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BaSnF4 is a prospective solid state electrolyte for fluoride ion batteries. However, the diffusion mechanism of the fluoride ions remains difficult to study, both in experiments and in simulations. In principle, ab initio molecular dynamics could allow to fill this gap, but this method remains very costly from the computational point of view. Using machine learning potentials is a promising method that can potentially address the accuracy issues of classical empirical potentials while maintaining high efficiency. In this work, we fitted a dipole polarizable ion model and trained machine learning potential for BaSnF4 and made comprehensive comparisons on the ease of training, accuracy and efficiency. We also compared the results with the case of a simpler ionic system (NaF). We show that contrarily to the latter, for BaSnF4 the machine learning potential offers much higher versatility. The current work lays foundations for the investigation of fluoride ion mobility in BaSnF4 and provides insight on the choice of methods for atomistic simulations. [ABSTRACT FROM AUTHOR]

The all-solid-state batteries (ASSBs) are of particular interest because of their higher energy density and improved safety. However, the interfacial instability and resulting high interfacial resistance between the cathode and solid electrolyte (SE) have become the major challenges for the practical application of ASSBs. Herein, we report a stable LiFePO4 cathode/γ-Li3PO4 SE interface and systemically investigate the mechanism of Li-ion transport at the interface and the effects of surface nitrogen doping using first-principles calculations. It is found that delithiation at the LiFePO4/γ-Li3PO4 interface initially occurs at the topmost layer of the LiFePO4 cathode side, and hopping through the interface barrier is a rate-limiting step for Li mobility. Nitrogen doping leads to local structural distortion occurred at the interface, affecting the interfacial Li+ diffusion kinetics. Furthermore, the underlying mechanisms in which the different N doping sites alter the Li diffusion barrier are analyzed. We find that, by a rational design, N doping could significantly enhance Li+ diffusion kinetics. Further analysis of the electronic structure of the interface system reveals that the Li3PO4 electrolyte is electrochemically stable against the LiFePO4 cathode in the N-doped interface. Our findings provide a microscopic understanding of the Li+ transport at solid–solid LiFePO4/γ-Li3PO4 interface and suggest that controlling synthesis condition can be critical for enhancing Li+ transport at the N-doped LiFePO4/γ-Li3PO4 interface in an ASSB. [ABSTRACT FROM AUTHOR]

Si nanoparticles with independently controlled size and oxygen content have been produced by plasma spraying physical vapor deposition followed by the retarded oxidation. These nanoparticles are used as the negative electrode of all-solid-state batteries with sulfide solid electrolyte, and the influence of size and oxygen content on battery performance has been analyzed. The cells containing Si nanoparticles smaller than 150 nm with the oxygen content x in SiO x smaller than 0.1 have attained relatively high capacity and a good stable cyclability simultaneously after 50 cycles. This could be due to the formation of unique and uniform synaptic-like Si network with small Si nanoparticles within the electrode maintaining a firm contact with the Cu foil, which contrasts to large lateral crack formation for the cell with large Si particles. [ABSTRACT FROM AUTHOR]

The document is a contents list for the New Journal of Chemistry, a publication by The Royal Society of Chemistry. It provides a list of articles and papers that will be published in the journal, covering a wide range of topics such as asymmetric reactions, sodium-ion storage, and bone tissue engineering. The journal aims to connect the world with the chemical sciences. The document also includes two corrections for previously published papers. [Extracted from the article]

Sulfide‐based all‐solid‐state lithium batteries (ASSLBs) are potential alternatives to conventional lithium‐ion batteries for enhancing energy density and battery safety. However, the industrial sector encounters technical challenges in the fabrication of high‐mass‐loaded composite cathodes to improve the energy densities of ASSLBs. Thus, the selection of an appropriate binder and cathode active material is very important for achieving a good cycling performance of ASSLBs. In this study, wet‐processable poly(ethylene‐co‐methyl acrylate‐co‐glycidyl methacrylate) (EMG) binder and full‐concentration gradient (FCG) LiNi0.78Co0.10Mn0.12O2 (NCM) cathode active material are employed to fabricate the composite cathode with high active mass loading (21.4 mg cm−2). The EMG binder provided strong binding properties to the cathode constituents and improved the electrical conductivity of the composite cathode. The FCG NCM mitigated the morphology damages caused by volume changes in the cathode active material during cycling. Consequently, the solid‐state lithium battery with the composite cathode employing EMG binder and FCG NCM delivered a high discharge capacity of 196.6 mAh g−1 corresponding to an areal capacity of 4.21 mAh cm−2 and showed good capacity retention of 85.1% after 300 cycles at 0.2 C rate and 30 °C. [ABSTRACT FROM AUTHOR]

All solid‐state batteries are desirable for a range of energy storage applications which require high energy density. Achieving a high energy density in a solid‐state battery requires the operation of an energy dense anode with a composite solid‐state cathode. Pores and/or voids within a solid state cathode are ion‐blocking and thus control over the concentration and distribution of pores in the initial electrode and cycled electrode is desirable. This study provides an understanding of the interplay between electrode microstructure and mechanics on active material utilization in solid state cathodes composed of NCM 811 and Li6PS5Cl. Decreasing the solid electrolyte particle size leads to greater active material‐electrolyte contact and less total deformation when exposed to an external load. Composite cathodes with greater compliance can potentially decrease strain between the active material and solid electrolyte, decrease delamination events and result in higher overall active material utilization and high capacity retention. [ABSTRACT FROM AUTHOR]

Incorporating lithium metal anodes in next‐generation batteries promises enhanced energy densities. However, lithium's reactivity results in the formation of a native surface film, affecting battery performance. Therefore, precisely controlling the chemical and morphological surface condition of lithium metal anodes is imperative for producing high‐performance lithium metal batteries. This study demonstrates the efficacy of laser treatment for removing superficial contaminants from lithium metal substrates. To this end, picosecond‐pulsed laser radiation is proposed for modifying the surface of lithium metal substrates. Scanning electron microscopy (SEM) revealed that different laser process regimes can be exploited to achieve a wide spectrum of surface morphologies. Energy‐dispersive X‐ray spectroscopy (EDX) confirmed substantial reductions of ≈80% in oxidic and carbonaceous surface species. The contamination layer removal translated into interfacial resistance reductions of 35% and 44% when testing laser‐cleaned lithium metal anodes in symmetric all‐solid‐state batteries (ASSBs) with lithium phosphorus sulfur chloride (LPSCl) and lithium lanthanum zirconium oxide (LLZO) solid electrolytes, respectively. Finally, a framework for integrating laser cleaning into industrial battery production is suggested, evidencing the industrial feasibility of the approach. In summary, this work advances the understanding of lithium metal surface treatments and serves as proof of principle for its industrial applicability. [ABSTRACT FROM AUTHOR]

A multiscale nanoengineering strategy, simultaneously including metal nanoparticle-atomized pathway and metal-organic framework-derived approach, is developed to realize the anchoring of atomic and nanosized transition-metal species in N-doped hierarchically tubular porous carbon for high-performance oxygen reduction and evolution reactions. [Display omitted] • A multiscale nanoengineering strategy, simultaneously including metal-organic framework-derived approach and metal nanoparticle-atomized pathway, to realize the anchoring of atomic and nanosized Fe/Co species on N-doped hierarchically tubular porous carbon substrate. • Fe/Co nanoparticles and single atoms are respectively utilized for accelerating OER and ORR, endowing the obtained material with a small OER/ORR potential gap of 0.684 V. • When the obtained material is used in the air electrode, 260 mW cm-2 of peak power density for liquid-state Zn-air battery, 110 mW cm-2 of peak power density for solid-state Zn-air battery, and 1000 charge-discharge cycles without decay are realized. The development of cost-effective, high-activity and stable catalysts to accelerate the sluggish kinetics of cathodic oxygen reduction/evolution reactions (ORR/OER) plays a critical part in commercialization application of rechargeable Zn-air batteries (RZABs). Herein, a multiscale nanoengineering strategy is developed to simultaneously stabilize Co-doped Fe nanoparticles originated from metal-organic framework-derived approach and atomic Fe/Co sites derived from metal nanoparticle-atomized way on N-doped hierarchically tubular porous carbon substrate. Thereinto, metal nanoparticles and single atoms are respectively used to expedite the OER and ORR. Consequently, the final material is acted as an oxygen electrode catalyst, displaying 0.684 V of OER/ORR potential gap, 260 mW cm-2 of peak power density for liquid-state RZAB, 110 mW cm-2 of peak power density for solid-state RZAB, and 1000 charge-discharge cycles without decay, which confirms great potential for energy storage and conversion applications. [ABSTRACT FROM AUTHOR]

