CN110937897B - 一种混合固体电解质质子导体材料及其制备方法 - Google Patents

一种混合固体电解质质子导体材料及其制备方法 Download PDF

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CN110937897B
CN110937897B CN201911345367.6A CN201911345367A CN110937897B CN 110937897 B CN110937897 B CN 110937897B CN 201911345367 A CN201911345367 A CN 201911345367A CN 110937897 B CN110937897 B CN 110937897B
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厉英
丁玉石
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Abstract

一种混合固体电解质质子导体材料及其制备方法，分子式为ABO3‑A1‑yA′yB1‑zB′zO3‑α，A为Ca、Sr和/或Ba，B为Sn、Zr、Hf、Pr、Ce、Th和/或Ti，A′为K、Na和/或Li，B′为Nd、Sm、Eu、Gd、Tb、Ho、Y、Dy、Er、Tm、Yb、Lu、In、Sc、Ga和/或Al；方法为：(1)准备A原料和B原料，混合球磨制成混合粉体Ⅰ；(2)压制成块，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，混合球磨制成混合粉体Ⅱ；(4)压制成块，煅烧制成煅烧物料Ⅱ；(5)煅烧物料Ⅰ和煅烧物料Ⅱ混合球磨获得混合粉体Ⅲ；(6)将压制成块在1300～1700℃烧结。本发明的产品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。

