantly evaporation obtain thick lurid gel, thereby in stainless steel reaction container, organic compound combustion obtains linen powder, then pre-burning 5 hours at 240 ℃, finally at 1000 ℃, calcine 5 hours, prepare the light yellow powder of BCZY of pure phase.In matrix powder, add 2.5% quality lithium carbonate, take ethanol as medium mixing and ball milling 6 hours, through super-dry, grind, sieve after, the electrolyte powder of mixing is weighed to 0.7 gram and pours into and in 12mm mould, carry out dry-pressing formedly, pressure is 150MPa, in lithium carbonate doped with cerium barium zirconate powder, in air atmosphere, in 1200 ℃, bury burning, 5 ℃/min of heating rates, are incubated 5 hours, then naturally cool to room temperature, make BCZY-2.5%Li 2cO 3compound electrolyte material, adopts Archimedes's drainage to measure its density, and its density reaches 85.8%, and material list reveals good sintering character.When 600 ℃, 650 ℃ and 700 ℃, conductivity is respectively 3.51 * 10 -3s/cm, 4.32 * 10 -3s/cm and 5.32 * 10 -3s/cm.
Embodiment 7
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, total metal ion: EDTA: citric acid (mol ratio)=1:1.5:1, be dissolved in 500mL deionized water, using ammoniacal liquor regulator solution pH value is 8, thereby add thermal agitation make moisture constantly evaporation obtain thick lurid gel, thereby in stainless steel reaction container, organic compound combustion obtains linen powder, then pre-burning 5 hours at 240 ℃, finally at 1000 ℃, calcine 5 hours, prepare the light yellow powder of BCZY of pure phase.At the anhydrous middle interpolation 2.5% quality lithium carbonate of matrix powder, take ethanol as medium mixing and ball milling 6 hours, through super-dry, grind, sieve after, the electrolyte powder of mixing is weighed to 0.7 gram and pours into and in 12mm mould, carry out dry-pressing formedly, pressure is 150MPa, in lithium carbonate doped with cerium barium zirconate powder, in air atmosphere, in 1300 ℃, bury burning, 5 ℃/min of heating rates, are incubated 5 hours, then naturally cool to room temperature, make BCZY-2.5%Li 2cO 3compound electrolyte material, adopts Archimedes's drainage to measure its density, and its density reaches 95.8%, and material list reveals good sintering character.When 600 ℃, 650 ℃ and 700 ℃, conductivity is respectively 7.35 * 10 -3s/cm, 9.87 * 10 -3s/cm and 1.31 * 10 -2s/cm.
Lithium carbonate/yttrium doped with cerium barium zirconate multiphase structure proton conductor material that the present invention proposes and preparation method thereof, be not limited to above-described embodiment, person skilled obviously can be changed content as herein described or suitably change and combination within not departing from content of the present invention, spirit and scope, realizes the present invention.Special needs to be pointed out is, all similar replacements and change apparent to those skilled in the artly, they are deemed to be included in spirit of the present invention, scope and content.

Claims (2)

1. lithium carbonate/yttrium doped with cerium barium zirconate multiphase structure proton conductor material, its form and molar content as follows:
With BaCe 0.7zr 0.1y 0.2o 3-δabbreviation BCZY is matrix, and additional mass percent is that 2.5% lithium carbonate is as liquid-phase sintering auxiliary agent;
The preparation method of this lithium carbonate/yttrium doped with cerium barium zirconate multiphase structure proton conductor material, adopts softening method to prepare in two steps:
(1) adopt nitrate-citrate gel auto-combustion method, with Ba (NO 3) 2, Zr (NO 3) 45H 2o, Ce (NO 3) 36H 2o, Y (NO 3) 36H 2o, ethylenediamine tetra-acetic acid ethylenediaminetetraacetic acid, citric acid, ammoniacal liquor are raw material, according to total ionizable metal salt: EDTA: citric acid is 1:1.5:1/1:2:1 mixed in molar ratio, add in deionized water and heat, with ammoniacal liquor, regulating pH is 6～8, add thermal agitation transpiring moisture, obtain thick colloid; This gel is reacted in stainless steel reaction container again, in 240 ℃ of pre-burnings, be incubated 5 hours, finally calcining at 1000 ℃, is incubated 5 hours, obtains light yellow BCZY powder;
(2) by the BCZY powder of step (1), be basis material, additional mass percent is 2.5% lithium carbonate, take absolute ethyl alcohol as the mixing of medium ball milling; Drying, powder is put into mould after grinding, sieving, dry-pressing formed under 150MPa, afterwards the coupons of gained is buried to burning in 1200～1300 ℃ of air atmospheres, be incubated 5 hours, making lithium carbonate/yttrium doped with cerium barium zirconate is BCZY-2.5%Li 2cO 3multiphase structure proton conductor material.
2. according to lithium carbonate/yttrium doped with cerium barium zirconate multiphase structure proton conductor material of claim 1, it is characterized in that, it is 1250 ℃ that described step (1) is buried burning temperature, 5 ℃/min of heating rates.
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