Shaping the Contact between Li Metal Anode and Solid‐State Electrolytes

Scientific and technological interest in solid‐state Li metal batteries (SSLMBs) arises from their excellent safety and promising high energy density. However, the practical application of SSLMBs is hindered by poor contact between the Li metal anode (LMA) and solid‐state electrolytes (SSEs). To circumvent this limitation, a pattern‐guided approach that shapes the LMA/SSE contact is disclosed to offer fast Li ion conduction in the interface. A thermally‐treated copper foam is used as the lithophilic pattern to confine and guide Li for forming a tight contact with garnet‐type SSE. The contact can be easily manipulated according to the shape of lithiophilic pattern, facilitating cell assembly. The resulting Li|patterned garnet|Li symmetric cell exhibits an interfacial resistance of 9.8 Ω cm², which is dramatically lower than that of 998 Ω cm² for Li|pristine garnet|Li symmetric cell. Being used in Li–sulfur batteries, the patterned garnet effectively eliminates the polysulfide shuttle and enables stable cycling performance, showing a low capacity decay of 0.035% per cycle over 1000 cycles. The fundamental contact process of metallic anodes/SSEs is carefully investigated. This contact strategy provides a new design concept to improve the interface wettability via a lithiophilic pattern for a variety of SSEs that cannot wet with metallic anodes.     

Intercalated Electrolyte with High Transference Number for Dendrite‐Free Solid‐State Lithium Batteries

Solid‐state lithium (Li) batteries using solid electrolytes and Li anodes are highly desirable because of their high energy densities and intrinsic safety. However, low ambient‐temperature conductivity and poor interface compatibility of solid electrolytes as well as Li dendrite formation cause large polarization and poor cycling stability. Herein, a high transference number intercalated composite solid electrolyte (CSE) is prepared by the combination of a solution‐casting and hot‐pressing method using layered lithium montmorillonite, poly(ethylene carbonate), lithium bis(fluorosulfonyl)imide, high‐voltage fluoroethylene carbonate additive, and poly(tetrafluoroethylene) binder. The electrolyte presents high ionic conductivity (3.5 × 10^?4 S cm^?1), a wide electrochemical window (4.6 V vs Li⁺/Li), and high ionic transference number (0.83) at 25 °C. In addition, a 3D Li anode is also fabricated via a facile thermal infusion strategy. The synergistic effect of high transference number intercalated electrolyte and 3D Li anode is more favorable to suppress Li dendrites in a working battery. The solid‐state batteries based on LiFePO₄ (Al₂O₃ @ LiNi_0.5Co_0.2Mn_0.3O₂), CSE, and 3D Li deliver admirable cycling stability with discharge capacity 145.9 mAh g^?1 (150.7 mAh g^?1) and capacity retention 91.9% after 200 cycles at 0.5 C (92.0% after 100 cycles at 0.2 C) at 25 °C. This work affords a splendid strategy for high‐performance solid‐state battery.     

High Energy Density All‐Solid‐State Batteries: A Challenging Concept Towards 3D Integration

Rechargeable all‐solid‐state batteries will play a key role in many autonomous devices. Planar solid‐state thin film batteries are rapidly emerging but reveal several drawbacks, such as a relatively low energy density and the use of highly reactive metallic lithium. In order to overcome these limitations a new 3D‐integrated all‐solid‐state battery concept with significantly increased surface area is presented. By depositing the active battery materials into high‐aspect ratio structures etched in, for example silicon, 3D‐integrated all‐solid‐state batteries are calculated to reach a much higher energy density. Additionally, by adopting novel high‐energy dense Li‐intercalation materials the use of metallic Lithium can be avoided. Sputtered Ta, TaN and TiN films have been investigated as potential Li‐diffusion barrier materials. TiN combines a very low response towards ionic Lithium and a high electronic conductivity. Additionally, thin film poly‐Si anodes have been electrochemically characterized with respect to their thermodynamic and kinetic Li‐intercalation properties and cycle life. The Butler‐Vollmer relationship was successfully applied, indicating favorable electrochemical charge transfer kinetics and solid‐state diffusion. Advantageously, these new Li‐intercalation anode materials were found to combine an extremely high energy density with fast rate capability, enabling future 3D‐integrated all‐solid‐state batteries.     

