CN117466652A - 一种提高质子导体电解质在二氧化碳中稳定性的制备方法 - Google Patents

一种提高质子导体电解质在二氧化碳中稳定性的制备方法 Download PDF

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CN117466652A
CN117466652A CN202311316590.4A CN202311316590A CN117466652A CN 117466652 A CN117466652 A CN 117466652A CN 202311316590 A CN202311316590 A CN 202311316590A CN 117466652 A CN117466652 A CN 117466652A
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ion
carbon dioxide
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戚惠颖
王晓靖
涂宝峰
张同环
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Shandong University of Science and Technology
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Abstract

本发明公开了一种提高质子导体电解质在二氧化碳中稳定性的制备方法，涉及固体氧化物电池和固体氧化物电解池技术领域，通过纳米添加剂表面修饰法，在固相反应法获取的铈酸钡和锆酸钡系列电解质表面，采用真空浸渍法制备碱土金属氧化物、或过渡金属氧化物、或VA主族金属氧化物的纳米结构添加剂，得到表面修饰添加剂的碱性质子导体电解质。本发明将得到的表面修饰纳米结构添加剂的碱性质子导体电解质应用到质子型碳氢陶瓷膜燃料电池或高温电解二氧化碳，可以有效增强电解质的稳定性及降低欧姆损失，由此大大提高固体氧化物燃料电池和电解池在二氧化碳气氛下的性能和稳定性。

