Low Interfacial Resistance Research Articles

Halogen-Bonding Nanoarchitectonics in Supramolecular Plasticizers for Breaking the Trade-Off between Ion Transport and Mechanical Strength of Polymer Electrolytes for High-Voltage Li-Metal Batteries.

The low ionic conductivity of poly(ethylene oxide) (PEO)-based polymer electrolytes at room temperature impedes their practical applications. The addition of a plasticizer into polymer electrolytes could significantly promote ion transport while inevitably decreasing their mechanical strength. Herein, we report a supramolecular plasticizer (SMP) to break the trade-off effect between ionic conductivity and mechanical properties in PEO-based polymer electrolytes. Accordingly, the SMP is constructed by tetraethylene glycol dimethyl ether (G4) and SbF3 through halogen bonds. The SMP-plasticized PEO electrolyte (PEO/SMP) presents a simultaneously enhanced ionic conductivity of 2.4 × 10-4 S cm-1 (25 °C) and a high mechanical strength of 8.1 MPa, compared to those of pristine PEO-based electrolytes. Benefiting from the halogen bonds between G4 and SbF3, the Li-O coordination in PEO/SMP is evidently weakened, and thus rapid Li+ transport is achieved. Furthermore, the PEO/SMP electrolyte possesses a wide electrochemical stability window of 4.5 V and, importantly, derives an inorganic-rich SEI with a low interfacial resistance on a lithium metal surface. By using PEO/SMP, the lithium-metal battery with the LiNi0.5Co0.2Mn0.3O2 cathode exhibits a good rate and long-term cycling performance with a capacity retention of 75.3% (500 cycles). This work offers a rational guideline for the design of polymer electrolytes suitable for high-performance lithium-metal batteries.

Bilayer Heterostructure Electrolytes Were Prepared by a UV-Curing Process for High Temperature Lithium-Ion Batteries

Solid-state electrolytes are widely anticipated to revitalize high-energy-density and high-safety lithium-ion batteries. However, low ionic conductivity and high interfacial resistance at room temperature pose challenges for their practical application. In this work, the dual-matrix concept is applied to the design of a bilayer heterogeneous structure. The electrolyte in contact with the cathode blends PVDF-HFP and oxidation-resistant PAN. In contrast, the electrolyte in contact with the anode blends PVDF-HFP and reduction-resistant PEO. A UV-curing process was used to fabricate the bilayer heterostructure electrolyte. The heterostructure electrolyte exhibits an ionic conductivity of 4.27 × 10−4 S/cm and a Li+ transference number of 0.68 at room temperature. Additionally, when assembled into LiFePO4/CPEs/Li batteries, it shows a high initial discharge capacity at room temperature (168 mAh g−1 at 0.1 C and 60 mAh g−1 at 2 C), with a capacity retention of 93.3% after 100 cycles at a current density of 0.2 C. Notably, at 60 °C, the battery maintains a discharge capacity of 90 mAh g−1 at 2 C, with a capacity retention of 97.4% after 100 cycles at 0.2 C. Therefore, solid-state batteries using this bilayer heterogeneous structure electrolyte demonstrate promising performance, including effective capacity output and cycling stability.

Self-forming Na3P/Na2O interphase on a novel biphasic Na3Zr2Si2PO12/Na3PO4 solid electrolyte for long-cycling solid-state Na-metal batteries

A novel biphasic Na3Zr2Si2PO12/Na3PO4 solid electrolyte is proposed to effectively address critical anode interface challenges for solid-state Na-metal batteries (SSSMBs). The Na3PO4 phase, at an optimal composition of ∼20 mol%, transforms the interface chemistry throughout the NZSP electrolyte, which results in dense electrolytes with high Young's modulus, rapid ion transport (6.2 × 10−4 S cm-1) at low activation barrier (0.19 eV), negligible electronic conductivity, and excellent sodiophilicity. The AIMD/DFT calculations and XPS analysis reveal a self-formed, (electro)chemically stable mixed Na+/electron-conducting interphase, comprising Na3P and Na2O, at the Na anode interface. The interphase not only homogenizes the Na+ flux distribution and accelerates the interfacial charge transport, but prevents continuous interfacial reactions, thereby stabilizing the anode interface against dendrite formation. Benefiting from the low-impedance, dendrite-free anode interface, Na symmetric cells demonstrate a low interface resistance of 12.7 Ω cm2 and exceptional cyclability of 3000 h. Additionally, full cells with Na3V2(PO4)3 cathodes achieve 93 % capacity retention after 550 cycles at 0.5 C. This research comprehensively elucidates and leverages the critical advantages of Na3PO4 in enhancing the bulk and interface properties of Na3Zr2Si2PO12 solid electrolytes. The design strategy of biphasic solid electrolytes presented here offers new insights into the developing high-performance solid electrolytes for advanced SSSMBs.