Description

一种混合固体电解质质子导体材料及其制备方法
技术领域
本发明涉及固体电解质质子导体技术领域，具体涉及一种混合固体电解质质子导体材料及其制备方法。
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混合固体电解质质子导体材料及其制备方法，采用未掺杂的ABO3材料作为基体，复合部分掺杂的ABO3材料，使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。
本发明的混合固体电解质质子导体材料为钙钛矿材料，分子式为ABO3-A1-yA′yB1- zB′zO3-α；其中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，并且按摩尔比ABO3:A1-yA′yB1-zB′zO3-α＝1:0.1～0.5。
本发明的混合固体电解质质子导体材料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制成混合粉体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制成混合粉体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Ⅰ和煅烧物料Ⅱ按摩尔比1:0.1～0.5混合后球磨，磨细至平均粒径≤10μm获得混合粉体Ⅲ；
6、将混合粉体Ⅲ压制成块，然后在1300～1700℃烧结5～20小时，随炉冷却至常温，制成混合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6中，压制成块的压制压力50～300MPa。
本发明的原理是：采用未掺杂的ABO3材料作为基体，在其中复合一部分掺杂的ABO3材料；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；复合一部分掺杂了的ABO3材料后，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；因此产品材料具备较高的质子电导率，同时限制住了氧离子空位及电子导电，具有良好的应用前景。
附图说明
图1为本发明实施例1中混合固体电解质质子导体材料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多功能电表测试混合固体电解质质子导体材料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材料在500～900℃时电导率≤0.66×10-3S/cm。
本发明实施例中的混合固体电解质质子导体材料在500～800℃时质子迁移数>0.90。
本发明实施例中进行步骤6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。
实施例1
混合固体电解质质子导体材料的分子式为ABO3-A1-yA′yB1-zB′zO3-α，其中A元素为Sr，B元素为Ce，B′元素为Yb，y＝0(没有元素A′)，z＝0.05，3-α取值随A1-yA′yB1-zB′zO3-α的总价态配平，按摩尔比ABO3:AB1-zB′zO3-α＝1:0.3；
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制成混合粉体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800℃煅烧20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、B原料和B′原料混合球磨，磨细至平均粒径≤5μm制成混合粉体Ⅱ；混合粉体Ⅱ中按摩尔比A:B:B′＝1:0.95:0.05；
将混合粉体Ⅱ压制成块，压制压力5MPa，然后在800℃煅烧20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Ⅰ和煅烧物料Ⅱ按摩尔比1:0.3混合后球磨，磨细至平均粒径≤10μm获得混合粉体Ⅲ；
将混合粉体Ⅲ压制成块，压制压力150MPa，然后在1500℃烧结10小时，随炉冷却至常温，制成混合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
混合固体电解质质子导体材料中A元素为Ca，B元素为Sn，A′元素为K，B′元素为Nd，y＝0.1，z＝0.1，并且按摩尔比ABO3:A1-yA′yB1-zB′zO3-α＝1:0.2；
方法同实施例1，不同点在于：
(1)混合粉体Ⅰ压制压力10MPa，在850℃煅烧19小时；
(2)混合粉体Ⅱ中按摩尔比A:A′:B:B′＝0.9:0.1:0.9:0.1；
(3)混合粉体Ⅱ压制压力10MPa，在850℃煅烧19小时；
(4)煅烧物料Ⅰ和煅烧物料Ⅱ按摩尔比1:0.1混合；
(5)混合粉体Ⅲ压制压力50～300MPa，在1300～1700℃烧结5～20小时。
实施例3
