CN111018525B - 一种双层固体电解质质子导体及其制备方法 - Google Patents

一种双层固体电解质质子导体及其制备方法 Download PDF

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CN111018525B
CN111018525B CN201911346215.8A CN201911346215A CN111018525B CN 111018525 B CN111018525 B CN 111018525B CN 201911346215 A CN201911346215 A CN 201911346215A CN 111018525 B CN111018525 B CN 111018525B
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厉英
丁玉石
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Abstract

一种双层固体电解质质子导体及其制备方法，由基体部分和涂层部分组成的双层结构，基体部分的分子式为A1‑yA′yB1‑zB′zO3‑α，涂层部分的分子式为ABO3；制备方法为：(1)准备A原料和B原料，混合球磨获得混合粉体Ⅰ；(2)压制后煅烧制成煅烧物料Ⅰ；(3)准备A原料、B原料、A′原料和B′原料，混合球磨获得混合粉体Ⅱ；(4)压制后煅烧制成煅烧物料Ⅱ；(5)煅烧物料Ⅱ压制成型，制成基体坯料；采用共压、流延、旋涂、磁控溅射或激光沉积，将煅烧物料Ⅰ覆盖在基体坯料上形成涂层；(6)双层坯料在1300～1700℃烧结。本发明的产品具备质子导电性，同时限制住了氧离子空位及电子导电。

Description

一种双层固体电解质质子导体及其制备方法
技术领域
本发明涉及固体电解质质子导体技术领域，具体涉及一种双层固体电解质质子导体及其制备方法。
背景技术
高温氧化物质子导体是一种能够在高温下传递质子的固体电解质材料，在氢传感器、燃料电池、常压合成氨、电化学加氢脱氢等领域，质子导体具有良好的应用前景。
在高温质子导体中掺杂的钙钛矿型ABO3材料具有良好的质子导电性能，ABO3为立方、四方或者正交晶系，其中A位通常为+2价阳离子(如Ba、Ca、Sr等)，B位为+4价阳离子(如Zr、Ce等)，通常以三价稀土元素对四价B位元素进行掺杂后，使原材料产生氧空位。氧空位捕获气氛中的水蒸气或者氢气可引入质子，产生质子导电；但是，氧空位也会产生导电；另外在气氛氧分压较高时，材料中的氧空位捕获气氛中的氧气，产生电子空穴；低氧时，材料中的氧离子进入气相，产生氧空位及自由电子，产生电子导电。因此，ABO3材料易产生质子-氧离子空位-电子混合导电，极大的限制了材料的应用。
ABO3材料中的氧空位将导致材料产生混合导电，但是无氧空位，ABO3材料也无法产生质子，不能构成质子导体。
由上述可知，目前的钙钛矿结构ABO3材料易产生质子-氧离子空位-电子混合导电，限制了材料的应用。
发明内容
本发明的目的是提供一种双层固体电解质质子导体及其制备方法，采用掺杂的ABO3材料为基体，在其表面覆盖一层未掺杂的ABO3材料层，使组合形成的材料具备质子导电性，同时限制住了氧离子空位及电子导电。
本发明的双层固体电解质质子导体由基体部分和涂层部分组成，基体部分为钙钛矿材料，分子式为A1-yA′yB1-zB′zO3-α，涂层部分为钙钛矿材料，分子式为ABO3；其中的A元素为Ca、Sr和/或Ba，B元素为Sn、Zr、Hf、Pr、Ce、Th和/或Ti，A′元素为K、Na和/或Li，B′元素为Nd、Sm、Eu、Gd、Tb、Ho、Y、Dy、Er、Tm、Yb、Lu、In、Sc、Ga和/或Al，y＝0～0.3，z＝0～0.3，并且y+z≥0.05；上述的3-α取值随A1-yA′yB1-zB′zO3-α的总价态配平。