Preparation and thermal conductivity properties of CF/SR composites with high orientation and low interfacial thermal resistance based on the synergistic effect of magnetic field, torsional vibration and Diels-Alder reaction

Preparation and thermal conductivity properties of CF/SR composites with high orientation and low interfacial thermal resistance based on the synergistic effect of magnetic field, torsional vibration and Diels-Alder reaction

Composite polymer electrolytes based on poly(ether-ester) and Li1.3Al0.3Ti1.7(PO4)3 enabling high-performance all-solid-state flexible lithium metal batteries

The quest for next-generation energy storage systems has led to the development of high-voltage all-solid-state lithium metal batteries (ASSLMBs), which promise unprecedented energy density and safety. However, the challenge lies in creating of a robust electrolyte that can meet high room temperature ionic conductivity, Li-ion transference number and a wide electrochemical stability window (ESW) while maintaining flexibility and compatibility with lithium metal anodes. Here, novel polyurethane-based composite polymer electrolytes (CPEs) have been successfully fabricated by the cross-linking reaction of poly(1,5-dioxepan-2-one) diols (poly(ether-ester) soft segment) and hexamethylene diisocyanate trimer (hard segment) (PDH) blending with inorganic NASICON-type ceramic fillers Li1.3Al0.3Ti1.7(PO4)3 (PDH@LATP). The resulting CPE exhibits an impressive ionic conductivity of 1.65 × 10−4 S cm−1 at room temperature and a Li-ion transference number of 0.63, which is attributed to the amorphous structure of PDH and the formation of an interconnected ionic pathway by the inorganic filler. The incorporation of LATP also improve the ESW of CPE to 5.3 V while maintaining good mechanical properties. Therefore, the assembled LiFePO4/PDH@LATP/Li batteries displayed low interfacial resistance, Li dendrite suppression, high specific capacity and excellent cyclic performance. The high-voltage LiNi0.5Co0.2Mn0.3O2/PDH@LATP/Li batteries also exhibits good cycling performance and durability. The design principles and materials presented herein provide a blueprint for the next wave of ASSLMBs.

Electrochemical Performance of LiTa2PO8-Based Succinonitrile Composite Solid Electrolyte without Sintering Process.

Solid-state batteries (SSBs) have been widely studied as next-generation lithium-ion batteries (LiBs) for many electronic devices due to their high energy density, stability, nonflammability, and chemical stability compared to LiBs which consist of liquid electrolytes. However, solid electrolytes exhibit poor electrochemical characteristics due to their interfacial properties, and the sintering process, which necessitates high temperatures, is an obstacle to the commercialization of SSBs. Hence, the aim of this study was to improve the interfacial properties of the lithium tantalum phosphate (LTPO) solid electrolyte by adding succinonitrile (SN) on the interface of the LTPO particle to enhance ionic conductivity without the sintering process. Electrochemical impedance spectroscopy (EIS), the Li symmetric cell test, and the galvanostatic cycle test were performed to verify the performance of the SN-containing LTPO composite electrolyte. The LTPO composite solid electrolyte exhibited a high ionic conductivity of 1.93 × 10-4 S/cm at room temperature (RT) compared to the conventional LTPO. Also, it showed good cycle stability, and low interfacial resistance with Li metal, ensuring electrochemical stability. On the basis of our experimental results, the performance of solid electrolytes could be improved by adding SN and lithium salt. In addition, the SN can be used to fabricate the solid electrolytes without the sintering process at high temperatures.

