CN104577169A - Gadolinium doped oxygen apatite type lanthanum silicate solid electrolyte and preparation method thereof - Google Patents

Gadolinium doped oxygen apatite type lanthanum silicate solid electrolyte and preparation method thereof Download PDF

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CN104577169A
CN104577169A CN201510009917.2A CN201510009917A CN104577169A CN 104577169 A CN104577169 A CN 104577169A CN 201510009917 A CN201510009917 A CN 201510009917A CN 104577169 A CN104577169 A CN 104577169A
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solid electrolyte
lanthanum silicate
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type lanthanum
silicate solid
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CN104577169B (en
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韩野
刘子萌
王哲
付晓杰
李士栋
赵思雪
邵常艳
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Shandong University of Science and Technology
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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
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • 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

Abstract

The invention discloses a gadolinium doped apatite type lanthanum silicate solid electrolyte and a preparation method thereof. The chemical formula of the gadolinium doped apatite type lanthanum silicate solid electrolyte is La(10-x)GdxSi6O27 (wherein x is more than 0 and not more than 0.6). The preparation method mainly comprises the following steps: weighing La(NO3).6H2O, Gd(NO3)3 and Si(OC2H5)4 in proportion, adding La(NO3)3.6H2O and Gd(NO3)3 in a mixed solution of absolute ethyl alcohol, distilled water and acetic acid, regulating pH value by using concentrated nitric acid and ammonium hydroxide, placing in a water bath, stirring and dropwise adding tetraethyl orthosilicate to form precursor gel, drying, roasting, calcining, grinding, carrying out compression molding and sintering to obtain the finished product. According to the preparation method, the process is simple, the operation is convenient and the energy consumption is low. The prepared product is uniform in quality and high in purity, and has high conductivity at low temperature being 450-750 DEG C.

Description

Gd2 O3 oxyapatite type lanthanum silicate solid electrolyte and preparation method thereof
Technical field
The present invention relates to a kind of solid electrolyte and preparation method thereof, particularly relate to a kind of Gd2 O3 oxyapatite type lanthanum silicate solid electrolyte and preparation method thereof, belong to Solid Oxide Fuel Cell technical field.
Background technology
Solid Oxide Fuel Cell (Solid Oxide Fuel Cell, be called for short SOFC) belong to third generation fuel battery energy origin system, the electrical energy devices of to be a kind of by the fuel in anode and the chemical energy in oxidant be the directly high efficiency total solids of electric energy, its high-energy conversion efficiency, clean pollution-free, safe ready, structure of whole solid state and the extensive adaptability etc. to pluralities of fuel gas, be mainly used in the fields such as aerospace, military affairs, automobile, small portable power supply, stationary electric power plant.
The critical piece of solid oxidized fuel cell is electrolyte, anode and negative electrode.In recent years, research and development is applicable to Novel electrolytic material one of study hotspot becoming this field of intermediate temperature solid oxide fuel cell.
At present, the solid electrolyte of extensive use is mainly yttria-stabilized zirconia, and it has higher ionic conductivity, good chemical stability and the advantage such as thermal stability, excellent gas dense.But due to its operating temperature too high (more than 1000 DEG C), thus bring a series of problem.Such as, shortcoming or the deficiencies such as solid oxide fuel cell seal is difficult, useful life is short, Components Matching is poor, operating cost is high.How effectively to reduce the working temperature of Solid Oxide Fuel Cell, develop the middle low-temperature electrolytes being suitable for solid oxide fuel cell applications, become focus and the direction of those skilled in the art's research:
Existing research shows: when Solid Oxide Fuel Cell works in the mesophilic range of 600-800 DEG C, the metallic interconnect materials of battery just can select relatively inexpensive stainless steel material, can reduce the chemical reaction between each interface simultaneously; And the reduction of temperature, also makes the sealing problem of fuel cell be readily solved.
When Solid Oxide Fuel Cell is 400-600 DEG C of work, rapid closedown and the unlatching of Solid Oxide Fuel Cell are just very easy to.