[Display omitted] Na metal batteries using inorganic solid-state electrolytes (SSEs) have attracted extensive attention due to their superior safety and high energy density. However, their development is plagued by the unclear structural/volumetric evolution of SSEs and the corresponding Na+ migration mechanisms. In this work, NaSn 2 F 5 (NSF) clusters are composed of nanoparticles (NPs) with matched lattices induced by dislocations, which can mitigate the volume swelling/shrinkage of the NPs. NSF behaves like a single ion conductor with a high Na+ transference number (t Na+) of 0.79. Specially, the ionic conductivity (σ) of NSF is increased from 7.64 × 10-6 to 5.42 × 10-5 S cm−1 after partial irreversible oxidation of Sn2+ (0.118 Å) → Sn4+ (0.069 Å) with the shrunk ionic radius during the charge process, giving more spaces for Na+ migration. Furthermore, a poly(acrylonitrile)-NaSn 2 F 5 -NaPF 6 composite polymer electrolyte (NSF CPE) was fabricated with a σ of 4.13 × 10-4 S cm−1 and a t Na+ of 0.60. The NSF CPE-based symmetric cell can operate over 3000 h due to the couplings between the different components in NSF CPE, which is beneficial for ion transfer and the construction of stable solid electrolyte interface. And the quasi -solid-state Na|NSF CPE|Na 3 V 2 (PO 4) 3 full cell displays excellent electrochemical performance. [ABSTRACT FROM AUTHOR]

[Display omitted] • Potassium polyacrylate (K-PAM) is proposed as a multifunctional electrolyte additive requiring only 0.05 g L–1. • K-PAM molecules adsorbed on the anode surface could form a synergistic cation–anion interface. • Symmetric Zn Zn cell assembled with K-PAM additive displays an outstanding cycling durability over 1250 h at a current density of 1 mA cm−2. • The optimized ZnSO 4 electrolyte with K-PAM additive endows the Zn VO 2 battery with a considerable cycle stability after 700 cycles at 1 A/g. Rechargeable aqueous Zn batteries have the edge in resource reserve, cost, energy and conversion efficiency due to the inherent features of metal Zn anodes. However, the application of Zn-based batteries is being seriously hindered by Zn dendrites and water-induced side-reactions. Here, potassium polyacrylate (K-PAM) is proposed as the electrolyte additive to form a synergistic cation–anion interface on Zn surface. The carboxyl anions and K+ cations are preferentially adsorbed on the Zn surface due to the intrinsic surfactant characteristics, which could homogenize Zn plating and suppress parasitic reactions. The synergistic regulation of K-PAM additive endows the Zn Zn symmetric cells with excellent cyclic durability of 1250 h at 1 mA cm−2, which is significantly better than the polyacrylic acid additive only with carboxyl anions. Moreover, trace K-PAM addition into traditional ZnSO 4 electrolyte endows the Zn Cu batteries with a considerable average Coulombic efficiency of 99.2 %. Additionally, higher capacity retention and excellent cycling stability of Zn VO 2 cells further mark K-PAM as a potentially impressive aqueous electrolyte additive for high-performance Zn-based batteries. This work will provide a promising method for the synergistic regulation with cations and anions of electrolyte additives to improve the stability and reversibility of Zn anodes. [ABSTRACT FROM AUTHOR]

With the electrochemical performance of batteries approaching the bottleneck gradually, it is increasingly urgent to solve the safety issue. Herein, all‐in‐one strategy is ingeniously developed to design smart, safe, and simple (3S) practical pouch‐type LiNi0.8Co0.1Mn0.1O2||Graphite@SiO (NCM811||Gr@SiO) cell, taking full advantage of liquid and solid‐state electrolytes. Even under the harsh thermal abuse and high voltage condition (100 °C, 3–4.5 V), the pouch‐type 3S NCM811||Gr@SiO cell can present superior capacity retention of 84.6% after 250 cycles (based pouch cell: 47.8% after 250 cycles). More surprisingly, the designed 3S NCM811||Gr@SiO cell can efficiently improve self‐generated heat T1 by 45 °C, increase TR triggering temperature T2 by 40 °C, and decrease the TR highest T3 by 118 °C. These superior electrochemical and safety performances of practical 3S pouch‐type cells are attributed to the robust and stable anion‐induced electrode‐electrolyte interphases and local solid‐state electrolyte protection layer. All the fundamental findings break the conventional battery design guidelines and open up a new direction to develop practical high‐performance batteries. [ABSTRACT FROM AUTHOR]

Inferior air stability is a primary barrier for large‐scale applications of garnet electrolytes in energy storage systems. Herein, a deeply hydrated hydrogarnet electrolyte generated by a simple ion‐exchange‐induced phase transition from conventional garnet, realizing a record‐long air stability of more than two years when exposed to ambient air is proposed. Benefited from the elimination of air‐sensitive lithium ions at 96 h/48e sites and unobstructed lithium conduction path along tetragonal sites (12a) and vacancies (12b), the hydrogarnet electrolyte exhibits intrinsic air stability and comparable ion conductivity to that of traditional garnet. Moreover, the unique properties of hydrogarnet pave the way for a brand‐new aqueous route to prepare lithium metal stable composite electrolyte on a large‐scale, with high ionic conductivity (8.04 × 10−4 S cm−1), wide electrochemical windows (4.95 V), and a high lithium transference number (0.43). When applied in solid‐state lithium batteries (SSLBs), the batteries present impressive capacity and cycle life (164 mAh g−1 with capacity retention of 89.6% after 180 cycles at 1.0C under 50 °C). This work not only designs a new sort of hydrogarnet electrolyte, which is stable to both air and lithium metal but also provides an eco‐friendly and large‐scale fabrication route for SSLBs. [ABSTRACT FROM AUTHOR]

Fe–N–C catalysts are emerging as promising alternatives to Pt‐based catalysts for the oxygen reduction reaction (ORR), while they still suffer from sluggish reaction kinetics due to the discontented binding affinity between the Fe‐N4 sites and oxygen‐containing intermediates, and unsatisfactory stability. Herein, a flexible multichannel carbon fiber membrane immobilized with atomically dispersed Fe‐N4 sites and neighboring Fe nanoclusters/nanoparticles (FeN4‐FeNCP@MCF) is synthesized. The optimized geometric and electronic structures of the Fe atomic sites brought by adjacent Fe nanoclusters/nanoparticles and hierarchically porous structure of the carbon matrix endow FeN4‐FeNCP@MCF with outstanding ORR activity and stability, considerably outperforming its counterpart with FeN4 sites only and the commercial Pt/C catalyst. Liquid and solid‐state flexible zinc–air batteries employing FeN4‐FeNCP@MCF both exhibit outstanding durability. Theoretical calculation reveals that the Fe nanoclusters can trigger remarkable electron redistribution of the FeN4 sites and modulate the hybridization of central Fe 3d and O 2p orbitals, facilitating the activation of O2 molecules and optimizing the adsorption capacity of oxygen‐containing intermediates on FeN4 sites, and thus accelerating the ORR kinetic. This work offers an effective approach to constructing coupling catalysts that have single atoms coexisting with nanoclusters/nanoparticles for efficient ORR catalysis. [ABSTRACT FROM AUTHOR]