Operando Differential Electrochemical Pressiometry for Probing Electrochemo‐Mechanics in All‐Solid‐State Batteries

Owing to an absence or lack of soft (and/or liquid) components, electrochemo‐mechanical effects are imperative for all‐solid‐state batteries (ASBs) based on inorganic solid electrolytes (SEs). As this aspect has been overlooked, relevant investigation has remained scarce. In this work, the development of a new operando differential electrochemical pressiometry (DEP) for ASBs is reported. The time‐ (or capacity‐) derivative differential pressure signals (dP/dt or dP/dQ) reflecting corresponding differential volume changes of electrode active materials feature the specific state of charges (SOCs). This finding leads to a precise estimation of the SOCs of graphite (Gr) electrodes in LiNi_0.70Co_0.15Mn_0.15O₂ (NCM)/Gr all‐solid‐state full cells using sulfide SEs with varying capacity ratios of negative to positive electrodes (n/p ratios); this is corroborated by complementary analysis using a three‐electrode electrochemical cell and ex situ X‐ray diffraction measurements. Furthermore, electrochemo‐mechanical behaviors of NCM/Gr full cells with Gr electrodes employing SEs excluding or including reductively unstable Li₁₀GeP₂S₁₂ are investigated. Notable volume changes caused by lithiation of Li₁₀GeP₂S₁₂ are detected. Importantly, significantly delayed SOC for Gr caused by a severe side reaction with Li₁₀GeP₂S₁₂ is disclosed by the operando DEP result.     

A High‐Performance Li–B–H Electrolyte for All‐Solid‐State Li Batteries

Highly Li‐ion conductive Li₄(BH₄)₃I@SBA‐15 is synthesized by confining the LiI doped LiBH₄ into mesoporous silica SBA‐15. Uniform nanoconfinement of P6₃ mc phase Li₄(BH₄)₃I in SBA‐15 mesopores leads to a significantly enhanced conductivity of 2.5 × 10^?4 S cm^?1 with a Li‐ion transference number of 0.97 at 35 °C. The super Li‐ion mobility in the interface layer with a thickness of 1.2 nm between Li₄(BH₄)₃I and SBA‐15 is believed to be responsible for the fast Li‐ion conduction in Li₄(BH₄)₃I@SBA‐15. Additionally, Li₄(BH₄)₃I@SBA‐15 also exhibits a wide apparent electrochemical stability window (0 to 5 V vs Li/Li⁺) and a superior Li dendrite suppression capability (critical current density 2.6 mA cm^?2 at 55 °C) due to the formation of stable interphases. More importantly, Li₄(BH₄)₃I@SBA‐15‐based Li batteries using either high‐capacity sulfur cathode or high‐voltage oxide cathode show excellent electrochemical performances, making Li₄(BH₄)₃I@SBA‐15 a very attractive electrolyte for next‐generation all‐solid‐state Li batteries.     

Reversible Conversion Reactions and Small First Cycle Irreversible Capacity Loss in Metal Sulfide‐Based Electrodes Enabled by Solid Electrolytes

Solid‐state batteries can potentially enable new classes of electrode materials which are unstable against liquid electrolytes. Here, SnS nanocrystals, synthesized by a wet chemical method, are used to fabricate a Li‐ion electrode, and the electrochemical properties of this electrode are examined in both solid and liquid electrolyte designs. The SnS‐based solid‐state cell delivers a capacity of 629 mAh g^?1 after 100 cycles and exhibits an unprecedentedly small irreversible capacity in the first cycle (8.2%), while the SnS‐based liquid cell shows a rapid capacity decay and large first cycle irreversible capacity (44.6%). Cyclic voltammetry (CV) experiments show significant solid electrolyte interphase (SEI) formation in the liquid cell during the first discharge while SEI formation by electrolyte reduction in the solid‐state cell appears negligible. Along with CV, X‐ray photoelectron spectroscopy and energy dispersive spectroscopy are used to investigate the differences between the solid‐state and liquid cells. The reaction chemistry of SnS in solid‐state cells is also studied in detail by ex situ X‐ray diffraction and X‐ray absorption spectroscopy. The overarching findings are that use of a solid electrolyte suppresses materials degradation and electrolyte reduction which leads to a small first cycle irreversible capacity and stable cycling.     