混合固体电解质质子导体材料中A元素为Ba，B元素为Zr，A′元素为Na，B′元素为Sm，y＝0.02，z＝0.05，按摩尔比ABO3:A1-yA′yB1-zB′zO3-α＝1:0.4；
方法同实施例1，不同点在于：
(1)混合粉体Ⅰ压制压力6MPa，在880℃煅烧18小时；
(2)混合粉体Ⅱ中按摩尔比A:A′:B:B′＝0.98:0.02:0.95:0.05；
(3)混合粉体Ⅱ压制压力6MPa，在880℃煅烧18小时；
(4)煅烧物料Ⅰ和煅烧物料Ⅱ按摩尔比1:0.15混合；
(5)混合粉体Ⅲ压制压力50MPa，在1300℃烧结20小时。
实施例4
混合固体电解质质子导体材料中A元素为Sr，B元素为Hf，A′元素为Li，B′元素为Eu、，y＝0.3，z＝0.03，并且按摩尔比ABO3:A1-yA′yB1-zB′zO3-α＝1:0.1；
方法同实施例1，不同点在于：
(1)混合粉体Ⅰ压制压力7MPa，在900℃煅烧17小时；
(2)混合粉体Ⅱ中按摩尔比A:A′:B:B′＝0.7:0.3:0.97:0.03；
(3)混合粉体Ⅱ压制压力7MPa，在900℃煅烧17小时；
(4)煅烧物料Ⅰ和煅烧物料Ⅱ按摩尔比1:0.2混合；
(5)混合粉体Ⅲ压制压力300MPa，在1700℃烧结5小时。
实施例5
混合固体电解质质子导体材料中A元素为Ca，B元素为Pr，A′元素为K，B′元素为Gd，y＝0.06，z＝0.3，并且按摩尔比ABO3:A1-yA′yB1-zB′zO3-α＝1:0.5；
方法同实施例1，不同点在于：
(1)混合粉体Ⅰ压制压力8MPa，在930℃煅烧16小时；
(2)混合粉体Ⅱ中按摩尔比A:A′:B:B′＝0.94:0.06:0.7:0.3；
(3)混合粉体Ⅱ压制压力8MPa，在930℃煅烧16小时；
(4)煅烧物料Ⅰ和煅烧物料Ⅱ按摩尔比1:0.25混合；
(5)混合粉体Ⅲ压制压力80MPa，在1350℃烧结19小时。
实施例6
混合固体电解质质子导体材料中A元素为Ba，B元素为Th，A′元素为Na，B′元素为Tb，y＝0.25，z＝0.01，并且按摩尔比ABO3:A1-yA′yB1-zB′zO3-α＝1:0.13；
方法同实施例1，不同点在于：
(1)混合粉体Ⅰ压制压力9MPa，在950℃煅烧15小时；
(2)混合粉体Ⅱ中按摩尔比A:A′:B:B′＝0.75:0.25:0.99:0.01；
(3)混合粉体Ⅱ压制压力9MPa，在950℃煅烧15小时；
(4)煅烧物料Ⅰ和煅烧物料Ⅱ按摩尔比1:0.35混合；
(5)混合粉体Ⅲ压制压力100MPa，在1380℃烧结18小时。
实施例7
混合固体电解质质子导体材料中A元素为Ca，B元素为Ti，A′元素为Li，B′元素为Ho，y＝0.16，z＝0.04，并且按摩尔比ABO3:A1-yA′yB1-zB′zO3-α＝1:0.16；
方法同实施例1，不同点在于：
(1)混合粉体Ⅰ压制压力10MPa，在980℃煅烧14小时；
(2)混合粉体Ⅱ中按摩尔比A:A′:B:B′＝0.84:0.16:0.96:0.04；
(3)混合粉体Ⅱ压制压力10MPa，在980℃煅烧14小时；
(4)煅烧物料Ⅰ和煅烧物料Ⅱ按摩尔比1:0.4混合；
(5)混合粉体Ⅲ压制压力120MPa，在1400℃烧结17小时。
实施例8
混合固体电解质质子导体材料中A元素为Sr，B元素为Th，A′元素为K，B′元素为Y，y＝0.08，z＝0.23，并且按摩尔比ABO3:A1-yA′yB1-zB′zO3-α＝1:0.22；
方法同实施例1，不同点在于：
(1)混合粉体Ⅰ压制后在1000℃煅烧13小时；
(2)混合粉体Ⅱ中按摩尔比A:A′:B:B′＝0.92:0.08:0.77:0.23；
(3)混合粉体Ⅱ压制后在1000℃煅烧13小时；
(4)煅烧物料Ⅰ和煅烧物料Ⅱ按摩尔比1:0.45混合；
(5)混合粉体Ⅲ压制压力160MPa，在1430℃烧结16小时。
实施例9
混合固体电解质质子导体材料中A元素为Sr，B元素为Ce，A′元素为Na，B′元素为Dy，y＝0.05，z＝0.18，并且按摩尔比ABO3:A1-yA′yB1-zB′zO3-α＝1:0.25；
方法同实施例1，不同点在于：
(1)混合粉体Ⅰ压制压力9MPa，在1050℃煅烧12小时；
(2)混合粉体Ⅱ中按摩尔比A:A′:B:B′＝0.95:0.05:0.82:0.18；
(3)混合粉体Ⅱ压制压力9MPa，在1050℃煅烧12小时；
(4)煅烧物料Ⅰ和煅烧物料Ⅱ按摩尔比1:0.5混合；
(5)混合粉体Ⅲ压制压力50～300MPa，在1300～1700℃烧结5～20小时。
实施例10
混合固体电解质质子导体材料中A元素为Ba，B元素为Pr，A′元素为Li，B′元素为Er，y＝0.02，z＝0.22，并且按摩尔比ABO3:A1-yA′yB1-zB′zO3-α＝1:0.28；
方法同实施例1，不同点在于：
(1)混合粉体Ⅰ压制压力8MPa，在1100℃煅烧11小时；
(2)混合粉体Ⅱ中按摩尔比A:A′:B:B′＝0.98:0.02:0.78:0.22；
(3)混合粉体Ⅱ压制压力8MPa，在1100℃煅烧11小时；
(4)煅烧物料Ⅰ和煅烧物料Ⅱ按摩尔比1:0.33混合；
(5)混合粉体Ⅲ压制压力180MPa，在1460℃烧结11小时。
