Air-Stable Binary Hydrated Eutectic Electrolytes with Unique Solvation Structure for Rechargeable Aluminum-Ion Batteries

Aluminum-ion batteries(AIBs)have been highlighted as a potential alternative to lithium-ion batteries for large-scale energy storage due to the abundant reserve,light weight,low cost,and good safety of Al.However,the development of AIBs faces challenges due to the usage of AlCl_(3)-based ionic liquid electrolytes,which are expensive,corrosive,and sensitive to humidity.Here,we develop a low-cost,non-corrosive,and air-stable hydrated eutectic electrolyte composed of aluminum perchlorate nonahydrate and methylurea(MU)ligand.Through optimizing the molar ratio to achieve the unique solvation structure,the formed Al(ClO_4)_(3)·9H_(2)O/MU hydrated deep eutectic electrolyte(AMHEE)with an average coordination number of 2.4 can facilely realize stable and reversible deposition/stripping of Al.When combining with vanadium oxide nanorods positive electrode,the Al-ion full battery delivers a high discharge capacity of 320 mAh g^(-1)with good capacity retention.The unique solvation structure with a low desolvation energy of the AMHEE enables Al^(3+)insertion/extraction during charge/discharge processes,which is evidenced by in situ synchrotron radiation X-ray diffraction.This work opens a new pathway of developing low-cost,safe,environmentally friendly and high-performance electrolytes for practical and sustainable AIBs.

Cointercalation-Free Ether-Based Deep Eutectic Electrolyte for All-Climate Battery

Lithium-ion batteries(LIBs)with ether-based electrolytes usually provide low cell performance when matched with the graphite(Gr)anodes due to cointercalation of Li+-solvent.Herein,a novel deep eutectic ether electrolyte with polyethylene glycol dimethyl ether(PEGDME)featuring low flammability and high safety is developed,and fluoroethylene carbonate(FEC)is adopted to mitigate the cointercalation phenomenon.Unlike the common effect of FEC’s role in the first solvation shell,our results reveal that FEC molecules affect the Li+-PEGDME insertion behavior through FECPEGDME intramolecular interaction.As a result,a high discharge capacity of 450 mA h g^(−1)is achieved in Li||Gr/SiO_(x)cells at 50℃,and 370 mA h g^(−1)can be realized,even at−20℃(three times higher than commercial carbonate electrolyte).Moreover,Gr/SiO_(x)||LiNi_(0.6)Co_(0.2)Mn_(0.2O2)full cells maintain good capacity retention in both coin cell and pouch cell configurations over a wide temperature range.Our work deciphers the role of FEC as an additive and proposes new electrolyte optimization strategies to achieve high-performance all-climate LIBs.

A highly ionic transference number eutectogel hybrid electrolytes based on spontaneous coupling inhibitor for solid-state lithium metal batteries

Polymer-based solid electrolytes have been extensively studied for solid-state lithium metal batteries to achieve high energy density and reliable security.But,its practical application is severely limited by low ionic conductivity and slow Li+transference.Herein,based on the“binary electrolytes”of poly(vinylidene fluoride-chlorotrifluoroethylene)(P(VDF-CTFE))and lithium salt(LiTFSI),a kind of eutectogel hybrid electrolytes(EHEs)with high Li+transference number was developed via tuning the spontaneous coupling of charge and vacated space generated by Li-cation diffusion utilizing the Li6.4La3Zr1.4Ta0.6O12(LLZTO)dopant.LLZTO doping promotes the dissociation of lithium salt,increases Li+carrier density,and boosts ion jumping and the coordination/decoupling reactions of Li+.As a result,the optimized EHEs-10%possess a high Li-transference number of 0.86 and a high Li+conductivity of 3.2×10–4 S·cm–1 at room temperature.Moreover,the prepared EHEs-10%composite solid electrolyte presents excellent lithiumphilic and compatibility,and can be tested stably for 1,200 h at 0.3 mA·cm–2 with assembled lithium symmetric batteries.Likewise,the EHEs-10%films match well with high-loading LiFePO4 and LiCoO2 cathodes(>10 mg·cm–2)and exhibit remarkable interface stability.Particularly,the LiFePO4//EHEs-10%//Li and LiCoO2//EHEs-10%//Li cells deliver high rate performance of 118 mAh·g–1 at 1 C and 93.7 mAh·g–1 at 2 C with coulombic efficiency of 99.3%and 98.1%,respectively.This work provides an in-depth understanding and new insights into our design for polymer electrolytes with fast Li+diffusion.