Inorganic solid electrolytes offer inherently unique transport, thermal, and mechanical attributes that can potentially address the fast‐charging barriers of safety, performance, and degradation exhibited by their liquid counterparts; however, to achieve reliable fast charging while retaining long cycle life remains a challenge for all‐solid‐state lithium batteries (ASSLBs), which is hindered by the electro‐chemo‐mechanical and transport issues at solid–solid interface. Herein, a high‐entropy strategy is reported to design ideal argyrodite electrolytes for fast‐charging ASSLBs with boosted transport kinetics and mitigated electrolyte‐electrode reactions via anionic site disordering. As proof of concept, multiple aliovalent cations (Si4+/Ge4+/Sn4+) and anions (Cl−) are introduced to Li6PS5Br (LPSBr) to prepare its high‐entropy counterpart, HE‐LPSBrCl. As the configuration entropy increases from 1.35 to 2.29 R, the disordering increases by 6.83‐fold and ionic conductivity increases by nearly one order of magnitude (7.96 mS cm−1 at 30 °C for HE‐LPSBrCl). The HE‐LPSBrCl full cells deliver a high capacity of 67.7 mA h g−1 at 10 C, 61.5 times higher than that of LPSBr counterparts, and retain 85.6% of the capacity (96.2 mA h g−1 at 5 C) after 1400 cycles. Unwanted mechanical penetration of Li and interfacial delamination and particle cracking of composite cathode at high rates are successfully suppressed. [ABSTRACT FROM AUTHOR]

Photo‐rechargeable zinc‐ion batteries (PRZIBs) have attracted much attention in the field of energy storage due to their high safety and dexterity compared with currently integrated lithium‐ion batteries and solar cells. However, challenges remain toward their practical applications, originating from the unsatisfactory structural design of photocathodes, which results in low photoelectric conversion efficiency (PCE). Herein, a flexible MoS2/SnO2‐based photocathode is developed via constructing a sunflower‐shaped light‐trapping nanostructure with 3D hierarchical and self‐supporting properties, enabled by the hierarchical embellishment of MoS2 nanosheets and SnO2 quantum dots on carbon cloth (MoS2/SnO2 QDs@CC). This structural design provides a favorable pathway for the effective separation of photogenerated electron‐hole pairs and the efficient storage of Zn2+ on photocathodes. Consequently, the PRZIB assembled with MoS2/SnO2 QDs@CC delivers a desirable capacity of 366 mAh g−1 under a light intensity of 100 mW cm−2, and achieves an ultra‐high PCE of 2.7% at a current density of 0.125 mA cm−2. In practice, an integrated battery system consisting of four series‐connected quasi‐solid‐state PRZIBs is successfully applied as a wearable wristband of smartwatches, which opens a new door for the application of PRZIBs in next‐generation flexible energy storage devices. [ABSTRACT FROM AUTHOR]

Achieving the solid–solid conversion of sulfur is a fundamental solution to eliminating the shuttling of soluble polysulfides and improving the cycling stability of lithium‐sulfur batteries. However, the sluggish solid reaction kinetics seriously challenge the battery performance. In this work, a micropore‐confined catalysis strategy to achieve the smooth solid–solid conversion of sulfur is proposed. It is realized by storing sulfur in a microporous carbon host with narrow pore size and uniformly distributed single‐atom Co catalytic sites. The microporous structure avoids the contact of electrolyte solvents with the inner sulfur, preventing the formation and dissolution of polysulfides and efficiently suppressing sulfur loss during cycling. The introduced single‐atom Co catalytic sites promote the charge transfer to accelerate the solid–solid conversion of sulfur. When coupled with a liquid carbonate electrolyte, the battery exhibits a remarkably high Coulombic efficiency (CE) of ≈99.88% and a minimal capacity decay rate of ≈0.016% per cycle for 1000 cycles at 0.5 C. Even when coupled with the solid‐state electrolyte, the battery still delivers a significantly high capacity of 1100 mAh g−1 and a remarkably high CE of ≈99.83% over 200 cycles. This work reveals a promising solution for developing practical stable Li─S batteries. [ABSTRACT FROM AUTHOR]

In this report, a facile wet chemical method using acetonitrile combined with thermal annealing was used to prepare Li2S‐P2S5 (LPS) based glass‐ceramic electrolytes with (1 wt%, 3 wt%, and 5 wt% Ce2S3) and without Ce2S3 doping. The crystal structure, ionic conductivity, and chemical stability of Li7P3S11 glass‐ceramic electrolytes were examined at varying temperatures (250–350°C). The results indicated that the highest ionic conductivity of 3.15 × 10−4 S cm−1 for pure Li7P3S11 was observed at a temperature of 325°C. By incorporating 1 wt% Ce2S3 and subjecting it to a heat treatment at 250°C, the glass ceramic electrolyte attained a remarkable ionic conductivity of 7.7 × 10−4 (S cm−1) at 25°C. Furthermore, it exhibited a stable and extensive electrochemical potential range, reaching up to 5 volts when compared to the Li/Li+ reference electrode. By tuning the glass transition and crystallization temperature, cerium doping seems to make Li7P3S11 more chemically stable, compared to its original 70Li2S‐30P2S5 counterpart. According to Raman and X‐ray photoelectron spectroscopy analyses, cerium doping inhibits the decomposition of highly conductive P2S74‐ (pyro‐thiophosphate) to PS43− and P2S64−. Doped LPS has a greater crystallinity and more uniform microstructure than pure LPS, according to XRD, Raman spectroscopy, and scanning electron microscopy analysis. Consequently, Li7P2.9Ce0.1S11 electrolyte shows great potential as a solid‐state electrolyte for constructing high‐performance sulfide‐based all‐solid‐state batteries. [ABSTRACT FROM AUTHOR]

Zinc anodes in aqueous batteries face challenges such as dendrite growth and interfacial instability. This study investigates the use of cysteine as an electrolyte additive to address these issues. By establishing the correlation between the size of zinc nuclei and the surface tensions/contact angle at the electrolyte‐anode interface, it is demonstrated that the addition of cysteine in the electrolyte alters the surface tensions/contact angle at the electrolyte‐anode interface and the nucleation process of zinc. This alteration results in the formation of smaller and more dispersed nuclei, as opposed to the formation of larger island grains. This has a profound impact on the subsequent deposition growth process, enabling smooth and uniform zinc electrodeposition without the formation of dendrites. Additionally, cysteine molecules create a stable interface during zinc plating and stripping, effectively preventing corrosion from side reactions. The incorporation of cysteine in the electrolyte significantly enhances cycling stability and extends the lifespan of zinc anodes in aqueous batteries. [ABSTRACT FROM AUTHOR]

The unregulated metallic deposition and continuous cracking of the fragile solid electrolyte interphase are considered the critical barriers that compromise the cyclability of lithium metal batteries (LMB), especially under low N/P ratio (<3) pairing modes. Herein, an ultra‐thin (5 µm), lightweight (0.25 mg cm−2), and moisture‐proof interfacial layer composed of the high‐entropy alloys (denoted as HEAs) and interweaved carbon nanotubes (CNTs) scaffold is constructed to modify the current collector, moreover, the thermally‐induced Li22Si5 alloy blended with the hydrophobic ethylene‐vinyl acetate copolymer (EVA) is infiltrated into the scaffold pores as the moisture‐proof cation reservoir. The HEA@CNT/Li22Si5@EVA interfacial layer not only maximizes the Li‐utilization degree with minimal voltage divergence in symmetric cells but also compensates for irreversible Li depletion in the pouch‐format anode‐less models. As the HEA@CNT/Li22Si5@EVA‐Cu substrate paired with the LiNi0.8Mn0.1Co0.1O2 cathode in a 200 mAh prototype, the phase evolution of oxide cathode and efficient Li utilization at the anode substrate can be real‐time monitored by the transmission‐mode operando X‐ray diffraction. This interfacial layer strategy affords multifunctionality to enable the LMB prototyping without excessive Li abuse. Consequently, cycling endurance and the balanced energy densities (420.1 Wh kg−1) are obtained on the whole cell. [ABSTRACT FROM AUTHOR]

