CN116789445B - 一系列用于制备高纯氧的稳定的高熵钙钛矿材料及其制备方法 - Google Patents

一系列用于制备高纯氧的稳定的高熵钙钛矿材料及其制备方法 Download PDF

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CN116789445B
CN116789445B CN202210272511.3A CN202210272511A CN116789445B CN 116789445 B CN116789445 B CN 116789445B CN 202210272511 A CN202210272511 A CN 202210272511A CN 116789445 B CN116789445 B CN 116789445B
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solution
entropy
edta
perovskite material
entropy perovskite
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CN116789445A (zh
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朱雪峰
王静忆
杨维慎
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Dalian Institute of Chemical Physics of CAS
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  • Compositions Of Oxide Ceramics (AREA)

Abstract

本发明提供一系列用于制备高纯氧的稳定的高熵钙钛矿材料及其制备方法。高熵钙钛矿Ba(1‑x)*0.5Sr(1‑x)*0.5MxCo(1‑y)*0.8Fe(1‑y)*0.2NyO3‑δ(M＝Ca,Gd,Sm,Nd,Pr,La,Y,Bi中的四种及以上；N＝Cu,Ni,Cr,Mn,Mg,Zn,Ga,Zr,Al,Nb,Ti,Sc,V中的四种及以上；x＝0.08‑0.20；y＝0.04‑0.16；任何一种元素掺杂含量不得低于1mol％；任何一种元素掺杂含量不得超过10mol％)。本发明是基于明星钙钛矿材料Ba0.5Sr0.5Co0.8Fe0.2O3‑δ为基础进行研究的，用于改善材料的透氧稳定性。一系列高熵钙钛矿材料通过溶胶凝胶法制得初级粉体，随后在不同的温度下煅烧得到用于透氧测试的致密的片。所述的高熵钙钛矿材料的混合熵不得低于2.5R(R＝8.314J mol‑1K‑1)。制备的一系列高熵钙钛矿材料在800℃具有优异的稳定性。

Description

一系列用于制备高纯氧的稳定的高熵钙钛矿材料及其制备 方法
技术领域
本发明属于无机膜领域，具体涉及一系列用于制备高纯氧的稳定的高熵钙钛矿材料及其制备方法。
背景技术
混合导体透氧膜是一类同时具有氧离子和电子导电性的致密无机陶瓷膜。在分离氧气的过程中，氧气是以氧离子的形式通过混合导体透氧膜材料结构中的晶格氧或者间隙氧进行传递。因此对氧气有着100％的选择性。钙钛矿型(其一般式为ABO3)透氧膜材料是目前研究最多，且氧渗透性能最好的材料。由于钙钛矿结构的离子掺杂可变性非常大，元素周期表中90％的金属离子都可以形成钙钛矿结构。因此，钙钛矿型透氧膜材料也是被研究的最集中、最深入的一类透氧膜材料。虽然对钙钛矿型(ABO3)透氧膜材料的研究最为广泛，但目前仍然很少有钙钛矿材料得到工业应用。这主要是因为大多数材料的长期稳定性较差。而随后发展的双相材料具有优异的稳定性，但其透氧量远不及单相钙钛矿材料。Steele指出膜材料的透氧量达到1mL cm-2min-1以上时才有经济应用的前景。通常稳定性和透氧量之间存在此消彼长的关系，找到稳定性好和透氧量高的材料成为一大研究热点。