Description

一种提高质子导体电解质在二氧化碳中稳定性的制备方法
技术领域
本发明涉及固体氧化物电池和固体氧化物电解池技术领域，尤其涉及一种提高质子导体电解质在二氧化碳中稳定性的制备方法。
背景技术
固体氧化物燃料电池(SOFC)和固体氧化物电解池(SOEC)因其能进行热电联供而效率高、不需要贵金属催化剂而成本低、燃料适用范围广等优势，目前成为备受关注的能源转换技术之一。根据电解质传导离子的不同，主要将其分为氧离子型和质子型SOFC，以及氧离子型和质子型SOEC。发展较早的氧离子型导体电解质会受到氧离子传导活化能较高限制，在中低温条件下欧姆电阻比质子型导体电解质要大很多，质子型SOFC/SOEC成为国内外研究热点方向。目前，质子型导体电解质材料主要有各类元素掺杂锆酸钡、铈酸钡、锆酸锶、铈酸锶等体系，其中锆酸钡和铈酸钡因质子导电性和稳定性等优势而成为当下质子型SOFC/SOEC主要应用的电解质材料。但由于该类质子型电解质通常采用B位掺杂来调控导电性和稳定性，A位通常完全为碱性金属离子占据，在采用碳氢燃料的SOFC或SOEC电解CO2时易发生酸碱反应而形成碳酸盐等导电阻隔相，使得界面电阻增大，由此在电池或者电解池运行中形成较大欧姆电阻而导致性能和稳定性下降。如何在含有二氧化碳等酸性气体中保持质子导体电解质较高的离子导电性和稳定性，是提高碳氢燃料质子型SOFC及质子型SOEC高温电解CO2性能和稳定性的关键问题之一。
目前会采用A位部分取代来降低电解质碱性，但可能会带来质子导体电解质导电性降低等问题。并且，过多的元素掺杂会引起晶体结构内部产生较大应力，在长期运行中可能会产生结构扭曲破坏而析出杂质相，带来组成和结构的改变，引起欧姆电阻增大、性能下降及稳定性等问题。因而，目前常用的部分掺杂取代法来提高质子导体电解质导电性及稳定性仍存在一些问题，会限制质子型固体氧化物电池和电解池的进一步推广和大规模应用。
发明内容
为解决掺杂锆酸钡和铈酸钡体系材料在二氧化碳酸性气体中的稳定性的技术问题，本发明公开了一种提高质子导体电解质在二氧化碳中稳定性的制备方法，设计采用真空浸渍法在电解质表面构筑纳米添加剂保护，以减少质子导体电解质在二氧化碳中的酸碱反应，增强质子传输活性。
为实现上述目的，本发明采用下述技术方案：一种提高质子导体电解质在二氧化碳中稳定性的制备方法，包括以下步骤：
步骤一，配置含有碱土金属离子的硝酸盐溶液，或者含有过渡金属离子的硝酸盐溶液，或者含有VA主族金属离子的硝酸盐溶液，并向其中加入适量络合剂，调节PH后，定容，得到络合剂与硝酸盐的混合溶液；
步骤二，用步骤一所得的络合剂与硝酸盐的混合溶液对钇掺杂锆酸钡或/和铈酸钡粉体按照浸渍总量的需求进行多次真空浸渍，对每次浸渍后的粉体进行低温煅烧，并对最后一次浸渍后的粉体进行高温煅烧。
进一步地，步骤一中，所述碱土金属离子包括镁离子、钙离子、锶离子中的一种；过渡金属离子包括锰离子、镍离子、铁离子、锌离子中的一种；VA主族金属离子为铋离子中的一种；
溶液中金属离子的定容浓度为0.05-0.25mol/L，PH值为5-6；
所述络合剂为甘氨酸、柠檬酸铵、EDTA中的一种或两种，络合剂的浓度为0.8-4.5mol/L。
进一步地，步骤二中，用络合剂与硝酸盐的混合溶液浸渍时，按照浓度由高到低的顺序进行浸渍，且浸渍过程中调节真空度由低到高；
浸渍次数为5-15次，真空度范围为0.5-0.1Mpa。
进一步地，步骤二中的浸渍总量为占钇掺杂锆酸钡或/和铈酸钡粉体的摩尔量，其中，镁离子浸渍总量为0.5mol％、1.0mol％、2.0mol％、3.0mol％、4.0mol％；钙离子浸渍总量为0.5mol％、4.0mol％；锶离子浸渍总量为0.5mol％；锰离子浸渍总量为1.0mol％、2.0mol％、3.0mol％；镍离子浸渍总量为0.5mol％、1.0mol％；铁离子浸渍总量为0.5mol％、1.0mol％、4.0mol％；锌离子浸渍总量为1.0mol％；铋离子浸渍总量为4.0mol％。
进一步地，步骤二中，低温煅烧温度为300-450度，煅烧时间为2-4小时，高温煅烧温度为700-900度，煅烧时间为2-6小时。
本发明的有益效果是，电解质表面上的纳米结构添加剂是由各种金属氧化物组成，一方面这些金属氧化物的碱性都比含钡电解质氧化物的碱性低，能够有效降低电解质表面强碱性含钡氧化物与酸性二氧化碳生成的碳酸盐等杂相的反应活性；另一方面，纳米结构添加剂与电解质之间可以形成高活性的异质界面，有助于提高质子导电性，由此降低电解质在整体的性能损耗及对稳定性的不利影响。
本发明严格筛选了碱土金属离子、或过渡金属离子、或VA主族金属离子及对应的浸渍总量，与不同离子性质及在电解质表面形成的纳米结构添加剂作用方式有关，由此突破传统在电解质材料本身内部晶体结构进行化学掺杂改性的思路。
本发明采用结合化学组分和表面结构两方面修饰的方法，最终获得表面修饰纳米添加剂的质子导体电解质材料，其在二氧化碳中稳定性及离子传输活性大大提高，有效降低欧姆电阻、提高稳定性。
该方法提高了质子导体电解质材料在二氧化碳中导电性及稳定性，有利于推动碳氢燃料质子型SOFC和质子型SOEC高温电解二氧化碳的发展应用。
附图说明
图1为实施例1在BZY电解质浸渍不同摩尔含量Mg2+的二氧化碳程序升温脱附曲线；
图2为实施例1在BZY电解质浸渍4mol％Mg2+制备的质子陶瓷膜燃料电池，通入20mL/min二氧化碳后的稳定性测试图；
图3中(a)为实施例2在BZY电解质浸渍0.5mol％Ca2+、Ni2+、Fe3+、Sr2+溶液的二氧化碳程序升温脱附曲线；图3中(b)在BZY电解质浸渍0.5mol％Fe3+的SEM图；
图4中(a)为实施例3在BZY电解质浸渍4.0mol％Bi3+、Ca2+、Fe3+溶液的二氧化碳程序升温脱附曲线；图4中(b)在BZY电解质浸渍4.0mol％Ca2+的SEM图；
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
质子型固体氧化物燃料电池和电解池常用电解质包括铈酸钡和锆酸钡掺杂体系，由于其A位完全为碱性较强的碱土金属离子且易富集在表面，而导致在产物和反应物存在二氧化碳时极易发生酸碱反应而产生较大界面电阻，进而产生欧姆电阻增加、电池性能和稳定性下降等问题。
实施例1
将1.2820g、2.5641g、5.1282g Mg(NO3)2 6H2O分别溶于40mL去离子水中，不断搅拌且加入9.0080g甘氨酸，采用硝酸和氨水调节PH至6，然后在100mL容量瓶中定容，分别得到0.05mol/L、0.1mol/L、0.2mol/L的镁离子浸渍溶液，甘氨酸浓度为1.2mol/L。
调节真空度为0.4Mpa，先在BaZr0.8Y0.2O3-δ(BZY)上浸渍0.2mol/L溶液2次，每次浸渍后在350度煅烧2小时；然后在0.1Mpa下浸渍0.1mol/L溶液3次，每次浸渍后在350度下煅烧2小时；再在0.05Mpa下浸渍0.05mol/L溶液5次，每次浸渍后在350度下煅烧2小时；最后一次浸渍后在800度下煅烧2小时，得到浸渍总量为4mol％样品。
采用二氧化碳程序升温脱附法测试Mg-4mol％，结果如图1所示，与纯BZY相比，其在各温度段均没有存出现明显的二氧化碳脱附峰。
将浸渍总量为4mol％样品制备为质子陶瓷膜燃料电池进行测试，通入20mL/min二氧化碳后，性能保持稳定超过80小时，如图2所示。
实施例2
将2.0200g、8.0799g Fe(NO3)3 9H2O分别溶于50mL去离子水中，不断搅拌且加入19.4572g柠檬酸铵，采用硝酸和氨水调节PH至6，然后在100mL容量瓶中定容，分别得到0.05mol/L、0.2mol/L铁离子浸渍溶液，柠檬酸铵浓度为0.8mol/L。
调节真空度为0.4Mpa，先在BaZr0.8Y0.2O3-δ(BZY)上浸渍0.2mol/L溶液1次，在450度煅烧2小时；然后在0.1Mpa下浸渍0.05mol/L溶液1次，并在900度下煅烧2小时，得到浸渍总量为0.5mol％样品。
采用二氧化碳程序升温脱附法测试Fe-0.5mol％，结果如图3所示，与纯BZY相比，其未出现二氧化碳脱附峰，且表面形成一些纳米结构的颗粒。
将浸渍总量为0.5mol％样品制备为质子陶瓷膜燃料电池进行测试，通入10mL/min二氧化碳后，性能可以保持稳定50小时以上。
实施例3
将1.1807g、2.3614g、5.9035gCa(NO3)2 4H2O分别溶于40mL去离子水中，不断搅拌且加入7.5067g甘氨酸，采用硝酸和氨水调节PH至6，然后在100mL容量瓶中定容，分别得到0.05mol/L、0.1mol/L、0.25mol/L的钙离子浸渍溶液，甘氨酸浓度为1.0mol/L。
调节真空度为0.3Mpa，先在BaZr0.8Y0.2O3-δ(BZY)上浸渍0.25mol/L溶液1次，在350度煅烧2小时；然后在0.15Mpa下浸渍0.1mol/L溶液4次，每次浸渍后在350度下煅烧2小时；再在0.05Mpa下浸渍0.05mol/L溶液5次，每次浸渍后在350度下煅烧2小时；最后一次在800度下煅烧2小时，得到浸渍总量为4mol％样品。
采用二氧化碳程序升温脱附法测试Ca-4mol％，结果如图4所示，与纯BZY相比，未出现二氧化碳脱附峰，且SEM显示其表面富有大量的纳米颗粒。
将浸渍总量为4mol％样品制备为质子陶瓷膜燃料电池进行测试，通入10mL/min二氧化碳后，性能保持稳定超过30小时。
当然，上述说明并非是对本发明的限制，本发明也并不仅限于上述举例，本技术领域的技术人员在本发明的实质范围内所做出的变化、改型、添加或替换，也应属于本发明的保护范围。

