All-solid-state Lithium Batteries Research Articles

Suppressing high voltage chemo-mechanical degradation in single crystal nickel-rich cathodes for high-performance all-solid-state lithium batteries

Sulfide-based all-solid-state lithium batteries (SASSLBs) suffer from electrochemo.mechanical damage to Ni-rich oxide-based cathode active materials (CAMs), primarilycaused by severe volume changes, results in significant stress and strain cuase micro-cracks, and interfacial contact loss at potentials > 4.3 V(vs. Li/Li+). Quantifying micro-cracks and voids in cathode active materials (CAMs) can reveal the degradation mechanisms of Ni-rich oxide-based cathodes during electrochemical cycling. Nonetheless, the origin of electrochemical-mechanical damage remains unclear. Herein, We have developed a multifunctional PEG-based soft buffer layer (SBL) on the surface of carbon black (CB). This layer functions as a percolation network in the single crystal LiNi0.83Co0.07Mn0.1O2 and Li6PS5Cl composite cathode layer, ensuring superior ionic conductivity, reducing void formation and particle cracking, and promoting uniform utilization of the cathode active material in all-solid-state lithium batteries (ASSLBs). STEM-HAADF combined with nanoscale X-ray holo-tomography and plasma-focused ion beam scanning electron microscopy confirmed that the PEG-based SBL mitigated strain induced by reaction heterogeneity in the cathode. This strain produces lattice stretches, distortions, and the formation of curved transition metal oxide layers near the surface, contributing to structural degradation at elevated voltages. Consequently, ASSLBs with a LiNi0.83Co0.07Mn0.1O2 cathode containing LCCB-10 (CB/PEG mass ratio: 100/10) demonstrate a high areal capacity (2.53 mAh g–1/0.32 mA g–1) and remarkable rate capability (0.58 mAh g–1 at 1.4 mA g–1), with 88% capacity retention over 1000 cycles.

A Rapid Synthesis of Amorphous LiTaOCl4 Solid Electrolytes Through a Two‐Step Reaction Pathway for High‐Rate and Long‐Cycling Lithium Batteries

AbstractA simplified process to prepare solid electrolytes (SEs) that fulfill long cyclability, fast‐charging performance, and wide‐temperature feasibility in all‐solid‐state lithium batteries (ASSLBs) is important. Here, amorphous LiTaOCl4 (aLTOC) SE is synthesized within only four hours via a two‐step reaction by high‐energy ball milling method, which exhibits high ionic conductivity and excellent interfacial compatibility. A bilayer SE based on aLTOC and sulfide along with corresponding ASSLBs, are constructed. Furthermore, slight evolution of the unusual microstructure in the chloride/sulfur interfacial region is observed and analyzed. Density functional theory calculations show that S tends to displace O sites in TaO2Cl4 octahedra instead of Cl sites. As a result of the enhanced interfacial stability and reduced formation of ionically insulating phases, the assembled ASSLBs achieve superior rate performance and cyclability in a wide temperature range. Notably, the ASSLBs show capacity retention of 84.4% and 77.6% after 2000 and 1000 cycles at current density of 10C at 30 and 60 °C, respectively. Importantly, even under −20 °C, the cell works stably over 1600 cycles with capacity retention of 76.3% at 0.5C. The work pave the way for the massive production of high‐performance amorphous chloride electrolytes and the realization of fast‐charging ASSLBs with long cycle life.

Phase-Transition-Promoted Interfacial Anchoring of Sulfide Solid Electrolyte Membranes for High-Performance All-Solid-State Lithium Battery.

