Lithium Azide as an Electrolyte Additive for All‐Solid‐State Lithium–Sulfur Batteries

Of the various beyond‐lithium‐ion battery technologies, lithium–sulfur (Li–S) batteries have an appealing theoretical energy density and are being intensely investigated as next‐generation rechargeable lithium‐metal batteries. However, the stability of the lithium‐metal (Li°) anode is among the most urgent challenges that need to be addressed to ensure the long‐term stability of Li–S batteries. Herein, we report lithium azide (LiN₃) as a novel electrolyte additive for all‐solid‐state Li–S batteries (ASSLSBs). It results in the formation of a thin, compact and highly conductive passivation layer on the Li° anode, thereby avoiding dendrite formation, and polysulfide shuttling. It greatly enhances the cycling performance, Coulombic and energy efficiencies of ASSLSBs, outperforming the state‐of‐the‐art additive lithium nitrate (LiNO₃).     

A Stable Quasi‐Solid‐State Sodium–Sulfur Battery

Ambient‐temperature sodium–sulfur (Na–S) batteries are considered a promising energy storage system due to their high theoretical energy density and low costs. However, great challenges remain in achieving a high rechargeable capacity and long cycle life. Herein we report a stable quasi‐solid‐state Na‐S battery enabled by a poly(S‐pentaerythritol tetraacrylate (PETEA))‐based cathode and a (PETEA‐tris[2‐(acryloyloxy)ethyl] isocyanurate (THEICTA))‐based gel polymer electrolyte. The polymeric sulfur electrode strongly anchors sulfur through chemical binding and inhibits the shuttle effect. Meanwhile, the in situ formed polymer electrolyte with high ionic conductivity and enhanced safety successfully stabilizes the Na anode/electrolyte interface, and simultaneously immobilizes soluble Na polysulfides. The as‐developed quasi‐solid‐state Na‐S cells exhibit a high reversible capacity of 877 mA h g^?1 at 0.1 C and an extended cycling stability.     

Tailored Organic Electrode Material Compatible with Sulfide Electrolyte for Stable All‐Solid‐State Sodium Batteries

All‐solid‐state sodium batteries (ASSSBs) with nonflammable electrolytes and ubiquitous sodium resource are a promising solution to the safety and cost concerns for lithium‐ion batteries. However, the intrinsic mismatch between low anodic decomposition potential of superionic sulfide electrolytes and high operating potentials of sodium‐ion cathodes leads to a volatile cathode–electrolyte interface and undesirable cell performance. Here we report a high‐capacity organic cathode, Na₄C₆O₆, that is chemically and electrochemically compatible with sulfide electrolytes. A bulk‐type ASSSB shows high specific capacity (184 mAh g^?1) and one of the highest specific energies (395 Wh kg^?1) among intercalation compound‐based ASSSBs. The capacity retentions of 76 % after 100 cycles at 0.1 C and 70 % after 400 cycles at 0.2 C represent the record stability for ASSSBs. Additionally, Na₄C₆O₆ functions as a capable anode material, enabling a symmetric all‐organic ASSSB with Na₄C₆O₆ as both cathode and anode materials.     

Na3SbS4: A Solution Processable Sodium Superionic Conductor for All‐Solid‐State Sodium‐Ion Batteries

All‐solid‐state sodium‐ion batteries that operate at room temperature are attractive candidates for use in large‐scale energy storage systems. However, materials innovation in solid electrolytes is imperative to fulfill multiple requirements, including high conductivity, functional synthesis protocols for achieving intimate ionic contact with active materials, and air stability. A new, highly conductive (1.1 mS cm^?1 at 25 °C, E_a=0.20 eV) and dry air stable sodium superionic conductor, tetragonal Na₃SbS₄, is described. Importantly, Na₃SbS₄ can be prepared by scalable solution processes using methanol or water, and it exhibits high conductivities of 0.1–0.3 mS cm^?1. The solution‐processed, highly conductive solidified Na₃SbS₄ electrolyte coated on an active material (NaCrO₂) demonstrates dramatically improved electrochemical performance in all‐solid‐state batteries.     

