Ultrafast-Loaded Nickel Sulfide on Vertical Graphene Enabled by Joule Heating for Enhanced Lithium Metal Batteries.

The design and fabrication of a lithiophilic skeleton are highly important for constructing advanced Li metal anodes. In this work, a new lithiophilic skeleton is reported by planting metal sulfides (e.g., Ni3S2) on vertical graphene (VG) via a facile ultrafast Joule heating (UJH) method, which facilitates the homogeneous distribution of lithiophilic sites on carbon cloth (CC) supported VG substrate with firm bonding. Ni3S2 nanoparticles are homogeneously anchored on the optimized skeleton as CC/VG@Ni3S2, which ensures high conductivity and uniform deposition of Li metal with non-dendrites. By means of systematic electrochemical characterizations, the symmetric cells coupled with CC/VG@Ni3S2 deliver a steady long-term cycle within 14 mV overpotential for 1800 h (900 cycles) at 1 mA cm-2 and 1 mAh cm-2. Meanwhile, the designed CC/VG@Ni3S2-Li||LFP full cell shows notable electrochemical performance with a capacity retention of 92.44% at 0.5 C after 500 cycles and exceptional rate performance. This novel synthesis strategy for metal sulfides on hierarchical carbon-based materials sheds new light on the development of high-performance lithium metal batteries (LMBs).

A scalable Li-Al-Cl stratified structure for stable all-solid-state lithium metal batteries.

Sulfides are promising electrolyte materials for all-solid-state Li metal batteries due to their high ionic conductivity and machinability. However, compatibility issues at the negative electrode/sulfide electrolyte interface hinder their practical implementation. Despite previous studies have proposed considerable strategies to improve the negative electrode/sulfide electrolyte interfacial stability, industrial-scale engineering solutions remain elusive. Here, we introduce a scalable Li-Al-Cl stratified structure, formed through the strain-activated separating behavior of thermodynamically unfavorable Li/Li9Al4 and Li/LiCl interfaces, to stabilize the negative electrode/sulfide electrolyte interface. In the Li-Al-Cl stratified structure, Li9Al4 and LiCl are enriched at the surface to serve as a robust solid electrolyte interphase and are diluted in bulk by Li metal to construct a skeleton. Enabled by its unique structural characteristic, the Li-Al-Cl stratified structure significantly enhances the stability of negative electrode/sulfide electrolyte interface. This work reports a strain-activated phase separation phenomenon and proposes a practical pathway for negative electrode/sulfide electrolyte interface engineering.

Deciphering the critical role of interstitial volume in glassy sulfide superionic conductors.

Sulfide electrolytes represent a crucial category of superionic conductors for all-solid-state lithium metal batteries. Among sulfide electrolytes, glassy sulfide is highly promising due to its long-range disorder and grain-boundary-free nature. However, the lack of comprehension regarding glass formation chemistry has hindered their progress. Herein, we propose interstitial volume as the decisive factor influencing halogen dopant solubility within a glass matrix. We engineer a Li3PS4-Li4SiS4 complex structure within the sulfide glassy network to facilitate the release of interstitial volume. Consequently, we increase the dissolution capacity of LiI to 40 mol% in 75Li2S-25P2S5 glass. The synthesized glass exhibits one of the highest ionic conductivities among reported glass sulfides. Furthermore, we develop a glassy/crystalline composite electrolyte to mitigate the shortcomings of argyrodite-type sulfides by utilizing our synthesized glass as the filler. The composite electrolytes effectively mitigate Li intrusion. This work unveils a protocol for the dissolution of halogen dopants in glass electrolytes.

Cubic Iodide Lix YI3+x Superionic Conductors through Defect Manipulation for All-Solid-State Li Batteries.