Solvent-free manufacturing is crucial for fabricating high-performance sulfide-electrolyte-based all-solid-state lithium batteries (ASSLBs), with advantages including side reaction inhibition, less contamination, and practical scalability. However, the fabricated sulfide electrolytes commonly suffer from brittleness, limited ion transport, and unsatisfactory interfacial stability due to the uncontrolled dispersion of the sulfide particles within the polymer binder matrix. Herein, a "solid-to-liquid" phase transition strategy is reported to fabricate flexible Li6PS5Cl (LPSCl) electrolytes. The polycaprolactone (PCL)-based binder (PLI) with phase-transition characteristics fills the gap of LPSCl particles and tightly grafts on the particle surface via ion-dipole interaction, bringing a thin and compact electrolyte membrane (80µm). The simultaneously high Li-ion conducting and electron insulating nature of PLI binder facilitates Li-ion transport and ensures good interfacial stability between electrolyte and anode. Consequently, the sulfide electrolyte membrane exhibits high ionic conductivity (8.5×10-4 S cm-1), enabling symmetric and full cells with 10 and 2.5 times longer cycling life compared with that of the cells with pristine LPSCl electrolyte, respectively. The demonstrated strategy is versatile and can be extended to ethylene vinyl acetate copolymer (EVA) that also brings enhanced electrochemical performance. The thin sulfide electrolyte with high interfacial stability potentially facilitates dendrite-free ASSLBs with high energy density.

Doping Strategies for Improving Performance of Li‐Argyrodite Solid‐State Electrolyte

Li‐argyrodite solid‐state electrolyte (SSE) holds promise for all‐solid‐state lithium batteries (ASSLB) but faces limitations in room‐temperature ionic conductivity, electrode/electrolyte interface compatibility, and air stability. Doping strategies offer a viable approach to address these challenges. This article provides a comprehensive review of the structure–property relationships and recent doping strategies for Li‐argyrodite electrolytes. First, the crystal structural features are analyzed to elucidate the intrinsic relationship between the structure and key properties, including ionic conductivity and the electrochemical window. Second, the mechanisms by different dopants affecting the performance of Li‐argyrodite electrolytes are investigated, focusing on ionic conductivity, air stability, thermal stability, electrochemical performance, and interfacial stability. Finally, the current status and future development trends of Li‐argyrodite SSE are summarized, and targeted strategies are proposed to enhance the application in ASSLB.

Coaxial Nanofiber Binders Integrating Thin and Robust Sulfide Solid Electrolytes for High‐Performance All‐Solid‐State Lithium Battery

AbstractTo access the theoretically high energy density of sulfide‐based all‐solid‐state lithium batteries (ASSLBs), a thin and robust sulfide electrolyte membrane is essential. Given the pivotal role of binder in preserving the structural integrity and interfacial stability of sulfide electrolytes upon cycling, it is desired to integrate binding capability, toughness, and stiffness into one binder, yet remains difficult. Herein, this challenge is addressed using a nanofiber‐reinforced strategy in the solvent‐free dry‐film process. A coaxial polyvinylidene poly(vinylidene fluoride‐co‐hexafluoropropylene) @ thermoplastic polyurethane (PVDF‐HFP@TPU) nanofiber binder is embedding into a Li6PS5Cl (LPSCl) matrix to obtain a sulfide thin‐layer (LPSCl‐P@T). During hot calendering of the sulfide‐binder mixture, the PVDF‐HFP shell layer melts and tightly binds LPSCl particles. The underlying TPU core layer, which maintains the fibrous structure, reinforces the structural stability of the membrane. Particularly, the fiber‐matrix connection is improved with the assistance of the molten PVDF‐HFP, collectively contributing to the effective dissipation of the mechanical stress. Controlled fusion of the core‐shell nanofiber also leads to enhanced interfacial anchoring of the cathode and electrolyte. The assembled cells with LPSCl‐P@T deliver stable cycling performances. The PVDF‐HFP@TPU nanofiber binder overcomes the long‐existing incompatible problems between binder toughness and stiffness, and shows promises in developing high‐performance sulfide‐based ASSLBs.

Improving the Stability of 75Li2S·25P2S5 Glass-Ceramic Electrolytes Against Lithium Metals Through Li2O Doping

The chemical and electrochemical stability between solid-state electrolytes (SSEs) and lithium metals is one of the crucial factors in the performance of all-solid-state lithium batteries (ASSLBs). Doping modification has been shown to improve the ionic conductivity and air stability of SSEs, but further research is needed to demonstrate its effectiveness in enhancing stability with lithium metal. In this work, a series of Li2O-doped 75Li2S·25P2S5 glass-ceramic electrolytes have been successfully synthesized using ball milling method. Powder X-ray diffraction (pXRD) and 7Li magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy results revealed that Li2O doping effectively reduced the percentage of residual Li2S in the ball milling stage and generated a high ionic conductivity phase Li7P3S11 during annealing. The electrolyte has the highest ionic conductivity (1.5 × 10−4 S cm−1 at room temperature) when doped with 1 mol% Li2O. Various electrochemical characterizations have shown that all doped electrolytes can effectively slow/suppress lithium dendrite formation while being chemically and electrochemically stable to some extent. Among these, 1 mol% Li2O-doped electrolyte performs the best, as the Li|1Li2O|Li cell maintains voltage and resistance nearly unchanged after 1000 h and 900 cycles, with no noticeable degradation in the material structure.

