Viscoelastic and Nonflammable Interface Design–Enabled Dendrite‐Free and Safe Solid Lithium Metal Batteries

Herein, a composite polymer electrolyte with a viscoelastic and nonflammable interface is designed to handle the contact issue and preclude Li dendrite formation. The composite polymer electrolyte (cellulose acetate/polyethylene glycol/Li_1.4Al_0.4Ti_1.6P₃O₁₂) exhibits a wide electrochemical window of 5 V (vs Li⁺/Li), a high Li⁺ transference number of 0.61, and an excellent ionic conductivity of above 10^?4 S cm^?1 at 60 °C. In particular, the intimate contact, low interfacial impedance, and fast ion‐transport process between the electrodes and solid electrolytes can be simultaneously achieved by the viscoelastic and nonflammable layer. Benefiting from this novel design, solid lithium metal batteries with either LiFePO₄ or LiCoO₂ as cathode exhibit superior cyclability and rate capability, such as a discharge capacity of 157 mA h g^?1 after 100 cycles at C/2 and 97 mA h g^?1 at 5C for LiFePO₄ cathode. Moreover, the smooth and uniform Li surface after long‐term cycling confirms the successful suppression of dendrite formation. The viscoelastic and nonflammable interface modification of solid electrolytes provides a promising and general strategy to handle the interfacial issues and improves the operative safety of solid lithium metal batteries.     

Unraveling the Intra and Intercycle Interfacial Evolution of Li6PS5Cl‐Based All‐Solid‐State Lithium Batteries

High‐performance rechargeable all‐solid‐state lithium metal batteries with high energy density and enhanced safety are attractive for applications like portable electronic devices and electric vehicles. Among the various solid electrolytes, argyrodite Li₆PS₅Cl with high ionic conductivity and easy processability is of great interest. However, the low interface compatibility between sulfide solid electrolytes and high capacity cathodes like nickel‐rich layered oxides requires many thorny issues to be resolved, such as the space charge layer (SCL) and interfacial reactions. In this work, in situ electrochemical impedance spectroscopy and in situ Raman spectroscopy measurements are performed to monitor the detailed interface evolutions in a LiNi_0.8Co_0.1Mn_0.1O₂ (NCM)/Li₆PS₅Cl/Li cell. Combining with ex situ characterizations including scanning electron microscopy and X‐ray photoelectron spectroscopy, the evolution of the SCL and the chemical bond vibration at NCM/Li₆PS₅Cl interface during the early cycles is elaborated. It is found that the Li⁺ ion migration, which varies with the potential change, is a very significant cause of these interface behaviors. For the long‐term cycling, the SCL, interfacial reactions, lithium dendrites, and chemo‐mechanical failure have an integrated effect on interfaces, further deteriorating the interfacial structure and electrochemical performance. This research provides a new insight on intra and intercycle interfacial evolution of solid‐state batteries.     

Interface Welding via Thermal Pulse Sintering to Enable 4.6 V Solid-State Batteries

NASICON-type Li_1.3Al_0.3Ti_1.7(PO4)₃ (LATP) is one of the most promising solid-state electrolytes (SSEs) to achieve high-energy-density solid-state batteries (SSBs) due to its high ionic conductivity, high-voltage stability, and low cost. However, its practical application is constrained by inadequate interfacial compatibility with cathode materials and significant incompatibility with lithium metal. In this work, a cost-effective interface welding approach is reported, utilizing an innovative thermal pulse sintering (TPS) to fabricate LATP-based solid-state batteries. Initially, the rapid thermal pulses enhance the ionic conductivity of LATP SSE by inducing selective growth of LATP nanowires, effectively occupying interparticle voids. Additionally, this process results in the formation of a dense layer (GCM) comprising graphene oxide, carbon nanotubes, and MXene with a controlled Li⁺ transport pathway, facilitating lithium stripping and plating processes. Moreover, these thermal pulses facilitate the interfacial fusion between LATP and cathode materials, while avoiding undesired phase diffusion. As a result, SSBs with a LiCoO₂ cathode deliver favorable cycle stability at 4.6 V, marking significant progress. This facile interface welding strategy represents a substantial step toward high-energy-density SSB development.     

