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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]

Polyethylene oxide (PEO) based electrolytes critically govern the security and energy density of solid-state batteries, but typically suffer from poor oxidation resistance at high voltages, which limits the energy density of batteries. Here, we report a Lewis-acid coordinated strategy to significantly improve the cyclic stability of 4.8 V-class PEO-based battery. The introduced Mg2+ and Al3+ with strong electron-withdrawing capability weaken the electron density of ether oxygen (EO) chains via chelation in the coordination structure, resulting in a locally limited interaction between the EO chains and the surface of cathodes at high state of charge. The batteries using Lewis-acid coordinated electrolytes and Ni-rich cathodes achieve high voltage stability of 4.8 V over 300 cycles. Further, the realization of industrial-scale electrolyte membranes, and Ah-level pouch cells over 586 Wh kg‒1 with good cyclic stability, suggests the potential of our strategy in practical applications of all-solid-state batteries. This work reports a Lewis-acid coordinated strategy to improve stability of a 4.8 V-class PEO-based battery. The batteries using Lewis-acid coordinated electrolytes and Ni-rich cathodes achieve high voltage stability of 4.8 V over 300 cycles. [ABSTRACT FROM AUTHOR]

All-solid-state batteries using transition metal sulfide cathodes have received a lot of attention because of both their high safety and energy density. In this work, a 95MoS6·5LiI composite is employed as the active material in all-solid-state batteries, showing improved capacity and cycle life due to the increase in electrochemical reaction kinetics. This work provides a reliable cathode material with high reversible capacity and cyclability for all-solid-state rechargeable batteries. [ABSTRACT FROM AUTHOR]

The synthesis of LiNiO2 (LNO) typically involves oxidizing Ni(II) to Ni(III), thus leading to NiLi point-defect formation. Here, materials containing Ni(IV) in the form of overlithiated Li1+xNi1−xO2 (0 ≤ x ≤ 1/3) are converted into LNO. This method produces low defect-density samples at high temperatures, offering an attractive route toward coarse-grained particles that are naturally coated by the byproduct Li2O. In thiophosphate-based solid-state batteries, this kind of self-coating effect shows a direct correlation between residual lithium content and cycling performance. [ABSTRACT FROM AUTHOR]

We introduce N-P pair into the carbon matrix to construct N,P-C electrocatalyst by a facile pyrolysis strategy. Benefiting from the moderate adsorption energy of *OH on the active sites (C adjacent to P atom in N-P), the achieved N,P-C-1000 displays outstanding alkaline ORR performance and high power density primary liquid and solid ZABs. [Display omitted] • N-P pair was introduced into the carbon matrix to construct N,P-C electrocatalyst by a facile pyrolysis strategy. • The catalyst exhibits superior ORR activity with a E 1/2 of 0.83 V, comparable to that of commercial 20 wt% Pt/C. • Its C-2p orbit has higher interaction strength with the intermediates, thus reducing the overall reaction energy barrier. • High power density primary liquid and solid ZABs are achieved using N,P-C-1000 as cathodic catalysts. Developing sustainable metal-free carbon-based electrocatalysts is essential for the deployment of metal-air batteries such as zinc-air batteries (ZABs), among which doping of heteroatoms has attracted tremendous interest over the past decade. However, the effect of the heteroatom covalent bonds in carbon matrix on catalysis was neglected in most studies. Here, an efficient metal-free oxygen reduction reaction (ORR) catalyst is demonstrated by the N-P bonds anchored carbon (termed N,P-C-1000). The N,P-C-1000 catalyst exhibits superior specific surface area of 1362 m2 g−1 and ORR activity with a half-wave potential of 0.83 V, close to that of 20 wt% Pt/C. Theoretical computations reveal that the p-band center for C-2p orbit in N,P-C-1000 has higher interaction strength with the intermediates, thus reducing the overall reaction energy barrier. The N,P-C-1000 assembled primary ZAB can attain a large peak power density of 121.9 mW cm−2 and a steady discharge platform of ∼1.20 V throughout 120 h. Besides, when served as the cathodic catalyst in a solid-state ZAB, the battery shows flexibility, conspicuous open circuit potential (1.423 V), and high peak power density (85.8 mW cm−2). Our findings offer a strategy to tune the intrinsic structure of carbon-based catalysts for improved electrocatalytic performance and shed light on future catalysts design for energy storage technologies beyond batteries. [ABSTRACT FROM AUTHOR]

Li-based all-solid-state batteries (ASSBs) are considered feasible candidates for the development of the next generation of high-energy rechargeable batteries. However, ASSBs are detrimentally affected by a limited rate capability and inadequate performance at high currents. To circumvent these issues, here we propose the use of Nb1.60Ti0.32W0.08O5-δ (NTWO) as negative electrode active material. NTWO is capable of overcoming the limitation of lithium metal as the negative electrode, offering fast-charging capabilities and cycle stability. Physicochemical and electrochemical characterizations of NTWO in combination with the Li6PS5Cl (LPSCl) solid-state electrolyte demonstrate that the formation of LiWS2 at the electrode|electrolyte interphase is the main responsible for the improved battery performance. Indeed, when an NTWO-based negative electrode and LPSCl are coupled with a LiNbO3-coated LiNi0.8Mn0.1Co0.1O2-based positive electrode, the lab-scale cell is capable of maintaining 80% of discharge capacity retention after 5000 cycles at 45 mA cm−2 at 60 °C and 60 MPa. All-solid-state batteries (ASSB) are designed to address the limitations of conventional lithium ion batteries. Here, authors developed a Nb1.60Ti0.32W0.08O5-δ negative electrode for ASSBs, which improves fast-charging capability and cycle stability. [ABSTRACT FROM AUTHOR]

Solid‐state lithium metal batteries based on fluorinated solid electrolytes have attracted attention due to their safety and stability advantages. However, the fluoride solid electrolytes face the problem of relatively low Li‐ion conductivity due to the lacking of suitable structural prototypes and their corresponding modulation modes. In this work, a chlorine‐doped fluoride solid electrolyte Li3AlF5.87Cl0.13 is developed with high ionic conductivity by thermal fluorination and weak chlorination of mixed ionic liquids. The Cl anion is doped into the cryolite‐like open framework structure, and the electrolyte particle boundaries are decorated by solidified thin‐layer (≈2 nm) ionic liquid. Both the bulk and interface modifications enable the improvement of Li‐ion conductivity to 2 × 10−4 S cm−1 at 30 °C, which is the highest level among fluoride solid electrolytes. The Li3AlF5.87Cl0.13 with residual solidified ionic liquid shows the excellent stability of interface contact with Li metal, and the corresponding Li symmetric cell exhibits a small overvoltage (≈100 mV) with outstanding cycle life (at least 500 h). For the first time, a conversion‐type solid‐state Li/FeF3 battery is developed based on this fluoride electrolyte, delivering a reversible capacity as high as 430 mAh g−1. The existence of natural F‐rich interface promotes the conversion reaction reversibility of FeF3 cathode. [ABSTRACT FROM AUTHOR]

