High Working Voltage Research Articles

A new zinc-ion battery cathode with high-performance: Loofah-like lanthanum manganese perovskite

Due to high safety and excellent rate performance, the aqueous Zn-ion battery is a promising energy storage battery for practical application. However, most manganese-based compounds suffer from poor cycling and rate performance. Herein, a new concept of Zn-ions battery is assembled with the loofah-like LaMnO3 perovskite as a novel cathode, achieving fast ion kinetics through the co-intercalation of Zn2+ and H+ cations. In this work, the Ni-doping strategy is adopted to improve the electrochemical performance of LaMnO3 perovskite as a cathode material for Zn-ion batteries. The resultant LaNixMn1-xO3 (x = 0.2) exhibits a superior capacity of 226 mAh g−1 after 80 cycles at 100 mA g−1 and high working voltages at 1.4 V and 1.26 V vs. Zn2+/Zn in the electrolyte of 2 M ZnSO4 + 0.2 M MnSO4. Even at 500 mA g−1, the new Zn/LaNixMn1-xO3 battery still delivers a discharge capacity of 113 mAh g−1 after 1000 cycles. At medium current density, the electrochemical process of the LaNixMn1-xO3 (x = 0.2) electrode is co-controlled by the solid diffusive and surface-capacitive process with a fast ion diffusion rate. The lanthanum manganese perovskite is a potential cathode material for Zn-ion batteries with long cycle performance and high rate cyclability. This work significantly opens up the way of perovskite materials as new cathodes for high-rate ZIBs.

Recent Progress and Perspectives on Alloying Anodes for Potassium‐Ion Batteries

AbstractPotassium‐ion batteries (PIBs) have been regarded as one of promising alternatives to lithium‐ion batteries (LIBs) due to the wide distribution, low‐cost potassium resources and high working voltage. Anode materials play a vital role in the future development of PIBs. Among the various anode materials, alloying anodes such as tin, antimony, phosphorus, bismuth and silicon show promising future and attracted wide attention owning to their wide distributed resources, favorable working voltage, and theoretically high capacities. However, the severe volume expansion during potassiation/depotassiation leads to pulverization and exfoliation from the current collector, resulting in capacity decay of PIBs. Efficient approaches, such as micro‐/nanostructures designing, carbon coating, and optimizing the interface between electrode and electrolyte have been utilized to solve these issues. In the present review, the research progress on alloying anode materials in PIBs is summarized. Considering the synthesis strategies, battery performance, battery working mechanisms, and structure‐performance relationships of these materials, the challenges and future development directions of alloying anode materials are suggested. Herein, we will provide an outlook for the development of high‐performance alloy‐based anode materials for PIBs and also indicate the future direction of electrode materials in PIBs.

An integrated surface coating strategy to enhance the electrochemical performance of nickel-rich layered cathodes

High-nickel layered oxides, LiNixCoyMnzO2 (0.6 ≤ x < 1), are promising cathode materials for producing batteries with high energy density and working voltage, while their poor cycling performance severely limits their commercial applications. Herein, an integrated surface coating/doping strategy is developed to significantly improve the structural stability and electrochemical performance of LiNi0.88Co0.06Mn0.06O2. The titanium ions from a thin TiNb2O7 coating layer diffuse inward during the high-temperature sintering process and a uniform protective layer forms on the surface of the secondary particles of the material. This protective layer suppresses side reactions, and the Ti4+ doping increases the thickness of the lithium layer and reduces the lithium/nickel mixing, thereby enhancing the diffusion of lithium ions in bulk electrode. The capacity retention of modified material after 200 cycles at 1 C is greatly improved from 59.8% of the pristine material to 87.2%. First-principles calculations confirm the interaction affinity of the TiNb2O7 coating on the layered LiNi0.88Co0.06Mn0.06O2 with Ti ion migration in the interlayer region. Moreover, the enhanced oxygen release energy and electronic conductivity benefiting from Ti4+ doping promote the cycling stability of the integrated cathode. The surface engineering strategy proposed herein is generally effective for the electrochemical improvement of nickel-rich ternary cathode materials.

