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CN106927815A - 钛酸盐固体电解质及其制备方法 - Google Patents

钛酸盐固体电解质及其制备方法 Download PDF

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CN106927815A
CN106927815A CN201710222475.9A CN201710222475A CN106927815A CN 106927815 A CN106927815 A CN 106927815A CN 201710222475 A CN201710222475 A CN 201710222475A CN 106927815 A CN106927815 A CN 106927815A
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苏聪学
覃杏柳
方亮
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Abstract

本发明公开了一种钛酸盐KLa2Ti3O9.5及其制备方法。所述制备方法为按KLa2Ti3O9.5的化学计量比称取相应的原料,然后通过球磨,高温预烧,再球磨,最后冷等静压后烧结得到KLa2Ti3O9.5。制备方法简单,适合大规模生产。该方法合成的KLa2Ti3O9.5在高温下具有较高的热稳定性及化学稳定性;而且在高温下具有很好的离子导电性,是一种优良的固体电解质材料。

Description

钛酸盐固体电解质及其制备方法
技术领域
本发明属于无机材料技术领域,具体涉及一种钛酸盐固体电解质及其制备方法。
背景技术
随着人类社会的发展以及工业化程度的进一步提高,开发高效、清洁、安全及经济的新型绿色能源成为了未来能源发展的必然趋势。由于离子导体具有重要的理论和实际应用价值,已在很多应用领域发展成为很有价值的材料或器件。作为离子导体中的一种材料,快离子导体材料,也称固体电解质,在高性能储能装置、燃料电池新能源材料、钠硫电池及氧分析器等领域的应用备受关注。比如氧离子导体和氢离子导体都可用作燃料电池的电解质隔膜,从而使可燃气体与氧气经电化学方法发生反应转变为电能。用氧化锆和其它快离子导体制成的气体探测器,不仅可以控制汽车发动机和锅炉燃烧室的燃烧过程以节约燃料和减少污染,而且还可以监测一些有害气体从而对环境保护作出贡献。用Na-β-Al2O3作电解质的钠-硫电池具有比铅酸电池高4~5倍的能量密度,它既可用作车辆的动力源,也可作为贮能电池使用。用快离子导体制作的固体电池具有自放电小、贮存寿命长和抗振动等优点,已在心脏起搏器电子手表、计算器和一些军用设备上获得应用。
高温燃料电池作为快离子导体(固体电解质)中的一种应用,近年来备受关注。高温燃料电池也称固体氧化物燃料电池,它们大多为基于氧空位机理的高对称的八面体和立方结构,如萤石基、钙钛矿基、Bi2O3基等固体电解质材料,但近年来,人们在低对称结构体系(如四面体、立方体、单斜等)中也寻找到高电导率的电解质材料,如黄长石结构体系,磷灰石结构体系,白钨矿结构等体系材料,而且导电机理不局限于氧空位。另外,在已报道的固体电解质材料来看,普遍存在实用性能差的缺点,主要体现在:一、工作温度过高,启动时间长,器件各组分间化学和力学兼容性差;二、导电率低;只能在800-1000℃高温下使用;三、还原气氛下某些元素如Ce部分还原成Ce3+,致使产生电子导电,甚至某些固体电解质材料在还原气氛下易分解;四、某些元素如Ga的挥发,而且工艺复杂,组件间化学兼容性差。由此可见,在理论上,人们难以通过结构来判断化合物是否具备作为快离子导体的应用;在实际应用上,人们难以找到具有实用的快离子导体材料,即具备较高的离子导电性、较低的工作温度(500℃左右)、使用温度下较高的热稳定性及化学稳定性、大规模生产的可操作性等特点。目前所报道的钾基钛酸盐普遍是利用湿化学法制备,虽然制备温度较低,但是反应时间过长,而且过程复杂,不利于工业化生产。
发明内容
本发明的目的是提供一种用于固体电解质的钛酸盐及其制备方法。
本发明涉及的用于固体电解质的钛酸盐的化学表示式为:KLa2Ti3O9.5
所述钛酸盐的制备方法具体步骤为:
(1)将K2CO3、La2O3和TiO2的原始粉末按KLa2Ti3O9.5的组成称量配料并放入球磨罐中,加入直径为7mm的氧化锆球和去离子水,球磨4小时,混合均匀磨细,取出烘干得到粉末原料;
(2)将步骤(1)烘干后的粉末原料压成柱状样品,置于陶瓷承烧板上,用坩埚罩住样品,然后置于马弗炉中,750℃煅烧,保温1小时,然后从750℃的管式炉中用钳子夹住承烧板并快速取出,使陶瓷承烧板上,坩埚内的样品快速冷却,冷却至室温后捣碎研磨成粉末;
(3)将步骤(2)研磨所得的粉末放入球磨罐中,加入直径分别为2mm和7mm的氧化锆球,粉末和氧化锆球在球磨罐里球磨15个小时,混合均匀磨细,得到粉末原料;