This document offers concise profiles of contributors to the Pioneering Investigators collection in Chemical Communications. The profiles provide information about the educational background, research interests, and notable achievements of each contributor. The researchers come from diverse backgrounds and specialize in areas such as organic chemistry, chemical engineering, and supramolecular chemistry. Their research covers topics such as catalysis, bioactive molecule synthesis, materials design, and sustainable energy technologies. These profiles offer a glimpse into the expertise and contributions of these researchers in the field of chemistry. [Extracted from the article]

Lithium-ion batteries are widely used due to high specific energy, but the ethylene carbonate in the electrolyte reacts violently with the oxygen component produced by the nickel-rich cathode, leading to lithium precipitation. For this reason, we propose a new electrolyte with Fluorine ethylene carbonate as the main solvent, which replaces the reaction source. It is verified that the capacity retention rate of the FEC-based battery reaches 96% after 300 cycles. Besides, FEC-based batteries withstand severe nail penetration tests without thermal runaway. In a heating test, the thermal runaway trigger for the FEC-based battery was delayed by 54 s. This work provides ideas for the subsequent development of safe electrolytes. [ABSTRACT FROM AUTHOR]

Lithium-titanium-sulfur cathodes have garnered interest due to their distinctive properties and potential applications in lithium-ion batteries. They present various benefits, including lower cost, enhanced safety, and greater energy density compared to the commonly used transition metal oxides. The current trend in lithium-ion batteries is to move to all-solid-state chemistries in order to improve safety and energy density. Several chemistries for solid electrolytes have been studied, tested, and characterized to evaluate the applicability in energy storage system. Among those, sulfur-based Argyrodites have been coupled with cubic rock-salt type Li2TiS3 electrodes. In this work, Li2TiS3 surfaces were investigated with DFT methods in different conditions, covering the possible configurations that can occur during the cathode usage: pristine, delithiated, and overlithiated. Interfaces were built by coupling selected Li2TiS3 surfaces with the most stable Argyrodite surface, as derived from a previous study, allowing us to understand the (electro)chemical compatibility between these two sulfur-based materials. [ABSTRACT FROM AUTHOR]

Next-generation energy storage systems rely heavily on the capability of fast charging as they allow electronic devices to be charged within a remarkably brief period. The practical applications of fastcharging technology are severely hindered by unsatisfactory electrochemical performance, e.g., low specific capacity, low areal capacity, low coulombic efficiency, and very limited life span, resulting in a fast-discharging process. This comprehensive review provides a concise overview of the obstacles faced and thereby the recent advancements made in the realm of fast-charging all-solid-state lithium batteries. Firstly, it explains the inherent challenges of solid-state electrolytes (SSEs) and conventional ASSLB design that impede fast-charging capabilities. Based on these challenges, the specifications and strategies for optimizing the SSEs, electrodes, and electrode/SSE interfaces are discussed to achieve the fast-charging phenomenon in ASSLBs. To give readers a better understanding of ASSLBs under fast-charging capabilities, a comprehensive conclusion and novel points of view are included in the prospects. [ABSTRACT FROM AUTHOR]

All-solid-state lithium–sulfur batteries (ASSLSBs) have gained significant attention due to their high energy density and excellent safety characteristics. However, the practical application of these batteries is hindered by interfacial issues between the solid electrolyte and electrode. The instability of this interface during charge–discharge cycles arises from side effects of the electrolyte and anode, as well as poor solid–solid contact. In this study, we employ first principles calculations to analyze the chemical stability at the interface between the Li1/2La1/2TiO3 (LLTO) electrolyte and the Li anode, with a focus on strategies to address this issue and stabilize the cathode–electrolyte interface. We systematically investigate various physicochemical properties at the LLTO‖Li and LLTO‖LiIn2 interfaces, including electron conductivity, work function, chemical stability, and Li+ diffusion across the interface. Our findings demonstrate that LLTO‖LiIn2 exhibits enhanced long-term storage capabilities for ASSLSBs while reducing overall costs. Alloying lithium anodes with In atoms weakens electron injection into the electrolyte within the anode, thereby reducing chances of electrolyte reduction and improving charge–discharge performance. Additionally, a lower Li+ diffusion barrier is observed at the LLTO‖LiIn2 interface which promotes efficient Li+ transport. This work provides valuable theoretical insights for developing effective interface engineering strategies between electrolytes and anodes. [ABSTRACT FROM AUTHOR]

All-solid-state sodium batteries, renowned for their leak-proof nature and enhanced safety profile, have become a pivotal focus of research. Their viability hinges on the development of robust solid electrolyte materials. Among these, Na 3 Zr 2 Si 2 PO 12 (NZSP) stands out as a particularly promising candidate. However, the practical utility of NZSP has been limited by its relatively modest room temperature conductivity. This paper introduces a novel modification strategy aimed at significantly enhancing room temperature conductivity of NZSP. In the series of experiments, NSZP was synthesized by traditional sintering process with Zn2+ doping and NaF additives. Through the substitution of Zr4+ ions with Zn2+ ions, this innovative approach not only raises the sodium ion concentration but also expands the bottleneck regions within the Na ion transport pathways. This augmentation ultimately translates into heightened grain conductivity. Additionally, the incorporation of NaF during the sintering process induces crystal growth in NZSP, thereby reducing grain boundary concentration and further amplifying grain conductivity's contribution to the overall ionic conductivity. Employing conventional sintering techniques, we successfully synthesized Na 3.3 Zr 1.95 Zn 0.05 Si 2.2 P 0.8 O 12 -0.25NaF (−0.25 NaF indicates that 0.25 mol NaF was added during sintering) electrolyte samples, which demonstrated an impressive high room temperature conductivity of 2.2 × 10−3 S cm−1. This value surpasses the ionic conductivity of undoped NZSP electrolytes by approximately an order of magnitude. Moreover, the Na 3.3 Zr 1.95 Zn 0.05 Si 2.2 P 0.8 O 12 -0.25NaF electrolyte exhibits a remarkable electrochemical window extending up to 4.9 V, accompanied by exceptional cycling stability. These properties render it an ideal candidate for a diverse array of cathode materials. [ABSTRACT FROM AUTHOR]

A critical bottleneck toward all-solid-state batteries lies in how the solid(electrode)-solid(electrolyte) interface is fabricated and maintained over repeated cycles. Conventional composite cathodes, with crystallographically distinct electrode/electrolyte interfaces of random particles, create complexities with varying (electro)chemical compatibilities. To address this, we employ an epitaxial model system where the crystal orientations of cathode and solid electrolyte are precisely controlled, and probe the interfaces in real-time during co-sintering by in situ electron microscopy. The interfacial reaction is highly dependent on crystal orientation/alignment, especially the availability of open ion channels. Interfaces bearing open ion paths of NCM are more susceptible to interdiffusion, but stabilize with the early formed passivation layer. Conversely, interfaces with closed ion pathway exhibit stability at intermediate temperatures, but deteriorate rapidly at high temperature due to oxygen evolution, increasing interfacial resistance. The elucidation of these distinct interfacial behaviors emphasizes the need for decoupling collective interfacial properties to enable rational design in solid-state batteries. A bottleneck in solid-state batteries is the solid electrode-electrolyte interface being maintained over repeated cycles. Here, the authors use an epitaxial model system to probe and control the interface in real time. [ABSTRACT FROM AUTHOR]

