Theoretical Energy Density Research Articles

Operando Optical Imaging of Cathode Swelling Process Inside Lithium Primary Batteries: Comparative Studies between Different Structured CFx.

As a crucial cathode material with ultrahigh theoretical capacity (865 mAh/g) and energy density (>2100 Wh/kg), fluorinated carbon (CFx) is promising for lithium primary batteries. However, the operating performance of CFx cathode is hindered by nonuniform volume expansion during discharging. To investigate this, we used operando confocal microscopy to visualize the thickness evolution of two different CFx cathodes and quantified their swelling ratios as a function of the discharge depth. Our findings show that CFx synthesized from hard carbon (FHC), featuring a disordered structure and abundant pores, exhibits a swelling ratio lower than that of conventional layered fluorinated graphite (FG). This is due to different electrochemical mechanisms: lithium enters FG interlayers nonuniformly through "edge propagation" pathways while lithiation occurs homogeneously in FHC, unraveled by single-particle Raman and photoluminescence measurement. This work enhances our understanding on CFx volume expansion, offering important opportunities to address the cathode swelling issue and optimize electrochemical performance in Li/CFx batteries.

Thermochemical energy storage with the solid-gas reaction of SrCO3 improved with CaCO3

Abstract In the context of thermochemical energy storage (TCES) for concentrating solar power (CSP) applications, metal carbonates’ reversible calcination and carbonation are gaining prominence, particularly in the SrCO3/SrO system. This system is notable for its high theoretical energy density of 10.61 GJ/m³ and operational temperatures up to 1,200 °C. However, like the CaCO3/CaO system, SrO experiences a significant drop in reactivity during cycling due to sintering and agglomeration of particles. In this work is proposed that the conversion effective will be improved by mixing the strontium carbonate with calcium carbonate. The best mix found was 80/20 SrCO3/CaCO3 with the operating parameters of calcination-carbonation temperatures of 1,200 °C and 900 °C, respectively. This reaction has a notably better stable conversion rate than pure strontium carbonate. The study was carried out using thermogravimetry analysis. The mixture was subjected to 9 cycles, and for the ninth cycle, there was an effective conversion of 33.14 %, which, compared to pure SrCO3, was 2.33 %; that was improved noticeably during the carbonation process. There was an increase in the percentage effective conversion of 30.81 %. Volumetric energy density was reduced from 6.93 to 2.81 GJ/m3 in the first and after nine cycles. The XRD analysis of the unprocessed mixture after 4 and 9 cycles showed no formation of new or secondary compounds, only the expected compounds: SrO, SrCO3, CaO, and CaCO3. This important change is explained during the carbonation looping because the CaO remains encapsulated in the SrCO3 and does not react completely at 900 °C. As a hypothesis, this encapsulation delays the sintering of the SrCO3. Using a T carb = 850 °C promotes the carbonation of CaO. By promoting CaO to react, the CaO encapsulated is released rapidly, and the material was sintering faster than the T carb = 900 °C. Comparing the seventh cycle at a T carb = 900 and 850 °C, it is observed that the effective conversion decreases from 0.4431 to 0.4202 and, in the same proportion, the volumetric energy density.

Non‐Aqueous Liquid Electrolytes for Li‐O2 Batteries

AbstractLi‐O2 batteries (LOBs) have become a research hotspot of energy storage devices because of its high theoretical energy density. Practical applications require that non‐aqueous LOBs can deliver stable and high reversible capacity, which heavily depends on the appropriate electrolyte system. Therefore, it is very important to select electrolytes that are hard to decompose and conducive to modulating the growth kinetics of discharge products. Herein, we will review the current progress and challenges of non‐aqueous liquid electrolytes for LOBs by analyzing the influence factors on electrolyte stability and introducing the design and modification methods of electrolytes with different solvent types. At last, the possible research tactics have been proposed to develop advanced electrolytes for improving electrochemical performance of LOBs.

Accelerated Ion-Electron Transport in Bi-Heterostructures Constructed Based on Ohmic Contacts for Efficient Bi-Directional Catalysis of Lithium-Sulfur Batteries.