Garnet solid state electrolytes (SSEs) have emerged as propitious candidates for solid‐state batteries (SSBs) with exceptional ionic conductivity and excellent (electro)chemical stability. However, the Li|garnet interface contact deterioration still remains a major challenge resulting in Li dendrite propagation. Herein, a method is proposed to strengthen the adhesion of garnet SSE and Li by incorporating Sr3N2 into the Li metal. Density functional theory (DFT) calculations reveal that the interfacial formation energy of Li|garnet is decreased by the obtained Li‐Sr‐N (LSN) composite, which can enable a shift from poor contact to intimate bonding at the Li|garnet interface and a homogenous Li+ flux as well as electric field distribution. Simultaneously, the produced Li3N and LiSrN, which are known for their strong Li adsorption affinity and rapid Li+ transfer kinetics, actively govern the Li plating process. Thereby this rational design brings a notable reduction in interfacial impedance (4.5 Ω cm2), along with the increased critical current density (1.3 mA cm−2) and enhanced cycle stability (1200 h at 0.3 mA cm−2). Furthermore, The LFP|garnet|LSN full cell has demonstrated remarkable cycling performance (95.9% capacity retention after 200 cycles at 1 C) and favorable rate capability (150.2 mAh g−1 at 0.1 C and 134.9 mAh g−1 at 1 C). The research provides a new sight into lithium modification that can restrain Li|garnet interface deterioration and lay the groundwork for future advancements in high‐performance garnet‐ based SSBs. [ABSTRACT FROM AUTHOR]

All-solid-state lithium batteries (ASSLBs) have aroused worldwide interests for their high safety and energy density. As known to all, solid-state electrolytes (SSEs) are one of the most important parts in ASSLBs, and how to develop SSEs with improved electrochemical performances is still the current research hot topic for researchers. However, the applications of ionic liquid @ metal–organic frameworks (IL@MOFs) for solid-state electrolytes are rarely reviewed. This review briefly describes the characteristics of ILs and MOFs and reviews the latest research advances of IL@MOFs-based SSEs in ASSLBs. The synthesis methods, applications, and current problems as well as future perspectives of IL@MOFs are included. We hope that this review might offer meaningful guidance for the development of next-generation SSEs. This review briefly introduces the characteristics of ILs and MOFs and systematically reviews the latest research progress of IL@MOFs-based SSEs in ASSLBs in recent years based on our previous works. We also summarize and look forward to the synthesis methods, applications, and current or possible future problems of IL@MOFs in ASSLBs to provide ideas for advancing the research and development of new-generation ASSLBs. [ABSTRACT FROM AUTHOR]

Machine learning (ML) exhibits substantial potential for predicting the properties of solid‐state electrolytes (SSEs). By integrating experimental or/and simulation data within ML frameworks, the discovery and development of advanced SSEs can be accelerated, ultimately facilitating their application in high‐end energy storage systems. This review commences with an introduction to the background of SSEs, including their explicit definition, comprehensive classification, intrinsic physical/chemical properties, underlying mechanisms governing their conductivity, challenges, and future developments. An in‐depth explanation of the ML methodology is also elucidated. Subsequently, the key factors that influence the performance of SSEs are summarized, including thermal expansion, modulus, diffusivity, ionic conductivity, reaction energy, migration barrier, band gap, and activation energy. Finally, it is offered perspectives on the design prerequisites for upcoming generations of SSEs, focusing on real‐time property prediction, multi‐property optimization, multiscale modeling, transfer learning, automation and high‐throughput experimentation, and synergistic optimization of full battery, all of which are crucial for accelerating the progress in SSEs. This review aims to guide the design and optimization of novel SSE materials for the practical realization of efficient and reliable SSEs in energy storage technologies. [ABSTRACT FROM AUTHOR]

Sulfide‐based all‐solid‐state lithium batteries (ASSLBs) featuring Ni‐rich layered oxide cathodes are emerging as the leading contenders for the next generation of rechargeable batteries with outstanding safety and energy density characteristics. However, the composites of Ni‐rich oxides and sulfide electrolytes continue to grapple with persistent challenges encompassing structural deterioration, adverse interfacial parasitic reactions, and sluggish kinetics within the carbon‐free cathodes. Here, a synergistic design to circumvent these issues via the coupling of Zr/F co‐doping and conductive cyclized polyacrylonitrile (cPAN) coating to tailor both the bulk and surface chemistry of the Ni‐rich layered oxide LiNi0.83Co0.12Mn0.05O2 (NCM83125) cathode is proposed. The cathode subjected to this coordinated modification strategy showcases exceptional performance in sulfide‐based ASSLBs. It demonstrates robust cycling performance, with a capacity retention of 95% observed after 300 cycles at a rate of 0.2 C, alongside satisfactory rate performance, achieving a capacity of 109 mAh g‒1 at a high rate of 3 C. [ABSTRACT FROM AUTHOR]

The energy storage and vehicle industries are heavily investing in advancing all-solid-state batteries to overcome critical limitations in existing liquid electrolyte-based lithium-ion batteries, specifically focusing on mitigating fire hazards and improving energy density. All-solid-state lithium–sulfur batteries (ASSLSBs), featuring earth-abundant sulfur cathodes, high-capacity metallic lithium anodes, and non-flammable solid electrolytes, hold significant promise. Despite these appealing advantages, persistent challenges like sluggish sulfur redox kinetics, lithium metal failure, solid electrolyte degradation, and manufacturing complexities hinder their practical use. To facilitate the transition of these technologies to an industrial scale, bridging the gap between fundamental scientific research and applied R&D activities is crucial. Our review will address the inherent challenges in cell chemistries within ASSLSBs, explore advanced characterization techniques, and delve into innovative cell structure designs. Furthermore, we will provide an overview of the recent trends in R&D and investment activities from both academia and industry. Building on the fundamental understandings and significant progress that has been made thus far, our objective is to motivate the battery community to advance ASSLSBs in a practical direction and propel the industrialized process. [ABSTRACT FROM AUTHOR]

The generation of solid electrolyte interphase (SEI) largely determines the comprehensive performance of all‐solid‐state batteries. Herein, a novel "carrier‐catalytic" integrated design is strategically exploited to in situ construct a stable LiF‐LiBr rich SEI by improving the electron transfer kinetics to accelerate the bond‐breaking dynamics. Specifically, the high electron transport capacity of Br‐TPOM skeleton increases the polarity of C−Br, thus promoting the generation of LiBr. Then, the enhancement of electron transfer kinetics further promotes the fracture of C−F from TFSI− to form LiF. Finally, the stable and homogeneous artificial‐SEI with enriched lithium dihalide is constructed through the in situ co‐growth mechanism of LiF and LiBr, which facilitatse the Li‐ion transport kinetics and regulates the lithium deposition behavior. Impressively, the PEO‐Br‐TPOM paired with LiFePO4 delivers ultra‐long cycling stability over 1000 cycles with 81 % capacity retention at 1 C while the pouch cells possess 88 % superior capacity retention after 550 cycles with initial discharge capacity of 145 mAh g−1at 0.2 C in the absence of external pressure. Even under stringent conditions, the practical pouch cells possess the practical capacity with stable electric quantities plateau in 30 cycles demonstrates its application potential in energy storage field. [ABSTRACT FROM AUTHOR]