In prior art, middle low-temperature solid electrolyte mainly contains: CeO 2base electrolyte, Bi 2o 3base electrolyte, perovskite type electrolyte etc.Wherein, CeO 2based solid electrolyte operating temperature range is narrow, unstable under low oxygen partial pressure and reducing atmosphere; Bi 2o 3base electrolyte is easily reduced under low oxygen partial pressure and reducing atmosphere, at low temperatures, and Bi 2o 3easily undergo phase transition; Mainly there is material preparation difficulty in perovskite type electrolyte, the shortcomings such as sintering character difference, and interfacial reaction may occur between electrolyte and electrode, affects the performance of battery.
Chinese patent application CN102709578A discloses a kind of indium or niobium doped with oxygen base apatite-type lanthanum silicate solid electrolyte material and preparation method thereof, and the chemical formula of its electrolyte is La 10si 6-xin xo 27-x/2or La 10si 6-xnb xo 27+x/2, its preparation method: by La 2o 3and SiO 2and In 2o 3(or Nb 2o 5) through wet mixing, dry and low temperature presintering, afterwards cold moudling after sieving, then cold isostatic compaction, last pressureless sintering obtains product.
But, there is shortcoming or the deficiency such as complex process, energy consumption height in this method, such as, it needs the temperature lower calcination 5-15h at 1473-1673K, obtain calcining powder, then after making idiosome, under the condition of 1773-1973K, sintering 5-30h, just can obtain indium or niobium doped with oxygen base apatite-type lanthanum silicate solid electrolyte material; In addition, its calcining heat and sintering temperature are all higher, and temperature retention time is longer.
Chinese patent application CN101572322B discloses a kind of rare-earth doped lanthanum silicate oxyapatite type method for preparing solid electrolyte, and its chemical formula is La 10-XrE x(SiO 4) 6o 3-0.5X, wherein x=0.24-2, RE are Y, Sm, Nd, Gd;
Its preparation method mainly comprises the following steps: by tetraethoxysilane, La 2o 3with rare-earth oxide mixing, add ethanol and nitration acid heat dissolving, then add urea and deionized water, and regulate mixed solution pH value 4-6 with ammoniacal liquor, add thermal agitation, obtain even colloidal sol through heating water bath;
The colloidal sol of above-mentioned steps gained is carried out dry converting and becomes xerogel, xerogel is lighted at 350 DEG C-400 DEG C, and self-propagating combustion 5-8min, obtains raw powder; Ground in ball mill by the raw powder of gained, the powder after grinding calcines 6-8h at 50-900 DEG C again, obtains rare-earth doped lanthanum silicate oxyapatite type solid electrolyte powder.
But above-mentioned rare-earth doped lanthanum silicate oxyapatite type method for preparing solid electrolyte, owing to adopting the sub-propagating combustion of collosol and gel, its technique is comparatively complicated, and technical process control difficulty is larger.
Summary of the invention
An object of the present invention, provides a kind of Gd2 O3 apatite-type lanthanum silicate solid electrolyte can under cryogenic conditions in 450-750 DEG C with high conductivity.
The technical scheme that the present invention is adopted for achieving the above object is, a kind of Gd2 O3 apatite-type lanthanum silicate solid electrolyte, its chemical formula is: La 10-xgd xsi 6o 27, wherein, 0 < x≤0.6.
The technique effect that technique scheme is directly brought is, apatite-type lanthanum silicate solid electrolyte has low-activation energy, high oxygen ionic conductivity, good chemical stability and lower thermal coefficient of expansion under middle low temperature environment;
And the lanthanum silicate of apatite type oxide structure has the replacement mode of multiple position, through the apatite-type lanthanum silicate solid electrolyte of Gd2 O3, reduce the second-phase content of lanthanum silicate, compared with non-doped with oxygen base apatite-type lanthanum silicate solid electrolyte, it has higher conductivity under low temperature in 450-750 DEG C, is conducive to improving the useful life of Solid Oxide Fuel Cell, reducing the difficulty of follow-up encapsulation.
Two of object of the present invention is, provide a kind of preparation method of above-mentioned Gd2 O3 apatite-type lanthanum silicate solid electrolyte material, its preparation technology is simple, energy consumption is low, and products therefrom quality is homogeneous, purity is high.