Although lithium-sulfur batteries have satisfactory theoretical specific capacity and energy density, they are difficult to further commercialize due to the shuttle effect of soluble polysulfides and slow sulfur oxidation kinetics. Based on this, in this work, the catalyst MXene-VS4-SnS2 (MVS), a dual heterostructured catalyst with ohmic contacts, is prepared by a one-step hydrothermal method and electrostatic self-adsorption for lithium-sulfur battery cathode materials. Experimental and theoretical results show that the ohmic contact induces spontaneous charge rearrangement, resulting in the formation of a fast charge transfer pathway at the MVS heterojunction interface, which helps to reduce the energy barrier for polysulfide reduction and Li2S oxidation during the discharge/charge process. In addition, the inherent sulfophilicity of VS4 and SnS2 promotes the conversion of S species, while the pleated MXene nanosheets not only provide a highly conductive network for the active sulfur but also retain a rich internal space to maintain the integrity of the cathode structure during the continuous cycling process. As a result, the MVS cathode exhibits excellent electrochemical performance even under high sulfur loading. The integration of excellent performance with a facile synthesis process provides a promising approach for designing highly efficient electrocatalysts suitable for the energy field.

Theory‐Guided Design of Unconventional Phase Metal Heteronanostructures for Higher‐Rate Stable Li‐CO2 and Li‐Air Batteries

AbstractLithium‐carbon dioxide (Li‐CO2) and Li‐air batteries hold great potential in achieving carbon neutral given their ultrahigh theoretical energy density and eco‐friendly features. However, these Li‐gas batteries still suffer from low discharging‐charging rate and poor cycling life due to sluggish decomposition kinetics of discharge products especially Li2CO3. Here we report the theory‐guided design and preparation of unconventional phase metal heteronanostructures as cathode catalysts for high‐performance Li‐CO2/air batteries. The assembled Li‐CO2 cells with unconventional phase 4H/face‐centered cubic (fcc) ruthenium‐nickel heteronanostructures deliver a narrow discharge‐charge gap of 0.65 V, excellent rate capability and long‐term cycling stability over 200 cycles at 250 mA g−1. The constructed Li‐air batteries can steadily run for above 150 cycles in ambient air. Electrochemical mechanism studies reveal that 4H/fcc Ru−Ni with high‐electroactivity facets can boost redox reaction kinetics and tune discharge reactions towards Li2C2O4 path, alleviating electrolyte/catalyst failures induced by the aggressive singlet oxygen from solo decomposition of Li2CO3.

N, F Co-Doped Carbon Material Self-Supporting Cathode for High-Performance Lithium-Oxygen Batteries.

The Li-O2 battery has emerged as a promising energy storage system due to its exceptionally high theoretical energy density of 3500 Wh kg-1. However, the sluggish kinetics associated with the formation and decomposition of discharge product Li2O2 poses several challenges in Li-O2 batteries, including excessive over-potential, limited rate performance, and reduced actual specific energy. Consequently, the development of cost-effective cathode catalysts with enhanced catalytic activity and long-term stability represents a viable approach to address these challenges. In this study, commercial melamine foam is utilized as a precursor material which was subjected to pyrolysis at elevated temperatures with PVDF to synthesize N, F co-doped self-supporting carbon cathode (NF-NSC). Remarkably, thanks to the synergistic effects of N, F heteroatomic in conjunction with the inherent three-dimensional reticular porous structure, NF-NSC exhibited enhanced electrochemical performance when utilized in Li-O2 batteries. Specifically, the NF-NSC cathode demonstrated an impressive discharge specific capacity of up to 35204 mAh g-1 alongside a low over-potential (0.86 V) and excellent cycling stability (146 cycles).

Entropy‐Modulated Short‐Chain Cathode for Low‐Temperature All‐Solid‐State Li−S Batteries

AbstractAll‐solid‐state Li−S batteries (ASSLSBs) due to high theoretical energy density and exceptional safety are highly desirable for electric aircraft. However, as the flight altitude rises, the low‐temperature performance is hampered by inadequate practical capacity. Here, we discover that low‐temperature sulfur utilization is constrained by the multi‐step endothermic conversion reaction. By introducing multi‐chalcogen to modulate the local entropy, a short‐chain molecule cathode is designed to shorten the reduction pathways and enhance low‐temperature discharge capacity. Furthermore, the mismatched lithiation lattice of the short‐chain cathode reduces the decomposition energy barriers, thus enhancing low‐temperature charge/discharge reversibility. The designed short‐chain cathode exhibits high cathode utilization (99.4 %) and cycling stability (400 cycles, 92.2 % retention) at room temperature, as well as delivers excellent discharge capacity (579.6 mAh g−1, −40 °C) and cycling performance (100 cycles, 98.4 % retention, 394.9 Wh kg−1electrode, −20 °C) at low temperature. This study presents new opportunities to stimulate the development of low‐temperature ASSLSBs.