Sodium‐ion batteries (SIBs) present a promising avenue for next‐generation grid‐scale energy storage. However, realizing all‐climate SIBs operating across a wide temperature range remains a challenge due to the poor electrolyte conductivity and instable electrode interphases at extreme temperatures. Here, we propose a comprehensively balanced electrolyte by pairing carbonates with a low‐freezing‐point and low‐polarity ethyl propionate solvent which enhances ion diffusion and Na+‐desolvation kinetics at sub‐zero temperatures. Furthermore, the electrolyte leverages a combinatorial borate‐ and nitrile‐based additive strategy to facilitate uniform and inorganic‐rich electrode interphases, ensuring excellent rate performance and cycle stability over a wide temperature range from −45 °C to 60 °C. Notably, the Na||sodium vanadyl phosphate cell delivers a remarkable capacity of 105 mAh g−1 with a high rate of 2 C at −25 °C. In addition, the cells exhibit excellent cycling stability over a wide temperature range, maintaining a high capacity retention of 84.7 % over 3,000 cycles at 60 °C and of 95.1 % at −25 °C over 500 cycles. The full cell also exhibits impressive cycling performance over a wide temperature range. This study highlights the critical role of electrolyte and interphase engineering for enabling SIBs that function optimally under diverse and extreme climatic environments. [ABSTRACT FROM AUTHOR]

The generation of solid electrolyte interphase (SEI) largely determines the comprehensive performance of all‐solid‐state batteries. Herein, a novel "carrier‐catalytic" integrated design is strategically exploited to in situ construct a stable LiF‐LiBr rich SEI by improving the electron transfer kinetics to accelerate the bond‐breaking dynamics. Specifically, the high electron transport capacity of Br‐TPOM skeleton increases the polarity of C−Br, thus promoting the generation of LiBr. Then, the enhancement of electron transfer kinetics further promotes the fracture of C−F from TFSI− to form LiF. Finally, the stable and homogeneous artificial‐SEI with enriched lithium dihalide is constructed through the in situ co‐growth mechanism of LiF and LiBr, which facilitatse the Li‐ion transport kinetics and regulates the lithium deposition behavior. Impressively, the PEO‐Br‐TPOM paired with LiFePO4 delivers ultra‐long cycling stability over 1000 cycles with 81 % capacity retention at 1 C while the pouch cells possess 88 % superior capacity retention after 550 cycles with initial discharge capacity of 145 mAh g−1at 0.2 C in the absence of external pressure. Even under stringent conditions, the practical pouch cells possess the practical capacity with stable electric quantities plateau in 30 cycles demonstrates its application potential in energy storage field. [ABSTRACT FROM AUTHOR]

Sodium‐ion batteries (SIBs) present a promising avenue for next‐generation grid‐scale energy storage. However, realizing all‐climate SIBs operating across a wide temperature range remains a challenge due to the poor electrolyte conductivity and instable electrode interphases at extreme temperatures. Here, we propose a comprehensively balanced electrolyte by pairing carbonates with a low‐freezing‐point and low‐polarity ethyl propionate solvent which enhances ion diffusion and Na+‐desolvation kinetics at sub‐zero temperatures. Furthermore, the electrolyte leverages a combinatorial borate‐ and nitrile‐based additive strategy to facilitate uniform and inorganic‐rich electrode interphases, ensuring excellent rate performance and cycle stability over a wide temperature range from −45 °C to 60 °C. Notably, the Na||sodium vanadyl phosphate cell delivers a remarkable capacity of 105 mAh g−1 with a high rate of 2 C at −25 °C. In addition, the cells exhibit excellent cycling stability over a wide temperature range, maintaining a high capacity retention of 84.7 % over 3,000 cycles at 60 °C and of 95.1 % at −25 °C over 500 cycles. The full cell also exhibits impressive cycling performance over a wide temperature range. This study highlights the critical role of electrolyte and interphase engineering for enabling SIBs that function optimally under diverse and extreme climatic environments. [ABSTRACT FROM AUTHOR]

Solid electrolytes hold substantial promise as vital components of all-solid-state batteries. Enhancing their performance necessitates simultaneous improvements in their stability and lithium conductivity. These properties can be calculated using first-principles simulations, provided that the crystal structure of the material and the diffusion pathway through the material are known. However, solid electrolytes typically incorporate dopants to enhance their properties, necessitating the optimization of the dopant configuration for the simulations. Yet, performing such calculations via the first-principles approach is so costly that existing approaches usually rely on predetermined dopant configurations informed by existing knowledge or are limited to systems doped with only a few atoms. The proposed method enables the optimization of the dopant configuration with the support of neural network potential (NNP). Our approach entails the use of molecular dynamics to analyze the diffusion after the optimization of the dopant configuration. The application of our approach to Li 10 MP 2 S 12 - x O x (M = Ge, Si, or Sn) reproduce the experimental results well. Furthermore, analysis of the lithium diffusion pathways suggests that the activation energy of diffusion undergoes a percolation transition. This study demonstrates the effectiveness of NNPs in the systematic exploration of solid electrolytes. [ABSTRACT FROM AUTHOR]

Solid-state electrolytes (SSEs) are the key materials in the new generation of all-solid-state lithium ion/metal batteries. Metal–organic frameworks (MOFs) are ideal materials for developing solid electrolytes because of their structural diversity and porous properties. However, there are several significant issues and obstacles involved, such as lower ion conductivity, a smaller ion transport number, a narrower electrochemical stability window and poor interface contact. In this review, a comprehensive analysis and summary of the unique ion-conducting behavior of MOF-based electrolytes in rechargeable batteries are presented, and the different design principles of MOF-based SSEs are classified and emphasized. Accordingly, four design principles for achieving these MOF-based SSEs are presented and the influence of SSEs combined with MOFs on the electrochemical performance of the batteries is described. Finally, the challenges in the application of MOF materials in lithium ion/metal batteries are explored, and directions for future research on MOF-based electrolytes are proposed. This review will deepen the understanding of MOF-based electrolytes and promote the development of high-performance solid-state lithium ion/metal batteries. This review not only provides theoretical guidance for research on new MOF-based SSE systems, but also contributes to further development of MOFs applied to rechargeable batteries. [ABSTRACT FROM AUTHOR]

All solid‐state lithium–sulfur batteries (ASSLSBs) have attracted significant attention due to their enhanced safety and superior energy density. However, the considerable volume change during cycling poses a challenge, resulting in electrochemical‐mechanical degradation. To address this issue, polypyrrole (PPy) is coated on a nitrogen‐doped carbon nanotube (NCNT) network to exhibit suitable conductivity and compatibility with sulfide electrolyte. Functionally, PPy@NCNT provides a continuous and conductive pathway, reducing the tortuosity of charge transport. Mechanically, operando pressure measurements and atomic force microscopy (AFM) tests are conducted, demonstrating that the flexible and viscoelastic structure of PPy@NCNT can alleviate local stress. The axial pressure on the cathode can be reduced by 11% with a sulfur area capacity of 3 mg cm−2 at 30 °C. At a high areal mass loading of 4.5 mg cm−2, a high areal capacity of 6 mAh cm−2 (1348 mAh g−1, 1C = 1675 mA g−1) is achieved at 0.1C, maintaining stability over 300 cycles at 0.2C. Remarkably, it can achieve an areal capacity of over 8.8 mAh cm−2 and stable cycling even at 60 °C. This study, being the first to regulate mechano‐electrochemical action in ASSLSBs with flexible conducting polymer, highlights the significance of integrating a continuous and elastic network into solid‐state conversion‐type cathodes. [ABSTRACT FROM AUTHOR]

