Due to higher energy density, high-voltage all-solid-state lithium batteries (ASSLBs) have attracted increasing attention. However, they require solid-state electrolytes (SSEs) with wide electrochemical stability windows (ESW, typically >4.2 V) and high-stability against the Li anode. Nevertheless, poly(ethylene oxide) (PEO), the most widely used solid polymer electrolyte (SPE), can’t tolerate a high-voltage over 4 V. Whether the main chain (–C–O–C–) or the terminal hydroxide group (–OH) is the limiting factor for the narrow ESW remains unknown. Herein, poly(ethylene glycol) (PEG) and poly(ethylene glycol)dimethyl ether (PEGDME) with different terminal groups are selected to answer this question. The results show that the reactive terminal –OH group is the limiting factor towards applicability against high voltage and the Li anode. Replacing –OH with more stable –OCH₃ can significantly extend the ESW from 4.05 to 4.3 V, while improving the Li-anode compatibility as well (Li–Li symmetric cells stably run for 2500 h at 0.2 mA cm⁻²). Its practical application is further proved by developing PEGDME-based ASSLB pouch cells. The 0.53 mA cm⁻² Li–LiFePO₄ and 0.47 mA h cm⁻² Li–LiNi_0.5Mn_0.3Co_0.2O₂ cells demonstrated high capacity retention of 97% and 90% after 210 cycles and 110 cycles, respectively. This work offers a new strategy for PEO-based high-voltage ASSLB development by changing the unstable terminal groups.

Solid-state lithium–sulfur batteries (SSLSBs) with high energy densities and high safety have been considered among the most promising energy storage devices to meet the demanding market requirements for electric vehicles. However, critical challenges such as lithium polysulfide shuttling effects, mismatched interfaces, Li dendrite growth, and the gap between fundamental research and practical applications still hinder the commercialization of SSLSBs. This review aims to combine the fundamental and engineering perspectives to seek rational design parameters for practical SSLSBs. The working principles, constituent components, and practical challenges of SSLSBs are reviewed. Recent progress and approaches to understand the interfacial challenges via advanced characterization techniques and density functional theory (DFT) calculations are summarized and discussed. A series of design parameters including sulfur loading, electrolyte thickness, discharge capacity, discharge voltage, and cathode sulfur content are systematically analyzed to study their influence on the gravimetric and volumetric energy densities of SSLSB pouch cells. The advantages and disadvantages of recently reported SSLSBs are discussed, and potential strategies are provided to address the shortcomings. Finally, potential future directions and prospects in SSLSB engineering are examined.

Lithium–sulfur (Li–S) batteries have been considered as one of the most promising energy storage devices that have the potential to deliver energy densities that supersede that of state-of-the-art lithium ion batteries. Due to their high theoretical energy density and cost-effectiveness, Li–S batteries have received great attention and have made great progress in the last few years. However, the insurmountable gap between fundamental research and practical application is still a major stumbling block that has hindered the commercialization of Li–S batteries. This review provides insight from an engineering point of view to discuss the reasonable structural design and parameters for the application of Li–S batteries. Firstly, a systematic analysis of various parameters (sulfur loading, electrolyte/sulfur (E/S) ratio, discharge capacity, discharge voltage, Li excess percentage, sulfur content, etc.) that influence the gravimetric energy density, volumetric energy density and cost is investigated. Through comparing and analyzing the statistical information collected from recent Li–S publications to find the shortcomings of Li–S technology, we supply potential strategies aimed at addressing the major issues that are still needed to be overcome. Finally, potential future directions and prospects in the engineering of Li–S batteries are discussed.Graphical