上述的双层固体电解质质子导体中，涂层部分与基体部分的厚度比为0.01～0.1。
本发明的双层固体电解质质子导体的制备方法按以下步骤进行：
1、准备A元素的氧化物、碳酸盐或硝酸盐作为A原料，准备B元素的氧化物、碳酸盐或硝酸盐作为B原料；将A原料和B原料混合球磨，磨细至平均粒径≤5μm，获得混合粉体Ⅰ；
2、将混合粉体Ⅰ压制成块，然后在800～1400℃煅烧5～20小时，随炉冷却至常温，制成煅烧物料Ⅰ；
3、准备A元素的氧化物、碳酸盐或硝酸盐作为A原料，准备B元素的氧化物、碳酸盐或硝酸盐作为B原料，准备A′元素的氧化物、碳酸盐或硝酸盐作为A′原料，准备B′元素的氧化物、碳酸盐或硝酸盐作为B′原料；将A原料、A′原料、B原料和B′原料混合球磨，磨细至平均粒径≤5μm，获得混合粉体Ⅱ；
4、将混合粉体Ⅱ压制成块，然后在800～1400℃煅烧5～20小时，随炉冷却至常温，制成煅烧物料Ⅱ；
5、将煅烧物料Ⅱ压制成型，制成基体坯料；然后采用共压、流延、磁控溅射或激光沉积方法，将煅烧物料Ⅰ覆盖在基体坯料上形成涂层，获得双层坯料；
6、将双层坯料在1300～1700℃烧结5～20小时，随炉冷却至常温，制成双层固体电解质质子导体材料。
上述的煅烧物料Ⅰ的分子式为ABO3，煅烧物料Ⅱ的分子式为A1-yA′yB1-zB′zO3-α。
上述的步骤2和4中，压制成块的压制压力5～10MPa。
上述的步骤5中，压制成型的压制压力50～300MPa。
上述的双层坯料中，基体坯料的厚度0.5～2mm，涂层厚度为基体坯料厚度的0.01～0.1倍。
本发明的原理是：未掺杂的ABO3材料中几乎不含有氧空位，可以限制材料中的氧离子空位及电子导电，同时未掺杂的ABO3材料晶体结构具备质子迁移的通道；A位或B位低价掺杂的ABO3材料中具备氧空位，可引入质子，使材料产生质子导电。因此，本发明提出在掺杂的ABO3材料表面覆盖一层未掺杂的ABO3材料，构建双层新材料，即具备质子导电性，同时限制住了氧离子空位及电子导电，可视为纯质子导体，具有良好的应用前景。
附图说明
图1为本发明实施例1中双层固体电解质质子导体的电导率及质子迁移数曲线图。
具体实施方式
本发明实施例中采用输力强1260A阻抗相位分析仪及吉时利2450多功能电表测试双层固体电解质质子导体的电导率和质子迁移数。
本发明实施例中采用的原料为市购分析纯试剂。
本发明实施例中采用的研磨罐为玛瑙材质。
本发明实施例中的混合固体电解质质子导体在500～900℃时电导率≤0.83×10-3S/cm。
本发明实施例中的混合固体电解质质子导体在500～800℃时质子迁移数>0.95。
本发明实施例中进行步骤5时采用等静压设备进行压制。
本发明实施例中的原料为元素A、A′、B和B′的碳酸盐、氧化物或硝酸盐。
本发明实施例中的双层固体电解质质子导体中，涂层部分与基体部分通过分子间力结合，该材料的孔隙率≤10％。
本发明实施例中的共压方法为文献《煅烧合成法制备Ni/YSZ金属陶瓷阳极及电化学行为研究》(Ringuede,A.；Bronin,D.I.；Frade,J.R Electrochemical Behaviour ofNi/YSZ Cermet Anodes Prepared by Combustion Synthesis，燃料电池.2001，1(3-4):238-242)记载的方法。
本发明实施例中的流延方法为《流延共烧法制备PSLZT多层复合NZFO材料及铁电、压电性能研究》(Ferroelectric and piezoelectric properties of PSLZT multilayer/NZFO co-sintered magnetoelectric composites fabricated by tape casting,欧洲陶瓷学会会刊，2019，39(16):5267-5276.)记载的方法。