Unveiling solid-solid contact states in all-solid-state lithium batteries: An electrochemical impedance spectroscopy viewpoint

All-solid-state lithium batteries (ASSLBs) are strongly considered as the next-generation energy storage devices for their high energy density and intrinsic safety. The solid-solid contact between lithium metal and solid electrolyte plays a vital role in the performance of working ASSLBs, which is challenging to investigate quantitatively by experimental approach. This work proposed a quantitative model based on the finite element method for electrochemical impedance spectroscopy simulation of different solid-solid contact states in ASSLBs. With the assistance of an equivalent circuit model and distribution of relaxation times, it is discovered that as the number of voids and the sharpness of cracks increase, the contact resistance Rc grows and ultimately dominates the battery impedance. Through accurate fitting, inverse proportional relations between contact resistance Rc and (1 − porosity) as well as crack angle was disclosed. This contribution affords a fresh insight into clarifying solid-solid contact states in ASSLBs.

PVDF Binder in All-Solid-State Lithium Batteries with NCM/Sulfide/PVDF Cathode, Oxide/PEO SE Layer, and Li-metal Anode

Sulfide-based solid electrolyte such as Li6PS5Cl (LPSCl) is unstable in contact with Li metal electrode due to decomposing to by-product resulting in poor performance. Therefore, the introduction of an interlayer to suppress reactivity is essential. In this study, instead of an interlayer, an oxide/polymer composite electrolyte was applied to suppress side reactions, while a sulfide-based electrolyte was used at the cathode to improve interfacial control between the cathode and the electrolyte. All-solid-state lithium batteries (ASLBs) were prepared by applying sulfide-based solid electrolyte (argyrodite, Li6PS5Cl) including NCM424, polyvinylidene fluoride (PVDF), and Super-P in a composite cathode layer, and a composite solid electrolyte (CSE) layer by mixing an oxide-based solid electrolyte (garnet, Al-doped Li7La3Zr2O12 (LLZO)), polymer (PEO, polyethylene oxide) and lithium metal as the anode. In this study, NCM424 powder was coated with LiNbO3 to prevent chemical reaction with the sulfide electrolyte. As the PVDF binder was applied to the cathode of the ASLB, the discharge capacity of the cell was approximately 163 mAh g−1 at 70 °C, 0.1 C, and 4.2 V cut-off and its capacity retention was 83% after 50 cycles. The effects of the PVDF were evaluated using both pouch-type cells. The capacity and cycle retention are greatly dependent on the PVDF content of the cathode materials and the drying temperature during the fabrication of the cathode. When the cathode with PVDF binder was dried at 130 °C, initial cycling was required for activation of the pouch cell, and it was possible to overcome this by adding a plasticizer.

Electronically Conductive Polymer Enhanced Solid-State Polymer Electrolytes for All-Solid-State Lithium Batteries

