A quasi-solid-state lithium battery is assembled by plasma sprayed amorphous Li₄Ti₅O₁₂(LTO) electrode and ceramic/polymer composite electrolyte with a little liquid electrolyte (10 µL/cm²) to provide the outstanding electrochemical stability and better normal interface contact. Scanning Electron Microscope (SEM), Scanning Transmission Electron Microscopy (STEM), Transmission Electron Microscopy (TEM), and Energy Dispersive Spectrometer (EDS) were used to analyze the structural evolution and performance of plasma sprayed amorphous LTO electrode and ceramic/polymer composite electrolyte before and after electrochemical experiments. By comparing the electrochemical performance of the amorphous LTO electrode and the traditional LTO electrode, the electrochemical behavior of different electrodes is studied. The results show that plasma spraying can prepare an amorphous LTO electrode coating of about 8 µm. After 200 electrochemical cycles, the structure of the electrode evolved, and the inside of the electrode fractured and cracks expanded, because of recrystallization at the interface between the rich fluorine compounds and the amorphous LTO electrode. Similarly, the ceramic/polymer composite electrolyte has undergone structural evolution after 200 test cycles. The electrochemical cycle results show that the cycle stability, capacity retention rate, coulomb efficiency, and internal impedance of amorphous LTO electrode are better than traditional LTO electrode. This innovative and facile quasi-solid-state strategy is aimed to promote the intrinsic safety and stability of working lithium battery, shedding light on the development of next-generation high-performance solid-state lithium batteries.

As the core of modern energy technology, lithium-ion batteries (LIBs) have been widely integrated into many key areas, especially in the automotive industry, particularly represented by electric vehicles (EVs). The spread of LIBs has contributed to the sustainable development of societies, especially in the promotion of green transportation. However, the high demand for battery performance and safety in these fields has made the high viscosity, volatility, and potential leakage inherent in traditional organic liquid electrolytes a constraint on their further expansion. Especially at low temperature, the increased viscosity of the electrolyte, reduced solubility of lithium salts, crystallization or solidification of the electrolyte, increased resistance to charge transfer due to interfacial by-products, and short-circuiting due to the growth of anode lithium dendrites all affect the performance and safety of LIBs. Therefore, improving the safety performance of LIBs under low-temperature environments has become a focus of current research. This paper primarily reviews the progress made in utilizing different types of electrolytes in LIBs to enhance safety and optimize low temperature performance and discusses the current research progress as well as the future development direction of the field.

Solid-state electrolytes are widely expected to enhance the performance of lithium-ion batteries, providing higher energy density and improved safety. However, challenges still need to be solved in their practical application due to low ionic conductivity and high interfacial resistance at room temperature. In this study, we successfully developed a high-performance gel polymer electrolyte (GPEs) by blending poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP) and polyacrylonitrile (PAN) through UV curing, cross-linking with ethoxylated trimethylolpropane triacrylate (ETPTA), and incorporating Li_6.4La₃Zr_1.4Ta_0.6O₁₂ (LLZTO). At room temperature, the ionic conductivity of the GPEs was 2.8 × 10⁻⁴ S/cm, with a lithium-ion transference number of 0.6. Moreover, during lithium plating/stripping tests, the assembled Li/PPEL/Li symmetric cell exhibited stable cycling for up to 600 h at a current density of 0.1 mA/cm². Notably, the GPEs enabled the LiFePO₄/GPEs/Li battery to achieve excellent performance, delivering high discharge capacities at room temperature (164.3 mAh g⁻¹ at 0.1 C and 88.8 mAh g⁻¹ at 1 C), with a capacity retention of 89.4% after 200 cycles at 0.5 C. Therefore, solid-state batteries using this electrolyte exhibit excellent performance, including adequate capacity and cycling stability.