本发明实施例中的磁控溅射方法为《磁控溅射法制备Mg、Al、Ga共掺杂ZnO导电玻璃及性能研究》(Liu,Y；Zhu,SM.Preparation and characterization of Mg,Al and Gaco-doped ZnO transparent conductive films deposited by magnetron sputtering，物理结论，2019,14:102514)记载的方法。
本发明实施例中的激光沉积方法为《脉冲激光法沉积法制备Al掺杂的Zn1-xMgxO带隙改性导电玻璃》(K.Matsubara,H.Tampo,H.Shibata,A.Yamada,P.Fons,K.Iwata,etal.Band-gap modified Al-doped Zn1-xMgxO transparent conducting filmsdeposited by pulsed laser deposition.物理应用快报，2004，85:1374-1376.)记载的方法。
本发明实施例中烧结造成的厚度变化忽略不计。
实施例1
双层固体电解质质子导体由基体部分和涂层部分组成的双层结构，基体部分的分子式为A1-yA′yB1-zB′zO3-α，涂层部分的分子式为ABO3；A元素为Sr，B元素为Ce，B′元素为Yb，y＝0(没有元素A′)，z＝0.1；3-α取值随AB1-zB′zO3-α的总价态配平；涂层部分与基体部分的厚度比为0.1；
制备方法为：
准备SrCO3作为A原料，准备CeO2作为B原料；将A原料和B原料混合球磨，磨细至平均粒径≤5μm，获得混合粉体Ⅰ；混合粉体Ⅰ中按摩尔比A:B＝1；
将混合粉体Ⅰ压制成块，压制压力5MPa，然后在1200℃煅烧10小时，随炉冷却至常温，制成煅烧物料Ⅰ，分子式为ABO3(SrCeO3)；
准备SrCO3作为A原料，准备CeO2作为B原料，准备Yb2O3作为B′原料；将A原料、A′原料、B原料和B′原料混合球磨，磨细至平均粒径≤5μm，获得混合粉体Ⅱ；混合粉体Ⅱ中按摩尔比A:B:B′＝1:0.9:0.1；
将混合粉体Ⅱ压制成块，压制压力5MPa，然后在1200℃煅烧10小时，随炉冷却至常温，制成煅烧物料Ⅱ，分子式为AB1-zB′zO3-α(SrCe0.9Yb0.1O3-α)；
将煅烧物料Ⅱ压制成型，压制压力50MPa，制成基体坯料，厚度1mm；然后采用共压方法，将煅烧物料Ⅰ覆盖在基体坯料上形成涂层，厚度为基体坯料厚度的0.1倍，获得双层坯料；
将双层坯料在1600℃烧结10小时，随炉冷却至常温，制成双层固体电解质质子导体材料，电导率及质子迁移数曲线如图1所示。
实施例2
双层固体电解质质子导体的中的A元素为Ca，B元素为Sn，A′元素为K，B′元素为Nd，y＝0.3，z＝0.3；涂层部分与基体部分的厚度比为0.1；
方法同实施例1，不同点在于；
(1)混合粉体Ⅰ压制压力10MPa，在800℃煅烧20小时；
(2)混合粉体Ⅱ中按摩尔比A:A′:B:B′＝0.7:0.3:0.7:0.3；
(3)混合粉体Ⅱ压制压力10MPa，在800℃煅烧20小时；
(4)煅烧物料Ⅱ压制压力300MPa，基体坯料厚度0.5mm；采用磁控溅射方法，将煅烧物料Ⅰ覆盖在基体坯料上形成涂层，厚度为基体坯料厚度的0.1倍；
(5)双层坯料在1300℃烧结20小时。
实施例3
双层固体电解质质子导体中的A元素为Ba，B元素为Zr，A′元素为Na，B′元素为Sm，y＝0.12，z＝0.01；涂层部分与基体部分的厚度比为0.01；
方法同实施例1，不同点在于；
(1)混合粉体Ⅰ压制压力6MPa，在900℃煅烧19小时；
(2)混合粉体Ⅱ中按摩尔比A:A′:B:B′＝0.88:0.12:0.99:0.01；
(3)混合粉体Ⅱ压制压力6MPa，在900℃煅烧19小时；