D‐Band Center Modulation of Metallic Co‐Incorporated Co7Fe3 Alloy Heterostructure for Regulating Polysulfides in Highly Efficient Lithium‐Sulfur Batteries

AbstractLithium‐sulfur (Li‐S) batteries, with their high theoretical energy density and cost‐effectiveness, have become one of the most promising next‐generation energy storage devices. However, they still face challenges such as the “shuttle effect” caused by the dissolution of polysulfide intermediates and the slow sulfur conversion kinetics. In this study, based on the Co7Fe3 alloy catalyst, additional Co metal is introduced to form a Co7Fe3Co catalyst with a heterostructure through a simple heat treatment process. This catalyst is incorporated into Ketjenblack (KB) to form a sulfur‐infused cathode material (designated as S/KB/Co7Fe3Co). Li‐S batteries using S/KB/Co7Fe3Co as the cathode demonstrate outstanding electrochemical performance, maintaining a reversible specific capacity of over 500 mAh g−1 after 1000 cycles at a current density of 1 C, with a capacity decay rate of 0.046% per cycle. DFT theoretical calculations and experimental results both reveal that the introduction of additional Co effectively regulates the d‐band center of the material, enhancing the adsorption of polysulfide intermediates by Co7Fe3Co and promoting bidirectional catalytic sulfur conversion. This work highlights the importance of the simple construction of heterostructured catalytic materials and their role in improving the performance of Li‐S batteries.

Engineering Electrolytes with Transition Metal Ions for the Rapid Sulfur Redox and In Situ Solidification of Polysulfides in Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries have been pursued due to their high theoretical energy density and superb cost-effectiveness. However, the dissolution-conversion mechanism of sulfur inevitably leads to shuttle effects and interface passivation issues, which impede Li-S battery practical application. Herein, the approach of adopting transition metal salts (CoI2) to engineering the electrolyte is proposed. Different from anchored transition metal catalysts in the cathode, soluble cobalt ions can chemically reduce and solidify polysulfides, alleviating the dependence of sulfur conversion on the conductive interface while suppressing the shuttle effect. Importantly, all elements in CoI2 are in the lowest valence state and solid complexes are formed after the redox reaction, which prevents the migration of high valent Co3+ to the anode, thus overcoming the poor compatibility between redox mediator and Li anode. Notably, I3- has the function of eliminating dead sulfur and dead lithium, which we apply to Li-S batteries. After activating I3- at a certain frequency, Li-S batteries indeed achieve a longer and more stable cycle life. By combining the regulatory behavior of anions and cations, the electrolyte is engineered for Li-S batteries with high capacity, long lifespan, and excellent rate performance.

Functional Separator with Poly(Acrylic Acid)-Enabled Li2CO3-Free Garnet Coating for Long-Cycling Lithium Metal Batteries.

Lithium metal batteries (LMBs) possess a theoretical energy density far surpassing that of commercial lithium-ion batteries (LIBs), positioning them as one of the most promising next-generation energy storage systems. Modifying separators with composite coatings comprising oxide solid-state electrolyte (SSE) particles and polymers can improve the cycling stability and safety of LMBs. However, exposure to air forms Li2CO3 on oxide SSE particles, diminishing their ion flux regulation at the electrode/electrolyte interface. Utilizing the reaction of Li2CO3 with polyacrylic acid (PAA) to form lithium polyacrylate (LiPAA), an ultra-thin composite coating on polyethylene (PE) separator with Li2CO3-free Li6.4La3Zr1.4Ta0.6O12 (LLZTO) particles and LiPAA binder is fabricated in one step. The exposed Li2CO3-free LLZTO surface increases the ionic conductivity and lithium ion (Li+) transference number of the functional separator, resulting in small resistance and uniform Li deposition of the Li metal anode. Consequently, the Li//LiCoO2 cell with the functional separator exhibits a significantly improved life of 980 cycles with 80.9% capacity retention under lean-electrolyte conditions. Both the Li//LiCoO2 coin cell and pouch cell using thin Li foil anode demonstrate good cycling stability and high mechanical robustness. This study provides a green and scalable approach for fabricating advanced separators for LMBs.