Design of a Multifunctional Interlayer for NASCION‐Based Solid‐State Li Metal Batteries

NASCION‐type Li conductors have great potential to bring high capacity solid‐state batteries to realization, related to its properties such as high ionic conductivity, stability under ambient conditions, wide electrochemical stability window, and inexpensive production. However, their chemical and thermal instability toward metallic lithium (Li) has severely hindered attempts to utilize Li as anode material in NASCION‐based battery systems. In this work, it is shown how a tailored multifunctional interlayer between the solid electrolyte and Li anode can successfully address the interfacial issues. This interlayer is designed by creating a quasi‐solid‐state paste in which the functionalities of LAGP (Li_1.5Al_0.5Ge_1.5(PO₄)₃) nanoparticles and an ionic liquid (IL) electrolyte are combined. In a solid‐sate cell, the LAGP‐IL interlayer separates the Li metal from bulk LAGP and creates a chemically stable interface with low resistance (≈5 Ω cm²) and efficiently prevents thermal runaway at elevated temperatures (300 °C). Solid‐state cells designed with the interlayer can be operated at high current densities, 1 mA cm^?2, and enable high rate capability with high safety. Here developed strategy provides a generic path to design interlayers for solid‐state Li metal batteries.     

Flexible Stable Solid‐State Al‐Ion Batteries

Rechargeable aluminum‐ion batteries (AIBs) are regarded as promising candidates for post‐lithium energy storage systems (ESSs). For addressing the critical issues in the current liquid AIB systems, here a flexible solid‐state AIB is established using a gel‐polymer electrolyte for achieving robust electrode–electrolyte interfaces. Different from utilization of solid‐state systems for alleviating the safety issues and enhancing energy density in lithium‐ion batteries, employment of polymeric electrolytes mainly focuses on addressing the essential problems in the liquid AIBs, including unstable internal interfaces induced by mechanical deformation and production of gases as well as unfavorable separators. Particularly, such gel electrolyte enables the solid‐state AIBs to present an ultra‐fast charge capability within 10 s at current density of 600 mA g^?1. Meanwhile, an impressive specific capacity ≈120 mA h g^?1 is obtained at current density of 60 mA g^?1, approaching the theoretical limit of graphite‐based AIBs. In addition to the well‐retained electrochemical performance below the ice point, the solid‐state AIBs also hold great stability and safety under various critical conditions. The results suggest that such new prototype of solid‐state AIBs with robust electrode–electrolyte interfaces promises a novel strategy for fabricating stable and safe flexible ESSs.     

Electrolytes Enriched by Crown Ethers for Lithium Metal Batteries

Lithium (Li) metal battery is considered the most promising next-generation battery due to its low potential and high theoretical capacity. However, Li dendrite growth causes serious safety problems. Herein, the 15-Crown-5 (15-C-5) is reported as an electrolyte additive based on solvation shell regulation. The strong complex effect between Li⁺ ion and 15-C-5 can reduce the concentration of Li ions on the electrode surface, thus changing the nucleation, and repressing the growth of Li dendrites in the plating process. Significantly, the strong coordination of Li⁺/15-C-5 would be able to make them aggregate around the Li crystal surface, which could form a protective layer and favor the formation of a smooth and dense solid electrolyte interphase with high toughness and Li⁺ ion conductivity. Therefore, the electrolyte system with 2.0 wt% 15-C-5 achieves excellent electrochemical performance with 170 cycles at 1.0 mA cm⁻² with capacity of 0.5 mA h cm⁻² in symmetric Li|Li cells. The obviously enhanced cycle and rate performance are also achieved in Li|LiNi_0.6Co_0.2Mn_0.2O₂ (NCM622) full cells. The 15-C-5 demonstrates to be a promising additive for the electrolytes toward safe and efficient Li metal batteries.     