Lithium Chlorides and Bromides as Promising Solid‐State Chemistries for Fast Ion Conductors with Good Electrochemical Stability

Enabling all‐solid‐state Li‐ion batteries requires solid electrolytes with high Li ionic conductivity and good electrochemical stability. Following recent experimental reports of Li₃YCl₆ and Li₃YBr₆ as promising new solid electrolytes, we used first principles computation to investigate the Li‐ion diffusion, electrochemical stability, and interface stability of chloride and bromide materials and elucidated the origin of their high ionic conductivities and good electrochemical stabilities. Chloride and bromide chemistries intrinsically exhibit low migration energy barriers, wide electrochemical windows, and are not constrained to previous design principles for sulfide and oxide Li‐ion conductors, allowing for much greater freedom in structure, chemistry, composition, and Li sublattice for developing fast Li‐ion conductors. Our study highlights chloride and bromide chemistries as a promising new research direction for solid electrolytes with high ionic conductivity and good stability.     

High Uptake and Fast Transportation of LiPF6 in a Porous Aromatic Framework for Solid‐State Li‐Ion Batteries

Solid‐state Li‐ion batteries (SSLIBs) have recently attracted substantial attention from scientists for the advantages of better safety performance. However, there are still several key challenges in SSLIBs that need to be addressed, such as low energy density, poor thermal stability or cycle stability, and large interface resistance. This contribution introduces a novel SSLIB with a porous aromatic framework (PAF‐1) accommodating LiPF₆ that was used as the solid‐state electrolyte (SSE) replacing the liquid electrolyte and diaphragm of traditional Li‐ion batteries. The charge, discharge capacity, rate performance and cycle stability of the SSLIB were remarkably enhanced.     

LiNbO_3-coated LiNi_(0.8)Co_(0.1)Mn_(0.1)O_2 cathode with high discharge capacity and rate performance for all-solid-state lithium battery

In order to obtain high power density, energy density and safe energy storage lithium ion batteries(LIB)to meet growing demand for electronic products, oxide cathodes have been widely explored in all-solidstate lithium batteries(ASSLB) using sulfide solid electrolyte. However, the electrochemical performances are still not satisfactory, due to the high interfacial resistance caused by severe interfacial instability between sulfide solid electrolyte and oxide cathode, especially Ni-rich oxide cathodes, in charge-discharge process. Ni-rich LiNi_(0.8)Co_(0.1)Mn_(0.1)O_2(NCM811) material at present is one of the most key cathode candidates to achieve the high energy density up to 300 Wh kg~(-1) in liquid LIB, but rarely investigated in ASSLB using sulfide electrolyte. To design the stable interface between NCM811 and sulfide electrolyte should be extremely necessary. In this work, in view of our previous work, LiNbO_3 coating with about 1 wt%content is adopted to improve the interfacial stability and the electrochemical performances of NCM811 cathode in ASSLB using Li_(10)GeP_2S_(12) solid electrolyte. Consequently, LiNbO_3-coated NCM811 cathode displays the higher discharge capacity and rate performance than the reported oxide electrodes in ASSLB using sulfide solid electrolyte to our knowledge.     

Deep‐Eutectic‐Solvent‐Based Self‐Healing Polymer Electrolyte for Safe and Long‐Life Lithium‐Metal Batteries

The deployment of high‐energy‐density lithium‐metal batteries has been greatly impeded by Li dendrite growth and safety concerns originating from flammable liquid electrolytes. Herein, we report a stable quasi‐solid‐state Li metal battery with a deep eutectic solvent (DES)‐based self‐healing polymer (DSP) electrolyte. This electrolyte was fabricated in a facile manner by in situ copolymerization of 2‐(3‐(6‐methyl‐4‐oxo‐1,4‐dihydropyrimidin‐2‐yl)ureido)ethyl methacrylate (UPyMA) and pentaerythritol tetraacrylate (PETEA) monomers in a DES‐based electrolyte containing fluoroethylene carbonate (FEC) as an additive. The well‐designed DSP electrolyte simultaneously possesses non‐flammability, high ionic conductivity and electrochemical stability, and dendrite‐free Li plating. When applied in Li metal batteries with a LiMn₂O₄ cathode, the DSP electrolyte effectively suppressed manganese dissolution from the cathode and enabled high‐capacity and a long lifespan at room and elevated temperatures.     