All-solid-state lithium batteries (ASSLBs) have gained enormous interest due to their potential high energy density, high performance, and inherent safety characteristics for advanced energy storage systems. Although solid-state ceramic (inorganic) electrolytes (SSCEs) have high ionic conductivity and high electrochemical stability, they experience some significant drawbacks, such as poor electrolyte/electrode interfacial properties and poor mechanical characteristics (brittle, fragile), which can hinder their adoption for commercialization. Typically, SSCE-based ASSLBs require high cell stack pressures exerted by heavy fixtures for regular operation, which can reduce the energy density of the overall battery packages. Polymer–SSCE composite electrolytes can provide inherently good interfacial contacts with the electrodes that do not require high cell stack pressures. In this study, we explore the feasibility of incorporating an electronically and ionically conducting polymer, polypyrrole (PPy), into a polymer backbone, polyvinylidene fluoride-co-hexafluoropropylene (PVDF-HFP), to improve the ionic conductivity of the resultant polymer–SSCE composite electrolyte (SSPE). The electronically conductive polymer-incorporated composite electrolyte showed superior room temperature ionic conductivity and electrochemical performance compared to the baseline sample (without PPy). The PPy-incorporated polymer electrolyte demonstrated a high resilience to high temperature operation compared with the liquid-electrolyte counterpart. This performance advantage can potentially be employed in ASSLBs that operate at high temperatures. In our recent development efforts, SSPEs with optimal formulations showed room temperature ionic conductivity of 2.5 × 10−4 S/cm. The data also showed, consistently, that incorporating PPy into the polymer backbone helped boost the ionic conductivity with various SSPE formulations, consistent with the current study. Electrochemical performance of ASSLBs with the optimized SSPEs will be presented in a separate publication. The current exploratory study has shown the feasibility and benefits of the novel approach as a promising method for the research and development of next-generation solid composite electrolyte-based ASSLBs.

Thermal vapor sulfurization of Ti3C2TX MXene to TiS2/carbon nanosheet cathode for long-life and high-loading all-solid-state lithium batteries

Stable and fast operation of all-solid-state lithium batteries (ASSBs) depends on durable and sufficient interfacial contacts between electrode components, especially when the loading and content of electrode active materials are high. Here, we propose promoting ionic/electronic transportations and contacts in sulfide electrolyte-based ASSBs by using TiS2/carbon nanosheets (TiS2/C-s) with large area-to-thickness aspect ratios as the cathode, which are prepared by simple thermal vapor sulfurization of exfoliated Ti3C2Tx MXene. The elastic 2D structure of the TiS2/C-s material can substantially improve interfacial contact with the solid electrolyte, minimize the diffusion distance of lithium ions, and buffer volume/stress changes during cycling, thereby ensuring the electro-chemo-mechanical stability and fast reaction kinetics of electrodes. Consequently, a 50 wt% TiS2/C-s cathode without any conductive carbon additives demonstrates a high discharge capacity (295 mAh g−1), long-term cyclic stability (94.7 and 74.7 % capacity retention after 250 cycles at 0.1 mA cm−2 and after 2300 cycles at 1 mA cm−2, respectively), and decent rate capability (126.0 mAh g−1 at 3 mA cm−2). Moreover, stable cycling with a high areal capacity (5.95 mAh cm−2) can also be achieved.

Promoted Stability and Reaction Kinetics in Ni-Rich Cathodes via Mechanical Fusing Multifunctional LiZr2(PO4)3 Nanocrystals for High Mass Loading All-Solid-State Lithium Batteries.

Sulfide all-solid-state lithium battery (ASSLB) with nickel-rich layered oxide as the cathode is promising for next-generation energy storage system. However, the Li+ transport dynamic and stability in ASSLB are hindered by the structural mismatches and the instabilities especially at the oxide cathode/sulfide solid electrolyte (SE) interface. In this work, we have demonstrated a simple and highly effective solid-state mechanofusion method (1500 rpm for 10 min) to combine lithium conductive NASICON-type LiZr2(PO4)3 nanocrystals (∼20 nm) uniformly and compactly onto the surface of the single crystallized LiNi0.8Co0.1Mn0.1O2, which can also attractively achieve Zr4+ doping in NCM811 and oxygen vacancies in the LZPO coating without solvent and annealing. Benefiting from the alleviated interface mismatches, sufficient Li+ ion flux through the LZPO coating, promoted structural stabilities for both NCM811 and sulfide SE, strong electronic coupling effect between the LZPO and NCM811, and enlarged (003) d-spacing with enriched Li+ migration channels in NCM811, the obtained LZPO-NCM811 exhibits superior stability (185 mAh/g at 0.1C for 200 cycles) and rate performance (105 mAh/g at 1C for 1300 cycles) with high mass loading of 27 mgNCM/cm2 in sulfide ASSLB. Even with a pronounced 54 mgNCM/cm2, LZPO-NCM811 manifests a high areal capacity of 9.85 mAh/cm2. The convenient and highly effective interface engineering strategy paves the way to large-scale production of various coated cathode materials with synergistic effects for high performance ASSLBs.