近期高熵合金和氧化物概念被提出并被广泛应用在CO还原，可逆OER，HER，光合成及储氢等领域。高熵合金(HEAs)是将至少五种元素结合到具有随机位点占用的单个晶格中，形成熵稳定的固溶体合金。由于化学复杂性和堆积无序，HEA晶格严重扭曲，原子扩散极其缓慢。因此，HEA具有极高的微观结构稳定性，优异的机械性能，耐辐照性，超导性和高催化活性。
众所周知，明星钙钛矿BSCF材料具有超高的透氧量，但其在低于825℃时会发生相变，导致其透量迅速衰减，而且该材料较差的强度也一直是阻碍其用于实际生产的关键性问题。因此，在BSCF材料中进行多元素掺杂从而合成以BSCF为主体的高熵钙钛矿材料将有望结合BSCF的高透氧量和高熵材料的优质特性，得到兼具高透氧量和高稳定性的高熵钙钛矿材料，有望应用于制备高纯氧的实际生产中。
发明内容
单相钙钛矿材料具有较高的透氧量，但其稳定性较差，在不牺牲钙钛矿材料透氧量的条件下改善材料的稳定性是实现工业化应用的关键问题。
本发明的目的是为了解决现有钙钛矿透氧膜材料长期稳定性欠佳问题，提出一系列掺杂策略以提高钙钛矿材料的稳定性，并用于制备高纯氧。
本发明提供一系列用于制备高纯氧的高熵钙钛矿材料，所述高熵钙钛矿材料为Ba(1-x)*0.5Sr(1-x)*0.5MxCo(1-y)*0.8Fe(1-y)*0.2NyO3-δ(M＝Ca,Gd,Sm,Nd,Pr,La,Y,Bi中的四种及以上；N＝Cu,Ni,Cr,Mn,Mg,Zn,Ga,Zr,Al,Nb,Ti,Sc,V中的四种及以上；x＝0.08-0.20；y＝0.04-0.16；任何一种元素掺杂含量不得低于1mol％，任何一种元素掺杂含量不得超过10mol％，δ表示非化学计量氧)。所述高熵钙钛矿材料是基于明星钙钛矿材料Ba0.5Sr0.5Co0.8Fe0.2O3-δ为基础进行研究的，用于改善材料的透氧稳定性；既保留了明星材料BSCF主相结构，且无杂相出现，具有较高的透氧量；所述高熵钙钛矿材料具有较高的混合熵，兼具优异的稳定性；所述高熵钙钛矿材料具有较好的强度；综上所述，所述高熵钙钛矿材料有望应用于制备高纯氧的实际生产中。
基于以上技术方案，优选的，所述高熵钙钛矿材料的A位掺杂元素至少为四种，B位掺杂元素至少为四种。
基于以上技术方案，优选的，所述的高熵钙钛矿材料应至少含有12种元素，A位掺杂量可在以下范围内变化：8-20mol％，B位掺杂量可在以下范围内变化：4-16mol％；任何一种元素掺杂含量不得低于1mol％，任何一种元素掺杂含量不得超过10mol％。
基于以上技术方案，优选的，所述高熵钙钛矿材料，可通过溶胶凝胶法合成，先通过溶胶凝胶法制得初级粉体，随后在不同的温度下煅烧得到用于透氧测试的致密的片。
基于以上技术方案，优选的，所述的高熵钙钛矿材料的混合熵不得低于2.5R(R＝8.314J mol-1K-1)。
本发明还提供一种上述高熵钙钛矿材料的制备方法，包括如下步骤：
(1)依次称取所需计量的金属硝酸盐，充分溶解于去离子水中，搅拌至澄清溶液，得到硝酸盐溶液；
(2)按照EDTA：柠檬酸：总金属离子为1:1.5:1的摩尔比称取EDTA和柠檬酸；将柠檬酸加入上述硝酸盐溶液中，得到澄清溶液，然后加入EDTA，溶液会变成悬浊液，之后加入氨水调节pH值至8-10，溶液变澄清；
(3)将上述溶液持续加热搅拌至溶胶状，转移至蒸发皿中，在电炉上焙烧，直至混合物自燃，得到初级粉体；
(4)将上述初级粉体转移至马弗炉中，于静态空气中950℃焙烧3h，得到高熵钙钛矿相粉体；
(5)将上述高熵钙钛矿相粉体压片，于静态空气中不同的温度下焙烧，得到钙钛矿材料测试片。
基于以上技术方案，优选的，步骤(5)所述的焙烧温度为1040-1150℃；焙烧时间为3-6h。
基于以上技术方案，优选的，步骤(5)所述的高熵钙钛矿材料测试片为致密无通孔结构。
本发明还提供一种上述高熵钙钛矿材料的应用，所述高熵钙钛矿材料可用于制备高纯氧，且在800℃具有优异的稳定性。
有益效果
(1)本发明的高熵钙钛矿材料：Ba(1-x)*0.5Sr(1-x)*0.5MxCo(1-y)*0.8Fe(1-y)*0.2NyO3-δ(M＝Ca,Gd,Sm,Nd,Pr,La,Y,Bi中的四种及以上；N＝Cu,Ni,Cr,Mn,Mg,Zn,Ga,Zr,Al,Nb,Ti,Sc,V中的四种及以上；x＝0.08-0.20；y＝0.04-0.16；任何一种元素掺杂含量不得低于1mol％，任何一种元素掺杂含量不得超过10mol％，δ表示非化学计量氧)，克服了高熵钙钛矿材料难以纯相的关键性问题。因高熵材料需至少包含五种元素，对于高熵钙钛矿材料而言，由于容差因子和阳离子半径的差异难以满足纯相的要求，合成出纯相的高熵钙钛矿材料是首要解决的问题，而本发明涉及的高熵钙钛矿材料特征在于掺杂元素总含量少，从而成功制备出纯相的高熵钙钛矿材料。