Anisotropically Electrochemical–Mechanical Evolution in Solid‐State Batteries and Interfacial Tailored Strategy

All‐solid‐state batteries have attracted attention owing to the potential high energy density and safety; however, little success has been made on practical applications of solid‐state batteries, which is largely attributed to the solid–solid interface issues. A fundamental elucidation of electrode–electrolyte interface behaviors is of crucial significance but has proven difficult. The interfacial resistance and capacity fading issues in a solid‐state battery were probed, revealing a heterogeneous phase transition evolution at solid–solid interfaces. The strain‐induced interfacial change and the contact loss, as well as a dense metallic surface phase, deteriorate the electrochemical reaction in solid‐state batteries. Furthermore, the in situ growth of electrolytes on secondary particles is proposed to fabricate robust solid–solid interface. Our study enlightens new insights into the mechanism behind solid–solid interfacial reaction for optimizing advanced solid‐state batteries.     

Revealing an Interconnected Interfacial Layer in Solid‐State Polymer Sodium Batteries

Replacing the commonly used nonaqueous liquid electrolytes in rechargeable sodium batteries with polymer solid electrolytes is expected to provide new opportunities to develop safer batteries with higher energy densities. However, this poses challenges related to the interface between the Na‐metal anode and polymer electrolytes. Driven by systematically investigating the interface properties, an improved interface is established between a composite Na/C metal anode and electrolyte. The observed chemical bonding between carbon matrix of anode with solid polymer electrolyte, prevents delamination, and leads to more homogeneous plating and stripping, which reduces/suppresses dendrite formation. Full solid‐state polymer Na‐metal batteries, using a high mass loaded Na₃V₂(PO₄)₃ cathode, exhibit ultrahigh capacity retention of more than 92 % after 2 000 cycles and over 80 % after 5 000 cycles, as well as the outstanding rate capability.     

Boosting Solid‐State Diffusivity and Conductivity in Lithium Superionic Argyrodites by Halide Substitution

Developing high‐performance all‐solid‐state batteries is contingent on finding solid electrolyte materials with high ionic conductivity and ductility. Here we report new halide‐rich solid solution phases in the argyrodite Li₆PS₅Cl family, Li_6?xPS_5?xCl_1+x, and combine electrochemical impedance spectroscopy, neutron diffraction, and ⁷Li NMR MAS and PFG spectroscopy to show that increasing the Cl^?/S^2? ratio has a systematic, and remarkable impact on Li‐ion diffusivity in the lattice. The phase at the limit of the solid solution regime, Li_5.5PS_4.5Cl_1.5, exhibits a cold‐pressed conductivity of 9.4±0.1 mS cm^?1 at 298 K (and 12.0±0.2 mS cm^?1 on sintering)—almost four‐fold greater than Li₆PS₅Cl under identical processing conditions and comparable to metastable superionic Li₇P₃S₁₁. Weakened interactions between the mobile Li‐ions and surrounding framework anions incurred by substitution of divalent S^2? for monovalent Cl^? play a major role in enhancing Li⁺‐ion diffusivity, along with increased site disorder and a higher lithium vacancy population.     

Interfacial Evolution of Lithium Dendrites and Their Solid Electrolyte Interphase Shells of Quasi‐Solid‐State Lithium‐Metal Batteries

Unstable electrode/solid‐state electrolyte interfaces and internal lithium dendrite penetration hamper the applications of solid‐state lithium‐metal batteries (SSLMBs), and the underlying mechanisms are not well understood. Herein, in situ optical microscopy provides insights into the lithium plating/stripping processes in a gel polymer electrolyte and reveals its dynamic evolution. Spherical lithium deposits evolve into moss‐like and branch‐shaped lithium dendrites with increasing current densities. Remarkably, the on‐site‐formed solid electrolyte interphase (SEI) shell on the lithium dendrite is distinctly captured after lithium stripping. Inducing an on‐site‐formed SEI shell with an enhanced modulus to wrap the lithium precipitation densely and uniformly can regulate dendrite‐free behaviors. An in‐depth understanding of lithium dendrite evolution and its functional SEI shell will aid in the optimization of SSLMBs.     