An In Situ Formed Surface Coating Layer Enabling LiCoO2 with Stable 4.6 V High‐Voltage Cycle Performances

The development of high‐voltage LiCoO₂ is essential for achieving lithium‐ion batteries with high volumetric energy density, however, it faces a great deal of challenges owing to the materials, structure and interfacial instability issues. In this work, a strategy is developed, through heat annealing a precoated surface layer to in situ form a high‐voltage‐stable surface coating layer, which is demonstrated to be highly effective to improve the high‐voltage performance of LiCoO₂. It is discovered that LiCoO₂ reacts with Li_1.5Al_0.5Ti_1.5(PO₄)₃ (LATP) at 700 °C to form exclusively spinel phases in addition to Li₃PO₄, which are structurally coherent to the layered lattice of LiCoO₂. The heat annealing of the precoated thin layer of LATP enables the formation of a high‐quality surface layer. Spinel phases possess high‐voltage‐stable structures with much weaker oxidizing ability of lattice oxygen than layered structure. In addition, the Li₃PO₄ is a good lithium‐ion conductor with excellent chemical stability at high voltages. All these benefits contribute to the construction of a uniform and conformal high‐voltage‐stable surface layer with favorable lithium conducting kinetics at the LiCoO₂ surface. The modified LiCoO₂ shows excellent 4.6 V high‐voltage cycle performance at both room temperature and 45 °C. The thermal stability is greatly enhanced as well.     

Correlating Electrode–Electrolyte Interface and Battery Performance in Hybrid Solid Polymer Electrolyte‐Based Lithium Metal Batteries

Solid polymer electrolytes (SPEs) are desirable in lithium metal batteries (LMBs) since they are nonflammable and show excellent lithium dendrite growth resistance. However, fabricating high performance polymer LMBs is still a grand challenge because of the complex battery system. In this work, a series of tailor‐designed hybrid SPEs are used to prepare LMBs with a LiFePO₄‐based cathode. High performance LMBs with both excellent rate capability and long cycle life are obtained at 60 and 90 °C. The well‐controlled network structure in this series of hybrid SPEs offers a model system to study the relationship between the SPE properties and the LMB performance. It is shown that the cycle life of the polymer LMBs is closely correlated with the SPE–Li interface ionic conductivity, underscoring the importance of the solid electrolyte interface in LMB operation. LMB performance is further correlated with the molecular network structure. It is anticipated that results from this study will shed light on designing SPEs for high performance LMB applications.     

Non-Sacrificial Additive Enables a Non-Passivating Cathode Interface for 4.6 V Li||LiCoO2 Batteries

Various electrolyte additives are developed to construct a cathode electrolyte interphase (CEI) layer for high-voltage LiCoO₂ since the cathode suffers severe interfacial degradation when increasing the cut-off voltage over 4.55 V. However, the CEI derived from the additive sacrificial reaction faces the risk of rupture due to the corrosion reaction and the volumetric variation of the cathode. Herein, a non-passivating cathode interface is realized for 4.6 V LiCoO₂ with a non-sacrificial electrolyte additive (TBAClO₄) by regulating the solvent environment at the interface rather than the preferential decomposition for CEI formation. Owing to the novel protection mechanism, the cell performance shows little dependence on the CEI-formation process. Therefore, an ultra-high initial coulombic efficiency (96.63%) and excellent cycling stability (81% capacity retention after 300 cycles) are achieved in Li||LiCoO₂ batteries. Moreover, even with the electrolyte containing 1000 ppm H₂O, the remarkable water capture ability of the additive together with its interfacial regulation enables the 4.6 V Li||LiCoO₂ battery to retain 80% capacity after 200 cycles. This non-sacrificial strategy provides new insights into high-voltage electrolyte additive design for high-energy-density lithium metal batteries.     