Organic-inorganic hybrid electrode engineering for high-performance asymmetric supercapacitor based on WO3-CeO2 nanowires with oxygen vacancies

Although WO3 with high theoretical capacitance has a future in the field of energy storage, its electrode processing to obtain high capacitance is still a challenge. Here, we propose an innovative electrode structure design by utilizing PEDOT and PEDOT:PSS to sequentially assemble with the oxygen vacancies-enriched WO3 and WO3-CeO2 hybrid nanowires on the glassy carbon (GC). As-prepared PEDOT:PSS/WO3/PEDOT/GC and PEDOT:PSS/WO3-CeO2/PEDOT/GC electrodes show high areal capacitance of 1139.6 and 1310 mF cm−2 at 2 mA cm−2, respectively, greater than 822.3 mF cm−2 of the WO3-PTFE-C/GC. The asymmetric supercapacitor based on PEDOT:PSS/WO3-CeO2/PEDOT and PEDOT:PSS/RuO2/PEDOT electrodes works at 1.6 V high working voltage, delivers an energy density of 0.61 Wh m−2 at power density of 8.22 W m−2. Therefore, the electrode structure design will be suitable to improve the capacitance performance of other low-conductivity active materials.

Single‐crystalline Ni‐rich LiNi 0 . 91 Co 0 . 06 Mn 0 . 03 O 2 cathode enables durable interfacial stability for high electrochemical performances

Despite the commercialization and tremendous attention of the Ni-rich LiNiCoMnO2 cathode due to high energy and working voltage, there are still hurdles to be improved. The conventional polycrystalline Ni-rich LiNiCoMnO2 suffers from decays of specific capacity and energy during long-term cycling. It originates from more deficiency of oxygen and microcracking, resulting in severe phase transition toward disordered rock salt phase. Herein, single-crystalline Ni-rich LiNi0.91Co0.06Mn0.03O2 is successfully prepared to overcome these inherent drawbacks of polycrystalline. Benefiting from reduced specific surface area and grain boundaries, single-crystalline Ni-rich LiNi0.91Co0.06Mn0.03O2 outperforms polycrystalline in all electrochemical performances. The single-crystalline LiNi0.91Co0.06Mn0.03O2 exhibits not only superior cycle stability of 84.7% at 40°C after 100 cycles but also high-capacity retention of 76.2% under 2 C via improving structural integrity. Therefore, this work reveals that single crystalline can be a breakthrough for stable and high electrochemical performances.

Phosphor copper-based flexible high voltage supercapacitors fabricated via laser irradiation and three-dimensional packaging

Supercapacitors (SCs) have garnered increasing attention as an alternative energy storage device but the relatively low potential window and energy density impede their application prospect. Herein, we propose a novel three-dimensional (3D) packaging method for the first time, utilizing high flexible phosphor-copper sheets (PCSs) sprayed with polytetrafluoroethylene (PTFE) and covered with polyimide (PI) films on their both sides as the serial medium followed by CO 2 laser irradiation to fabricate all-solid-state flexible high voltage supercapacitors (HVSCs). This method achieves double voltage output in the limited PI membrane compared with common 2D encapsulation. As a result, as-obtained HVSCs deliver not only an enhanced mechanical tensile strength up to 18.23 MPa but also the outstanding electrochemical performances, including ultrahigh working voltage window (10 V), high energy density (37.68 μWh/cm 2 ) and power density (3.38 mW/cm 2 ). Owing to the excellent flexibility, the HVSCs can be arbitrarily bent or twisted without obvious attenuation on capacitive property. After 10000 cycles, the capacitance retention of HVSCs still maintains to be 90.2%. This novel 3D packaging strategy may pave the way for developing high-performing SCs with wide operating voltage and high energy density for flexible displays, wearable equipment and integrated electrical devices. • PI films were pasted on the upper and lower surfaces of phosphor copper sheet. • Graphene formation from laser irradiation on PI film surface. • Phosphor copper-based supercapacitor was prepared by a novel 3D packaging method. • HVSCs deliver enhanced tensile strength, high working voltage and energy density.

Methylcellulose/Polymethyl Methacrylate/Al2O3 Composite Polymer Matrix towards Ni‐Rich Cathode/Lithium Metal Battery