While post‐synthesis processing steps are frequently applied in the preparation of cathode composites for solid‐state batteries to ensure homogeneous mixing and good contact with the cathode active material, little is known about the processes that occur during milling and how they influence structure and transport of solid electrolytes. Here, an extensive set of experimental methods and simulations are used to study the effects of post‐synthesis milling by a frequency and planetary ball mill on the highly conducting chloride‐rich argyrodite Li5.5PS4.5Cl1.5. Structural analyses show that processing can reduce the coherence length and increase the disorder. The reduced crystallite size correlates with a decrease in ionic conductivity in the post‐processed solid electrolytes. Simulating the ball milling processes by the discrete element method provides fundamental understanding and reveals the correlation of the loss in coherence with the specific energy input and the numbers of stressing events during the milling process. An observed decrease in particle size in ball milled samples leads to lower tortuosity in the cathode composites. As the loss in coherence and decrease in particle size have opposite effects on the performance, optimizing these processing conditions will play a significant role on the road to highly performing solid‐state batteries. [ABSTRACT FROM AUTHOR]

Garnet solid‐state electrolyte Li6.5La3Zr1.5Ta0.5O12 (LLZTO) holds significant promise. However, the practical utilization has been seriously impeded by the poor contact of Li|garnet and electron leakage. Herein, one new type of garnet‐based solid‐state battery is proposed with high performance through the disparity in interfacial energy, induced by the reaction between trace fluorinated carbon dots (FCDs) and Li. The work of adhesion of Li|garnet is increased by the acquired Li‐FCD composite, which facilitates an intimate Li|garnet interface with the promoted uniform Li+ deposition, revealed by density functional theory (DFT) calculations. It is further validated that a concentrated C−Li2O−LiF component at the Li|garnet interface is spontaneously constructed, due to the significant disparity in interfacial energy between C−Li2O−LiF|LLZTO and C−Li2O−LiF|Li. Furthermore, The electron transport and Li dendrites penetration are effectively hindered by the formed Li2O and LiF. The Li‐FCD|LLZTO|Li‐FCD symmetrical cells demonstrate stable cycling performance for over 3000 hours at 0.3 mA cm−2 and 800 hours at 0.5 mA cm−2. Furthermore, the LFP|garnet|Li‐FCD full cell exhibits remarkable cycling performance (91.6 % capacity retention after 500 cycles at 1 C). Our research has revealed a novel approach to establish a dendrite‐free Li|garnet interface, laying the groundwork for future advancements in garnet‐based solid‐state batteries. [ABSTRACT FROM AUTHOR]

Low ionic conductivity, narrow electrochemical window and poor mechanical property are the core problems that polymer solid electrolyte is difficult for practical application. Choosing suitable polymer and regulating the ion transport path through inorganic fillers is an important method to solve the above problems. Herein, a polymeric matrix composite solid electrolyte(CSE) was achieved by combining electrospun Li7La3Zr2O12 (LLZO) fibers and highly viscoelastic polypropylene oxide(PPO). The PPO matrix provides the CSE with good mechanical property to 56.75 MPa. While the addition of fibrous LLZO improves the ion transport channels of the CSE, which boosts the ionic conductivity, electrochemical window and ion transport number up to 4.59 × 10− 4 S cm− 1 at room temperature, 5.4 V and 0.74, respectively, when the content of LLZO fiber is 7.5 wt% of PPO polymer. The prepared PPO-LLZO fibers electrolyte can be used in high-voltage solid-state lithium battery and shows good rate and cycle performances. This composite solid electrolyte film and its simplified preparation conditions is beneficial for practical applications in solid-state batteries. [ABSTRACT FROM AUTHOR]

Compared to traditional lithium metal batteries, anode-free lithium metal batteries use bare current collectors as an anode instead of Li metal, making them highly promising for mass production and achieving high-energy density. The current collector, as the sole component of the anode, is crucial in lithium deposition-stripping behavior and greatly impacts the rate of Li depletion from the cathode. In this study, to investigate the lithiophilicity effect of the current collector on the solid electrolyte interface (SEI) film construction and cycling performance of anode-free lithium batteries, various lightweight paper-based current collectors were prepared by electroless plating Cu and lipophilic Ag on low-dust paper (LDP). The areal densities of the as-prepared LDP@Cu, LDP@Cu-Ag, and LDP@Ag were approximately 0.33 mg cm−2. The use of lipophilic Ag-coated collectors with varying loadings allowed for the regulation of lipophilicity. The impacts of these collectors on the distribution of SEI components and Li depletion rate in common electrolytes were investigated. The findings suggest that higher loadings of lipophilic materials, such as Ag, on the current collector increase its lipophilicity but also lead to significant Li depletion during the cycling process in full-cell anode-free Li metal batteries. Thus, moderately lithiophilic current collectors, such as LDP@Cu-Ag, show more potential for Li deposition and striping and stable SEI with a low speed of Li depletion. [ABSTRACT FROM AUTHOR]

Nowadays, lithium‐ion batteries (LIBs) are widely used in all walks of life and play a very important role. As complex systems composed of multiple materials with diverse chemical compositions, where different electrochemical reactions take place, battery interfaces are essential for determining the operation, performance, durability and safety of the battery. This work, set out to study the incorporation of lithium bis(fluorosulfonyl)amide (LiFSI) doped 1‐ethyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIm][TFSI]) ionic liquid into an archetype Ti‐based Metal Organic Framework (MOF) ((Ti) MIL125−NH2) to create a solid to quasi‐solid (depending on the amount of IL in the system), and how it affects not only ionic transport but also the structural properties of the IL/MOF electrolyte. Remarkably high ionic conductivity values (2.13×10−3 S ⋅ cm−1 at room temperature) as well as a lithium transference number (tLi=0.58) were achieved, supported by pulsed field gradient (PFG) NMR experiments. Electrochemical characterization revealed reversible plating‐stripping of lithium and lower overpotential after 750 h at 50 °C. Additionally, a proof‐of‐concept solid state battery was fabricated resulting in a discharge capacity of 160 mAh ⋅ g−1 at 50 °C and 0.1 C rate after 50 cycles. This work presents a suitable strategy to dendrite suppression capability, allowing its implementation as interface modifiers in next‐generation solid‐state batteries. [ABSTRACT FROM AUTHOR]