Single‐crystalline layered oxide (LiNi1‐x‐yMnxCoyO2) cathodes have been found to exhibit exceptional electrochemical properties when coupled with various inorganic solid electrolytes (ISEs) in all‐solid‐state batteries (ASSBs). Their advantages stem from the robust morphological integrity with the absence of grain boundaries and the high electrochemical oxidative stability. Here, ASSBs featuring single‐crystalline LiNiO2 (LNO) with the highest Ni content are reported, offering a high theoretical specific capacity of 275 mAh g‐1 alongside a high average discharge voltage (3.7 V vs Li+/Li). Through a careful investigation, it is demonstrated that micron‐sized single‐crystalline LNO (µSC‐LNO) composite cathodes with a halide ISE exhibit a high initial discharge capacity of 205 mAh g‐1 with an outstanding cycle performance over 200 cycles in room‐temperature ASSBs. The significance of engineering parameters is emphasized, such as particle size and specific density, in promoting a homogeneous and fast Li+ transport within the composite cathodes. Furthermore, the formation of undesirable interphase between the halide ISE in the cathode and sulfide ISE separator is elucidated, which may be a critical factor impeding long‐term cyclability of ASSBs. This work provides insights into the design of composite cathodes for high‐energy‐density ASSBs. [ABSTRACT FROM AUTHOR]

All‐solid‐state batteries suffer from high interface resistance and lithium dendrite growth leading to low Li plating/stripping Coulombic efficiency (CE) of <90% and low critical current density at high capacity. Here, simultaneously addresses both challenges are simultaneously addressed and the Li plating/stripping CE is significantly increased to 99.6% at 0.2 mA cm−2/0.2 mAh cm−2, and critical current density (CCD) of > 3.0 mA cm−2/3.0 mAh cm−2 by inserting a mixed ionic‐electronic conductive (MIEC) and lithiophobic LiF‐C‐Li3N‐Bi nanocomposite interlayer between Li6PS5Cl electrolyte and Li anode. The highly lithiophobic LiF‐C‐Li3N‐Bi interlayer with high ionic conductivity (10−5 S cm−1) and low electronic conductivity (3.4×10−7 S cm−1) enables Li to plate on the current collector (CC) surface rather than on Li6PS5Cl surface avoiding Li6PS5Cl electrolyte reduction. During initial Li plating on CC, Li penetrates into porous LiF‐C‐Li3N‐Bi interlayer and lithiates Bi nanoparticles into Li3Bi. The lithiophilic Li3Bi and Li3N nanoparticles in LiF‐C‐Li3N‐Li3Bi sub‐interlayer will move to CC along with plated Li, forming LiF‐C/Li3N‐Li3Bi lithiophobic/lithiophilic sublayer during the following Li stripping. This interlayer enables Co0.1Fe0.9S2/Li6PS5Cl/Li cell with an areal capacity of 1.4 mAh cm−2 to achieve a cycle life of >850 cycles at 150 mA g−1. The lithiophobic/lithiophilic interlayer enables solid‐state metal batteries to simultaneously achieve high energy and long cycle life. [ABSTRACT FROM AUTHOR]

Compared to traditional lithium‐ion batteries with liquid electrolytes, all‐solid‐state lithium batteries have attracted extensive attention due to their heightened safety and energy density. Lithium argyrodite materials are promising solid electrolytes (SE) due to their high ionic conductivity, low grain boundary resistance, and favorable mechanical properties. However, the poor chemical/electrochemical stability of lithium argyrodite electrolytes toward the bare lithium metal anode inhibits their applications in all‐solid‐state lithium metal batteries (ASSLMBs). Here, Li‐SnF2 composite anodeswas used to induce the formation of solid electrolyte interphase (SEI) composed of LiCl, LiF, and Li22Sn5 at the Li/SE interface. The high interface energy barriers for LiF and LiCl induces the uniform deposition of lithium ions, thus hindering the growth of lithium dendrites. Meanwhile, the fast Li‐ion diffusion coefficient of the Li22Sn5 alloy accelerates Li‐ion migration across the interface section. The symmetrical cell exhibits stable cycling performance over long durations over 300 h at 0.5 mA cm−2. Moreover, the LiNbO3@NCM712/Li5.5PS4.5Cl1.5/Li‐10%SnF2 battery delivers a high initial discharge capacity of 170.9 mAh g−1 at 0.1C and retains 72.9% of its original capacity after 500 cycles at 0.5C. The facial approach for Li‐SnF2 composite anode enables the production of ASSLMBs with superior electrochemical performance. [ABSTRACT FROM AUTHOR]

Solid-state lithium--oxygen batteries offer great promise in meeting the practical demand for high-energy-density and safe energy storage. We have developed fibrous gel polymer electrolytes (GPEs) using a polyacrylonitrile (PAN) matrix via electrospinning. The 3D structure of GPEs enhances electrolyte absorption, while the interconnected design promotes strong interactions between Li+ and polar groups within the PAN matrix, thereby improving ion transport efficiency. In practical tests, both lithium symmetric cells and Li--O2 batteries demonstrated the ability to operate at high current densities over long cycles. [ABSTRACT FROM AUTHOR]

Featuring high theoretical capacity, low cost, and low preparation temperature, Li‐free cathodes are considered promising for all‐solid‐state thin‐film lithium microbatteries (TFBs). In this work, a Li‐free cathode of amorphous FeOxSy film is prepared, followed by the fabrication and investigation of FeOxSy/LiPON/Li TFBs. It is found that the structural degradation at both the LiPON/Li and FeOxSy/LiPON interfaces results in a rapid capacity loss for the TFB during electrochemical cycling. To achieve both high rate capability and long cycle life for the TFB, a dual‐interface modification approach using amorphous Al2O3 as an interlayer is proposed. During the TFB cycling, the Al2O3 interlayer not only enables robust LiPON/Li contact by preventing the formation of Li voids but also blocks the diffusion of Fe element from FeOxSy to LiPON electrolyte, effectively suppressing the interfacial resistance growth. Consequently, the dual‐interface modified TFB achieves greatly improved rate capability (194.3 mAh g−1 at 5 A g−1) and cycle performance (71% capacity retention after 800 cycles), which are superior to the pristine TFB and single‐interface modified TFB. This work advances the fundamental understanding of the failure mechanisms at the solid‐solid electrode/electrolyte interfaces, offering a feasible interfacial modulation strategy to develop advanced all‐solid‐state lithium batteries. [ABSTRACT FROM AUTHOR]

In metal‐based flow battery, membranes significantly impact energy conversion efficiency and security. Unfortunately, damages to the membrane occur due to gradual accumulation of metal dendrites, causing short circuits and shortening cycle life. Herein, we developed a rigid hierarchical porous ceramic flow battery composite membrane with a sub‐10‐nm‐thick polyelectrolyte coating to achieve high ion selectivity and conductivity, to restrain dendrite, and to realize long cycle life and high areal capacity. An aqueous zinc‐iron flow battery prepared using this membrane achieved an outstanding energy efficiency of >80%, exhibiting excellent long‐term stability (over 1000 h) and extremely high areal capacity (260 mAh cm−2). Low‐field nuclear magnetic resonance (NMR) spectroscopy, small‐angle X‐ray scattering, in situ infrared spectroscopy, solid‐state NMR analysis, and nano‐computed tomography revealed that the rigid hierarchical pore structures and numerous hydrogen bonding networks in the membrane contributed to the stable operation and superior battery performance. This study contributes to the development of next‐generation metal‐based flow battery membranes for energy and power generation. [ABSTRACT FROM AUTHOR]

