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具有增强离子电导率的钼/镁共掺杂磷灰石型硅酸镧电解质的合成与致密化

Synthesis and Densification of Mo/Mg Co-Doped Apatite-type Lanthanum Silicate Electrolytes with Enhanced Ionic Conductivity.

作者信息

Li Jing, Cai Qiong, Horri Bahman Amini

机构信息

School of Chemistry and Chemical Engineering, University of Surrey, Guildford, GU2 7XH, UK.

出版信息

Chemistry. 2023 May 2;29(25):e202300021. doi: 10.1002/chem.202300021. Epub 2023 Mar 17.

Abstract

Apatite-type lanthanum silicate (LSO) electrolyte is one of the most promising candidates for developing intermediate-temperature solid oxide electrolysis cells and solid oxide full cells (IT-SOECs and SOFCs) due to its stability and low activation energy. However, the LSO electrolyte still suffers from unsatisfied ionic conductivity and low relative density. Herein, a new co-doped method is reported to prepare highly purified polycrystalline powders of Mg-Mo co-doped LSO (Mg/Mo-LSO) electrolytes with high excellent densification properties and improved ionic conductivity. Introducing the Mo and Mg ions into the LSO structure can increase the number of interstitial oxide ions and improve the degree of densification at lower sintering temperatures, more importantly, expand the migration channel of oxide ions to enhance the ionic conductivity. As a result, the relative density of the fabricated Mo/Mg-LSO electrolytes pellets could achieve more than 98 % of the theoretical density after sintering at 1500 °C for 4 h with a grain size of about 1-3 μm and the EIS results showed the ionic conductivity increased from 0.782 mS ⋅ cm for the pristine LSO to 33.94 mS ⋅ cm for the doped sample La Si Mg Mo O at 800 °C. In addition, the effect of different Mo doping contents was investigated systematically, in which La Si Mg Mo O possessed the highest ionic conductivity and relative density. The proposed Mo/Mg co-doped method in this work is one step forward in developing apatite-structured electrolytes offering excellent potential to address the common issues associated with the fabrication of dense, highly conductive, and thermochemically stable electrolytes for solid oxide electrolysers and fuel cells.

摘要

磷灰石型硅酸镧(LSO)电解质因其稳定性和低活化能,是开发中温固体氧化物电解槽和固体氧化物全电池(IT - SOECs和SOFCs)最有前景的候选材料之一。然而,LSO电解质的离子电导率仍不尽人意,且相对密度较低。在此,报道了一种新的共掺杂方法,用于制备具有优异致密化性能和改善离子电导率的高纯多晶Mg - Mo共掺杂LSO(Mg/Mo - LSO)电解质粉末。将Mo和Mg离子引入LSO结构可以增加间隙氧离子的数量,并在较低烧结温度下提高致密化程度,更重要的是,扩大氧离子的迁移通道以提高离子电导率。结果,制备的Mo/Mg - LSO电解质颗粒在1500℃烧结4小时后,相对密度可达到理论密度的98%以上,晶粒尺寸约为1 - 3μm,EIS结果表明,离子电导率从原始LSO的0.782 mS·cm增加到800℃下掺杂样品LaSiMgMoO的33.94 mS·cm。此外,系统研究了不同Mo掺杂含量的影响,其中LaSiMgMoO具有最高的离子电导率和相对密度。本文提出的Mo/Mg共掺杂方法在开发磷灰石结构电解质方面向前迈进了一步,为解决与固体氧化物电解槽和燃料电池致密、高导电和热化学稳定电解质制造相关的常见问题提供了优异的潜力。

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