Non-Flammable Liquid and Quasi-Solid Electrolytes toward Highly-Safe Alkali Metal-Based Batteries

Rechargeable alkali metal (i.e., lithium, sodium, potassium)-based batteries are considered as vital energy storage technologies in modern society. However, the traditional liquid electrolytes applied in alkali metal-based batteries mainly consist of thermally unstable salts and highly flammable organic solvents, which trigger numerous accidents related to fire, explosion, and leakage of toxic chemicals. Therefore, exploring non-flammable electrolytes is of paramount importance for achieving safe batteries. Although replacing traditional liquid electrolytes with all-solid-state electrolytes is the ultimate way to solve the above safety issues, developing non-flammable liquid electrolytes can more directly fulfill the current needs considering the low ionic conductivities and inferior interfacial properties of existing all-solid-state electrolytes. Moreover, the electrolyte leakage concern can be further resolved by gelling non-flammable liquid electrolytes to obtain quasi-solid electrolytes. Herein, a comprehensive review of the latest progress in emerging non-flammable liquid electrolytes, including non-flammable organic liquid electrolytes, aqueous electrolytes, and deep eutectic solvent-based electrolytes is provided, and systematically introduce their flame-retardant mechanisms and electrochemical behaviors in alkali metal-based batteries. Then, the gelation techniques for preparing quasi-solid electrolytes are also summarized. Finally, the remaining challenges and future perspectives are presented. It is anticipated that this review will promote a safety improvement of alkali metal-based batteries.     

Origin of High Ionic Conductivity of Sc-Doped Sodium-Rich NASICON Solid-State Electrolytes

Substitution of liquid electrolyte with solid-state electrolytes (SSEs) has emerged as a very urgent and challenging research area of rechargeable batteries. NASICON (Na₃Zr₂Si₂PO₁₂) is one of the most potential SSEs for Na-ion batteries due to its high ionic conductivity and low thermal expansion. It is proven that the ionic conductivity of NASICON can be improved to 10⁻³ S cm⁻¹ by Sc-doping, of which the mechanism, however, has not been fully understood. Herein, a series of Na_3+xSc_xZr_2−xSi₂PO₁₂ (0 ≤ x  ≤  0.5) SSEs are prepared. To gain a deep insight into the ion transportation mechanism, synchrotron-based X-ray absorption spectroscopy (XAS) is employed to characterize the electronic structure, and solid-state nuclear magnetic resonance (SS-NMR) is used to analyze the dynamics. In this study, Sc is successfully doped into Na₃Zr₂Si₂PO₁₂ to substitute Zr atoms. The redistribution of sodium ions at certain specific sites is proven to be critical for sodium ion movement. For x ≤ 0.3, the promotion of sodium ion movement is attributed to sodium ion concentration increase at the Na2 sites and decrease at the Na1 and Na3 sites. For x > 0.3, the inhibition of sodium ion movement is due to the phase change from monoclinic to rhombohedral and an increasing impurity content.     

The Influences of DMF Content in Composite Polymer Electrolytes on Li+-Conductivity and Interfacial Stability with Li-Metal

Trace N, N-dimethylformamide(DMF) containing composite polymer electrolytes (CPEs) has attracted much attention owing to the dramatically increased Li⁺-conductivity. But the amount of DMF is critical and needs to be clarified for the interfacial stability, since DMF is easily reduced by Li-metal. Herein, the influences of DMF in poly(ethylene oxide) (PEO) and poly(vinylidene fluoride) (PVDF) based CPEs are studied on the Li⁺-conductivity and interfacial stability. In PEO-based CPEs, owing to a stronger interaction of lithium bis(trifluoromethanesulfon)imide (LiTFSI) with PEO than DMF, DMF can not be confined and be easily evaporated off. Only ≈0.25wt.% DMF is absorbed on ceramic electrolyte fillers, giving two times increased Li⁺-conductivity compared with the DMF-free counterparts and generating stable interface with Li-metal; but over much DMF (≥2.2 wt.%) leads to serious interfacial reactions with Li-metal. While in PVDF-based CPEs, ≈8wt.% DMF is confined by LiTFSI owing to a stronger interaction of LiTFSI with DMF than with PVDF. Short-term stable interface with Li-metal can be obtained, but longer-term cycling or higher current density leads to the gradually aggravated reactions with Li-metal. Thanks to the high-voltage stability of PVDF based CPEs, better cycling performance is obtained when they are used as catholytes to match high-voltage cathodes.     