NiCo alloy-decorated nitrogen-doped carbon double-shelled hollow polyhedrons with abundant catalytic active sites to accelerate lithium polysulfides conversion

Lithium-sulfur (Li-S) batteries have received significant attention due to their high theoretical energy density. However, the inherent poor conductivity of S and lithium sulfide (Li2S), coupled with the detrimental shuttle effect induced by lithium polysulfides (LiPSs), impedes their commercialization. In this study, we develop NiCo alloy-decorated nitrogen-doped carbon double-shelled hollow polyhedrons (NC/NiCo DSHPs) as highly efficient catalysts for Li-S batteries. The distribution of NiCo alloy on both the inner and outer shells provides abundant catalytic active sites, effectively adsorbing LiPSs, mitigating the shuttle effect, and promoting the conversion between LiPSs and Li2S, even at high sulfur loadings. This results in enhanced redox kinetics within the Li-S system. Moreover, the highly conductive carbon material framework, enriched with carbon nanotubes and graphitic carbon layers, can greatly promote the efficient electron transportation. Additionally, the improved ion diffusion rates benefiting from the hollow structure can also be realized. By harnessing these synergistic effects, Li-S batteries incorporating the double-shelled NC/NiCo DSHP catalysts achieved a high specific capacity of 1310 mAh/g at 0.2C and a superior rate performance of 621 mAh/g at 4C. Furthermore, excellent cycling performance with ultralow capacity fading rate of only 0.045 % per cycle after 800 cycles at 1C was achieved. When sulfur loading reaches 6 mg cm−2, a high capacity of 4.6 mAh cm−2 at 0.1C after 100 cycles further validates the practical potential of this design. This study presents an innovative approach to alloy catalyst design, offering valuable insights for future research of Li-S batteries.

Interface engineering of heterostructural quantum dots towards high-rate and long-life lithium-sulfur full batteries

Despite being as next-generation energy storage systems with ultra-high theoretical energy density of 2600 Wh kg−1, lithium-sulfur (Li-S) batteries face serious hurdles due to the sluggish redox kinetics in S cathodes and uncontrollable growth of dendrites in Li anodes. To simultaneously address such issues, herein, we present an interface engineering strategy to develop a dual-functional host for S cathode and Li anode, which is constructed by heterostructural WC-WN0.67 quantum dots homogeneously embedded in N-doped graphene nanosheets (WC-WN0.67@NG). As a result, the Li-S full batteries deliver a high reversible capacity of 704 mA h g−1 even at a high rate of 4 C, and demonstrate a long-term cycling stability even at 2 C with a low degradation rate of 0.027 % over 1200 cycles. This work paves the way to facilitate the practical applications of Li-S batteries through interface engineering of dual-functional heterostructural quantum-dot host.

Cobalt nanoclusters Deposit on Nitrogen-Doped graphene Sheets as bifunctional electrocatalysts for high performance lithium – Oxygen batteries

Rechargeable lithium-oxygen (Li-O2) batteries are being considered as the next-generation energy storage systems due to their higher theoretical energy density. However, the practical application of Li-O2 batteries is hindered by slow kinetics and the formation of side products during the oxygen reduction and evolution reactions on the cathode. These reactions lead to high overpotentials during charging and discharging. To address these challenges, we propose a simple ultrasonic method for synthesizing cobalt nanoclusters embedded in nitrogen-doped graphene nanosheets (GrZnCo) derived from metal-organic frameworks (MOFs). The resulting material, due to the retention of metallic cobalt structure, exhibits better electronic conductivity. Additionally, the GrZnCo catalyst shows vigorous catalytic activity, which can improve reaction kinetics and suppress side reactions, thus lowering the charging overpotential. We have investigated the impact of different catalyst compositions (GrZnCox; x = 1, 3, 5) by varying the amounts of cobalt and zinc. The optimum catalyst, GrZnCo3, contains high cobalt-N active components, graphitic-N, pyridinic-N, pyrrolic-N, and abundant defect structures, which enhance the electrochemical performance. The defect-rich GrZnCo3 catalyst enables Li-O2 batteries to achieve a high discharge capacity of 13500 mAh·g−1 at 50 mA·g−1 and a remarkable long-term cycling performance of over 400 cycles at 100 mA·g−1 with a limited capacity of 500 mAh·g−1. This work demonstrates an effective approach to fabricate cost-effective electrocatalysts for various energy storage systems.

In Situ Synthesis of CoMoO4 Microsphere@rGO as a Matrix for High-Performance Li-S Batteries at Room and Low Temperatures.