A Novel Solid State Polymer Electrolyte for All Solid State Lithium Batteries

All-solid-state lithium batteries (ASSLBs) have gained enormous interest due to their potential high energy density, high performance, and inherent safety characteristics for advanced energy storage systems.1 Currently, solid-state ceramic (inorganic) electrolytes (SSCEs), solid-state polymer electrolytes (SSPEs), and a combination of the two (e.g., SSCE fillers in SSPEs) are being developed for ASSLBs.2 Although SSCEs have high ionic conductivity and high electrochemical stability,3 they experience some significant drawbacks, such as poor electrolyte/electrode interfacial properties and poor mechanical characteristics (brittle, fragile),4 which can hinder their adoption to commercialization. Typically, SSCE-based ASSLBs require high cell stack pressures exerted by heavy fixtures for regular operations, which can reduce the energy density of the overall battery packages.5 One promising solution to circumvent the aforementioned issues of SSCE-based ASSLBs is to develop SSPE-based AASLBs, since SSPEs can provide inherently good interfacial contacts with the electrodes that do not require high cell stack pressures. In addition, SSPEs are advantageous in making flexible batteries due to their elastic nature.6 In this study, a novel method was developed to prepare a high-performance SSPE-based ASSLB, where a π-conjugated polymer was incorporated into a baseline polymer backbone, resulting in an improvement in ionic conductivity, thermal stability, and electrochemical stability. The novel SSPE demonstrated a superior electrochemical performance than the baseline when used in ASSLBs. The strategy developed in this study may lead to a new direction for the research and development of next-generation SSPE-based ASSLBs.

Improving Room Temperature Performance of All-Solid-State Polymer Batteries through Cell Activation

Solid polymer electrolytes (SPE) are gaining increasing attention for use in all-solid-state lithium batteries (ASSLB) due to their enhanced safety and simplified processing.[1] However, their conventional operation requires elevated temperatures.[2, 3] Here, we propose a straightforward hot-press activation method to facilitate cell operation at room temperature (r.t., 30 °C) for SPE-based ASSLB. This activation method induces grain amorphization, leading to a substantial reduction in grain boundary resistance within the SPE and achieving a fourfold increase in r.t. ionic conductivity. Furthermore, by decoupling Li-ion transport processes, the activation significantly diminishes the electrode-electrolyte interfacial resistances for both the cathode and anode, thereby enhancing kinetics and overall cell performance at r.t.. Through the application of an optimized activation procedure, all-solid-state LiFeO4 (LFP)|SPE|Li cells exhibit noteworthy performance enhancements, demonstrating both high specific capacity and stable cycling at r.t.References Mauger, A., et al., Building Better Batteries in the Solid State: A Review. Materials, 2019. 12(23).Chen, R.J., et al., The pursuit of solid-state electrolytes for lithium batteries: from comprehensive insight to emerging horizons. Materials Horizons, 2016. 3(6): p. 487-516.Mindemark, J., et al., Beyond PEO—Alternative host materials for Li + -conducting solid polymer electrolytes. Progress in Polymer Science, 2018. 81: p. 114-143.

Unveiling the Mechanical and Electrochemical Evolution of Nanosilicon Composite Anodes in Sulfide-Based All-Solid-State Batteries

The utilization of silicon (Si) anodes in all-solid-state lithium batteries (ASLBs) provides the potential for high energy density. However, the compatibility of sulfide solid-state electrolytes (SEs) with Si and carbon is often questioned due to potential decomposition. To investigate this, operando X-ray absorption near-edge structure (XANES) spectroscopy, ex-situ scanning electron microscopy (SEM) and ex-situ X-ray nano-tomography (XnT) were utilized to study the chemistry and structure evolution of nano Si composite anodes. Results from XANES demonstrated a partial decomposition of SEs during the first lithiation stage, which was further accelerated by the presence of carbon. But the performance of first three cycles in Si-SE-C was stable, which proved the generated media is ionically conductive. XnT and SEM results showed that the addition of SEs and carbon improved the structural stability of the anode with fewer pores and voids. A chemo-elasto-plastic model revealed that SEs and carbon buffered the volume expansion of Si, thus enhancing mechanical stability. The balance between the pros and cons of SEs and carbon in enhancing reaction kinetics and structural stability enabled the Si composite anode to demonstrate the highest Si utilization with higher specific capacities and better rate than pure Si and Si composite anodes with only SEs.

