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Composites of a NASICON-type oxide-based solid electrolyte Li1.3Al0.3Ti1.7(PO4)3 (LATP) and an olivine-type lithium metal phosphates, LiFePO4 (LFP) or LiNiPO4 (LNP) were co-sintered at various temperatures in air and Ar/H2 atmosphere, and the reaction products were analyzed by X-ray diffraction (XRD), X-ray absorption fine structure (XAFS), and energy-dispersive X-ray spectroscopy (EDS). When the LFP/LATP composites were co-sintered in air, LFP oxidized to produce Fe3+ compounds such as Fe2O3, FePO4 and Li3Fe2(PO4)3, and furthermore, at 800-900 °C, the products further reacted with LATP to form a solid solution denoted as Fe-rich Lix(Al,Ti,Fe)2(PO4)3. On the other hand, in an Ar/H2 atmosphere, LFP and LATP retained the original olivine and NASICON-type structures up to 600 °C, but at 650 °C or higher, (part of) LFP reacted with LATP to form Fe2P2O7 and Fe-poor Liy(Al,Ti,Fe)2(PO4)3. In contrast, LNP/LATP composites remained unchanged throughout the temperature range in air, whereas they underwent drastic changes in an Ar/H2 atmosphere. Ni12P5 and a few minor species such as Ni2P, Li4P2O7 and Li3PO4 were produced at 500 °C, Ni2P, Li4P2O7 and Li3PO4 became more prominent at 600 °C, and various other phases including Liz(Al,Ti,Ni)2(PO4)3, which cannot be fully identified by XRD and XAFS, were formed. In addition, thermodynamic calculations were performed to predict the reaction products. The results showed partial agreement with the experimental observations, and the remaining discrepancies can be attributed to (1) the absence of the thermodynamic parameters of some products in the database used for the calculations, (2) the marginal energy differences between the predicted most stable and the kinetically hindered metastable phases, and (3) the insufficient consideration of the released and uptake of gaseous components including water, oxygen and hydrogen.

権利情報:

• Creative Commons BY Attribution 4.0 International
  

キーワード: all-solid-state batteries, co-sintering

刊行年月日: 2026-09-17

出版者: American Chemical Society (ACS)

掲載誌:

• The Journal of Physical Chemistry C (ISSN: 19327447) vol. 130 issue. 37 p. 12864-12874

研究助成金:

• Ministry of Education, Culture, Sports, Science and Technology JPMXP0219207397

原稿種別: 出版者版 (Version of record)

MDR DOI:

公開URL: https://doi.org/10.1021/acs.jpcc.6c03720

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更新時刻: 2026-09-25 15:49:53 +0900

MDRでの公開時刻: 2026-09-25 18:39:04 +0900