实施例11
混合固体电解质质子导体材料中A元素为Ca，B元素为Hf，A′元素为K，B′元素为Tm，y＝0.25，z＝0.01，并且按摩尔比ABO3:A1-yA′yB1-zB′zO3-α＝1:0.33；
方法同实施例1，不同点在于：
(1)混合粉体Ⅰ压制压力7MPa，在1150℃煅烧10小时；
(2)混合粉体Ⅱ中按摩尔比A:A′:B:B′＝0.75:0.25:0.99:0.01；
(3)混合粉体Ⅱ压制压力7MPa，在1150℃煅烧10小时；
(4)煅烧物料Ⅰ和煅烧物料Ⅱ按摩尔比1:0.26混合；
(5)混合粉体Ⅲ压制压力200MPa，在1550℃烧结9小时。
实施例12
混合固体电解质质子导体材料中A元素为Ca，B元素为Zr，A′元素为Na，B′元素为Lu，y＝0.19，z＝0.23，并且按摩尔比ABO3:A1-yA′yB1-zB′zO3-α＝1:0.36；
方法同实施例1，不同点在于：
(1)混合粉体Ⅰ压制压力6MPa，在1200℃煅烧9小时；
(2)混合粉体Ⅱ中按摩尔比A:A′:B:B′＝0.81:0.19:0.77:0.23；
(3)混合粉体Ⅱ压制压力6MPa，在1200℃煅烧9小时；
(4)煅烧物料Ⅰ和煅烧物料Ⅱ按摩尔比1:0.17混合；
(5)混合粉体Ⅲ压制压力220MPa，在1580℃烧结8小时。
实施例13
混合固体电解质质子导体材料中A元素为Sr，B元素为Sn，A′元素为Li，B′元素为In，y＝0.17，z＝0.13，并且按摩尔比ABO3:A1-yA′yB1-zB′zO3-α＝1:0.41；
方法同实施例1，不同点在于：
(1)混合粉体Ⅰ压制后在1250℃煅烧8小时；
(2)混合粉体Ⅱ中按摩尔比A:A′:B:B′＝0.83:0.17:0.87:0.13；
(3)混合粉体Ⅱ压制后在1250℃煅烧8小时；
(4)煅烧物料Ⅰ和煅烧物料Ⅱ按摩尔比1:0.44混合；
(5)混合粉体Ⅲ压制压力240MPa，在1600℃烧结7小时。
实施例14
混合固体电解质质子导体材料中A元素为Ba，B元素为Ti，A′元素为K，B′元素为Sc，y＝0.09，z＝0.16，并且按摩尔比ABO3:A1-yA′yB1-zB′zO3-α＝1:0.45；
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′＝0.91:0.09:0.84:0.16；
(3)混合粉体Ⅱ压制压力10MPa，在1300℃煅烧7小时；
(4)煅烧物料Ⅰ和煅烧物料Ⅱ按摩尔比1:0.31混合；
(5)混合粉体Ⅲ压制压力250MPa，在1630℃烧结6小时。
实施例15
混合固体电解质质子导体材料中A元素为Ca，B元素为Pr，A′元素为Na，B′元素为Ga，y＝0.08，z＝0.24，并且按摩尔比ABO3:A1-yA′yB1-zB′zO3-α＝1:0.48；
方法同实施例1，不同点在于：
(1)混合粉体Ⅰ压制压力8MPa，在1350℃煅烧6小时；
(2)混合粉体Ⅱ中按摩尔比A:A′:B:B′＝0.92:0.08:0.76:0.24；
(3)混合粉体Ⅱ压制压力8MPa，在1350℃煅烧6小时；
(4)煅烧物料Ⅰ和煅烧物料Ⅱ按摩尔比1:0.29混合；
(5)混合粉体Ⅲ压制压力280MPa，在1660℃烧结5小时。
实施例16
混合固体电解质质子导体材料中A元素为Sr，B元素为Hf，A′元素为Li，B′元素为Al，y＝0.17，z＝0.17，并且按摩尔比ABO3:A1-yA′yB1-zB′zO3-α＝1:0.32；
方法同实施例1，不同点在于：
(1)混合粉体Ⅰ压制压力6MPa，在1400℃煅烧5小时；
(2)混合粉体Ⅱ中按摩尔比A:A′:B:B′＝0.73:0.17:0.73:0.17；
(3)混合粉体Ⅱ压制压力6MPa，在1400℃煅烧5小时；
(4)煅烧物料Ⅰ和煅烧物料Ⅱ按摩尔比1:0.18混合；
(5)混合粉体Ⅲ压制压力300MPa，在1700℃烧结5小时。

Claims (1)

1.一种混合固体电解质质子导体材料的制备方法，其特征在于按以下步骤进行：
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制成混合粉体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800℃煅烧20小时，随炉冷却至常温，制成煅烧物料Ⅰ；
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、B原料和B´原料混合球磨，磨细至平均粒径≤5μm制成混合粉体Ⅱ；混合粉体Ⅱ中按摩尔比A: B:B´=1:0.95:0.05；
将混合粉体Ⅱ压制成块，压制压力5MPa，然后在800℃煅烧20小时，随炉冷却至常温，制成煅烧物料Ⅱ；
将煅烧物料Ⅰ和煅烧物料Ⅱ按摩尔比1:0.3混合后球磨，磨细至平均粒径≤10μm获得混合粉体Ⅲ；
将混合粉体Ⅲ压制成块，压制压力150MPa，然后在1500℃烧结10小时，随炉冷却至常温，制成混合固体电解质质子导体材料。
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