Rational Design of an Ionic Liquid‐Based Electrolyte with High Ionic Conductivity Towards Safe Lithium/Lithium‐Ion Batteries

It is a very urgent and important task to improve the safety and high‐temperature performance of lithium/lithium‐ion batteries (LIBs). Here, a novel ionic liquid, 1‐(2‐ethoxyethyl)‐1‐methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (PYR_1(2o2)TFSI), was designed and synthesized, and then mixed with dimethyl carbonate (DMC) as appropriate solvent and LiTFSI lithium salt to produce an electrolyte with high ionic conductivity for safe LIBs. Various characterizations and tests show that the highly flexible ether group could markedly reduce the viscosity and provide coordination sites for Li‐ion, and the DMC could reduce the viscosity and effectively enhance the Li‐ion transport rate and transference number. The electrolyte exhibits excellent electrochemical performance in Li/LiFeO₄ cells at room temperature as well as at a high temperature of 60 °C. More importantly, with the addition of DMC, the IL‐based electrolyte remains nonflammable and appropriate DMC can effectively inhibit the growth of lithium dendrites. Our present work may provide an attractive and promising strategy for high performance and safety of both lithium and lithium‐ion batteries.     

A Selection Rule for Hydrofluoroether Electrolyte Cosolvent: Establishing a Linear Free‐Energy Relationship in Lithium–Sulfur Batteries

Hydrofluoroethers (HFEs) have been adopted widely as electrolyte cosolvents for battery systems because of their unique low solvating behavior. The electrolyte is currently utilized in lithium‐ion, lithium–sulfur, lithium–air, and sodium‐ion batteries. By evaluating the relative solvating power of different HFEs with distinct structural features, and considering the shuttle factor displayed by electrolytes that employ HFE cosolvents, we have established the quantitative structure–activity relationship between the organic structure and the electrochemical performance of the HFEs. Moreover, we have established the linear free‐energy relationship between the structural properties of the electrolyte cosolvents and the polysulfide shuttle effect in lithium–sulfur batteries. These findings provide valuable mechanistic insight into the polysulfide shuttle effect in lithium–sulfur batteries, and are instructive when it comes to selecting the most suitable HFE electrolyte cosolvent for different battery systems.     

Lithium Ion Pathway within Li7La3Zr2O12‐Polyethylene Oxide Composite Electrolytes

Polymer–ceramic composite electrolytes are emerging as a promising solution to deliver high ionic conductivity, optimal mechanical properties, and good safety for developing high‐performance all‐solid‐state rechargeable batteries. Composite electrolytes have been prepared with cubic‐phase Li₇La₃Zr₂O₁₂ (LLZO) garnet and polyethylene oxide (PEO) and employed in symmetric lithium battery cells. By combining selective isotope labeling and high‐resolution solid‐state Li NMR, we are able to track Li ion pathways within LLZO‐PEO composite electrolytes by monitoring the replacement of ⁷Li in the composite electrolyte by ⁶Li from the ⁶Li metal electrodes during battery cycling. We have provided the first experimental evidence to show that Li ions favor the pathway through the LLZO ceramic phase instead of the PEO‐LLZO interface or PEO. This approach can be widely applied to study ion pathways in ionic conductors and to provide useful insights for developing composite materials for energy storage and harvesting.     

A Plastic–Crystal Electrolyte Interphase for All‐Solid‐State Sodium Batteries

The development of all‐solid‐state rechargeable batteries is plagued by a large interfacial resistance between a solid cathode and a solid electrolyte that increases with each charge–discharge cycle. The introduction of a plastic–crystal electrolyte interphase between a solid electrolyte and solid cathode particles reduces the interfacial resistance, increases the cycle life, and allows a high rate performance. Comparison of solid‐state sodium cells with 1) solid electrolyte Na₃Zr₂(Si₂PO₄) particles versus 2) plastic–crystal electrolyte in the cathode composites shows that the former suffers from a huge irreversible capacity loss on cycling whereas the latter exhibits a dramatically improved electrochemical performance with retention of capacity for over 100 cycles and cycling at 5 C rate. The application of a plastic–crystal electrolyte interphase between a solid electrolyte and a solid cathode may be extended to other all‐solid‐state battery cells.     