(2)由于本发明的高熵钙钛矿材料元素种类众多，因此具有至少2.5R的混合熵，高的混合熵导致原子扩散极其缓慢。因此，高熵钙钛矿材料具有优异的稳定性，成功解决单相钙钛矿材料稳定性差的关键问题。
(3)本发明的高熵钙钛矿材料是在明星钙钛矿材料Ba0.5Sr0.5Co0.8Fe0.2O3-δ的基础上进行掺杂，保留了BSCF的主相结构，且无明显杂相出现，800℃，相同条件下比传统稳定的双相膜材料的氧渗透通量高约5倍左右。因此高熵钙钛矿材料具有较高的氧渗透通量。
(4)本发明的高熵钙钛矿材料具有优异的机械强度，本发明的高熵钙钛矿材料具有比母体BSCF材料高约100％的三点弯曲强度，有望应用于实际的工业生产中。
具体实施方式
以下实施例将对本发明予以进一步的说明，但并不因此而限制本发明。
实施例1
依本发明的技术方案，依次称取所需计量的金属硝酸盐，充分溶解于去离子水中，搅拌至澄清溶液。然后按照摩尔比，EDTA：柠檬酸：总金属离子为1:1.5:1称取EDTA和柠檬酸。将柠檬酸加入上述硝酸盐溶液中，得到澄清溶液。然后加入EDTA，EDTA不溶解，溶液会变成悬浊液，然后加入氨水调节pH值至8-10，溶液变澄清。将上述溶液持续加热搅拌至溶胶状，转移至蒸发皿中，在电炉上焙烧，直至混合物自燃，燃烧掉大部分有机物后得到初级粉体Ca0.02Gd0.015Sm0.015Nd0.016Bi0.014Ba0.46Sr0.46Co0.672Fe0.168Zr0.05Zn0.03Mg0.03Cu0.05O3-δ。Ca0.02Gd0.015Sm0.015Nd0.016Bi0.014Ba0.46Sr0.46Co0.672Fe0.168Zr0.05Zn0.03Mg0.03Cu0.05O3-δ于静态空气中950℃预烧3h，得到的高熵钙钛矿相粉体，通过压片于1060℃焙烧5h得到致密的测试片。将测试片的两面涂覆该高熵钙钛矿相粉体和松油醇以质量比为1:1混合配制的催化剂，与陶瓷管上用银环密封测试。测试在800℃进行，膜的高氧分压侧通150mLmin-1合成空气(O2/N2＝21/79:mol/mol)，膜的低氧分压侧通50mLmin-1高纯氦。在长达500h的稳定性测试过程中，该高熵钙钛矿材料的透氧量稳定在1.51mLcm-2min-1，该材料具有133MPa的抗弯强度。
实施例2
依本发明的技术方案，依次称取所需计量的金属硝酸盐，充分溶解于去离子水中，搅拌至澄清溶液。然后按照摩尔比，EDTA：柠檬酸：总金属离子为1:1.5:1称取EDTA和柠檬酸。将柠檬酸加入上述硝酸盐溶液中，得到澄清溶液。然后加入EDTA，EDTA不溶解，溶液会变成悬浊液，然后加入氨水调节pH值至8-10，溶液变澄清。将上述溶液持续加热搅拌至溶胶状，转移至蒸发皿中，在电炉上焙烧，直至混合物自燃，燃烧掉大部分有机物后得到初级粉体La0.1Pr0.02Y0.02Bi0.02Ca0.02Nd0.02Ba0.4Sr0.4Co0.768Fe0.192Zr0.01Al0.01Ni0.01Ti0.01O3-δ。Ca0.02Gd0.015Sm0.015Nd0.016Bi0.014Ba0.46Sr0.46Co0.768Fe0.192Zr0.01Al0.01Ni0.01Ti0.01O3-δ于静态空气中950℃预烧3h，得到的高熵钙钛矿相粉体，通过压片于1040℃焙烧6h得到致密的测试片。将测试片的两面涂覆该高熵钙钛矿相粉体和松油醇以质量比为1:1混合配制的催化剂，与陶瓷管上用银环密封测试。测试在800℃进行，膜的高氧分压侧通150mLmin-1合成空气(O2/N2＝21/79:mol/mol)，膜的低氧分压侧通50mLmin-1高纯氦。在长达300h的稳定性测试过程中，该高熵钙钛矿材料的透氧量稳定在1.33mLcm-2min-1，该材料具有115MPa的抗弯强度。
实施例3