Halide solid electrolytes (SEs) have attracted significant attention due to their competitive ionic conductivity and good electrochemical stability. Among typical halide SEs (chlorides, bromides, and iodides), substantial efforts have been dedicated to chlorides or bromides, with iodide SEs receiving less attention. Nevertheless, compared with chlorides or bromides, iodides have both a softer Li sublattice and lower reduction limit, which enable iodides to possess potentially high ionic conductivity and intrinsic anti-reduction stability, respectively. Herein, we report a new series of iodide SEs: Lix YI3+x (x=2, 3, 4, or 9). Through synchrotron X-ray/neutron diffraction characterizations and theoretical calculations, we revealed that the Lix YI3+x SEs belong to the high-symmetry cubic structure, and can accommodate abundant vacancies. By manipulating the defects in the iodide structure, balanced Li-ion concentration and generated vacancies enables an optimized ionic conductivity of 1.04 × 10-3  S cm-1 at 25 °C for Li4 YI7 . Additionally, the promising Li-metal compatibility of Li4 YI7 is demonstrated via electrochemical characterizations (particularly all-solid-state Li-S batteries) combined with interface molecular dynamics simulations. Our study on iodide SEs provides deep insights into the relation between high-symmetry halide structures and ionic conduction, which can inspire future efforts to revitalize halide SEs.

Degradation Evolution for Li2 ZrCl6 Electrolytes in Humid Air and Enhanced Air Stability via Effective Indium Substitution.

Superionic halides have aroused interests in field of solid electrolytes such as Li2 ZrCl6 . However, they are still facing challenges including poor air stability which lacks in-depth investigation. Here, moisture instability of Li2 ZrCl6 is demonstrated and decomposition mechanism in air is clearly revealed. Li2 ZrCl6 decomposes into Li2 ZrO3 , ZrOCl2 ·xH2 O and LiCl during initial stage as halides upon moisture exposure. Later, these side products evolve into LiCl(H2 O) and Li6 Zr2 O7 after longer time exposure. More importantly, structure of destroyed halides cannot be recovered after postheating. Later, Indium is doped into Li2 ZrCl6 (9.7 × 10-5 S cm-1 ) to explore its effect on structure and properties. Crystal structure of ball-milled In-doped Li2 ZrCl6 electrolytes is converted from the Li3 YCl6 -like to Li3 InCl6 -like with increasing In content and ionic conductivity can also be enhanced (0.768-1.13) × 10-3 S cm-1 ). More importantly, good air stability of optimal Li2.8 Zr0.2 In0.8 Cl6 is achieved since halide hydrates are formed after air exposure instead of total decomposition and the hydrates can be restored to Li2.8 Zr0.2 In0.8 Cl6 after postheating. Moreover, reheated Li2.8 Zr0.2 In0.8 Cl6 after air exposure is successfully applied in solid-state LiNi0.8 Co0.1 Mn0.1 O2 /halides/Li6 PS5 Cl/Li-In battery. The results in this work can provide insights into air instability of Li2 ZrCl6 and effective strategy to regulate air stability of halides.

An Advanced Gel Polymer Electrolyte for Solid-State Lithium Metal Batteries.

All-solid-state lithium metal batteries (LMBs) are regarded as one of the most viable energy storage devices and their comprehensive properties are mainly controlled by solid electrolytes and interface compatibility. This work proposes an advanced poly(vinylidene fluoride-hexafluoropropylene) based gel polymer electrolyte (AP-GPEs) via functional superposition strategy, which involves incorporating butyl acrylate and polyethylene glycol diacrylate as elastic optimization framework, triethyl phosphate and fluoroethylene carbonate as flameproof liquid plasticizers, and Li7La3Zr2O12 nanowires (LLZO-w) as ion-conductive fillers, endowing the designed AP-GPEs/LLZO-w membrane with high mechanical strength, excellent flexibility, low flammability, low activation energy (0.137 eV), and improved ionic conductivity (0.42 × 10-3 S cm-1 at 20 °C) due to continuous ionic transport pathways. Additionally, the AP-GPEs/LLZO-w membrane shows good safety and chemical/electrochemical compatibility with the lithium anode, owing to the synergistic effect of LLZO-w filler, flexible frameworks, and flame retardants. Consequently, the LiFePO4/Li batteries assembled with AP-GPEs/LLZO-w electrolyte exhibit enhanced cycling performance (87.3% capacity retention after 600 cycles at 1 C) and notable high-rate capacity (93.3 mAh g-1 at 5 C). This work proposes a novel functional superposition strategy for the synthesis of high-performance comprehensive GPEs for LMBs.