(4)将步骤(3)球磨后的粉末原料冷等静压25MPa成型为直径1.3cm,厚度0.3cm的圆片,然后在马弗炉中800-850℃烧结,保温4小时后,自然冷却至室温,得到钛酸盐KLa2Ti3O9.5
本发明的优点:通过本制备方法得到的钛酸盐KLa2Ti3O9.5具有较高的离子导电性、使用温度下具有较高的热稳定性及化学稳定性;在烧结温度下结构保持不变,在300-500℃时电导率为10-3~10-2S/cm,是一种优良的快离子导体材料。另外制备方法简单、合成温度低,绿色环保成本低,相对于其他固体电解质材料的湿化学法制备工艺,本方法更适合工业生产与应用。
具体实施方式
下面结合实施例对本发明作进一步的说明,但本领域的技术人员了解,下述实施例不是对发明保护范围的限制,任何在本发明基础上的改进和变化都在本发明的保护范围之内。
实施例1:
(1)将K2CO3、La2O3和TiO2的原始粉末按KLa2Ti3O9.5的组成称量配料并放入球磨罐中,加入直径为7mm的氧化锆球和去离子水,球磨4小时,混合均匀磨细,取出烘干得到粉末原料;
(2)将步骤(1)烘干后的粉末原料压成柱状样品,置于陶瓷承烧板上,用坩埚罩住样品,然后置于马弗炉中,750℃煅烧,保温1小时,然后从750℃的管式炉中用钳子夹住承烧板并快速取出,使陶瓷承烧板上,坩埚内的样品快速冷却,冷却至室温后捣碎研磨成粉末;
(3)将步骤(2)研磨所得的粉末放入球磨罐中,加入直径分别为2mm和7mm的氧化锆球,粉末和氧化锆球在球磨罐里球磨15个小时,混合均匀磨细,得到粉末原料;
(4)将步骤(3)球磨后的粉末原料冷等静压25MPa成型为直径1.3cm,厚度0.3cm的圆片,然后在马弗炉中800℃烧结,保温4小时后,自然冷却至室温,得到钛酸盐KLa2Ti3O9.5
本实施例所得到的钛酸盐KLa2Ti3O9.5,在两底面涂上金胶,在550℃下烧结1小时。使用Solartron1260(英国Solartron公司)阻抗分析仪在不同温度下测定其交流阻抗。测定结果为300℃时电导率达到1.76×10-3S/cm,在500℃时电导率快速升到0.92×10-2S/cm。
实施例2:
(1)将K2CO3、La2O3和TiO2的原始粉末按KLa2Ti3O9.5的组成称量配料并放入球磨罐中,加入直径为7mm的氧化锆球和去离子水,球磨4小时,混合均匀磨细,取出烘干得到粉末原料;
(2)将步骤(1)烘干后的粉末原料压成柱状样品,置于陶瓷承烧板上,用坩埚罩住样品,然后置于马弗炉中,750℃煅烧,保温1小时,然后从750℃的管式炉中用钳子夹住承烧板并快速取出,使陶瓷承烧板上,坩埚内的样品快速冷却,冷却至室温后捣碎研磨成粉末;
(3)将步骤(2)研磨所得的粉末放入球磨罐中,加入直径分别为2mm和7mm的氧化锆球,粉末和氧化锆球在球磨罐里球磨15个小时,混合均匀磨细,得到粉末原料;
(4)将步骤(3)球磨后的粉末原料冷等静压25MPa成型为直径1.3cm,厚度0.3cm的圆片,然后在马弗炉中830℃烧结,保温4小时后,自然冷却至室温,得到钛酸盐KLa2Ti3O9.5
本实施例所得到的钛酸盐KLa2Ti3O9.5,在两底面涂上金胶,在550℃下烧结1小时。使用Solartron1260(英国Solartron公司)阻抗分析仪在不同温度下测定其交流阻抗。测定结果为300℃时电导率达到2.68×10-3S/cm,在500℃时电导率快速升到1.54×10-2S/cm。
实施例3:
(1)将K2CO3、La2O3和TiO2的原始粉末按KLa2Ti3O9.5的组成称量配料并放入球磨罐中,加入直径为7mm的氧化锆球和去离子水,球磨4小时,混合均匀磨细,取出烘干得到粉末原料;
(2)将步骤(1)烘干后的粉末原料压成柱状样品,置于陶瓷承烧板上,用坩埚罩住样品,然后置于马弗炉中,750℃煅烧,保温1小时,然后从750℃的管式炉中用钳子夹住承烧板并快速取出,使陶瓷承烧板上,坩埚内的样品快速冷却,冷却至室温后捣碎研磨成粉末;
(3)将步骤(2)研磨所得的粉末放入球磨罐中,加入直径分别为2mm和7mm的氧化锆球,粉末和氧化锆球在球磨罐里球磨15个小时,混合均匀磨细,得到粉末原料;
(4)将步骤(3)球磨后的粉末原料冷等静压25MPa成型为直径1.3cm,厚度0.3cm的圆片,然后在马弗炉中850℃烧结,保温4小时后,自然冷却至室温,得到钛酸盐KLa2Ti3O9.5
本实施例所得到的钛酸盐KLa2Ti3O9.5,在两底面涂上金胶,在550℃下烧结1小时。使用Solartron1260(英国Solartron公司)阻抗分析仪在不同温度下测定其交流阻抗。测定结果为300℃时电导率达到1.94×10-3S/cm,在500℃时电导率快速升到1.22×10-2S/cm。
由于钾离子、钠离子和锂离子在快离子导体中经常作为迁移离子,因此在本申请的实验条件下,制备LiLa2Ti3O9.5以及NaLa2Ti3O9.5陶瓷片,并在相同条件下测试其电导率,结果发现只有LiLa2Ti3O9.5具有最高的电导率1.06×10-5S/cm,而NaLa2Ti3O9.5因结构不稳定而得不到离子电导率。

