An Active Halide Catholyte Boosts the Extra Capacity for all-Solid-State Batteries.

Replacing flammable organic liquid electrolytes with nonflammable solid electrolytes (SEs) in lithium batteries is crucial for enhancing safety across various applications, including portable electronics, electric vehicles, and scalable energy storage. Since typical cathode materials do not possess superionic conductivity, Li-ion conduction in the cathode predominantly relies on incorporating a significant number of SEs as additives to form a composite cathode, which substantially compromises the energy density of solid-state lithium batteries. Here, we demonstrate a halide SE, Li3VCl6, which not only exhibits a decent Li+ conductivity, but more importantly, delivers a highly reversible capacity of approximately 80 mAh g-1 with an average voltage of 3 V versus Li+/Li. The ionic conductivity of Li3VCl6 experiences marginal fluctuations upon electrochemical lithiation/delithiation, as its prototypical solid-solution reaction results solely in a reduction of lithium vacancy. When combined with the traditional LiFePO4 cathode, the active Li3VCl6 catholyte enables an impressive capacity of 217.1 mAh g-1 LFP and about 50% increase in energy density compared with inactive catholytes. Harnessing the integrated mass of the catholyte-which can serve as an active material-presents an opportunity to boost the extra capacity, rendering it feasible in applications. This article is protected by copyright. All rights reserved.

Metal chloride cathodes for next-generation rechargeable lithium batteries.

Rechargeable lithium-ion batteries (LIBs) have prospered a rechargeable world, predominantly relying on various metal oxide cathode materials for their abilities to reversibly de-/intercalate lithium-ion, while also serving as lithium sources for batteries. Despite the success of metal oxide, issues including low energy density have raised doubts about their suitability for next-generation lithium batteries. This has sparked interest in metal chlorides, a neglected cathode material family. Metal chlorides show promise with factors like energy density, diffusion coefficient, and compressibility. Unfortunately, challenges like high solubility hamper their utilization. In this review, we highlight the opportunities for metal chlorides in the post-lithium-ion era. Subsequently, we summarize their dissolution challenges. Furthermore, we discuss recent advancements, encompassing liquid-state electrolyte engineering, solid-state electrolytes (SSEs) cooperation, and LiCl-based cathodes. Finally, we provide an outlook on future research directions of metal chlorides, emphasizing electrode fabrication, electrolyte design, the application of SSEs, and the exploration of conversion reactions.

A Stable Matrix Assisting Highly Compatible and Maintainable Lithium-Garnet Interface for Solid-State Batteries.

Solid-state Li metal batteries (SSLMBs) are attractive due to their capability to simultaneously offer high energy density and high-level safety when combining Li metal anodes, solid-state electrolytes (SSEs), and high-voltage cathodes together. However, SSLMBs may well incur short circuits caused by Li dendrites penetrations, which mainly originate from the instability and poor contact between Li metal and SSEs. Herein, by taking full advantage of the reaction products of Li and Li1.3Al0.3Ti1.7(PO4)3 (LATP), a lithium-LATP composite anode (Li-LATP) is obtained, in which a stable matrix is formed to enhance the contact between Li and the garnet-type SSEs, alleviating the volume change and preserving an intact interface during the charge/discharge process. Consequently, the Li-LATP/garnet/Li-LATP symmetric cell displays a fairly low interfacial resistance of 6 Ω cm2 and stable cycling performance for over 2500 h with a low overpotential. Furthermore, the LiCoO2/garnet/Li-LATP full cell also shows a high discharge capacity of 159 mAh g-1 and great cycling performance.

Na2.5Cr0.5Zr0.5Cl6: A New Halide-Based Fast Sodium-Ion Conductor.

All-solid-state batteries employing solid electrolytes (SEs) have received widespread attention due to their high safety. Recently, lithium halides are intensively investigated as promising SEs while their sodium counterparts are less studied. Herein, a new sodium-ion conductor with a chemical formula of Na2.5Cr0.5Zr0.5Cl6 is reported, which exhibits high room temperature ionic conductivity of 0.1 mS cm-1 with low migration energy barrier of ≈0.41 eV. Na2.5Cr0.5Zr0.5Cl6 has a Fm-3m structure with 41.67 mol.% of cationic vacancies owing to the occupation of Cr (8.33 mol.%) and Zr (8.33 mol.%) ions at Na sites. Supercell calculations show that the lowest columbic energy configuration has Cr/Zr/V (where V is the vacancy) clusters in the structure. Nonetheless, the clusters have mixed effects on the sodium ion conduction pathway, based on the Bond Valence Energy Landscape calculation. A global 3D Na-ion transport percolation network can be revealed in the lowest energy supercell. Effective pathways are connected through the NaCl6 and VCl6 nodes. Besides, Raman spectroscopy and 23Na solid-state nuclear magnetic resonance spectroscopy further prove the tunable structure of the SEs with different Cr to Zr ratios. The optimization between the concentration of Na+ and vacancies is crucial to create an improved network of Na+ diffusion channels.