依本发明的技术方案，依次称取所需计量的金属硝酸盐，充分溶解于去离子水中，搅拌至澄清溶液。然后按照摩尔比，EDTA：柠檬酸：总金属离子为1:1.5:1称取EDTA和柠檬酸。将柠檬酸加入上述硝酸盐溶液中，得到澄清溶液。然后加入EDTA，EDTA不溶解，溶液会变成悬浊液，然后加入氨水调节pH值至8-10，溶液变澄清。将上述溶液持续加热搅拌至溶胶状，转移至蒸发皿中，在电炉上焙烧，直至混合物自燃，燃烧掉大部分有机物后得到初级粉体Ca0.04Gd0.01Sm0.022Pr0.02Bi0.028Nd0.02Ba0.43Sr0.43Co0.688Fe0.172Cr0.02Al0.05Ga0.02Sc0.03V0.02O3-δ。Ca0.04Gd0.01Sm0.022Pr0.02Bi0.028Nd0.02Ba0.43Sr0.43Co0.688Fe0.172Cr0.02Al0.05Ga0.02Sc0.03V0.0 2O3-δ于静态空气中950℃预烧3h，得到的高熵钙钛矿相粉体，通过压片于1040℃焙烧4h得到致密的测试片。将测试片的两面涂覆该高熵钙钛矿相粉体和松油醇以质量比为1:1混合配制的催化剂，与陶瓷管上用银环密封测试。测试在800℃进行，膜的高氧分压侧通150mLmin-1合成空气(O2/N2＝21/79:mol/mol)，膜的低氧分压侧通50mLmin-1高纯氦。在长达600h的稳定性测试过程中，该高熵钙钛矿材料的透氧量稳定在1.26mLcm-2min-1，该材料具有156MPa的抗弯强度。
实施例4
依本发明的技术方案，依次称取所需计量的金属硝酸盐，充分溶解于去离子水中，搅拌至澄清溶液。然后按照摩尔比，EDTA：柠檬酸：总金属离子为1:1.5:1称取EDTA和柠檬酸。将柠檬酸加入上述硝酸盐溶液中，得到澄清溶液。然后加入EDTA，EDTA不溶解，溶液会变成悬浊液，然后加入氨水调节pH值至8-10，溶液变澄清。将上述溶液持续加热搅拌至溶胶状，转移至蒸发皿中，在电炉上焙烧，直至混合物自燃，燃烧掉大部分有机物后得到初级粉体La0.03Sm0.025Pr0.02Bi0.025Ba0.45Sr0.45Co0.672Fe0.168Zr0.02Al0.02Ga0.02Ni0.02Cu0.02V0.02Mn0.02Nb0.02O3-δ。La0.03Sm0.025Pr0.02Bi0.025Ba0.45Sr0.45Co0.672Fe0.168Zr0.02Al0.02Ga0.02Ni0.02Cu0.02V0.02Mn0.02Nb0.02O3-δ于静态空气中950℃预烧3h，得到的高熵钙钛矿相粉体，通过压片于1080℃焙烧3h得到致密的测试片。将测试片的两面涂覆该高熵钙钛矿相粉体和松油醇以质量比为1:1混合配制的催化剂，与陶瓷管上用银环密封测试。测试在800℃进行，膜的高氧分压侧通150mLmin-1合成空气(O2/N2＝21/79:mol/mol)，膜的低氧分压侧通50mLmin-1高纯氦。在长达620h的稳定性测试过程中，该高熵钙钛矿材料的透氧量稳定在1.43mLcm-2min-1，该材料具有152MPa的抗弯强度。
实施例5
依本发明的技术方案，依次称取所需计量的金属硝酸盐，充分溶解于去离子水中，搅拌至澄清溶液。然后按照摩尔比，EDTA：柠檬酸：总金属离子为1:1.5:1称取EDTA和柠檬酸。将柠檬酸加入上述硝酸盐溶液中，得到澄清溶液。然后加入EDTA，EDTA不溶解，溶液会变成悬浊液，然后加入氨水调节pH值至8-10，溶液变澄清。将上述溶液持续加热搅拌至溶胶状，转移至蒸发皿中，在电炉上焙烧，直至混合物自燃，燃烧掉大部分有机物后得到初级粉体La0.01Sm0.02Pr0.01Ca0.04Gd0.02Ba0.45Sr0.45Co0.704Fe0.176Zr0.03Al0.02Ni0.01Cu0.02Mg0.01Zn0.03O3-δ。La0.01Sm0.02Pr0.01Ca0.04Gd0.02Ba0.45Sr0.45Co0.704Fe0.176Zr0.03Al0.02Ni0.01Cu0.02Mg0.01Zn0.03O3-δ于静态空气中950℃预烧3h，得到的高熵钙钛矿相粉体，通过压片于1040℃焙烧3h得到致密的测试片。将测试片的两面涂覆该高熵钙钛矿相粉体和松油醇以质量比为1:1混合配制的催化剂，与陶瓷管上用银环密封测试。测试在800℃进行，膜的高氧分压侧通150mLmin-1合成空气(O2/N2＝21/79:mol/mol)，膜的低氧分压侧通50mLmin-1高纯氦。在长达600h的稳定性测试过程中，该高熵钙钛矿材料的透氧量稳定在1.37mLcm-2min-1，该材料具有128MPa的抗弯强度。