LLZTO Nanoparticle- and Cellulose Mesh-Coreinforced Flexible Composite Electrolyte for Stable Li Metal Batteries.

Composite electrolytes have been regarded as the most prospective electrolytes for commercial application because they acquire the advantages of both polymer and inorganic electrolytes, commonly exhibiting appreciated flexibility and suitable ionic conductivity. Nevertheless, the conventional solution-casting method with toxic solvent and poor interfacial contact still hamper their commercialization process. Moreover, electrolytes with higher ionic conductivity and transference number are urgently needed for satisfying fast-charging batteries. Herein, a novel composite electrolyte (LZEC) reinforced by mechanically robust LLZTO nanoparticles and flexible cellulose mesh was fabricated by a simple and advanced in situ thermal polymerization method, with adding of highly ion-conductive liquid plasticizer. Consequently, the rationally designed LZEC composite electrolyte exhibits superior flexibility and remarkable electrochemical properties in the form of high ionic conductivity, wide electrochemical stability window, and high Li+ transference number. Importantly, the in situ synthesis method is expected to help construct an enhanced electrolyte/electrode interface inside the battery, and the LZEC composite electrolyte is capable of suppressing Li dendrite growth effectively, as evidenced by the prolonged stable cycling of the Li/Li symmetric cell. Therefore, the LFP/LZEC/Li full cell exhibits superior rate performance and long cyclic life. These attractive properties make LZEC a potential composite electrolyte for boosting the practical application of safe and long-life Li metal batteries.

Highly Stable Potassium Metal Anodes with Controllable Thickness and Area Capacity.

K metal battery is a kind of high-energy-density storage device with economic advantages. However, due to the dendrite growth and difficult processing characteristics, it is difficult to prepare stable K metal anode with thin thickness and fixed area capacity, which severely limits its development. In this work, a multi-functional 3D skeleton (rGCA) is synthesized by simple vacuum filtration and thermal reduction, and K metal anodes with controllable thickness and area capacity (K content) can be fabricated by changing the raw material mass and graphene layer spacing of rGCA. Moreover, the graphene sheet layer of rGCA can relax stress and relieve volume expansion; carbon nanotubes can serve as the fast transport channel of electrons, reducing internal impedance and local current density; Ag nanoparticles can induce the uniform nucleation and deposition of K+ . The K metal composite anodes (rGCA-K) based on the conductive skeleton can effectively suppress dendrites and exhibit excellent electrochemical performance in symmetric and full cells. The controllable fabrication process of stable K metal anode is expected to help K metal batteries move toward the stage of commercial production.

Solid-State Electrolytes in Lithium-Sulfur Batteries: Latest Progresses and Prospects.

Solid-state lithium-sulfur batteries (SSLSBs) have attracted tremendous research interest due to their large theoretical energy density and high safety, which are highly important indicators for the development of next-generation energy storage devices. Particularly, safety and "shuttle effect" issues originating from volatile and flammable liquid organic electrolytes can be fully mitigated by switching to a solid-state configuration. However, their road to thecommercial application is still plagued with numerous challenges, most notably the intrinsic electrochemical instability of solid-state electrolytes (SSEs) materials and their interfacial compatibility with electrodes and electrolytes. In this review, a critical discussion on the key issues and problems of different types of SSEs as well as the corresponding optimization strategies are first highlighted. Then, the state-of-the-art preparation methods and properties of different kinds of SSE materials, and their manufacture, characterization and performance in SSLSBs are summarized in detail. Finally, a scientific outlook for the future development of SSEs and the avenue to commercial application of SSLSBs is also proposed.

Quasi-Solid Electrolyte Interphase Boosting Charge and Mass Transfer for Dendrite-Free Zinc Battery.