AbstractGel polymer electrolyte (GPE) has attracted extensive interest due to superior interfacial compatibility, excellent plasticity, and improved electrochemical stability. Polymer matrix is of great importance to the performance of lithium metal battery, especially for Ni‐rich cathode system with high working potential. Herein, a rigid‐flexible composite polymer matrix comprising methylcellulose (MC), polymethyl methacrylate (PMMA), and Al2O3 is prepared. After saturated with the liquid electrolyte of 1 M LiDFOB in EC/DMC (1:1, v:v), the obtained GPE exhibits a high ionic conductivity of 0.20 × 10−3 S cm−1 and a wide electrochemical stable window up to 5.6 V. The synergistic effect of inorganic fillers and the ester groups on polymer matrix are conducive to the uniform deposition of Li‐ion and advantageous to the formation of smooth and robust interfacial passivation layer. After assembled with Ni‐rich cathode LiNi0.8Co0.15Al0.05O2 (NCA), a capacity of 158.1 mAh g−1 is maintained after 200 cycles at 0.1 C, while a high value of 133.1 mAh g−1 is delivered at 2 C. These results indicate that the as‐prepared MC‐PMMA‐Al2O3 GPE (abbreviated as MPAA) is favorable for the interfacial compatibility of lithium metal batteries and shows superior electrochemical stability at high working voltage.

High Voltage-Stabilized Graphdiyne Cathode Interface.

Suppressing the irreversible interfacial reactions is an important scientific bottleneck in the development of stable high-energy-density lithium-ion battery. The interfacial chemistry of graphdiyne (GDY) on the high-voltage cathode of LiNi0.5 Mn1.5 O4 (LNMO) shows a very interesting process, in which the sp-hybridization carbon atoms chemically scavenge the hydrofluoric acid (HF) and in situ form the fluorinated GDY interface. It first turns the harmful HF into profit, and greatly enhances the interfacial stability and restrains the side reaction on the cathode under high working voltage. The GDY-coated LNMO cathode obviously alleviates the electrolyte degradation, achieves high Coulombic efficiency and reliability. Due to atomic-level selectivity and chemical trapping of HF by GDY, it effectively suppresses the dissolution of Mn, Ni elements. These results highlight the unparalleled advantages of GDY in the formation of high stable interfaces and protection of high-energy-density electrodes.

Insight into structural and electrochemical properties of Mg‐doped LiMnPO 4 /C cathode materials with first‐principles calculation and experimental verification

The LiMnPO4 material has the advantages of abundant raw materials, safety and environmental protection, low price, high theoretical capacity, high stable working voltage platform and so on, showing great potential in lithium-ion batteries. Dissimilar metal ion doping can essentially improve the electronic conductivity of LiMnPO4 and the material's charge and discharge performance, which is an ideal method to improve the electrochemical performance of LiMnPO4. In this paper, the optimal doping concentration of Mg-doped solid solution material was calculated by first principles. At the same time, the corresponding content of LiMn1−xMgxPO4/C cathode material was synthesized by hydrothermal method for experimental verification, so as to prepare the cathode material with excellent electrochemical performance. The results show that the doping of Mg cations does not change the phase of the main phase, but significantly changes the crystal structure parameters. The regulation of the band width directly affects the electronic conductivity of the material, which is directly proportional to the electrochemical performance. EIS and CV test results show that a proper amount of magnesium doping can effectively reduce the impedance of the material, and can effectively alleviate the polarization phenomenon of LiMnPO4 electrode material, accelerate the diffusion rate of Li+, and it is easier to obtain high capacity battery. LiMn23/24Mg1/24PO4/C showed the best electrochemical performance, with an initial capacity of 153.8 mAh/g at 0.05C ratio and a capacity retention rate of 97.5% after 100 cycles at 0.05C ratio. The theoretical calculation is in good agreement with the experimental results, which indicates that the theoretical calculation based on first principles can effectively provide a more reliable theoretical basis for experimental design and subsequent improvement.

Enhanced Electrochemical Performance of Supercapacitors via Atomic Layer Deposition of ZnO on the Activated Carbon Electrode Material.

Fabricating electrical double-layer capacitors (EDLCs) with high energy density for various applications has been of great interest in recent years. However, activated carbon (AC) electrodes are restricted to a lower operating voltage because they suffer from instability above a threshold potential window. Thus, they are limited in their energy storage. The deposition of inorganic compounds’ atomic layer deposition (ALD) aiming to enhance cycling performance of supercapacitors and battery electrodes can be applied to the AC electrode materials. Here, we report on the investigation of zinc oxide (ZnO) coating strategy in terms of different pulse times of precursors, ALD cycles, and deposition temperatures to ensure high electrical conductivity and capacitance retention without blocking the micropores of the AC electrode. Crystalline ZnO phase with its optimal forming condition is obtained preferably using a longer precursor pulse time. Supercapacitors comprising AC electrodes coated with 20 cycles of ALD ZnO at 70 °C and operated in TEABF4/acetonitrile organic electrolyte show a specific capacitance of 23.13 F g−1 at 5 mA cm−2 and enhanced capacitance retention at 3.2 V, which well exceeds the normal working voltage of a commercial EDLC product (2.7 V). This work delivers an additional feasible approach of using ZnO ALD modification of AC materials, enhancing and promoting stable EDLC cells under high working voltages.