Slurry Casted Ultrathin Li3Zr2Si2PO12 Electrolyte Film for Solid-State Lithium Metal Batteries.

Thin and flexible solid-state electrolyte (SSE) films with high ionic conductivity and low interfacial resistance are urgently required for lithium metal batteries (LMBs). However, it's still challenging to reduce the film thickness to <20µm, especially for those with high ceramic contents. Herein, a facile slurry casting method is developed to prepare the ultra-thin (14µm) Li3Zr2Si2PO12 (LZSP) films with ceramic content up to 91% using a composite polymer binder, polyvinylidene fluoride (PVDF), and polyethylene oxide (PEO). It shows that PEO not only enhanced the film flexibility but also makes it be easily peeled off to form a freestanding membrane, PLN. To promote the interfacial ion transport, PEO/lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) is introduced to the film surface, and the resultant tri-layer film, PPLN, shows a satisfying room temperature ionic conductivity of 0.116mScm-1, high Li+ transference number of 0.79, and good compatibility with metal lithium. As a result, LMBs using LiFePO4 cathode and PPLN electrolyte exhibit excellent safety as well as electrochemical performances in the wide temperature range between room temperature (RT) and 100°C.

Unravelling the anionic stability of an ether-based electrolyte with a hard carbon or metallic sodium anode for high-performance sodium-ion batteries

In hard carbon (HC) anodes, elucidating the relationship between the solid electrolyte interphase formation and the solvated Na+ co-intercalation mechanism is crucial, particularly considering different anionic salts in ether-based electrolytes. Here, we comprehensively explore the impact of different anionic salts on the electrochemical performance of HC/Na half-cell and elucidate the underlying mechanism through experimental studies and theoretical calculations. The surface morphology of the HC anode and its interphasial property are further investigated to evaluate the differences endowed by the presence of various anionic salts in diglyme (2G). The HC/Na half-cells with NaPF6-2G and sodium trifluoromethanesulfonate (NaCF3SO3)-2G display superior electrochemical performance with faster kinetics and lower interfacial resistance than those with NaClO4-2G, sodium bis-(fluorosulfonyl) imide (NaFSI)-2G and sodium bis-(trifluoromethanesulfonyl) imide (NaTFSI)-2G. NaClO4-2G forms a relatively thick interphase layer with high resistance at the electrode/electrolyte interface owing to its insufficient stability. NaFSI-2G and NaTFSI-2G exhibit severe side reactions with Na metal, producing a thick interphase layer on the HC surface with high interfacial resistance from excess electrolyte decomposition, thus deteriorating the electrochemical performance. In summary, the study on the stability of different anionic salts in ether-based electrolyte for the HC anode with the intercalation mechanism provides valuable insights for screening appropriate conductive salts for high-performance sodium-ion batteries, especially when considering Na metal counter/reference electrodes.

Excellent lubricating hydrogels with rapid photothermal sterilization for medical catheters coating

Bacterial infection and tissue damage caused by friction are two major threats to patients’ health in medical catheter implantation. Hydrogels with antibacterial and lubrication effects are competitive candidates for catheter coating materials. Photothermal therapy (PTT) is a highly efficient bactericidal method. Here, a composite hydrogel containing MXene nanosheets and hydrophilic 3-sulfopropyl methacrylate potassium salt (SPMK) is reported, which is synthesized through the one-pot method and heat-initiated polymerization. The hydrogel shows excellent antibacterial performance against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) in 3 min in the air or 20 min in the water environment under near-infrared light (NIR; 808 nm) irradiation. The friction coefficient of the hydrogel is about 0.11, which is 48% lower than that without SPMK. The rapid photothermal sterilization is attributed to the outstanding antibacterial ability and thermal effect of photoactivated MXene. The ultra-low friction is the result of the hydration lubrication mechanism. This study provides a potential strategy for the surface coatings of biomedical catheters, which enables rapid sterilization and extremely low interface resistance between catheters and biological tissues.

Synergistic Enhancement of Biaxial Stretching and Multilayer Composites in All-Solid-State Polymer Electrolytes.