The practical applications of zinc metal batteries are plagued by the dendritic propagation of its metal anodes due to the limited transfer rate of charge and mass at the electrode/electrolyte interphase. To enhance the reversibility of Zn metal, a quasi-solid interphase composed by defective metal-organic framework (MOF) nanoparticles (D-UiO-66) and two kinds of zinc salts electrolytes is fabricated on the Zn surface served as a zinc ions reservoir. Particularly, anions in the aqueous electrolytes could be spontaneously anchored onto the Lewis acidic sites in defective MOF channels. With the synergistic effect between the MOF channels and the anchored anions, Zn2+ transport is prompted significantly. Simultaneously, such quasi-solid interphase boost charge and mass transfer of Zn2+, leading to a high zinc transference number, good ionic conductivity, and high Zn2+ concentration near the anode, which mitigates Zn dendrite growth obviously. Encouragingly, unprecedented average coulombic efficiency of 99.8% is achieved in the Zn||Cu cell with the proposed quasi-solid interphase. The cycling performance of D-UiO-66@Zn||MnO2 (~ 92.9% capacity retention after 2000 cycles) and D-UiO-66@Zn||NH4V4O10 (~ 84.0% capacity retention after 800 cycles) prove the feasibility of the quasi-solid interphase.

Surface-modified and sulfide electrolyte-infiltrated LiNi0.6Co0.2Mn0.2O2 cathode for all-solid-state lithium batteries.

Sulfide-based all-solid-state lithium batteries (ASSLBs) with high-voltage Ni-rich layered cathodes have shown great potential in energy storage systems. However, the application of ASSLBs is hindered by severe interface issues and poor solid-solid contact between cathodes and sulfide electrolytes. In this work, a suitably thin Li1.5Al0.5Ge1.5(PO4)3 (LAGP) coating (0.41 mS cm-1) is introduced onto the surface of single-crystal LiNi0.6Co0.2Mn0.2O2 particles to mitigate interface side reactions. Subsequently, sheet-type electrodes are fabricated by the infiltration of Li10GeP2S12 to fill the voids and achieve highly dense solid-solid contact, thus preventing contact loss. The Li10GeP2S12-infiltrated ASSLBs with a LAGP buffer layer display a high initial discharge capacity of 141.5 mAh g-1 at 0.05 C and ultrastable cycling for 100 cycles at 0.1 C. An effective fabrication method for highly dense electrodes is proposed in this work, which provides a new direction for scalable industrial production.

Ionic Conductivity Enhancement of Li2ZrCl6 Halide Electrolytes via Mechanochemical Synthesis for All-Solid-State Lithium-Metal Batteries.

Superionic halides have returned to the spotlight of solid electrolytes because of their satisfactory ionic conductivity, soft texture, and stability toward high-voltage electrode materials. Among them, Li2ZrCl6 has aroused interests since abundant Zr element can reduce the cost of large-scale synthesis. However, the related research is very limited, including the detailed parameters during synthesis and the possible strategies for enhancing ionic conductivity. In this work, we have systematically investigated the effects of synthesis parameters on the structure and ionic conductivity of Li2ZrCl6 during the ball-milling annealing process. It is found that mild heat treatment (100 °C) can largely enhance the ionic conductivity of ball-milled electrolytes by 2-3 times, which has not been previously reported. Such enhancement is mainly attributed to the network-like micromorphology composed of nanorods, nanowires, or nanoballs, which is beneficial for lithium ion migration. Finally, the modified Li2ZrCl6 (4.46 × 10-4 S cm-1 @ RT) is also proved to be applicable in LiNi0.8Mn0.1Co0.1O2/ Li2ZrCl6/ Li6PS5Cl/Li-In all-solid-state lithium metal batteries (ASSLMBs). It presents high initial charge capacity of 176.4 mAh g-1 and satisfactory cycle stability since a discharge capacity of 90.8 mAh g-1 is maintained after 40 cycles at 0.1 C. The Li2ZrCl6 electrolytes synthesized via the mechanochemical method is promising to be applied in the high-voltage ASSLMBs, and its ionic conductivity can be enhanced by the strategies provided in our work.