The technical scheme that the present invention is adopted for achieving the above object is, a kind of preparation method of above-mentioned Gd2 O3 oxyapatite type lanthanum silicate solid electrolyte material, is characterized in that, comprise the following steps:
(1) 10-x:x:6 in molar ratio, wherein, 0 < x≤0.6, takes La (NO respectively 3) 36H 2o, Gd (NO 3) 3with Si (OC 2h 5) 4;
(2) by above-mentioned La (NO 3) 36H 2o and Gd (NO 3) 3join in the mixed solution of absolute ethyl alcohol, distilled water and acetic acid respectively, stir until obtain clear solution;
Limit is stirred, and limit uses red fuming nitric acid (RFNA) and ammoniacal liquor to coordinate adjust ph to 1-4;
(3) be that the solution of 1-4 is transferred in there-necked flask by above-mentioned pH value, be placed in the water bath of 70-85 DEG C, at the uniform velocity stir and slowly drip tetraethoxysilane, obtained aqueous precursor gel;
(4) above-mentioned aqueous precursor gel is placed in drying box, at 100-150 DEG C of temperature, dries 2-3 hour, obtained xerogel;
(5) by above-mentioned xerogel at 550-650 DEG C of roasting temperature 2-4 hour, cooling after take out;
Be placed in again in Muffle furnace, heating rate controlled, at 10 DEG C/min, be warming up to 950-1100 DEG C, calcining 4-6 hour, obtained powder;
(6) above-mentioned powder is ground to 100-200 order, adds appropriate binding agent, and pressurize 3-6min is compressing under 200-300MPa, obtains base substrate;
(7) be placed in Muffle furnace by above-mentioned base substrate, controlled by heating rate, for 2.5-3.5 DEG C/min, to be warming up to 1450-1600 DEG C, 4-5 is little of sintering in calcining, to obtain final product.
The technique effect that technique scheme is directly brought is, adopts sol-gel process Moist chemical synthesis, is convenient to accurately control each constituent content, and each raw material components in whole reaction system is mixed in the plastic stage.
This on the one hand, ensure that prepared Gd2 O3 apatite-type lanthanum silicate solid electrolyte has higher quality;
On the other hand, can effectively avoid because in system, certain raw material is excessive, or in system there is the reasons such as certain material composition excessive (namely system is uneven) in certain local, cause in product except host mutually except, also may there are too much other thing phases (as five oxidation two lanthanums, seven oxidation two lanthanums, silicon dioxide etc.), and then affect the problem of end product purity.
In addition, adopt sol-gal process synthesis apatite-type lanthanum silicate solid electrolyte presoma, improve the sintering activity of product, thus can reduce temperature retention time required in sintering process, and then reduce the energy consumption of whole preparation process.
Be preferably, above-mentioned mixed solution is according to following proportions: absolute ethyl alcohol, distilled water, acetic acid and Si (OC 2h 5) 4mol ratio between four is 3-6 ︰ 8-10 ︰ 0.8-1 ︰ 1.
The technique effect that this optimal technical scheme is directly brought is, the mixed solution of technique scheme is conducive to the gel that tetraethoxysilane defines better network configuration, thus effectively ensures that end product has the apatite-type crystal structure of higher quality.
For understanding the present invention better, the chemical reaction mechanism of existing brief description sol-gel process of the present invention:
Technique scheme (adds the acetic acid had as catalyst in the mixed solution of wherein second alcohol and water) by being dissolved in by tetraethoxysilane in the mixed solution of second alcohol and water, form even colloidal sol and gel by there is poly-condensation and hydrolysis, its main chemical reactions equation is:
Hydrolytic process:
(C 2H 5O) 4Si+H 2O→(C 2H 5O) 3Si(OH)+C 2H 5OH
Polycondensation process:
≡Si-OC 2H 5+HO-Si≡→Si-O-Si≡+C 2H 5OH
≡Si-OH+HO-Si≡→≡Si-O-Si≡+H 2O
Further preferably, above-mentioned binding agent is polyvinyl alcohol.
The technique effect that this optimal technical scheme is directly brought is, polyvinyl alcohol has stronger cementability, protecting colloid and gas barrier performance, and raw material is easy to obtain.