As an important component of lithium-ion batteries, all-solid-state electrolytes should possess high ionic conductivity, excellent flexibility, and relatively high mechanical strength. All-solid-state polymer electrolytes (ASSPEs) based on polymers seem to be able to meet these requirements. However, pure ASSPEs have relatively low ionic conductivity, and the addition of inorganic fillers such as lithium salts will reduce their flexibility and mechanical strength. To address the above issues, in this paper, the solvent-free method was used to prepare a poly(vinylidenefluoride-co-hexafluoropropylene)/lithium bis(trifluoromethanesulfonyl) imide/poly(ethylene oxide) all-solid-state polymer electrolyte, which was then subjected to 4 × 4 magnification synchronous bidirectional stretching. Subsequently, it was multilayered with PEO-based composite polymer electrolytes to obtain multilayered composite polymer electrolytes (MCPEs). Bidirectional stretching provides superior in-plane and out-of-plane mechanical properties to MCPEs by inducing molecular chain orientation, which suppresses the growth of lithium dendrites. Concurrently, it facilitates the formation of the β-crystal form of PVDF-HFP, thereby weakening the ion solvation effect and reducing the lithium-ion migration energy barrier. Multilayered compounding improves the interfacial contact between MCPEs and electrodes, thereby reducing the interfacial impedance. Experiments have demonstrated that the MCPEs prepared in this paper exhibit high ionic conductivity at room temperature (1.83 × 10-4 S cm-1), low interfacial resistance (547 Ω cm-2), excellent mechanical properties (26 MPa), and excellent cycling rate performance (a capacity retention rate of 90% after 110 cycles at 0.1 C), which can meet the performance requirements of lithium-ion batteries for ASSPEs.

Ti3C2Tx MXene/Graphene hybrid frameworks for constructing thermally conductive phase change composites with solar-thermal conversion ability

Application of three-dimensional (3D) carbon framework in phase change material (PCM) has aroused a tremendous interest. However, implementing a high alignment carbon framework with low interfacial thermal resistance (ITR) remain challenging. Herein, we demonstrated a synergetic effect strategy by Ti3C2Tx MXene and graphene nanoplate (GNP) to achieve a 3D thermally conductive framework with high alignment skeleton and low filler-to-filler ITR. Typically, the 3D anisotropic carbon framework is fabricated by unidirectional ice template freezing cellulose nanofibers (CNF)/GNP solution with the assistance of MXene. The abundant functional groups of MXene and the similar layered structure promote the dispersion stability of GNP in CNF aqueous solution, resulting in the significant improvement in GNP alignment and the filler-to-filler ITR. Therefore, the final phase change composites obtained by impregnating polyethylene glycol (PEG) into the framework achieves a satisfactory thermal conductivity (TC) of up to 3.49 W/m K at only 6.25 vol% filler loading. Combining the solar-thermal conversion ability of graphene and MXene, the PCM reveals a rapid energy conversion, transfer and storage capability. More importantly, the phase change enthalpy of the PCM can be as high as 164.3 J/g, with little change even after 50 heating-cooling cycles, and the existence of carbon framework can effectively prevent the leakage phenomenon in solid-liquid conversion process, ensuring its shape stability.

Construction of tree-ring mimetic 3D networks in polyvinyl alcohol/boron nitride composites for enhanced thermal management and mechanical properties

Constructing a three-dimensional (3D) filler network in polymer thermal interface materials (TIMs) is crucial for enhancing thermal conductivity and mechanical properties. However, the discontinuous and loose network of fillers are one of the main reasons hindering the joint improvement of thermal conductivity and mechanical properties. The construction of a regular and dense 3D continuous filler network remains a significant challenge. In this study, an innovative bidirectional freezing technique was designed to create a polyvinyl alcohol (PVA)/boron nitride (BN) composite with a tree-ring-like 3D network. This technique promotes the formation of 3D network consisting of long-range lamellar BN layers with a tree-ring-like structure by controlling the nucleation and growth of ice crystals along the bidirectional temperature gradient induced by a polytetrafluoroethylene (PTFE) cone. The resulting PVA/BN composite exhibits high thermal conductivity (6.25 W/m·K) due to the lower interfacial thermal resistance between fillers (1.271 × 10−7 K m2/W), and an enhanced tensile strength of 41.71 MPa, which is attributed to the regular and dense BN network. This study presents a feasible strategy for constructing a 3D continuous network structure in polymer-based TIMs, paving the way for advancements in thermal management solutions.