Promoting high-voltage stability through local lattice distortion of halide solid electrolytes.

Stable solid electrolytes are essential to high-safety and high-energy-density lithium batteries, especially for applications with high-voltage cathodes. In such conditions, solid electrolytes may experience severe oxidation, decomposition, and deactivation during charging at high voltages, leading to inadequate cycling performance and even cell failure. Here, we address the high-voltage limitation of halide solid electrolytes by introducing local lattice distortion to confine the distribution of Cl-, which effectively curbs kinetics of their oxidation. The confinement is realized by substituting In with multiple elements in Li3InCl6 to give a high-entropy Li2.75Y0.16Er0.16Yb0.16In0.25Zr0.25Cl6. Meanwhile, the lattice distortion promotes longer Li-Cl bonds, facilitating favorable activation of Li+. Our results show that this high-entropy halide electrolyte boosts the cycle stability of all-solid-state battery by 250% improvement over 500 cycles. In particular, the cell provides a higher discharge capacity of 185 mAh g-1 by increasing the charge cut-off voltage to 4.6 V at a small current rate of 0.2 C, which is more challenging to electrolytes|cathode stability. These findings deepen our understanding of high-entropy materials, advancing their use in energy-related applications.

A Tailored Interface Design for Anode-Free Solid-State Batteries.

Anode-free solid-state batteries (AFSSBs) are considered to be one of the most promising high-safety and high-energy storage systems. However, low Coulombic efficiency stemming from severe deterioration on solid electrolyte/current collector (Cu foil) interface and undesirable Li dendrite growth impede their practical application, especially when rigid garnet electrolyte is used. Here, an interfacial engineering strategy between garnet electrolyte and Cu foil is introduced for stable and highly efficient AFSSBs. By utilizing the high Li ion conductivity of LiC6 layer, interfacial self-adaption ability arising from ductile lithiated polyacrylic acid polymer layer and regulated Li deposition via Li-Ag alloying reaction, the garnet-based AFSSB delivers a stable long-term operation. Additionally, when combined with a commercial LiCoO2 cathode (3.1 mAh cm-2 ), the cell also exhibits an outstanding capacity retention due to the tailored interface design. The strategies for novel AFSSBs architecture thus offer an alternative route to design next-generation batteries with high safety and high density.

Ag Nanoparticles-Coated Shish-Kebab Superstructure Film for Wearable Heater.

Passive and active wearable heaters have received widespread attention due to their efficient utilization of solar energy and all-weather heating capabilities, but the current challenges are their preparation processes being time-consuming and equipment expensive. Herein, a simple and facilitated preparation method for the multifunctional wearable heater was developed, which springs Ag nanoparticles on the shish-kebab superstructure film via deposited melanin-like polydopamine as the adhesive. The light absorption ability of the resultant wearable heater in the visible region can be significantly enhanced by the addition of polydopamine, realizing a highly efficient photothermal conversion ability. Accordingly, it can achieve rapid warming ability whether passive heating (up to 45 °C about 60 s at 100 mW/cm2) or active heating (up to 72 °C about 40 s at 0.6 V), compared to ordinary cotton fabric. In addition, it can realize a 6.3 °C temperature difference with Cotton, showing excellent heat preservation ability. This study demonstrates a simple and low-cost approach for the prepared shish-kebab superstructure-based wearable heaters.

Combining Solid Solution Strengthening and Second Phase Strengthening for Thinning Li Metal Foils.