In sum, the present invention, relative to prior art, has following beneficial effect:
1, adopt the precursor product prepared by sol-gal process to be nanometer grade powder, do not need again through pulverizing or grinding, its technique is simple, easy and simple to handle;
And adopt sol-gel process, carry out Moist chemical synthesis, can accurately control each constituent content in the plastic stage, and each component can mix, products therefrom quality is homogeneous, purity is high;
2, preparation method of the present invention, reduces the temperature retention time in apatite-type lanthanum silicate solid electrolyte sintering process, thus energy-conservation;
3, compared with non-doped with oxygen base apatite-type lanthanum silicate solid electrolyte of the prior art, Gd2 O3 oxyapatite type lanthanum silicate solid electrolyte synthesized by the present invention is in 450-750 DEG C under low temperature, it has higher conductivity, this be conducive to improve Solid Oxide Fuel Cell useful life, reduce follow-up encapsulation difficulty.
Accompanying drawing explanation
The XRD collection of illustrative plates of the Gd2 O3 apatite-type lanthanum silicate solid electrolyte of Fig. 1 obtained by embodiment 1;
The XRD collection of illustrative plates of the Gd2 O3 apatite-type lanthanum silicate solid electrolyte of Fig. 2 obtained by embodiment 2;
The XRD collection of illustrative plates of the Gd2 O3 apatite-type lanthanum silicate solid electrolyte of Fig. 3 obtained by embodiment 3.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in detail.
Embodiment 1
According to mol ratio La:Si=10:6, take La (NO respectively 3) 3. 6h 2o, tetraethoxysilane and Gd (NO 3) 3, and join respectively in mixed solution, to dissolving completely;
This mixed solution is the mixed solution by following proportions:
Absolute ethyl alcohol, distilled water, acetic acid and Si (OC 2h 5) 4mol ratio between four is 5 ︰ 9 ︰ 1 ︰ 1;
Then coordinate adjust ph to 4 with red fuming nitric acid (RFNA) and ammoniacal liquor, be placed in 80 DEG C of water baths and at the uniform velocity stir, and slowly drip tetraethoxysilane, until form clear gel.
Gel is placed in 120 DEG C of drying box 2h to dry;
Then xerogel is placed in 550 DEG C of Muffle furnace roasting 6h, removing moisture and organic substance;
The product obtained is calcined 6h in 950 DEG C of Muffle furnaces, obtains the La that degree of crystallinity is good 9.8gd 0.2si 6o 27powder.
Gained will be calcined through grinding, make type at 250MPa pressure, and then sinter 4 hours through 1550 DEG C, obtain Gd2 O3 apatite-type lanthanum silicate solid electrolyte La 10si 6o 27material.
Embodiment 2
According to mol ratio La:Si:Gd=9.8:6:0.2, take La (NO respectively 3) 3. 6h 2o, tetraethoxysilane and Gd (NO 3) 3, and join respectively in mixed solution, to dissolving completely;
This mixed solution is the mixed solution by following proportions:
Absolute ethyl alcohol, distilled water, acetic acid and Si (OC 2h 5) 4mol ratio between four is 3 ︰ 8 ︰ 0.8 ︰ 1;
Then coordinate adjust ph to 3 with red fuming nitric acid (RFNA) and ammoniacal liquor, be placed in 80 DEG C of water baths and at the uniform velocity stir, and slowly drip tetraethoxysilane, until form clear gel.
Gel is placed in 120 DEG C of drying box 2h to dry; Then xerogel is placed in 600 DEG C of Muffle furnace roasting 4h, removing moisture and organic substance;
The product obtained is calcined 4h in 1000 DEG C of Muffle furnaces, obtains the La that degree of crystallinity is good 9.8gd 0.2si 6o 27powder.
Gained powder will be calcined through grinding, make type at 250MPa pressure, and then sinter 4 hours through 1550 DEG C, obtain Gd2 O3 apatite-type lanthanum silicate solid electrolyte La 9.8gd 0.2si 6o 27material.
