Modeling assisted synthesis of Zr-doped Li3-xIn1-xZrxCl6 with ultrahigh ionic conductivity for lithium-ion batteries

Exploring Layered Disorder in Lithium-Ion-Conducting Li3Y1–xInxCl6

“…A similar behavior has been observed for a sodium-ion conductor in which the Na 3– x Er 1– x Zr x Cl 6 series shows faster ion transport when compared to parent materials, Na 3 ErCl 6 and Na 2 ZrCl 6 . The Li 3– x In 1– x Zr x Cl 6 compositions depict rather minute change in the ionic conductivity due to change in the lithium-ion concentration together with local structural distortion. ,, One major advantage of lithium-ion-conducting ternary halides is the ease of solution-based synthesis when targeting Li 3 InCl 6 , which suggests easier processing of solid-state batteries. , However, a strong influence of processing parameters on the structure and ionic conductivity of such halides is generally observed. , For example, in addition to high-temperature trigonal phase, a metastable trigonal phase with different yttrium-ion and lithium-ion positions was found when the reaction temperature was below 327 °C for Li 3 YCl 6 . In another example, the mechanochemically synthesized trigonal phase of Li 2 ZrCl 6 undergoes a structural transition to a monoclinic phase upon annealing, together with a concurrent decrease in conductivity .…”

“…31 The Li 3−x In 1−x Zr x Cl 6 compositions depict rather minute change in the ionic conductivity due to change in the lithium-ion concentration together with local structural distortion. 22,32,33 One major advantage of lithium-ion-conducting ternary halides is the ease of solution-based synthesis when targeting Li 3 InCl 6 , which suggests easier processing of solid-state batteries. 34,35 However, a strong influence of processing parameters on the structure and ionic conductivity of such halides is generally observed.…”

Halide solid-state electrolytes for all-solid-state batteries: structural design, synthesis, environmental stability, interface optimization and challenges

“…100 Replacing In 3+ with different amounts of Zr 4+ or Hf 4+ in Li 3 InCl 6 could still maintain a monoclinic structure. 88,[106][107][108][109] In Li 3−x In 1−x Zr x Cl 6 , the Zr 4+ only occupied the 2b site (Fig. 9a) and the occupancy of In at the 4g site gradually decreased with the Zr content increasing.…”

“…Tetravalent Zr 4+ and Hf 4+ were usually doped into trivalent metal halides as aliovalent ions. 39,44,88,97,[106][107][108] The introduction of Zr 4+ into Li 3 YCl 6 and Li 3 ErCl 6 by a solid-state reaction at 450 °C resulted in crystal structure changes. 44 As Zr content increased, their crystal structure changed from the trigonal structure, rst to an orthorhombic-I structure and then to an orthorhombic-II structure (Fig.…”

Amorphous Chloride Solid Electrolytes with High Li-Ion Conductivity for Stable Cycling of All-Solid-State High-Nickel Cathodes

“…Presently, ductile sulfide and oxysulfide-based amorphous SEs exhibit acceptable Li-ion conductivities (10 –4 –10 –3 S cm –1 ). , Unfortunately, it remains a great challenge to achieve high areal capacity and high voltage cathodes based on oxide, sulfide, or oxysulfide amorphous SEs due to the undesirable trade-off between ionic conductivity and cathode interfacial compatibility. ,, Aside from previously explored oxide SEs, chloride SEs have been recently proven to overcome the poor oxidative stability of sulfide SEs . Excellent electrochemical performance up to several thousand cycles has also been demonstrated for bulk-type ASSLBs with crystalline halides in combination with bare high-voltage cathodes. − ,, Recently, the ionic conductivity of the crystalline halide is further boosted by the modulation of the framework − and the formation of glass-ceramic phase − and glass phase, , indicating its potential in future application of practical ASSLBs. In addition, unique halide-eutectic and clay-like fluoride-halides , had been revealed with glass phase and excellent ionic conductivity.…”