Critical Review of Fluorinated Electrolytes for High-Performance Lithium Metal Batteries

Lithium metal batteries (LMBs), due to their ultra-high energy density, are attracting tremendous attentions. However, their commercial application is severely impeded by poor safety and unsatisfactory cycling stability, which are induced by lithium dendrites, side reactions, and inferior anodic stability. Electrolytes, as the indispensable and necessary components in lithium metal batteries, play a crucial role in regulating the electrochemical performance of LMBs. Recently, the fluorinated electrolytes are widely investigated in high-performance LMBs. Thus, the design strategies of fluorinated electrolytes are thoroughly summarized, including fluorinated salts, fluorinated solvents, and fluorinated additives in LMBs, and insights of the fluorinated components in suppressing lithium dendrites, improving anodic stability and cycling stability. Finally, an outlook with several design strategies and challenges will be proposed for novel fluorinated electrolytes.     

Capacity Fading Mechanism in All Solid‐State Lithium Polymer Secondary Batteries Using PEG‐Borate/Aluminate Ester as Plasticizer for Polymer Electrolytes

Solid‐state lithium polymer secondary batteries (LPB) are fabricated with a two‐electrode‐type cell construction of Li|solid‐state polymer electrolyte (SPE)|LiFePO₄. Plasticizers of poly(ethylene glycol) (PEG)‐borate ester (B‐PEG) or PEG‐aluminate ester (Al‐PEG) are added into lithium‐conducting SPEs in order to enhance their ionic conductivity, and lithium bis‐trifluoromethansulfonimide (LiTFSI) is used as the lithium salt. An improvement of the electrochemical properties is observed upon addition of the plasticizers at an operation temperature of 60 °C. However, a decrease of discharge capacities abruptly follows after tens of stable cycles. To understand the origin of the capacity fading, electrochemical impedance techniques, ex‐situ NMR and scanning electron microscopy (SEM)/energy dispersive X‐ray spectroscopy (EDS) techniques are adopted. Alternating current (AC) impedance measurements indicate that the decrease of capacity retention in the LPB is related to a severe increase of the interfacial resistance between the SPE and cathode. In addition, the bulk resistance of the SPE film is observed to accompany the capacity decay. Ex situ NMR studies combined with AC impedance measurements reveal a decrease of Li salt concentration in the SPE film after cycling. Ex situ SEM/EDS observations show an increase of concentration of anions on the electrode surface after cycling. Accordingly, the anions may decompose on the cathode surface, which leads to a reduction of the cycle life of the LPB. The present study suggests that a choice of Li salt and an increase of transference number is crucial for the realization of lithium polymer batteries.     

High‐Power Lithium Metal Batteries Enabled by High‐Concentration Acetonitrile‐Based Electrolytes with Vinylene Carbonate Additive

To enable next‐generation high‐power, high‐energy‐density lithium (Li) metal batteries (LMBs), an electrolyte possessing both high Li Coulombic efficiency (CE) at a high rate and good anodic stability on cathodes is critical. Acetonitrile (AN) is a well‐known organic solvent for high anodic stability and high ionic conductivity, yet its application in LMBs is limited due to its poor compatibility with Li metal anodes even at high salt concentration conditions. Here, a highly concentrated AN‐based electrolyte is developed with a vinylene carbonate (VC) additive to suppress Li⁺ depletion at high current densities. Addition of VC to the AN‐based electrolyte leads to the formation of a polycarbonate‐based solid electrolyte interphase, which minimizes Li corrosion and leads to a very high Li CE of up to 99.2% at a current density of 0.2 mA cm^‐2. Using such an electrolyte, fast charging of Li||NMC333 cells is realized at a high current density of 3.6 mA cm^‐2, and stable cycling of Li||NMC622 cells with a high cathode loading of 4 mAh cm^‐2 is also demonstrated.     