(4)煅烧物料Ⅱ压制压力80MPa，基体坯料厚度2mm；采用激光沉积方法，将煅烧物料Ⅰ覆盖在基体坯料上形成涂层，厚度为基体坯料厚度的0.01倍；
(5)双层坯料在1350℃烧结19小时。
实施例4
双层固体电解质质子导体中的A元素为Ca，B元素为Hf，A′元素为Li，B′元素为Eu，y＝0.2，z＝0.25；涂层部分与基体部分的厚度比为0.02；
方法同实施例1，不同点在于；
(1)混合粉体Ⅰ压制压力7MPa，在950℃煅烧18小时；
(2)混合粉体Ⅱ中按摩尔比A:A′:B:B′＝0.8:0.2:0.75:0.25；
(3)混合粉体Ⅱ压制压力7MPa，在950℃煅烧18小时；
(4)煅烧物料Ⅱ压制压力100MPa，基体坯料厚度1.5mm；采用激光沉积方法，将煅烧物料Ⅰ覆盖在基体坯料上形成涂层，厚度为基体坯料厚度的0.02倍；
(5)双层坯料在1380℃烧结18小时。
实施例5
双层固体电解质质子导体中的A元素为Sr，B元素为Pr，A′元素为K，B′元素为Gd，y＝0.05，z＝0.11；涂层部分与基体部分的厚度比为0.05；
方法同实施例1，不同点在于；
(1)混合粉体Ⅰ压制压力8MPa，在980℃煅烧17小时；
(2)混合粉体Ⅱ中按摩尔比A:A′:B:B′＝0.95:0.05:0.89:0.11；
(3)混合粉体Ⅱ压制压力8MPa，在980℃煅烧17小时；
(4)煅烧物料Ⅱ压制压力120MPa，基体坯料厚度1.8mm；采用流延方法，将煅烧物料Ⅰ覆盖在基体坯料上形成涂层，厚度为基体坯料厚度的0.05倍；
(5)双层坯料在1400℃烧结16小时。
实施例6
双层固体电解质质子导体中的A元素为Ba，B元素为Th，A′元素为Na，B′元素为Tb，y＝0.18，z＝0.24；涂层部分与基体部分的厚度比为0.04；
方法同实施例1，不同点在于；
(1)混合粉体Ⅰ压制压力9MPa，在1000℃煅烧16小时；
(2)混合粉体Ⅱ中按摩尔比A:A′:B:B′＝0.82:0.18:0.76:0.24；
(3)混合粉体Ⅱ压制压力9MPa，在1000℃煅烧16小时；
(4)煅烧物料Ⅱ压制压力180MPa，基体坯料厚度1.8mm；采用流延方法，将煅烧物料Ⅰ覆盖在基体坯料上形成涂层，厚度为基体坯料厚度的0.04倍；
(5)双层坯料在1400℃烧结15小时。
实施例7
双层固体电解质质子导体中的A元素为Ca，B元素为Ti，A′元素为Li，B′元素为Ho，y＝0.05，z＝0.15；涂层部分与基体部分的厚度比为0.08；
方法同实施例1，不同点在于；
(1)混合粉体Ⅰ压制压力10MPa，在1020℃煅烧15小时；
(2)混合粉体Ⅱ中按摩尔比A:A′:B:B′＝0.95:0.05:0.85:0.15；
(3)混合粉体Ⅱ压制压力10MPa，在1020℃煅烧15小时；
(4)煅烧物料Ⅱ压制压力200MPa，基体坯料厚度0.9mm；采用磁控溅射方法，将煅烧物料Ⅰ覆盖在基体坯料上形成涂层，厚度为基体坯料厚度的0.08倍；
(5)双层坯料在1450℃烧结12小时。
实施例8
双层固体电解质质子导体中的A元素为Sr，B元素为Ce，A′元素为K，B′元素为Y，y＝0.04，z＝0.01；涂层部分与基体部分的厚度比为0.06；
方法同实施例1，不同点在于；
(1)混合粉体Ⅰ压制压力10MPa，在1050℃煅烧14小时；
(2)混合粉体Ⅱ中按摩尔比A:A′:B:B′＝0.96:0.04:0.99:0.01；
(3)混合粉体Ⅱ压制压力10MPa，在1050℃煅烧14小时；
(4)煅烧物料Ⅱ压制压力220MPa，基体坯料厚度1.5mm；采用流延方法，将煅烧物料Ⅰ覆盖在基体坯料上形成涂层，厚度为基体坯料厚度的0.06倍；
(5)双层坯料在1450℃烧结12小时。
实施例9
双层固体电解质质子导体中的A元素为Sr，B元素为Sn，A′元素为Na，B′元素为Dy，y＝0.28，z＝0.02；涂层部分与基体部分的厚度比为0.05；
