Nowadays, the majority of the studies on the substitution are focused on cations (such as Y³⁺, Ti⁴⁺, P⁵⁺, etc.) in Li_1.3Al_0.3Ti_1.7(PO₄)₃ (LATP), while there are few studies on the substitution of anion O²⁻. In this work, the modified LATP with a series of LiCl (LATPClx, x = 0.1, 0.2, 0.3, 0.4) additives is prepared to enhance ionic conductivity. The successful introduction of Cl⁻ makes the length of the c axis decrease from 20.822(2) to 20.792(1) Å, and the bulk conductivity of 2.13 × 10⁻³ S·cm⁻¹ is achieved in LATPCl0.3. Moreover, the Al/Ti-O₁/Cl₁ and Al/Ti-O₂/Cl₂ distance decrease, while the Li₁-O₂/Cl₂ distance increases. Lithium ions migrate more easily in the nanochannel of M3-M1-M3. In addition, the LiCl additive increases the relative density and the grain boundary conductivity of LATPClx compounds. Naturally, a higher ionic conductivity of 2.12 × 10⁻⁴ S·cm⁻¹ and a low activation energy of 0.30 eV are obtained in LATPCl0.3. Correspondingly, the symmetric cell exhibits a low overpotential of ±50 mV for over 200 h in LATPCl0.3. The solid-state Li∣LATPCl0.3∣NCM811 (NCM811 = LiNi_0.8Co_0.1Mn_0.1O₂) battery exhibits high initial capacity 185.1 mAh·g⁻¹ with a capacity retention rate of 95.4% after 100 cycles at 0.5 C. This result suggests that LiCl additive is an effective strategy to promote electrochemical properties of LATP solid electrolyte and can be considered for reference to other inorganic solid electrolytes systems.

目前关于取代的研究大多集中在Li _1.3 Al _0.3 Ti _1.7 (PO ₄ ) ₃ (LATP)中的阳离子(如Y ³⁺、Ti ⁴⁺、P ^{5+等)，而对阴离子O 2−}的取代研究较少。在这项工作中，制备了具有一系列LiCl（LATPCl x，x = 0.1、0.2、0.3、0.4）添加剂的改性LATP以增强离子电导率。^{Cl -}的成功引入使得c轴长度从20.822(2)减小到20.792(1) Å，体电导率为2.13 × 10 ^-3 S·cmLATPCl0.3 中实现^{-1 。}此外，Al/Ti-O ₁ /Cl ₁和Al/Ti-O ₂ /Cl ₂距离减小，而Li ₁ -O ₂ /Cl ₂距离增大。锂离子在M3-M1-M3的纳米通道中更容易迁移。此外，LiCl添加剂增加了LATPCl x化合物的相对密度和晶界电导率。当然，离子电导率更高，为 2.12 × 10 ^-4 S·cm ^-1LATPCl0.3 获得了 0.30 eV 的低活化能。相应地，对称电池在 LATPCl0.3 中表现出 ±50 mV 的低过电势超过 200 小时。固态Li∣LATPCl0.3∣NCM811（NCM811 = LiNi _0.8 Co _0.1 Mn _0.1 O ₂）电池表现出高初始容量185.1 mAh·g ^-1，在0.5 C下循环100次后容量保持率为95.4%。该结果表明LiCl添加剂是促进LATP固体电解质电化学性能的有效策略，可以考虑参考无机固体电解质系统。