All‐Solid‐State Asymmetric Supercapacitors with Metal Selenides Electrodes and Ionic Conductive Composites Electrolytes

All‐solid‐state flexible asymmetric supercapacitors (ASCs) are developed by utilization of graphene nanoribbon (GNR)/Co_0.85Se composites as the positive electrode, GNR/Bi₂Se₃ composites as the negative electrode, and polymer‐grafted‐graphene oxide membranes as solid‐state electrolytes. Both GNR/Co_0.85Se and GNR/Bi₂Se₃ composite electrodes are developed by a facile one‐step hydrothermal growth method from graphene oxide nanoribbons as the nucleation framework. The GNR/Co_0.85Se composite electrode exhibits a specific capacity of 76.4 mAh g^?1 at a current density of 1 A g^?1 and the GNR/Bi₂Se₃ composite electrode exhibits a specific capacity of 100.2 mAh g^?1 at a current density of 0.5 A g^?1. Moreover, the stretchable membrane solid‐state electrolytes exhibit superior ionic conductivity of 108.7 mS cm^?1. As a result, the flexible ASCs demonstrate an operating voltage of 1.6 V, an energy density of 30.9 Wh kg^?1 at the power density of 559 W kg^?1, and excellent cycling stability with 89% capacitance retention after 5000 cycles. All these results demonstrate that this study provides a simple, scalable, and efficient approach to fabricate high performance flexible all‐solid‐state ASCs for energy storage.     

Gradiently Sodiated Alucone as an Interfacial Stabilizing Strategy for Solid‐State Na Metal Batteries

All‐solid‐state metal batteries (ASSMBs) are attracting much attention due to their cost effectiveness, enhanced safety, room‐temperature performance and high theoretical specific capacity. However, the alkali metal anodes (such as Li and Na) are active enough to react with most solid‐state electrolytes (SSEs), leading to detrimental reactions at the metal–SSE interface. In this work, a molecular layer deposition (MLD) alucone film is employed to stabilize the active Na anode/electrolyte interface in the ASSMBs, limiting the decomposition of the sulfide‐based electrolytes (Na₃SbS₄ and Na₃PS₄) and Na dendrite growth. Such a strategy effectively improves the room‐temperature full battery performance as well as cycling stability for over 475 h in Na–Na symmetric cells. The modified interface is further characterized by X‐ray photoelectron spectroscopy (XPS) depth profiling, which provides spatially resolved evidence of the synergistic effect between the dendrite‐suppressed sodiated alucone and the insulating unsodiated alucone. The coupled layers reinforce the protection of the Na metal/electrolyte interface. Therefore, alucone is identified as an effective and bifunctional coating material for the enhancement of the metal/electrolyte interfacial stability, paving the way for rapid development and wide application of high‐energy ASSMBs.     

Applications of Tin Sulfide‐Based Materials in Lithium‐Ion Batteries and Sodium‐Ion Batteries

SnS_x (x = 1, 2) compounds are composed of earth‐abundant elements and are nontoxic and low‐cost materials that have received increasing attention as energy materials over the past decades, owing to their huge potential in batteries. Generally, SnS_x materials have excellent chemical stability and high theoretical capacity and reversibility due to their unique 2D‐layered structure and semiconductor properties. As a promising matrix material for storing different alkali metal ions through alloying/dealloying reactions, SnS_x compounds have broad electrochemical prospects in batteries. Herein, the structural properties of SnS_x materials and their advantages as electrode materials are discussed. Furthermore, detailed accounts of various synthesis methods and applications of SnS_x materials in lithium‐ion batteries, sodium‐ion batteries, and other new rechargeable batteries are emphasized. Ultimately, the challenges and opportunities for future research on SnS_x compounds are discussed based on the available academic knowledge, including recent scientific advances.     