Revealing the interfacial chemistry of silicon anodes with polysiloxane electrolyte additives

Silicon (Si) anodes are promising in lithium-ion batteries owing to their high specific capacity and suitable voltage platform. However, particle volume expansion (>300 %) and the continuous consumption of Li+ to form new interfacial layers result in poor cycle performance. We report a sustainable low-cost Si material derived from photovoltaic cutting waste, showing a high initial Coulombic efficiency (86.9 %). The cycle stability of Si/graphite is enhanced in terms of a 38 % capacity retention increase in the presence of vinyl-terminated polydimethylsiloxane (Vi-PDMS) additive. The C = C bond in Vi-PDMS plays a role in reacting with hydrogen fluoride (HF) by-products to prevent the side reaction between HF and solvent. The decomposed macromolecule Si-containing Li salt serves as a part of the solid electrolyte interphase film and has low interface resistance. This formed interphase layer effectively mitigates stress concentration at the contact surface between silicon particles and the current collector caused by expansion forces.

Highly selective photocatalytic CO2 reduction into C2H4 enabled by metal–organic framework-derived catalysts with high Cu+ content

The highly selective conversion of CO2 into valuable C2H4 is a highly important but particularly challenging reaction. Herein, the metal–organic frameworks MOF-74(Cu) with infinite Cu(II)-O chains and Cu-BTC (BTC=benzene-1,3,5-tricarboxylate) with paddle-wheel binuclear Cu(II) clusters are used as precursors. These MOFs are reduced by NaBH4 to obtain Cu0/Cuδ+-based photocatalysts denoted as R-MOF-74(Cu) and R-Cu-BTC, respectively. Significantly, R-MOF-74(Cu) achieves a high selectivity of 90.2 % for C2H4 with a yield rate of 6.5 μmol g−1 within 5 h due to its high Cu+ content. To the best of our knowledge, this C2H4 product selectivity is a record high among all the photocatalysts reported so far for photocatalytic CO2 reduction. In contrast, R-Cu-BTC only forms CO as a product with a cumulative yield of 0.7 μmol g−1 within 5 h. Photoelectrochemical characterization and electron paramagnetic resonance results show that R-MOF-74(Cu) has low interfacial transfer resistance, high photogenerated electron separation efficiency, and excellent CO2 activation and water oxidation performance. In addition, in situ Fourier transform infrared spectroscopy is used to determine the possible reaction pathway from CO2 to C2H4 over R-MOF-74(Cu). This work demonstrates the great potential of MOF-derived photocatalysts for the conversion of CO2 into C2H4 and provides guidance for future photocatalyst development.

Turning waste into wealth: Li2CO3 impurity conversion into ionic conductive and lithiophlic interphase for garnet-based solid-state lithium batteries

Garnet-type solid-state electrolytes (SSEs) show great potential because of high ionic conductivity and steadiness against metallic Li. However, the unstable property of garnet in air and poor interface contact with Li metal dramatically influence the electrochemical performance. In this manuscript, TiO2 gel is coated on the surface of Li6.75La3Zr1.75Ta0.25O12 (LLZTO) pellets by a spin coating process, to remove the surface impurity and in-situ construct an air-stable and lithiophilic LixTiyOz (LTO) layer on the garnet electrolyte surface. The LTO interface layer can enhance interface contact, improve ionic transport and suppress Li dendrite growth. The low interfacial resistance (18.40 Ω cm2) in Li|LTO@LLZTO|Li symmetric cells manifests good wettability. Density functional theory (DFT) calculation results indicate that the modification layer owns higher work of adhesion and interfacial energy, suggesting excellent stability and inhibition in Li dendrite growth. Specifically, the Li symmetric cells with LTO-modified electrolyte show an enhanced critical current density of 0.9 mA cm−2 and outstanding capability to survive long cycling over 5000 h at 0.1 mA cm−2. The assembled LiFePO4-based full cell displays both high reversible capacity and cycling capability. This work provides a promising strategy to take advantage of interfacial Li2CO3 impurities on the garnet electrolytes.