Embodiment 3
According to mol ratio La:Si:Gd=9.6:6:0.4, take La (NO respectively 3) 3. 6h 2o, tetraethoxysilane and Gd (NO 3) 3, and join respectively in mixed solution, to dissolving completely;
This mixed solution is the mixed solution by following proportions:
Absolute ethyl alcohol, distilled water, acetic acid and Si (OC 2h 5) 4mol ratio between four is 6 ︰ 10 ︰ 0.9 ︰ 1;
Then coordinate adjust ph to 2 with red fuming nitric acid (RFNA) and ammoniacal liquor, be placed in 80 DEG C of water baths and at the uniform velocity stir, and slowly drip tetraethoxysilane, until form clear gel.
Gel is placed in 120 DEG C of drying box 2h to dry; Then xerogel is placed in 650 DEG C of Muffle furnace roasting 3h, removing moisture and organic substance; The product obtained is calcined 3h in 1050 DEG C of Muffle furnaces, obtains the La that degree of crystallinity is good 9.8gd 0.2si 6o 27powder.
Gained powder will be calcined through grinding, make type at 250MPa pressure, and then sinter 4.5 hours through 1550 DEG C, obtain Gd2 O3 apatite-type lanthanum silicate solid electrolyte La 9.6gd 0.4si 6o 27material.
Embodiment 4
Mixed solution is the mixed solution by following proportions:
Absolute ethyl alcohol, distilled water, acetic acid and Si (OC 2h 5) 4mol ratio between four is 4 ︰ 8 ︰ 0.8 ︰ 1;
All the other are all with embodiment 2.
Embodiment 5
Mixed solution is the mixed solution by following proportions:
Absolute ethyl alcohol, distilled water, acetic acid and Si (OC 2h 5) 4mol ratio between four is 6 ︰ 8 ︰ 0.8 ︰ 1;
All the other are all with embodiment 2.
Embodiment 6
Mixed solution is the mixed solution by following proportions:
Absolute ethyl alcohol, distilled water, acetic acid and Si (OC 2h 5) 4mol ratio between four is 6 ︰ 10 ︰ 0.8 ︰ 1;
All the other are all with embodiment 2.
Choose embodiment 1-3 representatively property embodiment, lanthanum silicate solid electrolyte obtained is separately carried out X-ray diffraction analysis respectively, and analysis result is as follows:
The apatite-type lanthanum silicate solid electrolyte La of Fig. 1 obtained by embodiment 1 10si 6o 27xRD collection of illustrative plates.As can be seen from this XRD spectra, product diffraction maximum is obvious, and peak type is sharp-pointed, and product La is described 10si 6o 27for oxyapatite structure.
By obtained apatite-type lanthanum silicate solid electrolyte La 10si 6o 27potsherd polishes puts into distilled water, after clean with Ultrasonic Cleaning, uniform application one deck silver slurry on both faces, again filamentary silver is bonded on electrolyte ceramics sheet as lead-in wire, put into Muffle furnace after oven dry be slowly heated to 500 DEG C with the programming rate of 5 DEG C/min and be incubated 30min sintered electrode, within the scope of 450-750 DEG C, test the ac impedance spectroscopy under different temperatures respectively, calculate La by Zsimpwin software 10si 6o 27conductivity can reach 4.38 × 10 at 750 DEG C -3scm -1.
The Gd2 O3 apatite-type lanthanum silicate solid electrolyte La of Fig. 2 obtained by embodiment 2 9.8gd 0.2si 6o 27xRD collection of illustrative plates.As can be seen from this XRD spectra, product diffraction maximum is obvious, and peak type is sharp-pointed, and product La is described 9.8gd 0.2si 6o 27there is oxyapatite structure;
Repaiied by crystalline substance, after finding Gd2 O3, cell parameter slightly reduces, but does not change p6 3/ m apatite-type crystal structure.
By the apatite-type lanthanum silicate solid electrolyte La of gained 9.8gd 0.2si 6o 27potsherd polishes puts into distilled water, after clean with Ultrasonic Cleaning, uniform application one deck silver slurry on both faces, again filamentary silver is bonded on electrolyte ceramics sheet as lead-in wire, put into Muffle furnace after oven dry be slowly heated to 500 DEG C with the programming rate of 5 DEG C/min and be incubated 30min sintered electrode, within the scope of 450-750 DEG C, test the ac impedance spectroscopy under different temperatures respectively, calculate La by Zsimpwin software 9.8gd 0.2si 6o 27conductivity can reach 2.22 × 10 at 750 DEG C -2scm -1.