Boron-Doped Electrolytes as Interfacial Modifiers for High-Rate Stable Lithium Metal Batteries

In this article BF3 etching is applied to fabricate basic SEI (B-SEI) layers enriched with LiF and Li_xBF_y. Artificial solid electrolyte interface (A-SEI) with a “stromatolite” structure is formed on top of the B-SEI growth during the charge-discharge cycles. The structure of A-SEI is characterized laterally and longitudinally by distribution of TEM elements and depth-profile XPS, providing evidence for the elucidation of a new lattice-tuning Li+ “layered” deposition-type SEI structure. At the same time, the SEI is kept from electrolyte erosion fracturing during deposition, resulting in the growth of dendrites along the fracture and significantly enhanced cycling stability under high-rate cycling conditions. In particular, A-SEI endows significantly enhanced cycling capability to the full battery at high cycling rate and high current density. The full cell of A-SEI_@Li||LiPF₆||LFP exhibits an extended lifetime after 2000 cycles at current densities up to 10 C, and still process a CE above 99.0%.     

Electro–Chemo–Mechanical Issues at the Interfaces in Solid‐State Lithium Metal Batteries

Effective solid‐state interfacial contact of both the cathode and lithium metal anode with the solid electrolyte (SE) are required to improve the performance of solid‐state lithium metal batteries (SSBs). Electro–chemo–mechanical coupling (ECMC) strongly affects the interfacial stability of SSBs. On one hand, mechanical stress strongly influences interfacial contact and causes side reactions. On the other hand, electrochemical reactions such as lithium deposition cause mechanical deformation and stress at electrode/SE interfaces. To solve the degradation/failure problems of interfaces and provide guidelines to construct high‐performance SSBs, the ECMC at electrode/SE interfaces should be comprehensively investigated. In this review, the problems associated with ECMC at electrode/SE interfaces are summarized. The interfacial degradation/failure mechanisms, including the contact and electrochemical stability of interfaces, are introduced. Mechanical factors affecting interfacial contact and lithium deposition are highlighted. Experimental observation and computational analysis methods for electrode/SE interfaces are then summarized. Strategies to construct stable electrode/SE interfaces, such as assembling stress and wetting layers to improve interfacial contact, 3D SE structure, and plating stress relief to suppress lithium dendrite formation, are reviewed. The remaining challenges to better understanding ECMC and related solutions to aid SSB development are discussed.     

Low Resistance–Integrated All‐Solid‐State Battery Achieved by Li7La3Zr2O12 Nanowire Upgrading Polyethylene Oxide (PEO) Composite Electrolyte and PEO Cathode Binder

All‐solid‐state lithium metal battery is the most promising next‐generation energy storage device. However, the low ionic conductivity of solid electrolytes and high interfacial impedance with electrode are the main factors to limit the development of all‐solid‐state batteries. In this work, a low resistance–integrated all‐solid‐state battery is designed with excellent electrochemical performance that applies the polyethylene oxide (PEO) with lithium bis(trifluoromethylsulphonyl)imide as both binder of cathode and matrix of composite electrolyte embedded with Li₇La₃Zr₂O₁₂ (LLZO) nanowires (PLLN). The PEO in cathode and PLLN are fused at high temperature to form an integrated all‐solid‐state battery structure, which effectively strengthens the interface compatibility and stability between cathode and PLLN to guarantee high efficient ion transportation during long cycling. The LLZO nanowires uniformly distributed in PLLN can increase the ionic conductivity and mechanical strength of composite electrolyte efficiently, which induces the uniform deposition of lithium metal, thereby suppressing the lithium dendrite growth. The Li symmetric cells using PLLN can stably cycle for 1000 h without short circuit at 60 °C. The integrated LiFePO₄/PLLN/Li batteries show excellent cycling stability at both 60 and 45 °C. The study proposed a novel and robust battery structure with outstanding electrochemical properties.