Molecular-level Designed Polymer Electrolyte for High-Voltage Lithium–Metal Solid-State Batteries

In solid polymer electrolytes (SPEs) based Li–metal batteries, the inhomogeneous migration of dual-ion in the cell results in large concentration polarization and reduces interfacial stability during cycling. A special molecular-level designed polymer electrolyte (MDPE) is proposed by embedding a special functional group (4-vinylbenzotrifluoride) in the polycarbonate base. In MDPE, the polymer matrix obtained by copolymerization of vinylidene carbonate and 4-vinylbenzotrifluoride is coupled with the anion of lithium-salt by hydrogen bonding and the “σ-hole” effect of the C F bond. This intermolecular interaction limits the migration of the anion and increases the ionic transfer number of MDPE (t_Li⁺ = 0.76). The mechanisms of the enhanced t_Li⁺ of MDPE are profoundly understood by conducting first-principles density functional theory calculation. Furthermore, MDPE has an electrochemical stability window (4.9 V) and excellent electrochemical stability with Li–metal due to the CO group and trifluoromethylbenzene (ph-CF₃) of the polymer matrix. Benefited from these merits, LiNi_0.8Co_0.1Mn_0.1O₂-based solid-state cells with the MDPE as both the electrolyte host and electrode binder exhibit good rate and cycling performance. This study demonstrates that polymer electrolytes designed at the molecular level can provide a broader platform for the high-performance design needs of lithium batteries.     

Toward Forty Thousand-Cycle Aqueous Zinc-Iodine Battery: Simultaneously Inhibiting Polyiodides Shuttle and Stabilizing Zinc Anode through a Suspension Electrolyte

Aqueous zinc-iodine (Zn-I₂) batteries are promising candidates for grid-scale energy storage due to their safety and cost-effectiveness. However, the shuttle effect of polyiodides, Zn corrosion, and accumulation of by-products restrict their applications. Herein, a simple vermiculite nanosheets (VS) suspension electrolyte is designed for simultaneous confinement of polyiodides and stabilization of Zn anode. It is found that the generation of I₅⁻ as dominant intermediate and the precipitation reaction between I₅⁻ and alkaline by-products should cause irreversible iodine species loss. Benefiting from the high binding energy between polyiodides and silica-oxygen bonds of VS, dissolved polyiodides are effectively anchored on the surface of VS suspended in the bulk electrolyte to suppress the shuttle effect, which is confirmed by in situ Raman, Ultraviolet-visible characterizations and theoretical calculations. Furthermore, the self-assembly VS interfacial layer on the surface of Zn anode hinders side reactions induced by polyiodides. Meanwhile, the interlayer and surface excess negative charges of VS tend to be compensated by Zn²⁺ from diffuse layer, which serves as ion accelerators for transferring Zn²⁺ at the interface immediately, rendering dendrite-free Zn plating/stripping behavior. Consequently, the Zn-I₂ battery with VS electrolyte achieves an ultra-long lifespan of 40000 cycles with a negligible capacity decay at 20 C.     

Fluorinated Bifunctional Solid Polymer Electrolyte Synthesized under Visible Light for Stable Lithium Deposition and Dendrite-Free All-Solid-State Batteries

Solid polymer electrolytes (SPEs) that can offer flexible processability, highly tunable chemical functionality, and cost effectiveness are regarded as attractive alternatives for liquid electrolytes (LE) to address their safety and energy density limitations. However, it remains a great challenge for SPEs to stabilize Li⁺ deposition at the electrolyte–electrode interface and impede lithium dendrite proliferation compared with LE-based systems. Herein, a design of solid-state fluorinated bifunctional SPE (FB-SPE) that covalently tethers fluorinated chains with polyether-based segments is proposed and synthesized via photo-controlled radical polymerization (photo-CRP). In contrast to the conventional non-fluorinated polyether-derived SPEs, FB-SPE is able to provide conducting Li⁺ transport pathways up to ≈5.0 V, while simultaneously forming a Li F interaction that can enhance Li anode compatibility and prevent Li dendrites growth. As a result, the FB-SPE exhibits outstanding cycling stability in Li||Li symmetrical cells of over 1500 operating hours at as high current density as 0.2 mA cm⁻². A thin and uniform Li deposition layer and LiF-rich SEI at the surface of Li anode are found, and stable cycling with average coulombic efficiencies of 99% is demonstrated in Li||LFP and Li||NCM all-solid-state batteries based on such bifunctional fluorinated SPEs. The interesting fluorine effect and effective self-suppression of lithium dendrites will inform rational molecular design of novel electrolytes and practical development of all-solid-state Li metal batteries.     