Development of Efficient Ink Dispersion Process for Solid-State Electrolyte and Electrode Manufacturing

All-solid-state lithium batteries (ASSBs) have several advantages over lithium-ion batteries (LIBs) such as higher safety thresholds associated with solid electrolytes (SEs) and the possibility of using lithium metal or silicon anodes to achieve comparatively higher energy and power density. The SE can also prevent chemical interactions with dissolved active materials, and thus solve the issue of long-term instability of LIBs. However, there are also challenges associated with ASSBs manufacturing, such as local stress and contact-loss between SE and active materials in cathodes due to active material “breath”, poor contact and high ionic resistance at the SE-cathode interface, difficulty in fabricating thin SEs, and the absence of scalable and cost-effective manufacturing processes (J. Janek and W.G. Zeier, Nature Energy 8 (2023): 230-240). A key to tackling these issues begins with ink formulation for electrolyte and cathode coating, including ink compositions and rheological properties.In this study, we report the influence of ink preparation methods and conditions on the solid-state electrolyte and cathode coating qualities, where lithium lanthanum zirconium oxide (LLZO) and lithium nickel manganese cobalt oxide (NMC) are used as model systems. Various mixing methods, such as acoustic wave mixing, high-speed off-axis mixing, and thin film mixing, are compared. Their influence on ink viscosity and particle dispersion, coating thickness and microstructure uniformity, and electrolyte and electrode electrochemical properties will be discussed.

Poly(ethylene) Oxide Electrolytes for All-Solid-State Lithium Batteries Using Microsized Silicon/Carbon Anodes with Enhanced Rate Capability and Cyclability.

Silicon (Si) has been widely studied as one of the promising anodes for lithium-ion batteries (LIBs) because of its ultrahigh theoretical specific capacity and low working voltage. However, the poor interfacial stability of silicon against conventional liquid electrolytes has largely impeded its practical use. Therefore, the combination of silicon-based anodes and solid electrolytes has attracted a great deal of attention in recent years. Here, we demonstrate three types of microsized porous silicon/carbon (Si/C) electrodes (i.e., pristine, prelithiated by liquid electrolyte, and preinfiltrated by polymer electrolyte) that are paired with poly(ethylene) oxide (PEO)-based electrolytes for all-solid-state lithium batteries (ASSLBs). We found that when compared with ionic conductivity, the mechanical stability of the PEO electrolyte dominates the electrochemical performance of ASSLBs using Si/C electrodes at elevated temperature. Additionally, both prelithiated and preinfiltrated Si/C electrodes show higher specific capacity in comparison to the pristine electrode, which is attributed to continuous lithium-ion conducting pathways within the electrode and thus improved utilization of active material. Moreover, owing to good interfacial lithium-ion transport in the electrode, a solid-state half-cell with preinfiltrated Si/C electrode and PEO-lithium bis (trifluoromethanesulfonyl)imide electrolyte delivers a specific capacity of ∼1,000 mAh g-1 after 100 cycles under 800 mA g-1 at 60 °C with average Coulombic efficiency >98.9%. This work provides a strategy for rationally designing the microstructure of silicon-based electrodes with solid electrolytes for high-performance all-solid-state lithium batteries.

Rationally Designed Li-Ag Alloy with In-Situ-Formed Solid Electrolyte Interphase for All-Solid-State Lithium Batteries.