Cation-Disordered O3-Na0.8Ni0.6Sb0.4O2 Cathode for High-Voltage Sodium-Ion Batteries.

O3-type sodium-layered oxides (such as antimony-based O3 structures) have been suggested as one of the most fascinating cathode materials for sodium-ion batteries (SIBs). Honeycomb-ordered antimony-based O3 structures, however, unsatisfactorily exhibit complex phase transitions and sluggish Na+ kinetics during cycling. Herein, we prepared a completely cationic-disordered O3-type Na0.8Ni0.6Sb0.4O2 compound by composition regulation for SIBs. Surprisingly, the measured redox potentials for typical O3-P3 phase transition are located at 3.4 V. Operando X-ray diffraction confirms a reversible phase transition process from the O3 to P3 structure accompanied with a very small volume change (1.0%) upon sodium extraction and insertion. The low activation barrier energy of 400 meV and the fast Na+ migration of 10-11 cm2·s-1 are further obtained by first-principles calculations and galvanostatic intermittent titration technique, respectively. As a result, the O3-Na0.8Ni0.6Sb0.4O2 cathode displays a reversible capacity of 106 mA h g-1 at 0.1C (12 mA g-1), smooth charge-discharge curves, and a high average working voltage of 3.5 V during battery cycling. The results highlight the importance of searching for a new O3-type structure with cation-disordering and high working voltage for realizing high energy SIBs.

Electrolyte Chemistry Towards Improved Cycling Stability in Na‐Based Dual‐Ion Batteries with High‐Power/Energy Storage

AbstractDual‐ion batteries (DIBs) have attracted great research interests owing to the co‐utilization of cation and anion as charge carriers. Unlike the low energy density (Eden) of supercapacitors and halogen‐ion batteries also with anion working, graphite‐cathode‐based DIBs exhibit obviously higher Eden with high working voltage. However, general electrolytes cannot satisfy the high‐energy demand for Na‐based DIBs with high power density. Herein, we design an effective electrolyte with optimized performance to limit the occurrence of side reactions during cycling, improving the cycling stability and Eden of Na‐based DIBs. Such electrolyte‐modified Na‐DIBs exhibit higher discharge plateau and specific capacity compared to the pristine batteries, contribute preeminent Eden of 370.4 Wh/kg at a high‐power density of 8888.4 W/kg (2.0 A/g), and deliver higher capacity retention of 72 % after 1000 cycles under 40 °C (1.0 A/g). All of these improvements are attributed to the interphase protection of anode/cathode by modified electrolyte, and the increase of diffusion ability under high potential. This strategy not only provides reference significance for enhancing the performance of DIBs, but also promotes the development of DIBs with high‐power/energy and long‐term cycle working condition.

Dual‐Ion Batteries: High Oxidation Potential ≈6.0 V of Concentrated Electrolyte toward High‐Performance Dual‐Ion Battery (Adv. Energy Mater. 25/2021)

In article number 2100151, Yongbing Tang and co-workers develop a 4.0 m LiFSI/TMS high-concentration and high-voltage electrolyte, which shows significantly suppressed gas formation and enhanced anion intercalation reversibility under high working voltages. Based on this electrolyte system, the dual-ion battery (DIB) exhibits much improved electrochemical performance. This work provides an effective approach to improve the performance of DIBs.

Bismuth Nanoparticles Confined in Carbonaceous Nanospheres as Anodes for High-Performance Potassium-Ion Batteries

Bismuth (Bi) has been considered as a promising alloying-type anode for potassium-ion batteries (PIBs), owing to its high theoretical capacity and suitable working voltage plateaus. However, Bi suffers from dramatic volume fluctuation and significant pulverization during the discharge/charge processes, resulting in fast capacity decay. Herein, we synthesize Bi nanoparticles confined in carbonaceous nanospheres (denoted as Bi@C) for PIBs by first utilizing BiOCl nanoflakes as a hard template and a Bi precursor. The construction of the loose structure buffers the mechanical stresses resulting from the volume expansion of Bi during the alloying reaction and avoids the fracture of the electrode structure, thus improving the cycling performance. Moreover, the carbonaceous layers increase the electronic conductivity and disperse the Bi nanoparticles, enhancing the charge transportation and ionic diffusion, which further promotes the rate capability of Bi@C. It exhibits a superior capacity (389 mAh g-1 at 100 mA g-1 after 100 cycles), excellent cycling stability (206 mAh g-1 at 500 mA g-1 over 1000 cycles), and an improved rate capability (182 mAh g-1 at 2.0 A g-1). This work provides a new structuring strategy in alloying materials for boosting reversible and stable potassium-ion storage.