Solid‐state polymerized electrolytes exhibit advantageous properties, making them optimal candidates for next‐gen commercial solid‐state batteries. However, these electrolytes present significant challenges in terms of long‐term cycling stability, energy density, and safety. In this study, a ternary eutectic solid electrolyte (TESE) is prepared by combining deep eutectic solvents (DESs), polyvinylidene fluoride‐hexafluoropropylene (PVDF‐HFP), and fluorinated ethylene carbonate (FEC). TESE also facilitates uniform lithium deposition, interfacial stability, and long‐cycle stability. N‐Methylacetamide in DESs preferentially occupies the lithium dissolution sheath, which in turn initiates a concentration gradient‐driven decomposition of FEC and stimulates the generation of inorganic solid electrolyte interphase (SEI) layers. The lithium metal and graphite soft pack full batteries are successfully assembled, demonstrating that Li/P‐0.8‐FEC/LFP exhibits excellent long‐cycle performance, with a capacity of 139.9 mAh g−1 after 500 cycles at 1 C 25 °C, accompanied by 97.8 % capacity retention. Furthermore, the Gr/P‐0.8‐FEC/LFP commercial solid‐state flexible pack full cell exhibits stable cycling performance at a high rate of 1 C. Moreover, the device exhibits remarkable safety in a series of rigorous safety tests, including 100 repeated bendings, pinning, 7100 N force extrusion, and cutting. The study results demonstrate that the electrolyte exhibits excellent cycling performance and safety characteristics, indicating significant potential for commercialization. [ABSTRACT FROM AUTHOR]

The rise in the energy demand, the need to decrease the use of fossil fuels, expanding investments in renewable energy and boosting the electric vehicle market, opens the door to new technologies in clean energy accumulators. Lithium‐ion batteries are the most advanced technology in the market but have safety concerns due to the flammability of the electrolyte, which opens the door to innovations. One of these innovations is the solid‐state batteries (SSB), which, by using solid electrolytes, do not have the flammable risk, bringing safety to users while reaching similar energy and power densities. This work presents a review about SSB, based on qualitative and exploratory research, using the Web of Science (WoS) platform. Keywords used to gather information from the database were "solid state batteries" and "electrolytes". Only publications from 2018 to 2023 were selected. The main research focus is to solve the challenges posed by the different physical‐chemical phenomena of the SSB. This work focuses on the general comprehension of the SSB batteries, what are the factors that can affect it and the main solutions presented in the literature the last five years. [ABSTRACT FROM AUTHOR]

The practical application of solid‐state polymer lithium‐metal batteries (LMBs) is plagued by the inferior ionic conductivity of the applied polymer electrolytes (PEs), which is caused by the coupling of ion transport with the motion of polymer segments. Here, solvated molecules based on ionic liquid and lithium salt with strong Li+‐solvent interaction are inserted into an elaborately engineered perfluoropolymer electrolyte via ionic dipole interaction, extensively facilitating Li+ transport and improving mechanical properties. The intensified formation of solvation structures of contact ion pairs and ionic aggregates, as well as the strong electron‐withdrawal properties of the F atoms in perfluoropolymers, give the PE high electrochemical stability and excellent interfacial stability. As a result, Li||Li symmetric cells demonstrate a lifetime of 2500 h and an exceptionally high critical current density above 2.3 mA cm−2, Li||LiFePO4 batteries exhibit consistent cycling for 550 cycles at 10 C, and Li||uncoated LiNi0.8Co0.1Mn0.1O2 cells achieve 1000 cycles at 0.5 C with an average Coulombic efficiency of 98.45 %, one of the best results reported to date based on PEs. Our discovery sheds fresh light on the targeted synergistic regulation of the electro‐chemo‐mechanical properties of PEs to extend the cycle life of LMBs. [ABSTRACT FROM AUTHOR]

The positive electrode|electrolyte interface plays an important role in all-solid-state Li batteries (ASSLBs) based on garnet-type solid-state electrolytes (SSEs) like Li6.4La3Zr1.4Ta0.6O12 (LLZTO). However, the trade-off between solid-solid contact and chemical stability leads to a poor positive electrode|electrolyte interface and cycle performance. In this study, we achieve thermodynamic compatibility and adequate physical contact between high-entropy cationic disordered rock salt positive electrodes (HE-DRXs) and LLZTO through ultrafast high-temperature sintering (UHS). This approach constructs a highly stable positive electrode|electrolyte interface, reducing the interface resistance to 31.6 Ω·cm2 at 25 °C, making a 700 times reduction compared to the LiCoO2 | LLZTO interface. Moreover, the conformal and tight HE-DRX | LLZTO solid-state interface avoids the transition metal migration issue observed with HE-DRX in liquid electrolytes. At 150 °C, HE-DRXs in ASSLBs (Li|LLZTO | HE-DRXs) exhibit an average specific capacity of 239.7 ± 2 mAh/g at 25 mA/g, with a capacity retention of 95% after 100 cycles relative to the initial cycle—a stark contrast to the 76% retention after 20 cycles at 25 °C in conventional liquid batteries. Our strategy, which considers the principles of thermodynamics and kinetics, may open avenues for tackling the positive electrode|electrolyte interface issue in ASSLBs based on garnet-type SSEs. The positive electrode/electrolyte interface is crucial for the performance of all-solid-state lithium batteries. Here, authors use a sintering technique to form a conformal interface between high-entropy disordered rock salt electrodes and garnet-type electrolytes to reduce interfacial resistance. [ABSTRACT FROM AUTHOR]

The coupling of high-capacity cathodes and lithium metal anodes promises to be the next generation of high-energy-density batteries. However, the fast-structural degradations of the cathode and anode challenge their practical application. Herein, we synthesize an electrolyte additive, tris(2,2,3,3,3-pentafluoropropyl) borane (TPFPB), for ultra-stable lithium (Li) metal||Ni-rich layered oxide batteries. It can be preferentially adsorbed on the cathode surface to form a stable (B and F)-rich cathode electrolyte interface film, which greatly suppresses the electrolyte-cathode side reactions and improves the stability of the cathode. In addition, the electrophilicity of B atoms in TPFPB enhances the solubility of LiNO3 by 30 times in ester electrolyte to significantly improve the stability of the Li metal anode. Thus, the Li||Ni-rich layered oxide full batteries using TPFPB show high stability and an ultralong cycle life (up to 1500 cycles), which also present excellent performance even under high voltage (4.8 V), high areal mass loading (30 mg cm−2) and wide temperature range (−30∼60°C). The Li||LiNi0.9Co0.05Mn0.05O2 (NCM90) pouch cell using TPFPB with a capacity of 3.1 Ah reaches a high energy density of 420 Wh kg−1 at 0.1 C and presents outstanding cycling performance. [ABSTRACT FROM AUTHOR]