Thin lithium (Li) metal foils have been proved to be indispensable yet elusive for practical high-energy-density lithium batteries. Currently, the realization of such thin foils (<50 µm) is impeded by the inferior mechanical processability of metallic Li. In this work, we demonstrate that the combination of solid solution strengthening and second phase strengthening, achieved by the addition of silver fluoride (AgF) to Li metal, can substantially enhance both the strength and ductility of metallic Li. Benefiting from the improved machinability, we succeed in fabricating an ultrathin (down to 5 µm), freestanding, and mechanically robust Li-AgF composite foil. More interestingly, the in situ-formed LixAg-LiF skeleton in the composite facilitates Li diffusion kinetics and uniform Li deposition, where the thin Li-AgF electrode displays a prolonged cycle life over 500 h at 1 mA cm-2 and 1 mAh cm-2 in a carbonate electrolyte. Coupled with a commercial LiCoO2 cathode (3.4 mAh cm-2), the LiCoO2||Li-AgF cell delivers a notable capacity retention of ∼90% over 100 cycles at 0.5 C with a low negative/positive ratio of 2.5.

Engineering Li Metal Anode for Garnet-Based Solid-State Batteries.

ConspectusThe past 30 years have witnessed the great achievements of Li-ion batteries (LIBs) based on a graphite anode and liquid organic electrolytes. Yet the limited energy density of a graphite anode and unavoidable safety risks caused by flammable liquid organic electrolytes hinder further developments of LIBs. To reach higher energy density, Li metal anodes (LMAs) with high capacity and low electrode potential are a promising choice. However, LMAs suffer from more serious safety concerns than the graphite anode in liquid LIBs. The dilemma of safety and energy density remains an inevitable obstacle in the way of LIBs.Solid-state batteries (SSBs) offer new opportunities to simultaneously achieve intrinsic safety and high energy density. Among all types of SSBs that are based on oxides, polymers, sulfides, or halides, garnet-type SSBs seem to be one of the most attractive choices due to garnet's merits in high ionic conductivities (10-4-10-3 S/cm at room temperature), wide electrochemical windows (0-6 V), and intrinsically high safety. However, garnet-type SSBs are faced with large interfacial impedance and short-circuit problems caused by Li dendrites. Recently, engineered Li metal anodes (ELMAs) have shown unique advantages in tackling interface issues and attracted extensive research interest.In this Account, we focus on fundamental understandings and provide an in-depth review of ELMAs in garnet-based SSBs. Considering the limited space, we mainly discuss the recent progress made in our groups. First, we introduce the design guidelines for ELMAs and emphasize the unique role of theoretical calculation in predicting and optimizing ELMAs. Then we discuss the interface compatibility of ELMAs with garnet SSEs in details. Specifically, we have demonstrated the advantages of ELMAs in enhancing interface contact and suppressing Li dendrite growth. Next, we attentively analyze the gaps between laboratory and practical applications. We strongly recommend establishing a unified testing standard, with a practically desired areal capacity per cycle (>3.0 mAh/cm2) and a precisely controlled Li capacity excess. Finally, novel chances to enhance ELMAs' processability and fabricate thin Li foils are highlighted. We believe that this Account will offer an insightful analysis of ELMAs' recent advancements and push forward their practical applications.

Variations of tunnelling resistance between CNTs with strain in composites: non-monotonicty and influencing factors.

The electro-mechanical response of conductive carbon-nanotube(CNT)-polymer composites is vital when they are used as smart-sensing materials. Clarifying the variation trend of resistance with strain is the key to design and regulate the piezoresistive property of such material. Here, we present some finite element simulations to predict the electro-mechanical response using a geometrical model comprising two hollow cylindrical CNTs and a cuboid matrix. The electrical contact between CNTs is represented by some elements which account for quantum tunnelling effects and capture the sensitivity of conductivity to separation. Different from classical simulations using solid model or one-dimensional beam model, in which the tunnelling resistance between two CNTs changes monotonously with strain, the results in this work show that the trend is non-monotonic in some cases, i.e. it increases at first and then decreases with the uniaxial compressive strain when the elastic modulus of the matrix is high. In addition, factors affecting the different variation trends are discussed in details, which include geometric model, elastic modulus and Poisson's ratio of the matrix, and orientation angle.

Is graphite lithiophobic or lithiophilic?