Claims (1)

1.一种钛酸盐作为固体电解质的应用,其特征在于所述钛酸盐具有如下化学表示式:KLa2Ti3O9.5
所述钛酸盐在300-500℃时电导率为10-3~10-2S/cm;
所述钛酸盐的制备方法具体步骤为:
(1)将K2CO3、La2O3和TiO2的原始粉末按KLa2Ti3O9.5的组成称量配料并放入球磨罐中,加入直径为7mm的氧化锆球和去离子水,球磨4小时,混合均匀磨细,取出烘干得到粉末原料;
(2)将步骤(1)烘干后的粉末原料压成柱状样品,置于陶瓷承烧板上,用坩埚罩住样品,然后置于马弗炉中,750℃煅烧,保温1小时,然后从750℃的管式炉中用钳子夹住承烧板并快速取出,使陶瓷承烧板上,坩埚内的样品快速冷却,冷却至室温后捣碎研磨成粉末;
(3)将步骤(2)研磨所得的粉末放入球磨罐中,加入直径分别为2mm和7mm的氧化锆球,粉末和氧化锆球在球磨罐里球磨15个小时,混合均匀磨细,得到粉末原料;
(4)将步骤(3)球磨后的粉末原料冷等静压25MPa成型为直径1.3cm,厚度0.3cm的圆片,然后在马弗炉中800-850℃烧结,保温4小时后,自然冷却至室温,得到钛酸盐KLa2Ti3O9.5
CN201710222475.9A 2017-04-07 2017-04-07 钛酸盐固体电解质及其制备方法 Withdrawn CN106927815A (zh)

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CN111276734A (zh) * 2018-12-05 2020-06-12 新奥科技发展有限公司 一种传导钾离子的固态电解质、制备方法及钾固态电池
CN115149098A (zh) * 2022-07-07 2022-10-04 广州巨湾技研有限公司 一种高离子电导率钛酸镧锂固体电解质材料及其制备和应用
CN117105657A (zh) * 2023-09-18 2023-11-24 深圳市华辰新材料科技有限公司 纳米级钛酸镧的低温烧结制备方法及设备

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111276734A (zh) * 2018-12-05 2020-06-12 新奥科技发展有限公司 一种传导钾离子的固态电解质、制备方法及钾固态电池
CN111276734B (zh) * 2018-12-05 2021-10-26 新奥科技发展有限公司 一种传导钾离子的固态电解质、制备方法及钾固态电池
CN115149098A (zh) * 2022-07-07 2022-10-04 广州巨湾技研有限公司 一种高离子电导率钛酸镧锂固体电解质材料及其制备和应用
CN115149098B (zh) * 2022-07-07 2025-09-19 广州巨湾技研有限公司 一种高离子电导率钛酸镧锂固体电解质材料及其制备和应用
CN117105657A (zh) * 2023-09-18 2023-11-24 深圳市华辰新材料科技有限公司 纳米级钛酸镧的低温烧结制备方法及设备
CN117105657B (zh) * 2023-09-18 2024-05-07 深圳市华辰新材料科技有限公司 纳米级钛酸镧的低温烧结制备方法及设备

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