Due to superior energy density and safety, all-solid-state lithium-ion batteries (ASSLBs) are considered to be the perfect substitute for lithium-ion batteries. As the most important component of ASSLBs, solid-state electrolytes (SSEs) are an important part of promoting the commercial development of ASSLBs. However, low ionic conductivity and poor oxidation stability of SSEs are the main obstacles to their industrial preparation. Here, we chose garnet Li7La3Zr2O12 ceramics to prepare a three-dimensional (3D) rebar-like structure nanofiber framework by electrospinning, and infiltrating a polyethylene oxide (PEO) polymer matrix to form the reinforced concrete-like composite solid electrolytes (3D RC-CSEs). The regularly arranged and interconnected framework endows the 3D RC-CSEs with a fast ion transport channel (ion conductivity is 0.23 mS cm−1 at 30 ℃), the lithium-ion transference number is up to 0.47 and electrochemical stability window of 4.9 V (vs. Li+/Li). The Li|3D RC-CSEs|Li battery can achieve a stable cycle for 3200 h at 0.2 mA cm−2. The LFP|3D RC-CSEs|Li battery shows an excellent rate performance (discharge specific capacity of 123.1 mAh g−1 at 3 C) and great cycling performance (discharge specific capacity of 123.1 mAh g−1 after 600 cycles at 1 C) at 60 ℃. In addition, the 3D RC-CSEs showed that Young's modulus is 9.6 times of the PEO-LiTFSI. The unique structural design provides a practical strategy for commercial development. [ABSTRACT FROM AUTHOR]

All‐solid‐state batteries equipped with solid‐state electrolytes (SSEs) have gained significant interest due to their enhanced safety, energy density, and longevity in comparison to traditional liquid organic electrolyte‐based batteries. However, many SSEs, such as sulfides and hydrides, are highly sensitive to water, limiting their practical use. As one class of important perovskites, the Ruddlesden–Popper perovskite oxides (RPPOs), show great promise as SSEs due to their exceptional stability, particularly in terms of water resistance. In this review, the crystal structure and synthesis methods of RPPOs SSEs are first introduced in brief. Subsequently, the mechanisms of ion transportation, including oxygen anions and lithium‐ions, and the relevant strategies for enhancing their ionic conductivity are described in detail. Additionally, the progress made in developing flexible RPPOs SSEs, which are critical for flexible and wearable electronic devices, has also been summarized. Furthermore, the key challenges and prospects for exploring and developing RPPOs SSEs in all‐solid‐state batteries are suggested. This review presents in detail the synthesis methods, the ion transportation mechanism, and strategies to enhance the room temperature ionic conductivity of RPPOs SSEs, providing valuable insights on enhancing their ionic conductivity and thus for their practical application in solid‐state batteries. [ABSTRACT FROM AUTHOR]

A new silane coupling agent is designed to fabricate a self-healing composite electrolyte with dynamic disulfide bonds and hydrogen bonds, which exhibits superior Li compatibility, excellent electrochemical performance in full cells, and great application potential in flexible all-solid-state Li metal batteries. [Display omitted] Composite solid electrolytes (CSEs), which combine the advantages of solid polymer electrolytes and inorganic solid electrolytes, are considered to be promising electrolytes for all-solid-state lithium metal batteries. However, the current CSEs suffer from defects such as poor inorganic/organic interface compatibility, lithium dendrite growth, and easy damage of electrolyte membrane, which hinder the practical application of CSEs. Herein, a CSE (PBHL@LLZTO@DDB) with polyurethane (PBHL) as the polymer matrix and Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 (LLZTO) modified by silane coupling agent (DDB) as inorganic fillers (LLZTO@DDB) has been prepared. Disulfide bond exchange reactions between PBHL and LLZTO@DDB enable PBHL@LLZTO@DDB to form a dynamic three-dimensional (3D) inorganic/organic hybrid network, which promotes the uniform dispersion of LLZTO in PBHL@LLZTO@DDB, improves the Li+ conductivity (1.24 ± 0.08 × 10−4 S cm−1 at 30 ℃), and broadens the electrochemical stability window (5.16 V vs. Li+/Li). Moreover, a combination of hydrogen bonds and disulfide bonds endows PBHL@LLZTO@DDB with excellent self-healing properties. As such, both all-solid-state symmetric and full cells exhibit excellent cycle performance at ambient temperature. More importantly, the healed PBHL@LLZTO@DDB can almost completely restore its original electrochemical properties, indicating its application potential in flexible electronic products. [ABSTRACT FROM AUTHOR]

We examine the dynamic and ionic properties of a typical sulfide glass electrolyte 50Li2S${\rm Li}_2{\rm S}$–50SiS2${\rm SiS}_2$ using molecular dynamics simulations and a previously parameterized force‐field able to describe both the crystalline Li2SiS3${\rm Li}_2 {\rm SiS}_3$ phase and the corresponding glass. We especially focus on the effect of moderate pressures on the glassy and supercooled state since the design of all‐solid state batteries use molding conditions at moderate pressures in order to achieve contact between the electrolyte and the electrodes. The behavior of the conductivity σ(P)$\sigma (P)$ with pressure permits to define an activation volume and to infer the role of compressibility and diffusivity, the latter contributing dominantly to ionic conduction, whereas temperature does not seem to impact the structural properties. These features are linked with the underlying dynamics of the Li ions as studied here by computing the longitudinal and transversal atomic species current correlations. The resulting elasticity is found to be close to experimental values. [ABSTRACT FROM AUTHOR]

[Display omitted] The construction of solid-state electrolytes for flexible zinc-air batteries is extremely challenging. A flexible and highly conductive solid electrolyte designed with a "seaweed structure" is reported in this work. Sodium alginate serves as the backbone to form a robust network structure, and the grafted quaternary ammonium groups provide channels for rapid ion transport, achieving excellent flexibility and hydroxide conductivity. The conductivity of the modified electrolyte membrane (QASA) is 5.23 × 10−2 S cm−1 at room temperature and reaches up to 8.51 × 10−2 S cm−1 at 75 °C. In the QASA based battery, bending at any angle is realized, and the power density is up to 57.28 mW cm−2. This work provides a new way to prepare high conductivity, green solid-state zinc-air batteries, and opens up a research line of thought for flexible energy storage materials. [ABSTRACT FROM AUTHOR]

Applications of praseodymium doped ceria (PDC) in solid oxide fuel cells require a deep insight into the thermal expansion, stresses, and ionic conduction. Nonetheless, the investigation of thermo-mechanical properties and oxygen vacancy diffusion remains incomplete. Based on free Helmholtz energy, we formulate analytical expressions to directly connect thermal expansion coefficient, elastic moduli, oxygen vacancy–dopant binding and oxygen vacancy migration energies by employing statistical moment method (SMM). The SMM calculations capture the full anharmonicity of lattice thermal vibrations. Our analyses report the significant influences of temperature and dopant content on the thermal expansion coefficient, bulk and Young's moduli, oxygen vacancy–dopant binding and oxygen vacancy migration energies, and ionic conductivity. The role of Pr dopant on the oxygen vacancy diffusion is fully described by combining the symmetric energy profiles related to blocking effect and asymmetric energy profiles generated from trapping effect. By switching van der Waals (vdW) forces on and off in the SMM calculations, we first show that the vdW forces cause a positive effect on the mechanical properties but reduce the thermal expansion and resist the oxygen vacancy diffusion. Our findings are discussed concerning the results from other calculations and experiments in the literature. The insights on the thermo-mechanical properties and oxygen vacancy diffusion for PDC crystal can be generalized and applied to other ceramic materials that are essential for solid state batteries. [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]