Molecular Coupling and Self-Assembly Strategy toward WSe2 /Carbon Micro-Nano Hierarchical Structure for Elevated Sodium-Ion Storage.

Sodium (Na) ion-based dual-ion batteries (Na-DIBs) have attracted great attention, owing to their benefits of low cost, high working voltage, and environmental friendliness. However, the limited capacity and low tap density of currently reported anode materials restrict the further improvement of Na-DIBs. Herein, a micro-nano structure with vertically aligned WSe2 nanoflakes anchored tightly on a micron-sized carbon sphere (WSe2 /CS) is successfully constructed via combining the molecular coupling and self-assembly strategy. Within this hierarchical structure, the WSe2 nanoflakes can shorten the diffusion path for Na+ ions and alleviate structural deformation during the charge/discharge process; meanwhile, the micron-sized carbon core provides conductive support and helps improve the total tap density of the anode electrode. As a result, this micron-sized WSe2 /CS displays a high specific capacity of ≈252.8mAhg-1 and good cycling performance with ≈92% capacity retention after 1200 cycles. Moreover, by pairing this WSe2 /CS anode with environmental friendly graphite as cathode, a proof-of-concept Na-DIB shows 85.6% capacity retention after 1000 cycles, which is among the best performances of previously reported Na-DIBs.

Research Progress and Application of Modified Silicon-Based Anode Materials for Lithium-Ion Batteries

Silicon-based anode materials have been widely discussed by researchers because of its high theoretical capacity, abundant resources and low working voltage platform,which has been considered to be the most promising anode materials for lithium-ion batteries. However,there are some problems existing in the silicon-based anode materials greatly limit its wide application: during the process of charge/discharge, the materials are prone to about 300% volume expansion, which will resultin huge stress-strain and crushing or collapse on the anods; in the process of lithium removal, there is some reaction between active material and current collector, which creat an increase in the thickness of the solid phase electrolytic layer(SEI film); during charging and discharging, with the increase of cycle times, cracks will appear on the surface of silicon-based anode materials, which will cause the batteries life to decline. In order to solve these problems, firstly, we summarize the design of porous structure of nanometer sized silicon-based materials and focus on the construction of three-dimensional structural silicon-based materials, which using natural biomass, nanoporous carbon and metal organic framework as structural template. The three-dimensional structure not only increases the channel of lithium-ion intercalation and the rate of ion intercalation, but also makes the structure more stable than one-dimensional or two-dimensional. Secondly, the Si/C composite, SiOx composite and alloying treatment can improve the volume expansion effection, increase the rate of lithium-ion deblocking and optimize the electrochemical performance of the material. The composite materials are usually coated with elastic conductive materials on the surface to reduce the stress, increase the conductivity and improve the electrochemical performance. Finally, the future research direction of silicon-based anode materials is prospected.

Realizing reversible storage of trivalent aluminum ions using VOPO4·2H2O nanosheets as cathode material in aqueous aluminum metal batteries

Aqueous Al metal batteries (AAMBs) are a very promising safe and cost-efficient energy storage system for large-scale applications because of the natural non-flammability of aqueous electrolyte and the high abundance of Al in the earth’s crust. However, lack of proper cathode materials is the biggest stumbling block to the development of AAMBs. Here, VOPO4·2H2O nanosheets are successfully prepared using a refluxing method and an aqueous VOPO4·2H2O/Al metal battery is constructed by employing the as-prepared VOPO4·2H2O nanosheets as cathode, Al metal foil as anode, and Al(CF3SO3)3 aqueous solution as electrolyte. The electrochemical performance of the batteries is tested and it is optimized by selecting appropriate electrolyte. The batteries exhibit a high discharge capacity of 125.4mAhg−1 at a current density of 20 mA g−1, a high working voltage of ~0.9 V, and good capacity retention of 60% after 40 cycles. Moreover, a single-phase electrochemical reaction mechanism of the VOPO4·2H2O cathode is investigated by ex-situ XRD, TEM and XPS techniques. We believe that this work can promote the development of AAMBs and provide ideas for the design of cathode materials for other aqueous multivalent-ion batteries.