Lithium-sulfur batteries (Li-S batteries) have attracted wide attention due to their high theoretical energy density and the low cost of sulfur cathode material. However, the poor conductivity of the sulfur cathode, the polysulfide shuttle effect, and the slow redox kinetics severely affect their cycling performance and Coulombic efficiencies, especially under low-temperature conditions, where these effects are more exacerbated. To address these issues, this study designs and synthesizes a microspherical cobalt molybdate@reduced graphene oxide (CoMoO4@rGO) composite material as the cathode material for Li-S batteries. By growing CoMoO4 nanoparticles on the rGO surface, the composite material not only provides a good conductive network but also significantly enhances the adsorption capacity to polysulfides, effectively suppressing the shuttle effect. After 100 cycles at room temperature with a current density of 1 C, the reversible specific capacity of the battery stabilizes at 805 mAh g-1. Notably, at -20 °C, the S/CoMoO4@rGO composite achieves a reversible specific capacity of 840 mAh g-1. This study demonstrates that the CoMoO4@rGO composite has significant advantages in suppressing polysulfide diffusion and expanding the working temperature range of Li-S batteries, showing great potential for applications in next-generation high-performance Li-S batteries.

Automated Robotic Cell Fabrication Technology for Stacked‐Type Lithium‐Oxygen Batteries

AbstractRechargeable lithium‐oxygen batteries (LOBs) are gaining interest as next‐generation energy storage devices due to their superior theoretical energy density. While recent years have seen successful operation of LOBs with high cell‐level energy density, the technology for cell fabrication is still in its infancy. This is because the cell fabrication procedure for LOBs is quite different from that of conventional lithium‐ion batteries. The study presents a fully automated sequential robotic experimental setup for the fabrication of stacked‐type LOB cells. This approach allows for high accuracy and high throughput fabrication of the cells. The developed system enables the fabrication of over 80 cells per day, which is 10 times higher than conventional human‐based experiments. In addition, the high alignment accuracy during the electrode stacking and electrolyte injection process results in improved battery performance and reproducibility. The effectiveness of the developed system was also confirmed by investigating a multi‐component electrolyte to maximize battery performance. We believe the methodology demonstrated in the present study is beneficial for accelerating the research and development of LOBs.

A Review on Architecting Rationally Designed Metal-Organic Frameworks for the Next-Generation Li-S Batteries.

The modern era demands the development of energy storage devices with high energy density and power density. There is no doubt that lithium‒sulfur batteries (Li‒S) claim high theoretical energy density and have attracted great attention from researchers, but fundamental exploration and practical applications cannot converge to utilize their maximum potential. The design parameters of Li-S batteries involve various complex mechanisms, and their obliviousness has resulted in failure at the commercial level. This article presents a review on rationally designed metal-organic frameworks (MOFs) for improving next-generation Li-S batteries. The use of MOFs in Li-S batteries is of great interest because of their large surface area, porous structure, and selective permeability for ions. The working principles of Li-S batteries, the commercialization of Li-S batteries, and the use of MOFs as electrodes, electrolytes, and separators are critically examined. Finally, designed strategies (host structure, binder improvement, separator modification, lithium metal protection, and electrolyte optimization) are developed to increase the performance of Li-S batteries.

Anode‐Free Solid‐State Rechargeable Batteries: Mechanisms, Challenges, and Design Strategies

Anode‐free solid‐state alkali metal batteries (AFSSAMBs) have emerged as promising high‐performance battery systems, attracting significant scientific interest due to their exceptional safety, high theoretical energy density, and cost‐effectiveness. Recently, extensive research efforts have focused on addressing the key issues impeding their practical deployment, primarily centered around severe dendrite growth, unstable electrolyte‐electrode interface, and low Coulombic efficiency. Despite this progress, a comprehensive framework for the fundamental understanding of AFSSAMBs is still lacking. This paper presents a comprehensive concept, outlining detailed construction, mechanisms, challenges, and strategies of AFSSAMBs. First, the basic configuration and internal mechanisms of AFSSAMBs are summarized. Subsequently, we discuss the existing challenges hindering the cycling lifespan of AFSSAMBs, offering several promising approaches to overcome these obstacles. In the end, insightful perspectives and viewpoints are briefly proposed on the further developments of AFSSAMBs.