Fewer layer graphene principally has a higher surface area to support more catalytic sites for energy conversion, but it is still challenging to synthesize monolayer graphene without oxidation from graphite at a low cost. Here, a method for synergistically thinning graphene layers and constructing catalytic sites to create a superior bifunctional oxygen catalyst through vapor intercalation of multi‐layer graphene or its derivatives is described. The synthesized small sheet sizes of 1–2 layer graphene‐supported FeN4 and FeCo active sites exhibit superior reversible activity of oxygen reduction and evolution reactions with a low overall overpotential of 0.648 V. The sheet‐shaped catalyst is further used to fabricate flexible soft‐packed and wearable cable‐type quasi‐solid‐state zinc–air batteries, achieving high performances (>188 mW cm−2, >450 cycles) and enabling smartphone charging. DFT calculations reveal that fewer layer graphene coupled with atomic FeN4 and alloy FeCo sites enables lower Gibbs free energy for favorable OOH* intermediate adsorption/desorption benefiting superior oxygen redox process. This study introduces a strategy for scalable synthesis of 1–2 layer graphene from cheap microcrystalline graphite minerals for wearable and durable energy devices. [ABSTRACT FROM AUTHOR]

Solid‐state lithium metal batteries are under development for higher energy density and better safety. A key is to develop new electrolyte systems that are readily processible and capable to improve electrochemical cycling stability. In this study, A quasi‐solid‐state composite electrolyte based on low‐molecular‐weight polyethylene glycol dimethyl ether (PEGDME) in situ confined within polymerized methyl methacrylate (PMMA) backbone is designed and presented. The new design of the polymer matrix, together with Li+‐conducting ceramic fillers and appropriate lithium salts, has satisfactory Li‐ionic conductivity (1.1 × 10−4 S cm−1 at 30 C and 1.0 × 10−3 S cm−1 at 80 °C), good electrochemical stability (>4.7 V vs Li+/Li), and high compatibility with lithium metal anode, enabling room‐temperature operation and stable long‐term cycling of both Li||Li symmetric cells and lithium‐metal full cells (including LiFePO4 or LiCoO2 cathode). This work can extend the design boundaries of composite electrolytes meaningfully, and the idea of in situ polymerization limiting applies to almost all low‐molecular‐weight polymers, high‐molecular‐weight backbones, ceramic fillers, lithium salts, and additives in future development of room‐temperature solid‐state lithium metal batteries. [ABSTRACT FROM AUTHOR]

Solid‐state battery research has gained significant attention due to their inherent safety and high energy density. Silicon anodes have been promoted for their advantageous characteristics, including high volumetric capacity, low lithiation potential, high theoretical and specific gravimetric capacity, and the absence of lethal dendritic growth. Addressing concerns such as low conductivity, pulverization, fracture, dense solid electrolyte interface layer, and low coulombic efficiency has substantially improved the use of silicon electrodes in solid‐state batteries. Researchers have explored carbon additions, solid electrolyte suitability for Si anodes, pressure optimization, and particle size effects (nano/micro) to enhance energy density. Recent studies have investigated the conductivity mechanism, stack pressure, and anode‐solid electrolyte compatibility to improve energy density. Micro‐ and nano‐sized silicon have attracted attention in carbon‐based composites due to their exceptional conductivity, uniform distribution, efficient electron migration, and diffusion channels. The development of solid‐state batteries with high energy density, safety, and extended lifespan has been a major focus. This review sheds light on significant insights and strategic approaches for researchers working on solid‐state silicon‐based systems to overcome existing challenges. [ABSTRACT FROM AUTHOR]

Regulating the electric double layer (EDL) structure of the zinc metal anode by using electrolyte additives is an efficient way to suppress interface side reactions and facilitate uniform zinc deposition. Nevertheless, there are no reports investigating the proactive design of EDL‐regulating additives before the start of experiments. Herein, a functional group assembly strategy is proposed to design electrolyte additives for modulating the EDL, thereby realizing a long‐lasting zinc metal anode. Specifically, by screening ten common functional groups, N, N‐dimethyl‐1H‐imidazole‐1‐sulfonamide (IS) is designed by assembling an imidazole group, characterized by its high adsorption capability on the zinc anode, and a sulfone group, which exhibits strong binding with Zn2+ ions. Benefiting from the adsorption functionalization of the imidazole group, the IS molecules occupy the position of H2O in the inner Helmholtz layer of the EDL, forming a molecular protective layer to inhibit H2O‐induced side reactions. Meanwhile, the sulfone group in IS, acting as a binding site to Zn2+, promotes the de‐solvation of Zn2+ ions, facilitating compact zinc deposition. Consequently, the utilization of IS significantly extending the cycling stability of Zn||Zn and Zn||NaV3O8 ⋅ 1.5H2O full cell. This study offers an innovative approach to the design of EDL regulators for high‐performance zinc metal batteries. [ABSTRACT FROM AUTHOR]

The evolution of inorganic solid electrolytes has revolutionized the field of sustainable organic cathode materials, particularly by addressing the dissolution problems in traditional liquid electrolytes. However, current sulfide‐based all‐solid‐state lithium‐organic batteries still face challenges such as high working temperatures, high costs, and low voltages. Here, we design an all‐solid‐state lithium battery based on a cost‐effective organic cathode material phenanthrenequinone (PQ) and a halide solid electrolyte Li2ZrCl6. Thanks to the good compatibility between PQ and Li2ZrCl6, the PQ cathode achieved a high specific capacity of 248 mAh g−1 (96 % of the theoretical capacity), a high average discharge voltage of 2.74 V (vs. Li+/Li), and a good capacity retention of 95 % after 100 cycles at room temperature (25 °C). Furthermore, the interactions between the high‐voltage carbonyl PQ cathode and both sulfide and halide solid electrolytes, as well as the redox mechanism of the PQ cathode in all‐solid‐state batteries, were carefully studied by a variety of advanced characterizations. We believe such a design and the corresponding investigations into the underlying chemistry give insights for the further development of practical all‐solid‐state lithium‐organic batteries. [ABSTRACT FROM AUTHOR]