Claims (5)

1.一种提高质子导体电解质在二氧化碳中稳定性的制备方法，其特征在于，包括以下步骤：
步骤一，配置含有碱土金属离子的硝酸盐溶液，或者含有过渡金属离子的硝酸盐溶液，或者含有VA主族金属离子的硝酸盐溶液，并向其中加入适量络合剂，调节PH后，定容，得到络合剂与硝酸盐的混合溶液；
步骤二，用步骤一所得的络合剂与硝酸盐的混合溶液对钇掺杂锆酸钡或/和铈酸钡粉体按照浸渍总量的需求进行多次真空浸渍，对每次浸渍后的粉体进行低温煅烧，并对最后一次浸渍后的粉体进行高温煅烧，得到电解质最终粉体材料。
2.如权利要求1所述的一种提高质子导体电解质在二氧化碳中稳定性的制备方法，其特征在于，步骤一中，所述碱土金属离子包括镁离子、钙离子、锶离子中的一种；过渡金属离子包括锰离子、镍离子、铁离子、锌离子中的一种；VA主族金属离子为铋离子中的一种；
溶液中金属离子的定容浓度为0.05-0.25mol/L，PH值为5-6；
所述络合剂为甘氨酸、柠檬酸铵、EDTA中的一种或两种，络合剂的浓度为0.8-4.5mol/L。
3.如权利要求2所述的一种提高质子导体电解质在二氧化碳中稳定性的制备方法，其特征在于，步骤二中，用络合剂与硝酸盐的混合溶液浸渍时，按照浓度由高到低的顺序进行浸渍，且浸渍过程中调节真空度由低到高；
浸渍次数为5-15次，真空度范围为0.5-0.1Mpa。
4.如权利要求3所述的一种提高质子导体电解质在二氧化碳中稳定性的制备方法，其特征在于，步骤二中的浸渍总量为占钇掺杂锆酸钡或/和铈酸钡粉体的摩尔量，其中，镁离子浸渍总量为0.5mol％、1.0mol％、2.0mol％、3.0mol％、4.0mol％；钙离子浸渍总量为0.5mol％、4.0mol％；锶离子浸渍总量为0.5mol％；锰离子浸渍总量为1.0mol％、2.0mol％、3.0mol％；镍离子浸渍总量为0.5mol％、1.0mol％；铁离子浸渍总量为0.5mol％、1.0mol％、4.0mol％；锌离子浸渍总量为1.0mol％；铋离子浸渍总量为4.0mol％。
5.如权利要求4所述的一种提高质子导体电解质在二氧化碳中稳定性的制备方法，其特征在于，步骤二中，低温煅烧温度为300-450度，煅烧时间为2-4小时，高温煅烧温度为700-900度，煅烧时间为2-6小时。
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