Graphite and lithium metal are two classic anode materials and their composite has shown promising performance for rechargeable batteries. However, it is generally accepted that Li metal wets graphite poorly, causing its spreading and infiltration difficult. Here we show that graphite can either appear superlithiophilic or lithiophobic, depending on the local redox potential. By comparing the wetting performance of highly ordered pyrolytic graphite, porous carbon paper (PCP), lithiated PCP and graphite powder, we demonstrate that the surface contaminants that pin the contact-line motion and cause contact-angle hysteresis have their own electrochemical-stability windows. The surface contaminants can be either removed or reinforced in a time-dependent manner, depending on whether the reducing agents (C6→LiC6) or the oxidizing agents (air, moisture) dominate in the ambient environment, leading to bifurcating dynamics of either superfast or superslow wetting. Our findings enable new fabrication technology for Li-graphite composite with a controllable Li-metal/graphite ratio and present great promise for the mass production of Li-based anodes for use in high-energy-density batteries.

Graphitic Carbon Nitride (g-C3 N4 ): An Interface Enabler for Solid-State Lithium Metal Batteries.

Solid-state Li metal batteries (SSLMBs) have attracted considerable interests due to their promising energy density as well as high safety. However, the realization of a well-matched Li metal/solid-state electrolyte (SSE) interface remains challenging. Herein, we report g-C3 N4 as a new interface enabler. We discover that introducing g-C3 N4 into Li metal can not only convert the Li metal/garnet-type SSE interface from point contact to intimate contact but also greatly enhance the capability to suppress the dendritic Li formation because of the greatly enhanced viscosity, decreased surface tension of molten Li, and the in situ formation of Li3 N at the interface. Thus, the resulting Li-C3 N4 |SSE|Li-C3 N4 symmetric cell gives a significantly low interfacial resistance of 11â€…Ω cm2 and a high critical current density (CCD) of 1500 µA cm-2 . In contrast, the same symmetric cell configuration with pristine Li metal electrodes has a much larger interfacial resistance (428â€…Ω cm2 ) and a much lower CCD (50 µA cm-2 ).

Lithium-Graphite Paste: An Interface Compatible Anode for Solid-State Batteries.

All-solid-state batteries (ASSBs) with ceramic-based solid-state electrolytes (SSEs) enable high safety that is inaccessible with conventional lithium-ion batteries. Lithium metal, the ultimate anode with the highest specific capacity, also becomes available with nonflammable SSEs in ASSBs, which offers promising energy density. The rapid development of ASSBs, however, is significantly hampered by the large interfacial resistance as a matched lithium/ceramic interface that is not easy to pursue. Here, a lithium-graphite (Li-C) composite anode is fabricated, which shows a dramatic modification in wettability with garnet SSE. An intimate Li-C/garnet interface is obtained by casting Li-C composite onto garnet-type SSE, delivering an interfacial resistance as low as 11 Ω cm2 . As a comparison, pure Li/garnet interface gives a large resistance of 381 Ω cm2 . Such improvement can be ascribed to the experiment-measured increased viscosity of Li-C composite and simulation-verified limited interfacial reaction. The Li-C/garnet/Li-C symmetric cell exhibits stable plating/striping performance with small voltage hysteresis and endures a critical current density up to 1.0 mA cm-2 . The full cell paired with LiFePO4 shows stable cycle performance, comparable to the cell with liquid electrolyte. The present work demonstrates a promising strategy to develop ceramic-compatible lithium metal-based anodes and hence low-impedance ASSBs.

Wood-Derived Nanopaper Dielectrics for Organic Synaptic Transistors.

The use of biocompatible and biodegradable materials in electronic devices can be an important trend in the development of the next-generation green electronics. In addition, by integrating the advantages of low power consumption, low-cost processing, and flexibility, organic synaptic devices will be promising elements for the construction of brain-inspired computers. However, previously reported electrolyte-gated synaptic transistors are mainly made of non-biocompatible and non-biodegradable electrolytes. Woods are widely considered as one kind of sustainable and renewable materials. We found that wood-derived cellulose nanopapers have ionic conductivity and, therefore, can be used as dielectric materials for organic synaptic transistors. The fabricated wood-derived cellulose nanopapers exhibit decent ionic conductivity of 7.3 × 10-4 S m-1 and a high lateral coupling effective capacitance of 18.65 nF cm-2 at 30 Hz. The laterally coupled organic synaptic transistors using wood-derived cellulose nanopapers as the dielectric layer present excellent transistor performances at the operating voltage below 1.5 V. More significantly, some important synaptic behaviors, such as excitatory postsynaptic current, signal-filtering characteristics, and dendritic integration are successfully simulated in our synaptic transistors. Because the development of electronic devices with biocompatible and biodegradable materials is essential, this work may inspire new directions for the development of "green" neuromorphic electronics.