In metal‐based flow battery, membranes significantly impact energy conversion efficiency and security. Unfortunately, damages to the membrane occur due to gradual accumulation of metal dendrites, causing short circuits and shortening cycle life. Herein, we developed a rigid hierarchical porous ceramic flow battery composite membrane with a sub‐10‐nm‐thick polyelectrolyte coating to achieve high ion selectivity and conductivity, to restrain dendrite, and to realize long cycle life and high areal capacity. An aqueous zinc‐iron flow battery prepared using this membrane achieved an outstanding energy efficiency of >80%, exhibiting excellent long‐term stability (over 1000 h) and extremely high areal capacity (260 mAh cm−2). Low‐field nuclear magnetic resonance (NMR) spectroscopy, small‐angle X‐ray scattering, in situ infrared spectroscopy, solid‐state NMR analysis, and nano‐computed tomography revealed that the rigid hierarchical pore structures and numerous hydrogen bonding networks in the membrane contributed to the stable operation and superior battery performance. This study contributes to the development of next‐generation metal‐based flow battery membranes for energy and power generation. [ABSTRACT FROM AUTHOR]

Developing argyrodite-type, chlorine-rich, sodium-ion, solid-state electrolytes with high conductivity is a long-term challenge that is crucial for the advancement of all-solid-state batteries (ASSBs). In this study, chlorine-rich, argyrodite-type Na6−xPS5−xCl1+x solid solutions were successfully developed with a solid solution formation range of 0 ≤ x ≤ 0.5. Na5.5PS4.5Cl1.5 (x = 0.5), displaying a highest ionic conductivity of 1.2 × 10−3 S/cm at 25 °C, which is more than a hundred times higher than that of Na6PS5Cl. Cyclic voltammetry and electrochemical impedance spectroscopy results demonstrated that the rich chlorine significantly enhanced the ionic conductivity and electrochemical stability, in addition to causing a reduction in activation energy. The Na5.5PS4.5Cl1.5 composite also showed the characteristics of a pure ionic conductor without electronic conductivity. Finally, the viability of Na5.5PS4.5Cl1.5 as a sodium electrolyte for all-solid-state sodium batteries was checked in a lab-scale ASSB, showing stable battery performance. This study not only demonstrates new composites of sodium-ionic, solid-state electrolytes with relatively high conductivity but also provides an anion-modulation strategy to enhance the ionic conductivity of argyrodite-type sodium solid-state ionic conductors. [ABSTRACT FROM AUTHOR]

All‐solid‐state lithium batteries (ASSLBs) are promising energy‐storage devices with high energy density and safety. However, the discharge capacity of ASSLBs that use sulfide solid electrolytes (SEs) and Ni‐rich cathode active materials (CAMs) deteriorates significantly during electrochemical cycling. Interfacial coatings between CAM and sulfide SEs are known to effectively alleviate capacity deterioration. Among the various coating materials, lithium phosphate (LPO) was selected and synthesized via atomic layer deposition (ALD). The crystal phase of the LPO thin film irreversibly changed, and the Li‐ion conductivity deteriorated after heat treatment. Additionally, particle ALD (P‐ALD) of LPO was successfully performed to completely passivate the CAM particles. Torque cells with the LPO‐coated CAMs showed excellent capacity retention, whereas the cells without the LPO coating showed a significantly deteriorated discharge capacity with increased internal resistances. The passivation effect of the LPO coating was confirmed by the cross‐sectional images from a FIB and scanning electron microscopy with energy‐dispersive X‐ray spectroscopy (SEM–EDS) dual system. We believe that the study will help us investigate the effects of side reactions between sulfide SEs and CAMs on the performance and stability of P‐ALD. [ABSTRACT FROM AUTHOR]

As an ideal candidate for the next generation of large‐scale energy storage devices, sodium‐ion batteries (SIBs) have received great attention due to their low cost. However, the practical utility of SIBs faces constraints imposed by geographical and environmental factors, particularly in high‐altitude and cold regions. In these areas, the low‐temperature (LT) performance of SIBs presents a pressing technological challenge that requires significant breakthroughs. In LT environments, the electrochemical reaction kinetics of SIBs are sluggish, the electrode/electrolyte interface is unstable, and the diffusion of sodium ions in electrode materials is slow, leading to a decrease in battery performance. Therefore, the reasonable design of electrolyte and electrode materials is of great significance for optimizing the LT performance of SIBs. In this review, the research progress of LT SIBs electrolytes, cathode, and anode materials, as well as sodium metal batteries and solid‐state electrolytes is systematically summarized in recent years, aiming to understand the design principles of LT SIBs, clarify the basic research and development of high‐performance SIBs in practical applications, and promote the development of SIBs technology in the full temperature range. [ABSTRACT FROM AUTHOR]

Lithium‐sulfur batteries utilizing sulfide solid electrolytes hold considerable potential for achieving both high energy density and enhanced safety. However, the substantial volume changes experienced by sulfur during cycling result in mechanical stress accumulation, leading to mechanical degradation and thereby degrading overall electrochemical performance. In this study, a stress‐buffer strategy is proposed to address this challenge by engineering a mechanically resilient crosslinked structure for the composite sulfur cathode. This structure is accomplished through the integration of a highly flexible thermoplastic elastomer (ethylene vinyl acetate, EVA), which enables stress release during sulfur volume variations by the repeated stretching and shrinking of EVA, thereby maintaining stable ionic/electronic diffusion channels within the electrode. By virtue of the mechanically stable architecture, the stress evolution experienced by the entire sulfur electrode is substantially reduced, witnessing a remarkable decrease of ≈33.7%. Consequently, the S‐EVA composite cathode demonstrates exceptional electrochemical performance, especially cycling stability. Notably, the S‐EVA composite cathode, with a high loading of 7.5 mg cm−2, exhibits stable cycling performance close to 3.0 mAh cm−2 within 50 cycles. This work not only offers novel insights into mitigating the mechanical stress within the electrode but also paves the way for developing durable high‐performance all‐solid‐state batteries. [ABSTRACT FROM AUTHOR]

Li metal is a promising negative-electrode material for high-energy-density all-solid-state batteries. However, the surface of Li metal is prone to oxidation, which results in the formation of a contamination layer at the Li metal–solid electrolyte interface. This interfacial contamination layer is the root cause of short-circuiting and poor cycle stability, thus hindering the development of all-solid-state batteries. Prior studies have not quantitatively assessed the effect of the above layer on battery performance. Herein, the degradation mechanisms affecting the interface are investigated using alternating-current impedance measurements and Li plating–stripping cycle tests for a symmetric cell. A thin contamination layer results in a Li–electrolyte interface with a low resistance of 0.20 kΩ cm2 and stable Li plating–stripping behavior at a current density of 3 mA cm−2, whereas a thick contamination layer results in a high interfacial resistance of 2.0 kΩ cm2. The thinning of the contamination layer on Li metal enhances the stability of the Li–electrolyte interface and Li plating–stripping kinetics. [ABSTRACT FROM AUTHOR]

The operation of solid-state Li batteries, which are promising power supplies for portable electronic devices and electric vehicles, is accompanied by heating. Therefore, investigating the thermal stability of battery systems is essential. In this study, we report the impact of annealing on the interface of a Li3PO4 electrolyte and LiNi0.5Mn1.5O4 electrode in thin-film batteries. The batteries with the interface annealed at 200 °C show low Li3PO4–LiNi0.5Mn1.5O4 interface resistance of 7.2 Ω cm2. Furthermore, the batteries exhibit stable charge–discharge characteristics with high current density up to 1170 μA cm−2, similar to those of batteries with the non-annealing interface. The batteries with the interface annealed at 450 °C show high Li3PO4–LiNi0.5Mn1.5O4 interface resistance of 490 Ω cm2, resulting in low battery performance. X-ray photoemission spectroscopy indicates that the P in Li3PO4 is reduced by high-temperature annealing, possibly causing the performance degradation of batteries. This study provides an in-depth understanding of the interfaces of solid-state batteries and is expected to facilitate the development of thermally stable batteries. [ABSTRACT FROM AUTHOR]