实施例6
依本发明的技术方案，依次称取所需计量的金属硝酸盐，充分溶解于去离子水中，搅拌至澄清溶液。然后按照摩尔比，EDTA：柠檬酸：总金属离子为1:1.5:1称取EDTA和柠檬酸。将柠檬酸加入上述硝酸盐溶液中，得到澄清溶液。然后加入EDTA，EDTA不溶解，溶液会变成悬浊液，然后加入氨水调节pH值至8-10，溶液变澄清。将上述溶液持续加热搅拌至溶胶状，转移至蒸发皿中，在电炉上焙烧，直至混合物自燃，燃烧掉大部分有机物后得到初级粉体La0.03Pr0.01Y0.02Bi0.02Gd0.02Ba0.45Sr0.45Co0.704Fe0.176Al0.03Nb0.01Mn0.01Cu0.03Mg0.02Zn0.02O3-δ。La0.03Pr0.01Y0.02Bi0.02Gd0.02Ba0.45Sr0.45Co0.704Fe0.176Al0.03Nb0.01Mn0.01Cu0.03Mg0.02Zn0.02O3-δ于静态空气中950℃预烧3h，得到的高熵钙钛矿相粉体，通过压片于1040℃焙烧3h得到致密的测试片。将测试片的两面涂覆该高熵钙钛矿相粉体和松油醇以质量比为1:1混合配制的催化剂，与陶瓷管上用银环密封测试。测试在800℃进行，膜的高氧分压侧通150mLmin-1合成空气(O2/N2＝21/79:mol/mol)，膜的低氧分压侧通50mLmin-1高纯氦。在长达600h的稳定性测试过程中，该高熵钙钛矿材料的透氧量稳定在1.13mLcm-2min-1，该材料具有130MPa的抗弯强度。
实施例7
依本发明的技术方案，依次称取所需计量的金属硝酸盐，充分溶解于去离子水中，搅拌至澄清溶液。然后按照摩尔比，EDTA：柠檬酸：总金属离子为1:1.5:1称取EDTA和柠檬酸。将柠檬酸加入上述硝酸盐溶液中，得到澄清溶液。然后加入EDTA，EDTA不溶解，溶液会变成悬浊液，然后加入氨水调节pH值至8-10，溶液变澄清。将上述溶液持续加热搅拌至溶胶状，转移至蒸发皿中，在电炉上焙烧，直至混合物自燃，燃烧掉大部分有机物后得到初级粉体La0.03Pr0.01Ca0.1Bi0.02Gd0.02Ba0.41Sr0.41Co0.68Fe0.17Zr0.05Al0.03Cu0.03Mg0.02Zn0.02O3-δ。La0.03Pr0.01Ca0.1Bi0.02Gd0.02Ba0.41Sr0.41Co0.68Fe0.17Zr0.05Al0.03Cu0.03Mg0.02Zn0.02O3-δ于静态空气中950℃预烧3h，得到的高熵钙钛矿相粉体，通过压片于1040℃焙烧5h得到致密的测试片。将测试片的两面涂覆该高熵钙钛矿相粉体和松油醇以质量比为1:1混合配制的催化剂，与陶瓷管上用银环密封测试。测试在800℃进行，膜的高氧分压侧通150mLmin-1合成空气(O2/N2＝21/79:mol/mol)，膜的低氧分压侧通50mLmin-1高纯氦。在长达600h的稳定性测试过程中，该高熵钙钛矿材料的透氧量稳定在1.41mLcm-2min-1，该材料具有138MPa的抗弯强度。
实施例8
依本发明的技术方案，依次称取所需计量的金属硝酸盐，充分溶解于去离子水中，搅拌至澄清溶液。然后按照摩尔比，EDTA：柠檬酸：总金属离子为1:1.5:1称取EDTA和柠檬酸。将柠檬酸加入上述硝酸盐溶液中，得到澄清溶液。然后加入EDTA，EDTA不溶解，溶液会变成悬浊液，然后加入氨水调节pH值至8-10，溶液变澄清。将上述溶液持续加热搅拌至溶胶状，转移至蒸发皿中，在电炉上焙烧，直至混合物自燃，燃烧掉大部分有机物后得到初级粉体Y0.03La0.03Ca0.1Bi0.02Gd0.02Ba0.4Sr0.4Co0.68Fe0.17Zr0.07Al0.01Cu0.02Ti0.02V0.02Ga0.01O3-δ。