方法同实施例1，不同点在于；
(1)混合粉体Ⅰ压制压力10MPa，在1080℃煅烧13小时；
(2)混合粉体Ⅱ中按摩尔比A:A′:B:B′＝0.72:0.28:0.98:0.02；
(3)混合粉体Ⅱ压制压力10MPa，在1080℃煅烧13小时；
(4)煅烧物料Ⅱ压制压力240MPa，基体坯料厚度2mm；采用共压方法，将煅烧物料Ⅰ覆盖在基体坯料上形成涂层，厚度为基体坯料厚度的0.05倍；
(5)双层坯料在1500℃烧结8小时。
实施例10
双层固体电解质质子导体中的A元素为Sr，B元素为Pr，A′元素为Li，B′元素为Er，y＝0.11，z＝0.12；涂层部分与基体部分的厚度比为0.08；
方法同实施例1，不同点在于；
(1)混合粉体Ⅰ压制压力10MPa，在1100℃煅烧12小时；
(2)混合粉体Ⅱ中按摩尔比A:A′:B:B′＝0.89:0.11:0.88:0.12；
(3)混合粉体Ⅱ压制压力10MPa，在1100℃煅烧12小时；
(4)煅烧物料Ⅱ压制压力260MPa，基体坯料厚度1.6mm；采用共压方法，将煅烧物料Ⅰ覆盖在基体坯料上形成涂层，厚度为基体坯料厚度的0.08倍；
(5)双层坯料在1500℃烧结8小时。
实施例11
双层固体电解质质子导体中的A元素为Sr，B元素为Ce，A′元素为K，B′元素为Tm，y＝0.23，z＝0.13；涂层部分与基体部分的厚度比为0.04；
方法同实施例1，不同点在于；
(1)混合粉体Ⅰ压制压力10MPa，在1150℃煅烧11小时；
(2)混合粉体Ⅱ中按摩尔比A:A′:B:B′＝0.77:0.23:0.87:0.13；
(3)混合粉体Ⅱ压制压力10MPa，在1150℃煅烧11小时；
(4)煅烧物料Ⅱ压制压力280MPa，基体坯料厚度1.5mm；采用流延方法，将煅烧物料Ⅰ覆盖在基体坯料上形成涂层，厚度为基体坯料厚度的0.04倍；
(5)双层坯料在1550℃烧结7小时。
实施例12
双层固体电解质质子导体中的A元素为Sr，B元素为Ce，A′元素为Na，B′元素为Lu，y＝0.04，z＝0.16；涂层部分与基体部分的厚度比为0.04；
方法同实施例1，不同点在于；
(1)混合粉体Ⅰ压制压力10MPa，在1200℃煅烧9小时；
(2)混合粉体Ⅱ中按摩尔比A:A′:B:B′＝0.96:0.04:0.84:0.16；
(3)混合粉体Ⅱ压制压力10MPa，在1200℃煅烧9小时；
(4)煅烧物料Ⅱ压制压力300MPa，基体坯料厚度1.5mm；采用磁控溅射方法，将煅烧物料Ⅰ覆盖在基体坯料上形成涂层，厚度为基体坯料厚度的0.04倍；
(5)双层坯料在1550℃烧结7小时。
实施例13
双层固体电解质质子导体中的A元素为Sr，B元素为Ce，A′元素为Li，B′元素为In，y＝0.13，z＝0.26；涂层部分与基体部分的厚度比为0.02；
方法同实施例1，不同点在于；
(1)混合粉体Ⅰ压制压力10MPa，在1250℃煅烧8小时；
(2)混合粉体Ⅱ中按摩尔比A:A′:B:B′＝0.87:0.13:0.74:0.16；
(3)混合粉体Ⅱ压制压力10MPa，在1250℃煅烧8小时；
(4)煅烧物料Ⅱ压制压力300MPa，基体坯料厚度2mm；采用激光沉积方法，将煅烧物料Ⅰ覆盖在基体坯料上形成涂层，厚度为基体坯料厚度的0.02倍；
(5)双层坯料在1600℃烧结6小时。
实施例14
双层固体电解质质子导体中的A元素为Sr，B元素为Ce，A′元素为K，B′元素为Sc，y＝0.3，z＝0.3；涂层部分与基体部分的厚度比为0.06；
方法同实施例1，不同点在于；
(1)混合粉体Ⅰ压制压力10MPa，在1300℃煅烧7小时；
(2)混合粉体Ⅱ中按摩尔比A:A′:B:B′＝0.7:0.3:0.7:0.3；
(3)混合粉体Ⅱ压制压力10MPa，在1300℃煅烧7小时；