Highlights: Ultra-thin asymmetric composite solid-state electrolytes with ultralight areal density were designed for solid-state lithium metal batteries, achieving interfacial stability to Li metal and high-voltage cathode. The improved mechanical properties of the electrolyte contribute to the inhibition of Li dendrite growth was demonstrated by both experimental and theoretical simulations. The assembled pouch cell exhibited a high gravimetric/volume energy density of 344.0 Wh kg−1/773.1 Wh L−1. Solid-state lithium metal batteries (SSLMBs) show great promise in terms of high-energy–density and high-safety performance. However, there is an urgent need to address the compatibility of electrolytes with high-voltage cathodes/Li anodes, and to minimize the electrolyte thickness to achieve high-energy–density of SSLMBs. Herein, we develop an ultrathin (12.6 µm) asymmetric composite solid-state electrolyte with ultralight areal density (1.69 mg cm−2) for SSLMBs. The electrolyte combining a garnet (LLZO) layer and a metal organic framework (MOF) layer, which are fabricated on both sides of the polyethylene (PE) separator separately by tape casting. The PE separator endows the electrolyte with flexibility and excellent mechanical properties. The LLZO layer on the cathode side ensures high chemical stability at high voltage. The MOF layer on the anode side achieves a stable electric field and uniform Li flux, thus promoting uniform Li+ deposition. Thanks to the well-designed structure, the Li symmetric battery exhibits an ultralong cycle life (5000 h), and high-voltage SSLMBs achieve stable cycle performance. The assembled pouch cells provided a gravimetric/volume energy density of 344.0 Wh kg−1/773.1 Wh L−1. This simple operation allows for large-scale preparation, and the design concept of ultrathin asymmetric structure also reveals the future development direction of SSLMBs. [ABSTRACT FROM AUTHOR]

Gel‐polymer electrolyte (GPE) is a pragmatic choice for high‐safety sodium batteries but still plagued by interfacial compatibility with both cathode and anode simultaneously. Here, salt‐in‐polymer fibers with NaF salt inlaid in polylactide (PLA) fiber network was fabricated via electrospinning and subsequent in situ forming gel‐polymer electrolyte in liquid electrolytes. The obtained PLA‐NaF GPE achieves a high ion conductivity (2.50×10−3 S cm−1) and large Na+ transference number (0.75) at ambient temperature. Notably, the dissolution of NaF salt occupies solvents leading to concentrated‐electrolyte environment, which facilitates aggregates with increased anionic coordination (anion/Na+ >1). Aggregates with higher HOMO realize the preferential oxidation on the cathode so that inorganic‐rich and stable CEI covers cathode' surface, preventing particles' breakage and showing good compatibility with different cathodes (Na3V2(PO4)3, Na2+2xFe2‐x(SO4)3, Na0.72Ni0.32Mn0.68O2, NaTi2(PO4)3). While, passivated Na anode induced by the lower LUMO of aggregates, and the lower surface tension between Na anode and PLA‐NaF GPE interface, leading to the dendrites‐free Na anode. As a result, the assembled Na || Na3V2(PO4)3 cells display excellent electrochemical performance at all‐climate conditions. [ABSTRACT FROM AUTHOR]

The solid‐state electrolyte interface (SEI) between the solid‐state polymer electrolyte and the lithium metal anode dramatically affects the overall battery performance. Increasing the content of lithium fluoride (LiF) in SEI can help the uniform deposition of lithium and inhibit the growth of lithium dendrites, thus improving the cycle stability performance of lithium batteries. Currently, most methods of constructing LiF SEI involve decomposing the lithium salt by the polar groups of the filler. However, there is a lack of research reports on how to affect the SEI layer of Li‐ion batteries by increasing the charge transfer number. In this study, a porous organic polymer with "charge storage" properties was prepared and doped into a polymer composite solid electrolyte to study the effect of sufficient charge transfer on the decomposition of lithium salts. The results show in contrast to porphyrins, the unique structure of POF allows for charge transfer between each individual porphyrin. Therefore, during TFSI− decomposition to the formation of LiF, TFSI− can obtain sufficient charge, thereby promoting the break of C−F and forming the LiF‐rich SEI. Compared with single porphyrin (0.423 e−), POF provides 2.7 times more charge transfer to LiTFSI (1.147 e−). The experimental results show that Li//Li symmetric batteries equipped with PEO‐POF can be operated stably for more than 2700 h at 60 °C. Even the Li//Li (45 μm) symmetric cells are stable for more than 1100 h at 0.1 mA cm−1. In addition, LiFePO4//PEO‐POF//Li batteries have excellent cycling performance at 2 C (80 % capacity retention after 750 cycles). Even LiFePO4//PEO‐POF//Li (45 μm) cells have excellent cycling performance at 1 C (96 % capacity retention after 300 cycles). Even when the PEO‐base is replaced with a PEG‐base and a PVDF‐base, the performance of the cell is still significantly improved. Therefore, we believe that the concept of charge transfer offers a novel perspective for the preparation of high‐performance assemblies. [ABSTRACT FROM AUTHOR]

All‐solid‐state sodium metal batteries are promising for large‐scale energy storage applications owing to their intrinsic safety and cost‐effectiveness. However, they generally suffer from sodium dendrite growth or rapid capacity fading, especially at high rates, mainly due to poor wettability, sluggish ionic transport, or low interfacial stability of the solid electrolytes. Herein, we report a novel composite, NaB3H8 ⋅ xNH3@NaB3H8 (x<1), as a new class of solid electrolyte for high‐rate batteries. NaB3H8 ⋅ xNH3@NaB3H8 is obtained from the sticky NaB3H8 ⋅ NH3 after removal of NH3 partially at room temperature. It delivers an ionic conductivity of 0.84 mS cm−1 at 25 °C and reaches 20.64 mS cm−1 at 45 °C after an order‐disorder phase transformation. It also reveals a good capability of dendrite suppression and remarkable stability against sodium metal. These performances enable the all‐solid‐state Na//TiS2 battery with a high capacity of 232.4 mAh g−1 (97.2 % of theoretical capacity) and long‐term cycling stability at 1 C. Notably, this battery shows superior long‐life cycling stability even at 5 and 10 C, which has been rarely reported in all‐solid‐state sodium metal batteries. This work opens a new group of solid electrolytes, contributing to fast‐charging or high‐power‐density sodium metal batteries. [ABSTRACT FROM AUTHOR]

Gel‐polymer electrolyte (GPE) is a pragmatic choice for high‐safety sodium batteries but still plagued by interfacial compatibility with both cathode and anode simultaneously. Here, salt‐in‐polymer fibers with NaF salt inlaid in polylactide (PLA) fiber network was fabricated via electrospinning and subsequent in situ forming gel‐polymer electrolyte in liquid electrolytes. The obtained PLA‐NaF GPE achieves a high ion conductivity (2.50×10−3 S cm−1) and large Na+ transference number (0.75) at ambient temperature. Notably, the dissolution of NaF salt occupies solvents leading to concentrated‐electrolyte environment, which facilitates aggregates with increased anionic coordination (anion/Na+ >1). Aggregates with higher HOMO realize the preferential oxidation on the cathode so that inorganic‐rich and stable CEI covers cathode' surface, preventing particles' breakage and showing good compatibility with different cathodes (Na3V2(PO4)3, Na2+2xFe2‐x(SO4)3, Na0.72Ni0.32Mn0.68O2, NaTi2(PO4)3). While, passivated Na anode induced by the lower LUMO of aggregates, and the lower surface tension between Na anode and PLA‐NaF GPE interface, leading to the dendrites‐free Na anode. As a result, the assembled Na || Na3V2(PO4)3 cells display excellent electrochemical performance at all‐climate conditions. [ABSTRACT FROM AUTHOR]