Understanding the Mechanical Behavior of Sulfide Solid Electrolyte Membranes for Practical Applications in All-Solid-State Batteries

All-solid-state batteries (ASSBs) hold great promise as next-generation energy storage systems due to their enhanced stability and high energy density compared to traditional lithium-ion batteries. This improvement stems from the use of a solid electrolyte (SE) instead of a highly volatile liquid electrolyte and the incorporation of a lithium metal anode. In general, sulfide-based SSBs require adequate pressurization conditions to establish an intimate interface between the solid particles, ensuring a continuous electron/ion conduction path. At the cell level, maintaining external stack pressure during operation is crucial to preserve conformal solid-solid contact. Furthermore, when scaling up, fabrication pressure should be carefully considered to enhance electrode densification without causing damage. In particular, the fabrication of thin, robust, and scalable SE membranes faces practical challenges due to a limited amount of polymeric binder and the low intrinsic ductility of SEs after densification. Understanding the mechanical behavior of these SE membranes is essential to ensure their structural stability during manufacturing.In this study, we systematically examined the mechanical properties of SE and SE membranes. The deformability of various types of sulfide SEs was assessed using a powder compaction test, departing from the commonly used indentation method. The yield pressure, which indicates the deformability of the SE powder, is influenced by the composition and synthesis conditions of the SEs. The stress-strain behaviors of the SE membranes were obtained through tensile and flexural tests for both as-prepared and pressed samples, respectively. The tensile and bending behaviors of the SE membranes strongly depend on the combination of the SE and polymeric binder. The utilization of a ductile SE and a rubbery polymer binder can enhance the flexibility and ductility of the membrane, leading to increased densification degree and low interfacial resistance even under lower fabrication pressure. The details of cell configuration, fabrication procedure, and the resulting performances of the cell will be discussed in this talk.

Microstructural Characterization of Porous Transport Layer Coatings

The porous transport layer (PTL) is a key component in polymer electrolyte membrane (PEM) water electrolyzers and serves the role of controlling the transport of reactants and products to and from the anode. Maintaining a low interfacial contact resistance between the titanium (Ti) fiber or sinter PTL and the iridium (Ir) anode catalyst is critical to maintaining the performance of the electrolyzer cell. This requires costly precious metal coatings, typically Pt, to inhibit the formation of native oxide layers during long-term cell operation. Strategies to reducing the thickness of these costly coatings including surface treatments, such as etching and abrasion, alternative low-cost coating materials, and implementation of microporous layers. It is crucial to understanding the morphologies and degradation mechanisms of these new strategies in order to accelerate the development of cheaper, more robust PTL coatings.In this work, correlative ex situ characterization methods, including laser confocal microscopy (LCM), focused ion beam (FIB), scanning electron microscopy (SEM), time-of-flight secondary ion mass spectrometry (ToF-SIMS), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and scanning transmission electron microscopy (STEM), are utilized to explore the impact surface treatments, such as etching and abrasion, on the Pt coatings uniformity and surface roughness. The thickness, local topography, and continuity of the Pt coating were quantified and correlated with interfacial contact resistance and electrochemical cell performance measurements. Changes to the thickness and composition of the coatings and oxide layers after single-cell tests will also be reported. Overall, these findings aim to guide the development of PTL treatments and coatings, ensuring the creation of highly durable and efficient PEM water electrolyzers that align with the U.S. Department of Energy's Hydrogen Shot goal of reducing the cost of clean hydrogen production to $1 per kilogram by 2031.Funding for this work was provided by U.S. Department of Energy Office of Energy Efficiency and Renewable Energy, Hydrogen and Fuel Cell Technologies Office through the H2NEW Consortium. Electron microscopy research conducted as part of a user project at the Center for Nanophase Materials Sciences (CNMS), which is a US Department of Energy, Office of Science User Facility at Oak Ridge National Laboratory.