Y0.03La0.03Ca0.1Bi0.02Gd0.02Ba0.4Sr0.4Co0.68Fe0.17Zr0.07Al0.01Cu0.02Ti0.02V0.02Ga0.01O3-δ于静态空气中950℃预烧3h，得到的高熵钙钛矿相粉体，通过压片于1050℃焙烧5h得到致密的测试片。将测试片的两面涂覆该高熵钙钛矿相粉体和松油醇以质量比为1:1混合配制的催化剂，与陶瓷管上用银环密封测试。测试在800℃进行，膜的高氧分压侧通150mLmin-1合成空气(O2/N2＝21/79:mol/mol)，膜的低氧分压侧通50mLmin-1高纯氦。在长达600h的稳定性测试过程中，该高熵钙钛矿材料的透氧量稳定在1.27mLcm-2min-1，该材料具有146MPa的抗弯强度。
实施例9
依本发明的技术方案，依次称取所需计量的金属硝酸盐，充分溶解于去离子水中，搅拌至澄清溶液。然后按照摩尔比，EDTA：柠檬酸：总金属离子为1:1.5:1称取EDTA和柠檬酸。将柠檬酸加入上述硝酸盐溶液中，得到澄清溶液。然后加入EDTA，EDTA不溶解，溶液会变成悬浊液，然后加入氨水调节pH值至8-10，溶液变澄清。将上述溶液持续加热搅拌至溶胶状，转移至蒸发皿中，在电炉上焙烧，直至混合物自燃，燃烧掉大部分有机物后得到初级粉体Ca0.1Bi0.02Gd0.02Sm0.02Ba0.42Sr0.42Co0.736Fe0.184Zr0.02Cu0.02Ni0.02Zn0.02O3-δ。Ca0.1Bi0.02Gd0.02Sm0.02Ba0.42Sr0.42Co0.736Fe0.184Zr0.02Cu0.02Ni0.02Zn0.02O3-δ于静态空气中950℃预烧3h，得到的高熵钙钛矿相粉体，通过压片于1090℃焙烧6h得到致密的测试片。将测试片的两面涂覆该高熵钙钛矿相粉体和松油醇以质量比为1:1混合配制的催化剂，与陶瓷管上用银环密封测试。测试在800℃进行，膜的高氧分压侧通150mLmin-1合成空气(O2/N2＝21/79:mol/mol)，膜的低氧分压侧通50mLmin-1高纯氦。在长达600h的稳定性测试过程中，该高熵钙钛矿材料的透氧量稳定在1.20mLcm-2min-1，该材料具有122MPa的抗弯强度。
实施例10
依本发明的技术方案，依次称取所需计量的金属硝酸盐，充分溶解于去离子水中，搅拌至澄清溶液。然后按照摩尔比，EDTA：柠檬酸：总金属离子为1:1.5:1称取EDTA和柠檬酸。将柠檬酸加入上述硝酸盐溶液中，得到澄清溶液。然后加入EDTA，EDTA不溶解，溶液会变成悬浊液，然后加入氨水调节pH值至8-10，溶液变澄清。将上述溶液持续加热搅拌至溶胶状，转移至蒸发皿中，在电炉上焙烧，直至混合物自燃，燃烧掉大部分有机物后得到初级粉体Bi0.02Gd0.02Sm0.02Pr0.1Ba0.42Sr0.42Co0.72Fe0.18Zr0.02Cu0.02Ni0.02Al0.02Sc0.01Ti0.01O3-δ。Bi0.02Gd0.02Sm0.02Pr0.1Ba0.42Sr0.42Co0.72Fe0.18Zr0.02Cu0.02Ni0.02Al0.02Sc0.01Ti0.01O3-δ于静态空气中950℃预烧3h，得到的高熵钙钛矿相粉体，通过压片于1070℃焙烧6h得到致密的测试片。将测试片的两面涂覆该高熵钙钛矿相粉体和松油醇以质量比为1:1混合配制的催化剂，与陶瓷管上用银环密封测试。测试在800℃进行，膜的高氧分压侧通150mLmin-1合成空气(O2/N2＝21/79:mol/mol)，膜的低氧分压侧通50mLmin-1高纯氦。在长达600h的稳定性测试过程中，该高熵钙钛矿材料的透氧量稳定在1.11mLcm-2min-1，该材料具有108MPa的抗弯强度。
实施例11