Polyethylene oxide (PEO)‐based solid‐state batteries hold great promise as the next‐generation batteries with high energy density and high safety. However, PEO‐based electrolytes encounter certain limitations, including inferior ionic conductivity, low Li+ transference number, and poor mechanical strength. Herein, we aim to simultaneously address these issues by utilizing one‐dimensional zwitterionic cellulose nanofiber (ZCNF) as fillers for PEO‐based electrolytes using a simple aqueous solution casting method. Multiple characterizations and theoretical calculations demonstrate that the unique zwitterionic structure imparts ZCNF with various functions, such as disrupting PEO crystallization, dissociating lithium salts, anchoring anions through cationic groups, accelerating Li+ migration by anionic groups, as well as its inherent reinforcement effect. As a result, the prepared PL‐ZCNF electrolyte exhibits remarkable ionic conductivity (5.37×10−4 S cm−1) and Li+ transference number (0.62) at 60 °C without sacrificing mechanical strength (9.2 MPa), together with high critical current density of 1.1 mA cm−2. Attributed to these merits of PL‐ZCNF, the LiFePO4|PL‐ZCNF|Li solid‐state full‐cell delivers exceptional rate capability and cycling performance (900 cycles at 5 C). Notably, the assembled pouch‐cell can maintain steady operation over 1000 cycles with an impressive 93.7 % capacity retention at 0.5 C and 60 °C, highlighting the great potential of PL‐ZCNF for practical applications. [ABSTRACT FROM AUTHOR]

Visual electrochemiluminescence (ECL) emission from L012 and hydrogen peroxide is generated from an all-solid-state electrochemical cell with a polyacrylamide hydrogel as the solid electrolyte. The emission is strong enough to be visualized with the naked eye, which offers a new idea for the design of an all-solid-state ECL based sensor in air. [ABSTRACT FROM AUTHOR]

NASICON-type sodium vanadium phosphate (Na3V2(PO4)3) as a cathode for sodium-ion batteries has attracted widespread research interest due to its high operating voltage (∼3.3 V) and stable three-dimensional structural framework. However, it suffers from low specific capacity due to its poor electronic conductivity and limited redox features. To increase the specific discharge capacity of Na3V2(PO4)3, structural modifications are necessary. Thus, it is important to probe the influence of synthetic routes on the electrochemical performance of NASICON-type Na3V2(PO4)3 (NVP). Herein, sodium vanadium phosphate was synthesized using a sol–gel method (NVP-SG) and a solid-state route (NVP-SS). NVP cathodes were tested and examined for laboratory prototype CR-2032 coin-type sodium-ion batteries. The NVP-SG cathode exhibited a passable discharge capacity of 130 mA h g−1 at a 0.1C rate, whereas the NVP-SS cathode delivered a high discharge capacity of 160 mA h g−1 at a 0.1C rate. The detailed charge storage modes of NVP synthesized through solid-state (NVP-SS) and sol–gel (NVP-SG) synthesis were examined by means of Dunn's analysis. Dunn's analysis confirmed that the charge storage is dominated by the diffusive mode at the peak potential region and the capacitive mode at the non-peak potential regions. [ABSTRACT FROM AUTHOR]

Safety concerns associated with lithium batteries suggest the development of solid-state batteries as a promising variant. In this work, we doped a lithium boracite (Li4B7O12Cl) with Mg2+ to modify the Li+ sites and observed significant improvement in ionic conductivity by two orders of magnitude (from 3.03 × 10−7 S cm−1 to 2.81 × 10−5 S cm−1 at room temperature). We attribute the enhanced ion conductivity to the artificially induced Li vacancies resulting from Mg doping. The as-fabricated symmetrical battery (Li‖Li3.6Mg0.2B7O12Cl‖Li) exhibited good cycling performance with a stable voltage output even after 60 hours of cycling. The battery showed a coulombic efficiency retention of ∼99.7% after the cycling test. Our work demonstrates that Li4B7O12Cl is a superior solid electrolyte for solid-state batteries and the introduction of Li vacancies can be an efficient approach to greatly improve the ionic conductivity of other electrolytes. [ABSTRACT FROM AUTHOR]

In the current challenging energy storage and conversion landscape, solid‐state lithium metal batteries with high energy conversion efficiency, high energy density, and high safety stand out. Due to the limitations of material properties, it is difficult to achieve the ideal requirements of solid electrolytes with a single‐phase electrolyte. A composite solid electrolyte is composed of two or more different materials. Composite electrolytes can simultaneously offer the advantages of multiple materials. Through different composite methods, the merits of various materials can be incorporated into the most essential part of the battery in a specific form. Currently, more and more researchers are focusing on composite methods for combining components in composite electrolytes. The ion transport capacity, interface stability, machinability, and safety of electrolytes can be significantly improved by selecting appropriate composite methods. This review summarizes the composite methods used for the components of composite electrolytes, such as filler blending, embedded framework, and multilayer bonding. It also discusses the future development trends of all‐solid‐state lithium batteries (ASSLBs). [ABSTRACT FROM AUTHOR]

All‐solid‐state‐batteries (ASSBs) based on a halide solid electrolyte (SE) and a lithium‐metal based anode typically have poor cyclability without a buffer layer (such as Li3PS4 or Li6PS5Cl) to prevent the degradation reactions. Here excellent cycling stability of ASSB consisting of an uncoated single‐crystal LiNi0.8Co0.1Mn0.1O2 cathode and a Li3YCl6 (LYC) SE separator in direct contact with a Li‐In anode are demonstrated. Through a combination of electrochemical measurements, synchrotron micro‐X‐ray absorption and diffraction analyses, and density functional theory calculations, reveal for the first time that along with the standard Li+ transport during charge/discharge, indium in the Li‐In anode also participates in the redox reactions. The in‐situ generated In3+ preferentially occupies the vacant Li sites in the trigonal LYC lattice, leading to the formation, growth, and eventual stabilization of an anode‐electrolyte interphase (AEI) layer consisting of an In‐doped Li3‐xInxYCl6 (x = ≈0.2) phase. It is discussed how the presence of such an AEI layer prevents LYC decomposition and suppresses dendrite formation and propagation, enabling stable cycling of ASSB with ≈90% capacity retention over 1000 cycles. This work sheds light on the dynamic evolution of the halide SE and alloy anode interphase, and opens new avenues in the future design of long‐lasting high‐energy all‐solid‐state‐batteries. [ABSTRACT FROM AUTHOR]

A quantitative understanding of the Li distribution inside all-solid-state Li-ion batteries is important for improving the performance of batteries. We constructed a time-of-flight (TOF) elastic recoil detection analysis (ERDA) system for operando measurements of thin-film Li-ion batteries. The TOF-ERDA measurement provides elementally resolved spectra with a depth resolution much higher than that of conventional stopper-foil ERDA. The Li depth profiles in a cathode film and solid electrolyte were obtained quantitatively to a depth of 100 nm using a 9-MeV Cu ion beam with reflection geometry. In this study, we conducted TOF-ERDA for a thin-film battery having a cathode made from LiCoO2, an oxide-based solid electrolyte [lithium aluminum titanium phosphate (LATP)], and an anode made from Fe2(MoO4)3 to demonstrate the ability of the measurement system and reveal the Li distribution near the interface with improved resolution. The depth resolution at the interface (30 nm from the surface) was estimated to be 12–14 nm. We quantitatively obtained the Li density in the LiCoO2 cathode and the variation in the Li distribution around the LiCoO2/LATP interface and inside the LATP electrolyte upon charging/discharging. TOF-ERDA is thus a powerful tool for the high-resolution quantitative depth analysis of Li in thin-film batteries in operando. [ABSTRACT FROM AUTHOR]