Synergistic Interfacial Bonding in Reduced Graphene Oxide Fiber Cathodes Containing Polypyrrole@sulfur Nanospheres for Flexible Energy Storage.

Flexible lithium sulfur batteries with high energy density and good mechanical flexibility are highly desirable. Here, we report a synergistic interface bonding enhancement strategy to construct flexible fiber-shaped composite cathodes, in which polypyrrole@sulfur (PPy@S) nanospheres are homogeneously implanted into the built-in cavity of self-assembled reduced graphene oxide fibers (rGOFs) by a facile microfluidic assembly method. In this architecture, sulfur nanospheres and lithium polysulfides are synergistically hosted by carbon and polymer interface, which work together to provide enhanced interface chemical bonding to endow the cathode with good adsorption ability, fast reaction kinetics, and excellent mechanical flexibility. Consequently, the PPy@S/rGOFs cathode shows enhanced electrochemical performance and high-rate capability. COMSOL Multiphysics simulations and density functional theory (DFT) calculations are conducted to elucidate the enhanced electrochemical performance. In addition, a flexible Li-S pouch cell is assembled and delivers a high areal capacity of 5.8 mAh cm-2 at 0.2 A g-1 . Our work offers a new strategy for preparation of advanced cathodes for flexible batteries.

A Silk Protein-Based Eutectogel as a Freeze-Resistant and Flexible Electrolyte for Zn-Ion Hybrid Supercapacitors.

A eutectogel (ETG) based on immobilizing a zinc salt deep eutectic solvent (DES) in a silk protein backbone is prepared by a coagulating bath method as a solid electrolyte for Zn-ion hybrid supercapacitors (ZHSCs). The Zn salt DES is composed by ethylene glycol (EG), urea, choline chloride (ChCl), and zinc chloride (ZnCl2) with a molar ratio of 6:10:3:3. A strong bonding of the DES liquid to the silk protein backbone is formed between protein macromolecules and the DES due to plenty of hydrogen bonds in both materials. The as-prepared ETG membrane is dense and has no obvious void defects, which possesses a fracture strength of 7.58 MPa and environmental stability. As a solid electrolyte, the ETG membrane exhibits a higher Zn2+ transference number of about 0.60 and a high ionic conductivity (12.31 mS cm-1 at room temperature and 3.63 mS cm-1 at -20 °C). A ZHSC (Zn∥ETG∥C) with the silk protein-based ETG electrolyte is assembled by Zn and active carbon as the anode and the cathode, respectively, which delivers a specific capacitance of 342.8 F g-1 at a current density of 0.2 A g-1 and maintains excellent cycling stability with 80% capacitance retention after 20,000 cycles at a high current rate (5 A g-1) at room temperature. Moreover, the Zn∥ETG∥C device can safely work under a lower temperature of about -18 °C and damaging situations, such as folding states and even cutting tests. The interface evolutions between the Zn anode and the ETG electrolyte are explored, and it was found that a ZnCO3/Zn(CH2OCO2)2 solid electrolyte interphase is in situ formed on the Zn anode, which can inhibit the growth of Zn dendrites. This work provides a new way to fabricate advanced electrolytes for applications in Zn-ion hybrid supercapacitors.

A Novel Ethanol-Mediated Synthesis of Superionic Halide Electrolytes for High-Voltage All-Solid-State Lithium-Metal Batteries.