依本发明的技术方案，依次称取所需计量的金属硝酸盐，充分溶解于去离子水中，搅拌至澄清溶液。然后按照摩尔比，EDTA：柠檬酸：总金属离子为1:1.5:1称取EDTA和柠檬酸。将柠檬酸加入上述硝酸盐溶液中，得到澄清溶液。然后加入EDTA，EDTA不溶解，溶液会变成悬浊液，然后加入氨水调节pH值至8-10，溶液变澄清。将上述溶液持续加热搅拌至溶胶状，转移至蒸发皿中，在电炉上焙烧，直至混合物自燃，燃烧掉大部分有机物后得到初级粉体Bi0.01Gd0.02La0.04Sm0.03Ca0.1Ba0.4Sr0.4Co0.72Fe0.18Zr0.03Ni0.02Al0.02Mg0.02Zn0.01O3-δ。Bi0.01Gd0.02La0.04Sm0.03Ca0.1Ba0.4Sr0.4Co0.72Fe0.18Zr0.03Ni0.02Al0.02Mg0.02Zn0.01O3-δ于静态空气中950℃预烧3h，得到的高熵钙钛矿相粉体，通过压片于1040℃焙烧5h得到致密的测试片。将测试片的两面涂覆该高熵钙钛矿相粉体和松油醇以质量比为1:1混合配制的催化剂，与陶瓷管上用银环密封测试。测试在800℃进行，膜的高氧分压侧通150mLmin-1合成空气(O2/N2＝21/79:mol/mol)，膜的低氧分压侧通50mLmin-1高纯氦。在长达600h的稳定性测试过程中，该高熵钙钛矿材料的透氧量稳定在1.47mLcm-2min-1，该材料具有113MPa的抗弯强度。
实施例12
依本发明的技术方案，依次称取所需计量的金属硝酸盐，充分溶解于去离子水中，搅拌至澄清溶液。然后按照摩尔比，EDTA：柠檬酸：总金属离子为1:1.5:1称取EDTA和柠檬酸。将柠檬酸加入上述硝酸盐溶液中，得到澄清溶液。然后加入EDTA，EDTA不溶解，溶液会变成悬浊液，然后加入氨水调节pH值至8-10，溶液变澄清。将上述溶液持续加热搅拌至溶胶状，转移至蒸发皿中，在电炉上焙烧，直至混合物自燃，燃烧掉大部分有机物后得到初级粉体Bi0.02Gd0.02La0.02Ca0.1Ba0.42Sr0.42Co0.72Fe0.18Zr0.02Ni0.02Cu0.02Mg0.02Zn0.02O3-δ。Bi0.02Gd0.02La0.02Ca0.1Ba0.42Sr0.42Co0.72Fe0.18Zr0.02Ni0.02Cu0.02Mg0.02Zn0.02O3-δ于静态空气中950℃预烧3h，得到的高熵钙钛矿相粉体，通过压片于1040℃焙烧5h得到致密的测试片。将测试片的两面涂覆该高熵钙钛矿相粉体和松油醇以质量比为1:1混合配制的催化剂，与陶瓷管上用银环密封测试。测试在800℃进行，膜的高氧分压侧通150mLmin-1合成空气(O2/N2＝21/79:mol/mol)，膜的低氧分压侧通50mLmin-1高纯氦。在长达600h的稳定性测试过程中，该高熵钙钛矿材料的透氧量稳定在1.47mLcm-2min-1，该材料具有123MPa的抗弯强度。
对比例13
依本发明的技术方案，依次称取所需计量的金属硝酸盐，充分溶解于去离子水中，搅拌至澄清溶液。然后按照摩尔比，EDTA：柠檬酸：总金属离子为1:1.5:1称取EDTA和柠檬酸。将柠檬酸加入上述硝酸盐溶液中，得到澄清溶液。然后加入EDTA，EDTA不溶解，溶液会变成悬浊液，然后加入氨水调节pH值至8-10，溶液变澄清。将上述溶液持续加热搅拌至溶胶状，转移至蒸发皿中，在电炉上焙烧，直至混合物自燃，燃烧掉大部分有机物后得到初级粉体Bi0.02Gd0.02La0.02Ca0.1Ba0.42Sr0.42Co0.8Fe0.2O3-δ。Bi0.02Gd0.02La0.02Ca0.1Ba0.42Sr0.42Co0.8Fe0. 2O3-δ于静态空气中950℃预烧3h，得到的高熵钙钛矿相粉体，通过压片于1100℃焙烧6h得到致密的测试片。将测试片的两面涂覆该高熵钙钛矿相粉体和松油醇以质量比为1:1混合配制的催化剂，与陶瓷管上用银环密封测试。测试在800℃进行，膜的高氧分压侧通150mLmin-1合成空气(O2/N2＝21/79:mol/mol)，膜的低氧分压侧通50mLmin-1高纯氦。在长达600h的稳定性测试过程中，该钙钛矿材料的透氧量由最初的1.64mLcm-2min-1衰减至1.44mLcm-2min-1，该材料具有81MPa的抗弯强度。
对比例14