(4)煅烧物料Ⅱ压制压力300MPa，基体坯料厚度1.5mm；采用流延方法，将煅烧物料Ⅰ覆盖在基体坯料上形成涂层，厚度为基体坯料厚度的0.06倍；
(5)双层坯料在1600℃烧结6小时。
实施例15
双层固体电解质质子导体中的A元素为Sr，B元素为Ce，A′元素为Na，B′元素为Ga，y＝0.15，z＝0.05；涂层部分与基体部分的厚度比为0.05；
方法同实施例1，不同点在于；
(1)混合粉体Ⅰ压制压力10MPa，在1350℃煅烧6小时；
(2)混合粉体Ⅱ中按摩尔比A:A′:B:B′＝0.85:0.15:0.95:0.05；
(3)混合粉体Ⅱ压制压力10MPa，在1350℃煅烧6小时；
(4)煅烧物料Ⅱ压制压力200MPa，基体坯料厚度2mm；采用磁控溅射方法，将煅烧物料Ⅰ覆盖在基体坯料上形成涂层，厚度为基体坯料厚度的0.05倍；
(5)双层坯料在1700℃烧结5小时。
实施例16
双层固体电解质质子导体中的A元素为Sr，B元素为Ce，A′元素为Li，B′元素为Al，y＝0.02，z＝0.18；涂层部分与基体部分的厚度比为0.03；
方法同实施例1，不同点在于；
(1)混合粉体Ⅰ压制压力10MPa，在1400℃煅烧5小时；
(2)混合粉体Ⅱ中按摩尔比A:A′:B:B′＝0.98:0.02:0.82:0.18；
(3)混合粉体Ⅱ压制压力10MPa，在1400℃煅烧5小时；
(4)煅烧物料Ⅱ压制压力150MPa，基体坯料厚度1mm；采用激光沉积方法，将煅烧物料Ⅰ覆盖在基体坯料上形成涂层，厚度为基体坯料厚度的0.03倍；
(5)双层坯料在1700℃烧结5小时。

Claims (2)

1.一种双层固体电解质质子导体，其特征在于由基体部分和涂层部分组成，基体部分为钙钛矿材料，分子式为A1-yA´yB1-zB´zO3-α，涂层部分为钙钛矿材料，分子式为ABO3；其中的A元素为Ca、Sr和/或Ba，B元素为Sn、Zr、Hf、Pr、Ce、Th和/或Ti，A´元素为K、Na和/或Li，B´元素为Nd、Sm、Eu、Gd、Tb、Ho、Y、Dy、Er、Tm、Yb、Lu、In、Sc、Ga和/或Al，y=0~0.3，z=0~0.3，并且y+z≥0.05；上述的3-α取值随A1-yA´yB1-zB´zO3-α的总价态配平；所述的涂层部分与基体部分的厚度比为0.01~0.1。
2.一种权利要求1所述的双层固体电解质质子导体的制备方法，其特征在于按以下步骤进行：
（1）准备A元素的氧化物、碳酸盐或硝酸盐作为A原料，准备B元素的氧化物、碳酸盐或硝酸盐作为B原料；将A原料和B原料混合球磨，磨细至平均粒径≤5μm，获得混合粉体Ⅰ；
（2）将混合粉体Ⅰ压制成块，然后在800~1400℃煅烧5~20小时，随炉冷却至常温，制成煅烧物料Ⅰ；煅烧物料Ⅰ的分子式为ABO3；压制成块的压制压力5~10MPa；
（3）准备A元素的氧化物、碳酸盐或硝酸盐作为A原料，准备B元素的氧化物、碳酸盐或硝酸盐作为B原料，准备A´元素的氧化物、碳酸盐或硝酸盐作为A´原料，准备B´元素的氧化物、碳酸盐或硝酸盐作为B´原料；将A原料、A´原料、B原料和B´原料混合球磨，磨细至平均粒径≤5μm，获得混合粉体Ⅱ；煅烧物料Ⅱ的分子式为A1-yA´yB1-zB´zO3-α；
（4）将混合粉体Ⅱ压制成块，然后在800~1400℃煅烧5~20小时，随炉冷却至常温，制成煅烧物料Ⅱ；压制成块的压制压力5~10MPa；
（5）将煅烧物料Ⅱ压制成型，制成基体坯料；压制成型的压制压力50~300MPa；然后采用共压、流延、磁控溅射或激光沉积方法，将煅烧物料Ⅰ覆盖在基体坯料上形成涂层，获得双层坯料；双层坯料中，基体坯料的厚度0.5~2mm，涂层厚度为基体坯料厚度的0.01~0.1倍；
（6）将双层坯料在1300~1700℃烧结5~20小时，随炉冷却至常温，制成双层固体电解质质子导体材料。
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