Harmonized Interphase Refinement for Robust Garnet Solid‐State Batteries

AbstractGarnet electrolyte Li6.5La3Zr1.5Ta0.5O12 (LLZTO) has been identified as a promising candidate for solid‐state batteries (SSBs). However, the implementation of garnet‐based SSBs is severely restricted owing to the Li dendrite originating from the uneven Li+ deposition and the electron leakage. Herein, one high‐performance garnet‐based SSB is proposed through the enhancement of interfacial dynamics and the inhibition of electron penetration, induced by an artificial harmonized interphase (LSF). The formation of a tightly bonded LLZTO|Li interface is facilitated by the Li3Sb with lower interfacial energies against LLZTO and Li, elucidated by the density functional theory (DFT) calculations. Furthermore, electron leakage and dendrite infiltration are effectively suppressed by the LiF with the electron‐insulating nature and an exceptional γE value. Therefore, a low interfacial resistance of 4.8 Ω cm2 is successfully achieved by the utilization of the functional LSF interphase layer, and the Li|LLZTO‐LSF|Li symmetric cell displayed prolonged Li plating/stripping stability over 1200 h at 0.3 mA cm−2. Moreover, the LFP|LLZTO‐LSF|Li full cell also exhibited notable cycling performance (93.1% capacity retention after 200 cycles at 1 C). The utilization of a synergistic interlayer has been identified as an effective strategy for the advancement of garnet‐based solid‐state lithium batteries.

Synergistically Engineering Grains and Grain Boundaries toward Li Dendrite-Free Li7La3Zr2O12.

Cation-doped cubic Li7La3Zr2O12 is regarded as a promising solid electrolyte for safe and energy-dense solid-state lithium batteries. However, it suffers from the formation of Li2CO3 and high electronic conductivity, which give rise to an unconformable Li/Li7La3Zr2O12 interface and lithium dendrites. Herein, composite AlF3-Li6.4La3Zr1.4Ta0.6O12 solid electrolytes were created based on thermal AlF3 decomposition and F/O displacement reactions under a high-temperature sintering process. When the AlF3 is thermally decomposed, it leaves Al2O3/AlF3 meliorating the grain boundaries and F- ions partially displacing O2- ions in the grains. Due to the higher electronegativity of F- in the grains and the grain-boundary modification, these AlF3-Li6.4La3Zr1.4Ta0.6O12 deliver optimized electronic conduction and chemical stability against the formation of Li2CO3. The Li/AlF3-Li6.4La3Zr1.4Ta0.6O12/Li cell exhibits a low interfacial resistance of ∼16 Ω cm2 and an ultrastable long-term cycling behavior for 800 h under a current density of 200 μA/cm2, leading to Li//LiCoO2 solid-state batteries with good rate performance and cycling stability.

Stabilizing the interface between high-Ni oxide cathode and Li6PS5Cl for all-solid-state batteries via dual-compatible halides

All-solid-state batteries (ASSBs) with enhanced safety are promising next-generation energy storage systems for electric vehicles. However, the utilization of ASSBs is hindered by the high interfacial resistances between high-Ni-oxide cathodes and sulfide solid electrolytes (SEs). Passivating interphases form on the cathode in contact with the SE upon charging, deteriorating the power capability and cyclability. Inspired by the excellent stability of halides at high voltages, herein, we propose the interfacial engineering of LiNixCoyMnzO2 (NCM) and Li6PS5Cl (LPSCl) using Li+-conductive halides with ʻdual compatibilityʼ. The charge-transport and interfacial resistances of the halide-coated NCM (NCM@halide) electrodes are analyzed using a transmission-line-based impedance model. Impedance analyses indicate that the interfacial halide nanolayers slightly increase the Li+-transport resistance, but the NCM@halide electrodes exhibit considerably lower interfacial resistances than bare NCM. Furthermore, the interfacial resistance is highly dependent on the halide composition: NCM@Li2ZrCl6 shows a lower interfacial resistance than NCM@Li3InCl6 and NCM@Li3YCl6, resulting in superior rate-capability and cycling stability. The composition-dependent electrochemical properties of the NCM@halide electrodes are discussed in terms of the dual compatibility of the halides with NCM and LPSCl. This study offers an effective approach for addressing the interfacial challenges of sulfide-based ASSBs with high-Ni oxide cathodes.