Halide electrolytes are rising stars among inorganic solid-state electrolytes due to their high ionic conductivity and good compatibility with high-voltage electrodes. However, their traditional synthesis methods including ball-milling annealing are usually energy-intensive and time-consuming compared with liquid-mediated routes. What's more, the only method in aqueous solution is not perfect considering detrimental effect of trace water for battery performances. Here, we propose a novel ethanol-mediated synthesis route for superionic Li3InCl6 electrolyte via energy-friendly dissolution and post-treatment. The organics in ethanol-mediated precursor disappear in form of light gas during post-treatment. And Li3InCl6 with best thermal stability and ionic conductivity (0.79 mS cm-1, 20 °C) can be successfully prepared after postheating for 3 h at 200 °C. Besides, it is also found that the ionic conductivity of Li3InCl6 is positively correlated with peak intensity ratio of (131) plane/(001) plane since crystal plane and preferred orientation can directly affect polyhedrons through which lithium ions migrate in crystalline conductors. The assembled LiNi0.8Co0.1Mn0.1O2/Li3InCl6/Li10GeP2S12/Li-In cell presents high initial charge capacity of 174.8 mAh g-1 at 0.05 C and a good rate performance of 122.9 mAh g-1 at 1 C. Especially, the retention rate of charge capacity can reach 94.8% after 200 cycles. The ethanol-mediated synthesized Li3InCl6 is a novel promising electrolyte which can be coupled with high-voltage cathode for the application of all-solid-state lithium-metal batteries.

Ionic Liquid-Impregnated ZIF-8/Polypropylene Solid-like Electrolyte for Dendrite-free Lithium-Metal Batteries.

Metal-organic framework (MOF)-based solid-like electrolytes have attracted more prospective due to the combined merits of solid-state electrolytes and liquid electrolytes. However, most MOF-based solid-like electrolytes using organic liquid electrolytes cannot fundamentally solve the safety issues of lithium-metal batteries, and the ionic conductivity and mechanical strength of the electrolytes should be further enhanced. Herein, the ionic liquid-impregnated polypropylene (PP) porous membrane with integrally distributed ZIF-8 nanoparticles is designed. The solid-like electrolyte possesses an increased ionic conductivity of 2.09 × 10-4 S cm-1 at 25 °C, lithium-ion transference number (0.45), mechanical strength, electrochemical window, and excellent nanowetted interfaces. Furthermore, the Li symmetrical cell shows excellent Li plating/stripping properties for 550 h at 0.1 mA cm-2 and 0.1 mA h cm-2. The LiFePO4/Li full battery with the solid-like electrolyte demonstrates an excellent rate capability and cycling stability with the initial discharge capacity of 157.9 mA h g-1 and a capacity retention ratio of 91.23% after 450 cycles at 0.2 C. The work offers a new avenue toward MOF-based solid-like electrolytes for high-safety lithium-metal batteries.

Multifunctional Hyphae Carbon Powering Lithium-Sulfur Batteries.

Biotechnology can bring new breakthroughs on design and fabrication of energy materials and devices. In this work, a novel and facile biological self-assembly technology to fabricate multifunctional Rhizopus hyphae carbon fiber (RHCF) and its derivatives on a large scale for electrochemical energy storage is proposed. Crosslinked hollow carbon fibers are successfully prepared by conversion of Rhizopus hyphae, and macroscopic production of centimeter-level carbon balls consisting of hollow RHCFs is further realized. Moreover, the self-assembled RHCF balls show strong adsorption characteristics on metal ions and can be converted into a series of derivatives such as RHCF/metal oxides. Notably, the designed RHCF derivatives are demonstrated with powerful multifunctionability as cathode, anode, and separator for lithium-sulfur batteries (LSBs). The RHCF can act as the host material to combine with metal oxide (CoO) and S, Li metal, and a polypropylene (PP) separator to form a new RHCF/CoO-S cathode, an RHCF/Li anode, and an RHCF/PP separator, respectively. Consequently, the optimized LSB full cell presents excellent cycling performance and superior high-rate capacity (881.3 mA h g-1 at 1 C). This work provides a new method for large-scale preparation of hollow carbon fibers and derivatives for advanced energy storage and conversion.

Ultrafast Synthesis of I-Rich Lithium Argyrodite Glass-Ceramic Electrolyte with High Ionic Conductivity.