Gel electrolytes for lithium-ion batteries continue to replace the organic liquid electrolytes in conventional batteries due to their advantages of being less prone to leakage and non-explosive and possessing a high modulus of elasticity. However, the development of gel electrolytes has been hindered by their generally low ionic conductivity at room temperature and high interfacial impedance with electrodes. In this paper, a poly (vinylidene fluoride)-hexafluoropropylene copolymer (PVdF-HFP) with a flexible structure, Li₆PS₅Cl (LPSCl) powder of the sulfur–silver–germanium ore type, and lithium perchlorate salt (LiClO₄) were prepared into sulfide gel composite electrolyte films (GCEs) via a thermosetting process. The experimental results showed that the gel composite electrolyte with 1% LPSCl in the PVdF-HFP matrix exhibited an ionic conductivity as high as 1.27 × 10⁻³ S·cm⁻¹ at 25 °C and a lithium ion transference number of 0.63. The assembled LiFePO₄||GCEs||Li batteries have excellent rate (130 mAh·g⁻¹ at 1 C and 54 mAh·g⁻¹ at 5 C) and cycling (capacity retention was 93% after 100 cycles at 0.1 C and 80% after 150 cycles at 0.2 C) performance. This work provides new methods and strategies for the design and fabrication of solid-state batteries with high ionic conductivity and high specific energy.

Lithium-ion batteries have garnered significant attention owing to their exceptional energy density, extended lifespan, rapid charging capabilities, eco-friendly characteristics, and extensive application potential. These remarkable features establish them as a critical focus for advancing next-generation battery technologies. However, the commonly used organic liquid electrolytes in batteries are explosive, volatile, and possess specific toxic properties, resulting in persistent safety concerns that remain to be addressed. Composite polymer electrolytes (CPEs) exhibit enhanced safety and stable electrochemical performance, emerging as one of the most promising alternatives. However, single polymers often need to meet the multifaceted performance requirements of batteries. In this study, a composite polymer electrolyte was prepared using solution casting, consisting of a blend of polyurethane (TPU) and polyacrylonitrile (PAN), along with the ceramic filler Li_1.3Al_0.3Ti_1.7(PO₄)₃ (LATP) and lithium perchlorate (LiClO₄). The optimal formulation, which included 40 wt% TPU, 60 wt% PAN, and 10 wt% LATP, exhibited a commendable ionic conductivity of 2.1 × 10⁻⁴ S cm⁻¹, a lithium-ion transference number (t_Li⁺) of 0.60, and notable electrochemical stability at 30 °C. The LiFePO₄/Li battery assembled with this CPE demonstrated excellent cycling stability and rate capability at room temperature. It delivered a discharge specific capacity of 130 mAh g⁻¹ at 1C. Under a charge–discharge rate of 0.2C, the battery achieved a discharge specific capacity of 168 mAh g⁻¹, retaining 98% of its capacity after 100 cycles at 25 °C. Additionally, the CPE exhibited robust safety performance. Consequently, this composite polymer electrolyte holds significant promise for application in lithium-ion batteries.

Poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP)-based gel polymer electrolytes (GPEs) are considered a promising electrolyte candidate for polymer lithium-ion batteries (LIBs) because of their free-standing shape, versatility, security, flexibility, lightweight, reliability, and so on. However, due to problems such as low ionic conductivity, PVDF-HFP can only be used on a small scale when used as a substrate alone. To overcome the above shortcomings, GPEs were designed and synthesized by a UV curing process by adding NASICON-type Li_1.5Al_0.5Ge_1.5(PO₄)₃ (LAGP) and garnet-type Li_6.46La₃Zr_1.46Ta_0.54O₁₂ (LLZTO) to PVDF-HFP. Experimentally, GPEs with 10% weight LLZTO in a PVDF-HFP matrix had an ionic conductivity of up to 3 × 10⁻⁴ S cm⁻¹ at 25 °C. When assembled into LiFePO₄/GPEs/Li batteries, a discharge-specific capacity of 81.5 mAh g⁻¹ at a current density of 1 C and a capacity retention rate of 98.1% after 100 cycles at a current density of 0.2 C occurred. Therefore, GPEs added to LLZTO have a broad application prospect regarding rechargeable lithium-ion batteries.