Critical Review on the Unique Interactions and Electroanalytical Challenges Related to Cathodes ‐ Solutions Interfaces in Non‐Aqueous Mg Battery Prototypes

AbstractRechargeable batteries based on Mg metal anodes may be a promising alternative to current Li‐ion battery systems. However, the development of practical rechargeable Mg batteries (RMBs) is hindered by the absence of cathode materials that can reversibly intercalate Mg ions with a reasonably fast kinetic, while still exhibiting high capacity and high working voltages. In this minireview we summarize our recent progress in understanding cathodes/electrolyte solutions interfaces in non‐aqueous Mg systems. While most studies in the field of cathode materials for RMBs focus on the solid‐state diffusion phenomena of the bare Mg ion within the solid hosts, this minireview summarizes several important findings that demonstrate how the electrochemical response of the cathode material is also significantly influenced by the solution chemistry and structure. We provide a comprehensive description of the sequential steps taking place in the electrochemical intercalation reactions, with an emphasis on the charge transfer process across the solution/electrode interfaces. We discuss the different manner in which the electrolyte solutions′ chemical characteristics can impact each step of the intercalation process and why this information is important for the development of new cathode materials for rechargeable Mg batteries. We believe that these types of fundamental investigations are crucial steps for the realization of this interesting battery technology.

Rational design of Na0.67Ni0.2Co0.2Mn0.6O2 microsphere cathode material for stable and low temperature sodium ion storage

Layered transition metal oxides with a classic composition of Na0.67Ni0.33Mn0.67O2 have attracted extensive attention due to their high specific capacity and suitable working voltage. However, its inherent structural defects can lead to a prone to phase change upon charging/discharging and cause degradation of electrochemical performance. In this work, a suitable Co-substituted Na0.67Ni0.2Co0.2Mn0.6O2 microsphere is designed and synthesized. The introduction of cobalt can effectively increase the interlayer spacing of transition metal oxides (TMO2), resulting in a faster Na+ diffusion kinetics. Such a structure enables the charge compensation from different redox couples (Ni2+/3+/4+, Co3+/4+ and Mn3+/4+), leading to a high specific capacity. Furthermore, the drawbacks of P2-O2 phase transition and Na+/vacancy ordering can be simultaneously restrained by a suitable content of Co substitution, which is confirmed by both cyclic voltammetry test and in-situ X-ray diffraction (XRD). The optimized Na0.67Ni0.2Co0.2Mn0.6O2 demonstrates a superior long-term cycle stability with a capacity retention rate of 83% over 200 cycles at 2 C. The electrochemical performance under extreme low-temperature (−40 °C) of this Na0.67Ni0.2Co0.2Mn0.6O2 material has also been explored for the first time, and the DNa+ values of this material can be maintained decently within a range from 10−11 to 10−10 cm2s−1. A high reversible discharge capacity of 132.2 mAh g−1 at 0.2 C is achieved at −40 °C, which is 80% of that at room temperature, indicating a satisfactory sodium storage performance at extremely low temperature.

Toward High Performance All‐Solid‐State Lithium Batteries with High‐Voltage Cathode Materials: Design Strategies for Solid Electrolytes, Cathode Interfaces, and Composite Electrodes

AbstractAll‐solid‐state lithium batteries (ASSLBs) with nonflammable solid electrolytes (SEs) deliver greatly enhanced safety characteristics. Furthermore, ASSLBs composed of cathodes with high working voltages, such as LiCoO2, LiNixCoyMnzO2 (x + y + z = 1, NCM), LiNixCoyAlzO2 (x + y + z = 1, NCA), LiMnxFeyPO4 (x + y = 1, LMFP), and LiNi0.5Mn1.5O4 (LNMO), and a lithium metal anode can achieve comparable or better performance compared with that of LLBs in terms of energy density. Therefore, high‐voltage ASSLBs have been regarded as the most promising next‐generation batteries. Although significant progress has been achieved in high‐voltage ASSLBs research, their development still faces multiple challenges. To facilitate further effective and target‐oriented research on high‐voltage ASSLBs, a summary of recent research progress is urgently needed. In this review, recent research progress in high‐voltage ASSLBs is summarized from the perspectives of SEs modification, interfacial challenges and their corresponding solutions for cathodes, and high‐voltage composite cathode design for practical applications. Finally, the authors’ perspectives on the state of current ASSLBs research, aiming to propose possible research directions for the future development of high‐voltage ASSLBs.