A New Lithium‐Ion Conductor LiTaSiO5: Theoretical Prediction,Materials Synthesis,and Ionic Conductivity

Owing to the nonleakage and incombustibility, solid electrolytes are crucial for solving the safety issues of rechargeable lithium batteries. In this work, a new class of solid electrolyte, acceptor‐doped LiTaSiO₅, is designed and synthesized based on the concerted migration mechanism. When Zr⁴⁺ is doped to the Ta⁵⁺ sites in LiTaSiO₅, the high‐energy lattice sites are partly occupied by the introduced lithium ions, and the lithium ions at those sites interact with the lithium ions placed in the low‐energy sites, thereby favoring the concerted motion of lithium ions and lowering the energy barrier for ion transport. Therefore, the concerted migration of lithium ions occurs in Zr‐doped LiTaSiO₅, and a 3D lithium‐ion diffusion network is established with quasi‐1D chains connected through interchain channels. The lithium‐ion occupation, as revealed by ab initio calculations, is validated by neutron powder diffraction. Zr‐doped LiTaSiO₅ electrolytes are successfully synthesized; Li_1.1Ta_0.9Zr_0.1SiO₅ shows a conductivity of 2.97 × 10^?5 S cm^?1 at 25 °C, about two orders of magnitude higher than that of LiTaSiO₅, and it increases to 3.11 × 10^?4 S cm^?1 at 100 °C. This work demonstrates the power of theory in designing new materials.     

Nitrate Additives Coordinated with Crown Ether Stabilize Lithium Metal Anodes in Carbonate Electrolyte

Lithium metal anodes (LMAs) are promising for next-generation batteries but have poor compatibility with the widely used carbonate-based electrolytes, which is a major reason for their severe dendrite growth and low Coulombic efficiency (CE). A nitrate additive to the electrolyte is an effective solution, but its low solubility in carbonates is a problem that can be solved using a crown ether, as reported. A rubidium nitrate additive coordinated with 18-crown-6 crown ether stabilizes the LMA in a carbonate electrolyte. The coordination promotes the dissolution of NO₃⁻ ions and helps form a dense solid electrolyte interface that is Li₃N-rich which guides uniform Li deposition. In addition, the Rb (18-crown-6)⁺ complexes are adsorbed on the dendrite tips, shielding them from Li deposition on the dendrite tips. A high CE of 97.1% is achieved with a capacity of 1 mAh cm⁻² in a half cell, much higher than when using the additive-free electrolyte (92.2%). Such an additive is very compatible with a nickel-rich ternary cathode at a high voltage, and the assembled full battery with a cathode material loading up to 10 mg cm⁻² shows an average CE of 99.8% over 200 cycles, indicating a potential for practical use.     

Stable Light-Emitting Electrochemical Cells Using Hyperbranched Polymer Electrolyte

The choice of an adequate electrolyte is a fundamental aspect in polymer light-emitting electrochemical cells (PLECs) as it provides the in situ electrochemical doping and influences the performance of these devices. In this study, a hyperbranched polymer (Hybrane DEO750 8500) blended with a Li salt is used as a novel electrolyte in state-of-the-art Super Yellow (a polyphenylenevinylene) based LECs. Due to the desirable properties of the hyperbranched polymer and the homogeneous and smooth films that it forms with the emitting polymer, PLEC with excellent electroluminescent properties are obtained using a pulsed current bias scheme. The devices are very stable, with lifetimes in excess of 2000 h with initial luminance values above 450 cd m⁻², a peak efficiency of 12.6 lm W⁻¹, and sub-minute turn-on times. The stability of the devices is also studied by measuring the photoluminescence (PL) of the semiconductor during electroluminescent operation. The findings suggest that it is possible to observe the quenching of the PL in vertically stacked devices due to the advancement of the doped fronts in the film and an immediate PL recovery when the bias is removed.     

Ultra-Thin Single-Particle-Layer Sodium Beta-Alumina-Based Composite Polymer Electrolyte Membrane for Sodium-Metal Batteries

Inorganic/organic composite polymer electrolytes (CPEs) with good flexibility and electrode contact have been pursued for solid−state sodium-metal batteries. However, the application of CPEs for high energy density solid−state sodium-metal batteries is still limited by the low Na⁺ conductivity, large thickness, and low ion transference number. Herein, an ultra-thin single-particle-layer (UTSPL) composite polymer electrolyte membrane with a thickness of ≈20 µm straddled by a sodium beta−alumina ceramic electrolyte (SBACE) is presented. A ceramic Na⁺-ion electrolyte that bridges or percolates across an ultra-thin and flexible polymer membrane provides: 1) the strength and flexibility from the polymer membrane, 2) excellent electrolyte/electrode interfacial contact, and 3) a percolation path for Na⁺-ion transfer. Owing to this novel design, the obtained UTSPL-35SBACE membrane exhibits a high Na⁺-ion conductivity of 0.19 mS cm⁻¹ and a transference number of 0.91 at room temperature, contributing to long−term cycling stability of symmetric sodium cells with a small overpotential. The assembled quasi-solid-state cell with the as−prepared UTSPL-35SBACE membrane displays superior cycling performance with a discharge capacity of 105 mAh g⁻¹ at 0.5 °C rate after 100 cycles and excellent rate performance (82 mAh g⁻¹ at 5 °C rate) at room temperature with the potassium manganese hexacyanoferrate (KMHCF)@CNTs/CNFs cathode, where KMHCF refers to potassium manganese hexacyanoferrate.