Synergistic Interaction of Strongly Polar Zinc Selenide and Highly Conductive Carbon Nanoframeworks Accelerates Redox Kinetics of Polysulfides.

Lithium-sulfur batteries (LSBs) have become strong competitors in secondary battery systems because of their superior theoretical capacity and energy density. However, due to the serious shuttle effect of soluble long-chain lithium polysulfides (LiPSs) and the slow solid-solid reaction kinetics, LSBs face some specific challenges, such as a short cycle life and low rate performance. The introduction of selenide/carbon composites derived from zeolite imidazolate frameworks (ZIFs) into separator coatings is a direct and effective solution to the aforementioned problems. Here, a zinc selenide/carbon catalyst material (ZnSe@C) was constructed and employed to modify commercial polypropylene (PP) separators to accelerate the conversion of intermediates. The highly polar ZnSe effectively fixes the active material on the cathode side by transferring electrons between elements with LiPSs and improves the utilization rate of sulfur. Concurrently, the highly conductive carbon nanoskeleton generated following the pyrolysis of ZIF-8 ensures the rapid transfer of charges during the catalytic reaction. The prepared ZnSe@C has a large specific surface area (250.07 m2 g-1) and mesoporous ratio (78.03%), which not only enhances adsorption and catalysis but also promotes the penetration of the electrolyte and the transport of Li+. Based on this, ZnSe@C/PP separator cells exhibit a low average capacity decay rate of 0.051% per cycle after 500 cycles at 1 C.

A Bandgap‐Tuned Tetragonal Perovskite as Zero‐Strain Anode for Potassium‐Ion Batteries

AbstractPIBs are emerging as a promising energy storage system due to high abundance of potassium resources and theoretical energy density, however, progress of PIBs is severely hindered by structural instability and poor cycling of anode material during continual insertion and extraction of larger‐sized K+. Hence, developing anode material with structural stability and stable cycling remains a great challenge. Herein, band gap‐tuned Mo‐doped and carbon‐coated lead titanate (CMPTO) with zero‐strain K+ storage is presented as ultra‐stable PIBs anode. Mo doping introduces narrowed band gap and optimized crystal lattice for enhanced intrinsic electron and ion transfer. Demonstrated by in situ XRD characterizations, the crystal structure stays stable with unchanged peak positions, fully revealing zero‐strain characteristic of CMPTO anode during potassium storage for stable cyclic capability. Ultimately, CMPTO anode achieved ultra‐stable cycling performance of 7000 cycles at 500 mA g−1 with high capacity retention of 90 % and considerable specific capacity of 130.9 mAh g−1 after 600 cycles at 100 mA g−1; with relatively large density, CMPTO realized eminent volumetric capacity of 1111.09 mAh cm−3 and ultra‐long cycling life of 10000 cycles at 7041 mA cm−3. This work introduces a promisingly new route into developing anode materials with ultra‐stable performance for PIBs.

Review on polymer electrolytes for lithium‐sulfurized polyacrylonitrile batteries

AbstractLithium‐sulfur (Li‐S) batteries are deemed as the next generation of energy storage devices due to high theoretical specific capacity (1675 mAh g−1) and energy density (2600 Wh kg−1). However, the commercial application has always been constrained by lithium polysulfide (LiPSs) shuttling effects and still has a long way to go. Sulfurized polyacrylonitrile (SPAN) is a promising alternative candidate to replace traditional sulfur cathode and is conducive to eliminating LiPSs by realizing “solid‐solid” direct conversion in conventional carbonate electrolytes. However, an over 25% irreversible capacity loss is exhibited inevitably in the first discharge process, the inherent structure of SPAN and the related reaction mechanism remain unclear. In this review, the structure characteristics and electrochemical behaviors of SPAN are summarized for better interpreting current knowledge and favoring the design of high performance materials. In the past few decades, many problems in traditional Li‐S batteries have been solved by improving electrolytes. Polymer electrolytes (PEs) have been widely used due to structural designability, multi‐functionality, exceptional chemical stability, and excellent processability. Surprisingly, the relevant researches on PEs compatible with SPAN remains limited currently. Therefore, the recent modification strategies of gel polymer electrolytes and solid polymer electrolytes in Li‐SPAN batteries are introduced in terms of Li+ transfer and interface engineering, the design principles are concluded, the specific challenges encountered by polymer‐based electrolytes are summarized and the instructive directions for future research on PEs are demonstrated, facilitating the commercialization of Li‐SPAN batteries.