All-solid-state lithium batteries (ASSLBs) with sulfide-based solid electrolytes have attracted significant attention as promising energy storage devices, owing to their high energy density and enhanced safety. However, the combination of a lithium metal anode and a sulfide solid electrolyte results in performance degradation, owing to lithium dendrite growth and the side reactions of lithium metal with the solid electrolyte. To address these issues, a Ag-based Li alloy with a favorable solid electrolyte interphase (SEI) was prepared using electrodeposition and applied to the ASSLB as an anode. The electrochemically formed SEI layer on the Li-Ag alloy primarily comprised LiF and Li2O with high mechanical strength and Li3N with high ionic conductivity, which suppressed the formation of lithium dendrites and short-circuiting of the cell. The symmetric cell with the Li-Ag alloy achieved a critical current density of 1.6 mA cm-2 and maintained stable cycling for over 2000 h at a current density of 0.6 mA cm-2. Consequently, the all-solid-state lithium cell assembled with the Li-Ag alloy anode with SEI, Li6PS5Cl solid electrolyte, and LiNi0.78Co0.10Mn0.12O2 cathode delivered a high discharge capacity of 185 mAh g-1 and exhibited good cycling performance in terms of cycling stability and rate capability at 25 °C.

Constructing An Oxyhalide Interface for 4.8 V-Tolerant High-Nickel Cathodes in All-Solid-State Lithium-Ion Batteries.

All-solid-state lithium batteries (ASSBs) have received increasing attentions as one promising candidate for the next-generation energy storage devices. Among various solid electrolytes, sulfide-based ASSBs combined with layered oxide cathodes have emerged due to the high energy density and safety performance, even at high-voltage conditions. However, the interface compatibility issues remain to be solved at the interface between the oxide cathode and sulfide electrolyte. To circumvent this issue, we propose a simple but effective approach to magic the adverse surface alkali into a uniform oxyhalide coating on LiNi0.8Co0.1Mn0.1O2 (NCM811) via a controllable gas-solid reaction. Due to the enhancement of the close contact at interface, the ASSBs exhibit improved kinetic performance across a broad temperature range, especially at the freezing point. Besides, owing to the high-voltage tolerance of the protective layer, ASSBs demonstrate excellent cyclic stability under high cutoff voltages (500 cycles~94.0 % at 4.5 V, 200 cycles~80.4 % at 4.8 V). This work provides insights into using a high voltage stable oxyhalide coating strategy to enhance the development of high energy density ASSBs.

A modified PVDF-HFP/PMMA crosslinked co-polymer for high-performance all-solid-state lithium metal batteries

For all-solid-state lithium batteries (ASSLBs), polymer-blended solid composite electrolytes (SCEs) have drawn wide interest owing to their significance in improving the interfacial solid-solid contacts and inhibiting the growth of lithium dendrites. In this work, SCEs based on PVDF-HFP/PMMA matrix containing MOFs (NH2-MIL-53(Al)) and LiTFSI were designed and synthesized employing an easy solution casting method. The synthesized samples were examined by XRD, SEM, EDS, and electrochemical tests. It was found that MPP-2 SCE not only has excellent ionic conductivity at 60 °C of 5.54 × 10−4 S cm−1, but also exhibits superior interfacial compatibility in Li||Li symmetric batteries, which can constantly cycle for about 800 h at 0.1 mA cm−2 with no short-circuiting. The assembled Li|MPP-2|LiFePO4 cell exhibited a first discharge specific capacity of up to 157.1 mAh g−1 at 60 °C and 0.2 C. This work may help to further advance the progress of ASSLBs in the future.

Ni-Rich Layered Oxide Cathodes/Sulfide Electrolyte Interface in Solid-State Lithium Battery.

Because of the high specific capacity and low cost, Ni-rich layered oxide (NRLO) cathodes are one of the most promising cathode candidates for the next high-energy-density lithium-ion batteries. However, they face structure and interface instability challenges, especially the battery safety risk caused by using an intrinsic flammable organic liquid electrolyte. In this regard, a solid electrolyte with high safety is of great significance to promote the development of energy storage. Among them, sulfide electrolytes are considered to be the most potential substitutes for liquid electrolytes because of their high ionic conductivity and good processing properties. Nevertheless, the interfacial incompatibility between the sulfide electrolyte and NRLO cathode is the critical challenge for high-performance sulfide all-solid-state lithium batteries (ASSLBs). In this review, we summarize the problems of the Ni-rich cathode/sulfide solid electrolyte interface and the strategies to improve the interface stability. On the basis of these insights, we highlight the scientific problems and technological challenges that need to be resolved urgently and propose several potential directions to further improve the interface stability. The objective of this study is to provide a comprehensive understanding and insightful recommendations for the enhancement of the sulfide ASSLBs with NRLO cathode.