Li1.3Al0.3Ti1.7(PO4)3 (LATP) electrolyte has a great potential for application in solid‐state lithium metal batteries. However, due to the poor interfacial contact and thermodynamic instability between LATP and Li metal, a series of interfacial problems, such as high interfacial resistance, undesirable interfacial reaction and dendrite growth are deeply criticized. Herein, a hybrid LiCl/LixSn conductive interlayer is constructed through an in situ electrochemical reaction of SnCl4 with Li metal to effectively improve the compatibility and stability of the Li/LATP interface. LiCl with both electronic insulation and high ionic conductivity can provide fast Li+ diffusion channel, block electron injection, avoid side reactions, and effectively inhibit dendrite growth. LixSn can reduce interfacial impedance, eliminate local electric field concentration, and significantly improve interfacial wettability. Under the protection of LiCl/LixSn hybrid interlayer, the initial resistance of the symmetric battery is reduced from 1066.3 to 133.6 Ω cm−2, achieving a high critical current density of 1.4 mA cm−2. At 0.1 mA cm−2/0.1 mAh cm−2 and 0.2 mA cm−2/0.2 mAh cm−2, the symmetric battery can cycle stably for more than 4000 h at 25 °C. Moreover, the full battery displays a high capacity retention ratio of 90.4% after 420 cycles at 0.5 C. [ABSTRACT FROM AUTHOR]

[Display omitted] • PTFE-based dry-processed technology is used to prepare flexible Li 6 PS 5 Cl membrane and FeS 2 composite cathode membrane. • Due to the robust adhesion of PTFE, intimate contact is obtained at 100 MPa which is one-fifth of conventional pressure. • PTFE attaches the electrochemical sluggish products to an ion–electron conductive network to improve cyclic stability. • The flexible FeS 2 -ASSLBs exhibit excellent cyclic stability under the stack pressure of 100 MPa. All-solid-state lithium batteries (ASSLBs) are considered promising energy storage systems due to their high energy density and inherent safety. However, scalable fabrication of ASSLBs based on transition metal sulfide cathodes through the conventional powder cold-pressing method with ultrahigh stacking pressure remains challenging. This article elucidates a dry process methodology for preparing flexible and high-performance FeS 2 -based ASSLBs under low stack pressure by utilizing polytetrafluoroethylene (PTFE) binder. In this design, fibrous PTFE interweaves Li 6 PS 5 Cl particles and FeS 2 cathode components, forming flexible electrolyte and composite cathode membranes. Beneficial to the robust adhesion, the composite cathode and Li 6 PS 5 Cl membranes are tightly compacted under a low stacking pressure of 100 MPa which is a fifth of the conventional pressure. Moreover, the electrode/electrolyte interface can sustain adequate contact throughout electrochemical cycling. As expected, the FeS 2 -based ASSLBs exhibit outstanding rate performance and cyclic stability, contributing a reversible discharged capacity of 370.7 mAh g−1 at 0.3C after 200 cycles. More importantly, the meticulous dQ/dV analysis reveals that the three-dimensional PTFE binder effectively binds the discharge products with sluggish kinetics (Li 2 S and Fe) to the ion–electron conductive network in the composite cathode, thereby preventing the electrochemical inactivation of products and enhancing electrochemical performance. Furthermore, FeS 2 -based pouch-type cells are fabricated, demonstrating the potential of PTFE-based dry-process technology to scale up ASSLBs from laboratory-scale mold cells to factory-scale pouch cells. This feasible dry-processed technology provides valuable insights to advance the practical applications of ASSLBs. [ABSTRACT FROM AUTHOR]

Solid-state electrolyte structures using sodium polyaluminate ceramics, have been fabricated for the first time using direct ink writing; a material extrusion-based additive manufacturing process. A series of test samples were prepared using a high solids loading (80 wt%; 51.2 vol%) ceramic paste formulations with suitable rheological characteristics for 3D printing. Following optimum densification via conventional sintering at 1600 °C for 30 min, the additively manufactured electrolyte test samples exhibited an ionic conductivity of σ = 0.14 ± 0.019 S·cm−1 at 300 °C and density of ρ = 3.1 ± 0.02 g·cm−3 (relative density of 95%). These results suggest that direct ink writing of sodium polyaluminates is a promising approach for electrolyte manufacture. Additionally, this approach shows great potential for manufacturing complete solid-state battery structures, through multi-material direct ink writing. [ABSTRACT FROM AUTHOR]

The utilization of Si anode in sulfide‐based all‐solid‐state batteries (ASSBs) has gained more research attention in recent years to overcome the interface challenges associated with ASSB‐containing Li metal anode. However, the volume expansion feature of the Si, stress/strain evolution inside the electrode, and the parasitic side reaction at the Si/sulfide SE interface are the most predominant limiting factors for practical device applications. It is necessary to investigate and understand the interface challenges through in‐depth analysis in real‐time battery operation to design highly efficient ASSBs for commercial device applications. Hence, this perspective paper provides a summary of the characterization tools and the analysis results related to the Si/sulfide SE interface. Moreover, in this perspective, we emphasize the importance of further investigation of the interface through more advanced in‐depth/operando analysis tools to gain insightful information about the anodic interface, which could be useful for the researchers to design efficient research strategies for solving the challenging issues associated with the anodic interface. [ABSTRACT FROM AUTHOR]

High-temperature sintering is crucial to achieve good crystallinity and fast-ion conduction in oxide-type solid-electrolytes such as lithium garnets, NASICONs and LISICONs, leading to stiff ceramics which are difficult to integrate in all-solid-state batteries. Developing conventional oxide-based solid-electrolytes in deformable forms that maintain good ion transport properties and allow facile formulation of bulk-type solid-state batteries, hence, remains a challenge. Here, a new γ-Li3PO4/GeO2 composite, that adopts a novel nanostructured architecture and retains deformability after calcination at 500 °C, is successfully synthesized and densified by cold-pressing. Cold-pressed pellets of the new composite showed an ion conductivity that is four orders of magnitude higher than that of the parent γ-Li3PO4 and comparable to those of high-temperature stiff Li3+xP1−xGexO4 ceramics. The γ-Li3PO4/GeO2 composite is stable against high voltages (up to 5 V vs Li+/Li), which suggests a safe use in contact with high-voltage cathodes. The new composite can also be modified to serve as an active anode layer in solid-state cells due to the electrochemical activity of GeO2 at low voltages (<1 V vs. Li+/Li). This study emphasizes the potential of using low-temperature synthesis to develop novel oxide-based nanoarchitectures for all-solid-state battery applications. [ABSTRACT FROM AUTHOR]