A soft co-crystalline solid electrolyte for lithium-ion batteries

Abstract

Soft solid electrolyte materials are promising alternative choices for conventional battery electrolytes. Here, we have synthesized, characterized and calculated structural, thermal and electrochemical properties of an adiponitrile-based lithium-ion electrolyte which combines the advantages of organic and ceramic materials. This solid material is (Adpn)2LiPF6, (Adpn = adiponitrile) wherein (Adpn)-based channels solvate Li + ions through weak C≡N---Li + contacts.The surface of the crystal is a liquid nanolayer that binds the grains so that ionically conductive pellets are easily formed without high pressure/temperature treatments, which self-heals if fractured and which provide liquid-like conduction paths through the grain boundaries. High conductivity (σ ~ 10 -4 S/cm) and high lithium-ion transference number (tLi + = 0.54) result from weak interactions between "hard" (charge-dense) Li + ions and "soft" (electronically polarizable) -C≡N, compared with the stronger interactions of previously reported "hard" ether oxygen contacts of polyethylene oxide (PEO) or glymes. The proposed mechanism of conduction is one in which Li + ion migration occurs preferentially along the low activation energy path at the co-crystal grain boundaries and within the interstitial regions between the co-crystals, with bulk conductivity comprising a smaller but extant contribution to the observed conductivity. (Adpn)2LiPF6(s) has a wide electrochemical stability window of 0 to 5 V. Li 0 /(Adpn)2LiPF6/LiFePO4 cells exhibit cycling for > 50 cycles at C/20, C/10, C/5 rates with capacities of 140 mAh-g -1 to 100 mAh-g -1 and Coulombic efficiencies ~ 99%, and mitigation of the deleterious reactions with Li metal due to the high ionic strength. LTO/(Adpn)2LiPF6/NMC622 full cells were cycled at C-rates of C/20 to 1C with Coulombic efficiencies > 96%, with no dendritic failure after 100 cycles. Novel MD approaches addressing multiple conduction pathways and PWDFT calculations offer insights into the molecular basis of the physical and conductivity properties.

Computational approach inspired advancements of solid-state electrolytes for lithium secondary batteries: from first-principles to machine learning

“…147–149 Prabhat et al successfully synthesized an adiponitrile-LiPF 6 co-crystal that exhibited significantly high ion conductivity (around 10 −4 S cm −1 ) and a Li + transference number of 0.54. 150 Interestingly, DFT calculations (Fig. 3(f)) indicated that the Li + conduction in the bulk of the co-crystal had a large energy barrier, contradicting the experimental measurements.…”

Bridging the gap between academic research and industrial development in advanced all-solid-state lithium–sulfur batteries

“…Despite these challenges, there are promising emerging approaches, such as polymer electrolytes utilizing salt-mediated crystal formation, which have gained popularity in recent studies. 39,40 In some cases, polymer electrolytes are created through in situ polymerization within the cell using a precursor solution instead of pre-formed polymers. When the polymerization and subsequent drying process occur at temperatures above the boiling point of the solvent for a sufficient duration, the resulting electrolyte can be considered a solid-state electrolyte rather than a liquid-state or quasi-solid-state counterpart.…”

Solid Electrolyte Interphase Architecture for a Stable Li‐electrolyte Interface

“…SSEs can increase the energy density of the batteries and enhance battery safety without issues such as flammability and electrolyte leakage in liquid electrolytes. [121][122][123] The ideal SSEs should be Li ion conductive, electron insulating, thermodynamically stable, and lithophilic. Besides, the SSEs must possess high Young's modulus, elasticity, and conformal contact with Li metal.…”