Direct Observation of a Li‐Ionic Space‐Charge Layer Formed at an Electrode/Solid‐Electrolyte Interface

When two different materials come into contact, mobile carriers redistribute at the interface according to their potential difference. Such a charge redistribution is also expected at the interface between electrodes and solid electrolytes. The redistributed ions significantly affect the ion conduction through the interface. Thus, it is essential to determine the actual distribution of the ionic carriers and their potential to improve ion conduction. We succeeded in visualizing the ionic and potential profiles in the charge redistribution layer, or space‐charge layer (SCL), formed at the interface between a Cu electrode and Li‐conductive solid electrolyte using phase‐shifting electron holography and spatially resolved electron energy‐loss spectroscopy. These electron microscopy techniques clearly showed the Li‐ionic SCL, which dropped by 1.3 V within a distance of 10 nm from the interface. These techniques could contribute to the development of next‐generation electrochemical devices.     

An Adjustable‐Porosity Plastic Crystal Electrolyte Enables High‐Performance All‐Solid‐State Lithium‐Oxygen Batteries

The limited triple‐phase boundaries (TPBs) in solid‐state cathodes (SSCs) and high resistance imposed by solid electrolytes (SEs) make the achievement of high‐performance all‐solid‐state lithium‐oxygen (ASS Li‐O₂) batteries a challenge. Herein, an adjustable‐porosity plastic crystal electrolyte (PCE) has been fabricated by employing a thermally induced phase separation (TIPS) technique to overcome the above tricky issues. The SSC produced through the in‐situ introduction of the porous PCE on the surface of the active material, facilitates the simultaneous transfer of Li⁺/e^?, as well as ensures fast flow of O₂, forming continuous and abundant TPBs. The high Li⁺ conductivity, softness, and adhesion of the dense PCE significantly reduce the battery resistance to 115 Ω. As a result, the ASS Li‐O₂ battery based on this adjustable‐porosity PCE exhibits superior performances with high specific capacity (5963 mAh g^?1), good rate capability, and stable cycling life up to 130 cycles at 32 °C. This novel design and exciting results could open a new avenue for ASS Li‐O₂ batteries.     

2D Materials as Ionic Sieves for Inhibiting the Shuttle Effect in Batteries

Alternatives of commercial lithium‐ion batteries (LIBs) have drawn huge attention due to the large demand of energy storage systems and the lack of resources for traditional LIBs. Promising candidates include but are not limited to Li‐S batteries, organic batteries and flow batteries. However, the dissolution of active materials and the consequent shuttle effect, as one of the main challenges in these candidates, always leads to significant capacity loss and poor cycling life. The rising two‐dimensional (2D) materials, with well‐defined structures and attractive physical and chemical properties, provide a new vision to solve these problems via suppressing the shuttle of the dissolved active materials. Herein, we present a minireview on the advances and perspectives of 2D materials as ionic sieves for inhibiting the shuttle effect in batteries.     

Nickel‐Rich Layered Lithium Transition‐Metal Oxide for High‐Energy Lithium‐Ion Batteries

High energy‐density lithium‐ion batteries are in demand for portable electronic devices and electrical vehicles. Since the energy density of the batteries relies heavily on the cathode material used, major research efforts have been made to develop alternative cathode materials with a higher degree of lithium utilization and specific energy density. In particular, layered, Ni‐rich, lithium transition‐metal oxides can deliver higher capacity at lower cost than the conventional LiCoO₂. However, for these Ni‐rich compounds there are still several problems associated with their cycle life, thermal stability, and safety. Herein the performance enhancement of Ni‐rich cathode materials through structure tuning or interface engineering is summarized. The underlying mechanisms and remaining challenges will also be discussed.