The Gd2 O3 apatite-type lanthanum silicate solid electrolyte La of Fig. 3 obtained by embodiment 3 9.6gd 0.4si 6o 27xRD collection of illustrative plates.
As can be seen from this XRD spectra, product diffraction maximum is obvious, and peak type is sharp-pointed, and product La is described 9.6gd 0.4si 6o 27there is oxyapatite structure;
Repaiied by crystalline substance, after finding Gd2 O3, cell parameter slightly reduces, but does not change p6 3/ m apatite-type crystal structure.
Gained electrolyte ceramics sheet is polished put into distilled water Ultrasonic Cleaning clean after, uniform application one deck silver slurry on both faces, again filamentary silver is bonded on electrolyte ceramics sheet as lead-in wire, put into Muffle furnace after oven dry be slowly heated to 500 DEG C with the programming rate of 5 DEG C/min and be incubated 30min sintered electrode, within the scope of 450-750 DEG C, test the ac impedance spectroscopy under different temperatures respectively, calculate La by Zsimpwin software 9.8gd 0.4si 6o 27conductivity can reach 1.03 × 10 at 750 DEG C -3scm -1.
Illustrate: the obtained separately lanthanum silicate solid electrolyte of embodiment 4-6 all has oxyapatite structure, and the conductivity testing result at 750 DEG C is respectively: 2.04 × 10 -2scm -1, 2.10 × 10 -2scm -1, 2.13 × 10 -2scm -1.

Claims (4)

1. a Gd2 O3 oxyapatite type lanthanum silicate solid electrolyte material, is characterized in that, chemical formula is La 10-xgd xsi 6o 27, wherein, 0 < x≤0.6.
2. the preparation method of Gd2 O3 oxyapatite type lanthanum silicate solid electrolyte material as claimed in claim 1, is characterized in that, comprise the following steps:
(1) 10-x:x:6 in molar ratio, wherein, 0 < x≤0.6, takes La (NO respectively 3) 36H 2o, Gd (NO 3) 3with Si (OC 2h 5) 4;
(2) by above-mentioned La (NO 3) 36H 2o and Gd (NO 3) 3join in the mixed solution of absolute ethyl alcohol, distilled water and acetic acid respectively, stir until obtain clear solution;
Limit is stirred, and limit uses red fuming nitric acid (RFNA) and ammoniacal liquor to coordinate adjust ph to 1-4;
(3) be that the solution of 1-4 is transferred in there-necked flask by above-mentioned pH value, be placed in the water bath of 70-85 DEG C, at the uniform velocity stir and slowly drip tetraethoxysilane, obtained aqueous precursor gel;
(4) above-mentioned aqueous precursor gel is placed in drying box, at 100-150 DEG C of temperature, dries 2-3 hour, obtained xerogel;
(5) by above-mentioned xerogel at 550-650 DEG C of roasting temperature 2-4 hour, cooling after take out;
Be placed in again in Muffle furnace, heating rate controlled, at 10 DEG C/min, be warming up to 950-1100 DEG C, calcining 4-6 hour, obtained powder;
(6) above-mentioned powder is ground to 100-200 order, adds appropriate binding agent, and pressurize 3-6min is compressing under 200-300MPa, obtains base substrate;
(7) be placed in Muffle furnace by above-mentioned base substrate, controlled by heating rate, for 2.5-3.5 DEG C/min, to be warming up to 1450-1600 DEG C, 4-5 is little of sintering in calcining, to obtain final product.
3. the preparation method of Gd2 O3 oxyapatite type lanthanum silicate solid electrolyte material according to claim 2, it is characterized in that, described mixed solution is according to following proportions:
Absolute ethyl alcohol, distilled water, acetic acid and Si (OC 2h 5) 4mol ratio between four is 3-6 ︰ 8-10 ︰ 0.8-1 ︰ 1.
4. the preparation method of Gd2 O3 oxyapatite type lanthanum silicate solid electrolyte material according to claim 2, it is characterized in that, described binding agent is polyvinyl alcohol.
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