Lithium argyrodites are one of the most promising sulfide electrolytes due to their high ionic conductivity and ductile feature. Among them, Li6 PS5 I (LPSI) exhibits better stability against Li metal but a rather low ionic conductivity (only ≈10-6 S cm-1 ) because of the absence of S2- /I- disorder. Herein, argyrodite Li6- x PS5- x I1+ x glass-ceramic electrolytes with high iodine content are synthesized using ultimate-energy mechanical alloying method. S2- /I- disorder is successfully introduced into the system by doping LiI during this one-pot process. Determined by 6 Li magic angle spinning nuclear magnetic resonance and ab initio molecular dynamics simulations, the introduction of iodine promotes Li+ inter-cage jumps, leading to an enhanced long-range Li+ conducting. The Li5.6 PS4.6 I1.4 glass-ceramic electrolyte (LPSI1.4 -gc) possesses high ionic conductivity (2.04 mS cm-1 ) and excellent stability against Li metal. The Li symmetric cell with the LPSI1.4 -gc electrolyte demonstrates ultralong cycling stability over 3200 h at 0.2 mA cm-2 . LiCoO2 /Li6 PS5 Cl/Li all-solid-state battery applying LPSI1.4 -gc as the anode interlayer also presents prominent cycling and rate performance. This work provides a novel type of electrolyte with high ionic conductivity and stability against Li metal.

High Performance Single-Crystal Ni-Rich Cathode Modification via Crystalline LLTO Nanocoating for All-Solid-State Lithium Batteries.

Sulfide-based all-solid-state lithium batteries (ASSLBs) assembled with Ni-rich layered cathodes are currently promising candidates for achieving high-energy-density and high-safety energy storage systems. However, the interfacial challenges between sulfide electrolyte and Ni-rich layered cathode, such as space charge layer, side reaction, and poor physical contact, greatly limit the practicality of all-solid-state batteries. In this work, an optimal crystalline Li0.35La0.55TiO3 (LLTO) surface coating with a thickness of roughly 6 nm and a high Li ion conductivity of 0.3 mS cm-1 was adopted to enhance the structural stability of the single-crystal LiNi0.6Co0.2Mn0.2O2 (S-NCM622) cathode in ASSLBs. Furthermore, due to the high ionic conductivity and chemical stability of the LLTO coating layer, the interfacial problems, involving interfacial reaction and a space charge layer, in sulfide-based all-solid-state batteries have been effectively solved. As a result, the assembled ASSLBs with the S-NCM622@LLTO cathode exhibit high initial capacity (179.7 mAh g-1) at 0.05 C and excellent cycling performance with 84.5% capacity retention after 100 cycles at 0.1 C at room temperature. This work proposes an effective strategy to enhance the performance of Ni-rich layered cathodes for next-generation high-energy-density sulfide-based lithium batteries.

Single-Crystal-Layered Ni-Rich Oxide Modified by Phosphate Coating Boosting Interfacial Stability of Li10 SnP2 S12 -Based All-Solid-State Li Batteries.

All-solid-state lithium batteries (ASSLBs) adopting sulfide electrolytes and high-voltage layered oxide cathodes have moved into the mainstream owing to their superior safety and immense potential in high energy density. However, the poor electrochemical compatibility between oxide cathodes and sulfide electrolytes remains a challenge for high-performance ASSLBs. In this study, a nanoscale Li1.4 Al0.4 Ti1.6 (PO4 )3 (LATP) phosphate coating is reasonably constructed on the surface of single-crystal LiNi0.6 Co0.2 Mn0.2 O2 particles to achieve cathode/electrolyte interfacial stability. The conformal LATP layer with inherent high-voltage stability can effectively suppress the oxidation decomposition of the electrolyte and demonstrate chemical inertness to both the oxide cathode and Li10 SnP2 S12 electrolyte. ASSLBs with an LATP-modified cathode exhibited a high initial discharge capacity (152.1 mAh g-1 ), acceptable rate capability, and superior cycling performance with a capacity retention of 87.6% after 100 cycles at 0.1 C. Interfacial modification is an effective approach for achieving high-performance sulfide-based ASSLBs with superior interfacial stability.