LLZSP (Li1.67La0.18Na0.36ZrSi1.21P0.58Ox) Powder as Solid-State Electrolyte for Lithium-Ion Battery, 25-100 g/bottle, CLIBSSELLZSP

Li1.67La0.18Na0.36ZrSi1.21P0.58Ox (LLZSP) is an advanced, multi-cation co-doped NASICON-structured solid electrolyte powder. Rather than a simple binary substitution, this complex composition belongs to an engineered solid-solution system designed to solve the two primary bottlenecks of conventional NASICON conductors (Li(1+x)Zr2SixP(3-x)O12 and LATP): high grain-boundary activation energy and severe reduction/degradation at lithium-metal interfaces.

The material is constructed around the 3D corner-sharing [ZrO6] octahedra and [(Si,P)O4] tetrahedra backbone of the NASICON crystal lattice. Each dopant targets a distinct crystallographic or transport parameter: (1) La^{3+} Substitution (0.18 mol): With a large ionic radius (r ~ 1.03 Å), lanthanum expands the critical bottleneck radius connecting adjacent interstitial Li(1) and Li(2) cavities. This lattice expansion lowers the activation energy (E_a) for Li+ hopping and suppresses grain-boundary segregation. (2) Na+ Co-Doping (0.36 mol): Sodium acts as an interstitial structural modifier and transient sintering flux. It creates a mixed-alkali site-disorder that destabilizes localized lithium clustering, increasing the fraction of mobile, disordered Li+ carriers. (3) Si/P Polyhedral Ratio (1.21: 0.58): Modulates the overall negative charge of the framework, dictating the equilibrium concentration of charge-compensating mobile Li+ ions (1.67 formula units) while balancing framework polarizability.

The practical applications are: (1) Inorganic Filler for Composite Polymer Electrolytes (CPEs): Sub-micron LLZSP powder (D50 ~ 0.3–0.6 um) is blended into polymer matrices (PVDF-HFP, PEO, or poly(acrylonitrile)) at 15–35 wt%. Because LLZSP does not form an insulating Li2CO3 surface shell in ambient air or organic solvents (DMF/NMP), it forms clean, low-resistance Lewis acid-base interfacial channels with polar polymer segments, suppressing interfacial impedance. (2) Tape-Casting Thin Solid Separator Sheets: Sintered or composite-cast into thin membranes (20–40 um). The low skeletal density ~ 3.4 g/cm3 vs. >5.1 g/cm3 for garnets) translates into a ~ 33% reduction in separator dead-weight, preserving high gravimetric cell energy density (Wh/kg). (3) Co-Sintered / Catholyte Composite Cathodes: Blended directly into positive electrode slurries (with high-Ni NMC or LFP) to provide continuous, high-rate 3D Li+ pathways throughout thick, high-areal-capacity (>3.5 mAh/cm2) electrodes.

Notes: Please try to store the LLZSP powders in a dry place (glovebox is best).

References: 

1. L. Zhu, et al. Enhancing ionic conductivity in solid electrolyte by relocating diffusion ions to under-coordination sites, Science Advances, 2022, DOI: 10.1126/sciadv.abj76
2. N. Zhang, et al. Slurry Casted Ultrathin Li3Zr2Si2PO12 Electrolyte Film for Solid-State Lithium Metal Batteries, Small, 2024, 20, 2402164