An Unprecedented Fireproof, Anion‐Immobilized Composite Electrolyte Obtained via Solidifying Carbonate Electrolyte for Safe and High‐Power Solid‐State Lithium‐Ion Batteries

Abstract

The update of electrolytes from a liquid state to a solid state is considered effective in improving the safety and energy density of lithium‐ion batteries (LIBs). Although numerous efforts have been made, solid‐state electrolytes’ (SSEs) insufficient charge transfer capability remains a significant obstruction to practical applications. Herein, a fireproof and anion‐immobilized composite electrolyte is designed by solidifying carbonate electrolyte, exhibiting superior Li‐ion conductivity (11.5 mS cm−1 at 30 °C) and Li‐ion transference number (0.90), which endows LIBs excellent rate capability and cycling stability. Elaborate characteristics and theoretical calculations demonstrate the presence of robust anion‐molecule coordination (composed of lithium bond and Coulomb force) enables a more efficient ion transport, where the mobility of Li+ ion is enhanced meanwhile the anions are immobilized. This work highlights how the strong interactions between electrolyte components can be used to simultaneously regulate the migration of Li+ ion and anion, and realize a one‐step conversion of inflammable liquid‐state electrolyte to nonflammable solid‐state electrolyte.

Lithium Salt Dissociation Promoted by 18‐Crown‐6 Ether Additive toward Dilute Electrolytes for High Performance Lithium Oxygen Batteries

“…The electrophilic/nucleophilic sites of DMSO, ClO 4 − and 18C6 were predicted via molecular electrostatic potential (MESP) calculation (Figure 1j). In a 18C6 molecule, the C−O−C groups exhibit nucleophilicity, while C−H and C−C groups show electrophilicity, which have electrostatic adsorption effect on negatively charged ClO 4 − anions to promote lithium salt dissociation [13] . Meanwhile, DMSO molecules with strong nucleophilic S=O groups are more involved in the first solvation sheath to bind with Li + [14] .…”

“…À anions to promote lithium salt dissociation. [13] Meanwhile, DMSO molecules with strong nucleophilic S=O groups are more involved in the first solvation sheath to bind with Li + . [14] To optimize the concentration of 18C6 additive, MD simulations of electrolytes containing 50 mM 18C6 (50-18C6) and 200 mM 18C6 (200-18C6) are given in Figure S4, and the CNs of different electrolytes are aggregated in Figure S5.…”

Hollow‐Particles Quasi‐Solid‐State Electrolytes with Biomimetic Ion Channels for High‐Performance Lithium‐Metal Batteries

“…[17] Hou et al [18] identified solvent-assisted jumping as the main route of lithium-ion transport in the MOF-688 material and explained the key role of solvents. Yang et al [19] used the molecule-anion coordination to promote the dissociation of lithium salts, increase the concentration of free lithium ions, and achieve the fixation of anions, which weakened the dynamic traction of lithium ions when moving, and greatly enhanced the transport dynamics of lithium ions. He et al [20] developed a multispectral characterization strategy combined with first-principles calculations and found that the solvation structure and conduction mechanism of Li + in QSSEs were similar to those in highconcentration LEs.…”

“…Yang et al. [ 19 ] used the molecule‐anion coordination to promote the dissociation of lithium salts, increase the concentration of free lithium ions, and achieve the fixation of anions, which weakened the dynamic traction of lithium ions when moving, and greatly enhanced the transport dynamics of lithium ions. He et al.…”

Pendant Length-Dependent Electrochemical Performances for Conjugated Organic Polymers as Solid-State Polymer Electrolytes in Lithium Metal Batteries

“…With the ever-increasing demand for efficient and clean energy, electric energy has become the optimum alternative to traditional fossil energy . Lithium battery, as a clean and portable energy storage device, has been widely used in social production and life. − However, most lithium batteries suffer from serious safety problems such as easy leakage, flammability, and explosion due to the used liquid electrolyte. − With the progress of technology and the application of wearable electronic equipment, the demand for flexible high-energy devices has reached a zenith. − By virtue of their outstanding safety, excellent flexibility, and high energy density, solid-state polymer electrolytes (SPEs) have evoked great interest of researchers. Compared with inorganic solid-state electrolytes with poor interface performance, difficulty to process, and high brittleness, SPEs show better processability for large-scale production.…”