依本发明的技术方案，依次称取所需计量的金属硝酸盐，充分溶解于去离子水中，搅拌至澄清溶液。然后按照摩尔比，EDTA：柠檬酸：总金属离子为1:1.5:1称取EDTA和柠檬酸。将柠檬酸加入上述硝酸盐溶液中，得到澄清溶液。然后加入EDTA，EDTA不溶解，溶液会变成悬浊液，然后加入氨水调节pH值至8-10，溶液变澄清。将上述溶液持续加热搅拌至溶胶状，转移至蒸发皿中，在电炉上焙烧，直至混合物自燃，燃烧掉大部分有机物后得到初级粉体Ba0.5Sr0.5Co0.736Fe0.184Zr0.02Ni0.02Cu0.02Al0.02O3-δ。Ba0.5Sr0.5Co0.736Fe0.184Zr0.02Ni0.02Cu0.02Al0.02O3-δ于静态空气中950℃预烧3h，得到的高熵钙钛矿相粉体，通过压片于1140℃焙烧6h得到致密的测试片。将测试片的两面涂覆该高熵钙钛矿相粉体和松油醇以质量比为1:1混合配制的催化剂，与陶瓷管上用银环密封测试。测试在800℃进行，膜的高氧分压侧通150mLmin-1合成空气(O2/N2＝21/79:mol/mol)，膜的低氧分压侧通50mLmin-1高纯氦。在长达600h的稳定性测试过程中，该钙钛矿材料的透氧量由最初的2.10mLcm-2min-1衰减至1.93mLcm-2min-1，该材料具有76MPa的抗弯强度。
对比例15
依本发明的技术方案，依次称取所需计量的金属硝酸盐，充分溶解于去离子水中，搅拌至澄清溶液。然后按照摩尔比，EDTA：柠檬酸：总金属离子为1:1.5:1称取EDTA和柠檬酸。将柠檬酸加入上述硝酸盐溶液中，得到澄清溶液。然后加入EDTA，EDTA不溶解，溶液会变成悬浊液，然后加入氨水调节pH值至8-10，溶液变澄清。将上述溶液持续加热搅拌至溶胶状，转移至蒸发皿中，在电炉上焙烧，直至混合物自燃，燃烧掉大部分有机物后得到初级粉体Ba0.5Sr0.5Co0.8Fe0.2O3-δ。将Ba0.5Sr0.5Co0.8Fe0.2O3-δ于静态空气中950℃预烧3h，得到的高熵钙钛矿相粉体，通过压片于1150℃焙烧6h得到致密的测试片。将测试片的两面涂覆该高熵钙钛矿相粉体和松油醇以质量比为1:1混合配制的催化剂，与陶瓷管上用银环密封测试。测试在800℃进行，膜的高氧分压侧通150mLmin-1合成空气(O2/N2＝21/79:mol/mol)，膜的低氧分压侧通50mLmin-1高纯氦。在长达300h的稳定性测试过程中，该钙钛矿材料的透氧量由最初的2.18mLcm-2min-1衰减至1.81mLcm-2min-1，该材料具有65MPa的抗弯强度。
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。

Claims (6)

1.一系列高熵钙钛矿材料，其特征在于，所述高熵钙钛矿材料为Ba(1-x)*0.5Sr(1-x)* 0.5MxCo(1-y)*0.8Fe(1-y)*0.2NyO3-δ，其中M为Ca、Gd、Sm、Nd、Pr、La、Y、Bi中的四种及以上；N为Cu、Ni、Cr、Mn、Mg、Zn、Ga、Zr、Al、Nb、Ti、Sc、V中的四种及以上，x＝0.08-0.20，y＝0.04-0.16；M和N中任何一种元素掺杂含量不得低于1mol％，任何一种元素掺杂含量不得超过10mol％，δ表示非化学计量氧。
2.根据权利要求1所述的高熵钙钛矿材料，其特征在于：所述高熵钙钛矿材料的混合熵不得低于2.5R，R＝8.314J mol-1K-1。
3.一种权利要求1-2中任意一项所述高熵钙钛矿材料的制备方法，其特征在于：包括如下步骤：
(1)依次称取所需计量的金属硝酸盐，充分溶解于去离子水中，搅拌至澄清溶液，得到硝酸盐溶液；
(2)按照EDTA：柠檬酸：总金属离子为1:1.5:1的摩尔比称取EDTA和柠檬酸，将柠檬酸加入上述硝酸盐溶液中，得到澄清溶液，然后加入EDTA，溶液会变成悬浊液，之后加入氨水调节pH值至8-10，溶液变澄清；
(3)将上述溶液持续加热搅拌至溶胶状，转移至蒸发皿中，在电炉上焙烧，直至混合物自燃，得到初级粉体；
(4)将上述初级粉体转移至马弗炉中，于静态空气中950℃焙烧3h，得到钙钛矿相粉体；
(5)将上述钙钛矿相粉体压片，于静态空气中焙烧，得到钙钛矿材料测试片。
4.根据权利要求3所述的制备方法，其特征在于：步骤(5)所述的焙烧温度为1040-1150℃；焙烧时间为3-6h。
5.根据权利要求3所述的制备方法，其特征在于，步骤(5)所述的钙钛矿材料测试片为致密无通孔结构。
6.一种权利要求1-2中任意一项所述的高熵钙钛矿材料的应用，其特征在于，所述高熵钙钛矿材料可用于制备高纯氧。
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