Insight of a Phase Compatible Surface Coating for Long‐Durable Li‐Rich Layered Oxide Cathode

Li‐rich layered oxides (LLOs) can deliver almost double the capacity of conventional electrode materials such as LiCoO₂ and LiMn₂O₄; however, voltage fade and capacity degradation are major obstacles to the practical implementation of LLOs in high‐energy lithium‐ion batteries. Herein, hexagonal La_0.8Sr_0.2MnO_3?y (LSM) is used as a protective and phase‐compatible surface layer to stabilize the Li‐rich layered Li_1.2Ni_0.13Co_0.13Mn_0.54O₂ (LM) cathode material. The LSM is Mn? O? M bonded at the LSM/LM interface and functions by preventing the migration of metal ions in the LM associated with capacity degradation as well as enhancing the electrical transfer and ionic conductivity at the interface. The LSM‐coated LM delivers an enhanced reversible capacity of 202 mAh g^?1 at 1 C (260 mA g^?1) with excellent cycling stability and rate capability (94% capacity retention after 200 cycles and 144 mAh g^?1 at 5 C). This work demonstrates that interfacial bonding between coating and bulk material is a successful strategy for the modification of LLO electrodes for the next‐generation of high‐energy Li‐ion batteries.     

Taming Interfacial Instability in Lithium–Oxygen Batteries: A Polymeric Ionic Liquid Electrolyte Solution

There is a growing concern about the cyclability and safety, in particular, of the high‐energy density lithium–metal batteries. This concern is even greater for Li–O₂ batteries because O₂ that is transported from the cathode to the anode compartment, can exacerbate side reactions and dendrite growth of the lithium metal anode. The key to solving this dilemma lays in tailoring the solid electrolyte interphase (SEI) formed on the lithium metal anode in Li–O₂ batteries. Here it is reported that a new electrolyte, formed from LiFSI as the salt and a mixture of tetraethylene glycol dimethyl ether and polymeric ionic liquid of P[C₅O₂N_MA,11]FSI as the solvent, can produce a stable electrode (both cathode and anode)|electrolyte interface in Li–O₂ batteries. Specifically, this new electrolyte, when in contact with lithium metal anodes, has the ability to produce a uniform SEI with high ionic conductivity for Li⁺ transport and desired mechanical property for suppression of dendritic lithium growth. Moreover, the electrolyte possesses a high oxidation tolerance that is very beneficial to the oxygen electrochemistry on the cathode of Li–O₂ batteries. As a result, enhanced reversibility and cycle life are realized for the resultant Li–O₂ batteries.     

Stable Seamless Interfaces and Rapid Ionic Conductivity of Ca–CeO2/LiTFSI/PEO Composite Electrolyte for High‐Rate and High‐Voltage All‐Solid‐State Battery

Stable and seamless interfaces among solid components in all‐solid‐state batteries (ASSBs) are crucial for high ionic conductivity and high rate performance. This can be achieved by the combination of functional inorganic material and flexible polymer solid electrolyte. In this work, a flexible all‐solid‐state composite electrolyte is synthesized based on oxygen‐vacancy‐rich Ca‐doped CeO₂ (Ca–CeO₂) nanotube, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), and poly(ethylene oxide) (PEO), namely Ca–CeO₂/LiTFSI/PEO. Ca–CeO₂ nanotubes play a key role in enhancing the ionic conductivity and mechanical strength while the PEO offers flexibility and assures the stable seamless contact between the solid electrolyte and the electrodes in ASSBs. The as‐prepared electrolyte exhibits high ionic conductivity of 1.3 × 10^?4 S cm^?1 at 60 °C, a high lithium ion transference number of 0.453, and high‐voltage stability. More importantly, various electrochemical characterizations and density functional theory (DFT) calculations reveal that Ca–CeO₂ helps dissociate LiTFSI, produce free Li ions, and therefore enhance ionic conductivity. The ASSBs based on the as‐prepared Ca–CeO₂/LiTFSI/PEO composite electrolyte deliver high‐rate capability and high‐voltage stability.     

Efficient Li‐Ion‐Conductive Layer for the Realization of Highly Stable High‐Voltage and High‐Capacity Lithium Metal Batteries

Recently, a consensus has been reached that using lithium metal as an anode in rechargeable Li‐ion batteries is the best way to obtain the high energy density necessary to power electronic devices. Challenges remain, however, with respect to controlling dendritic Li growth on these electrodes, enhancing compatibility with carbonate‐based electrolytes, and forming a stable solid–electrolyte interface layer. Herein, a groundbreaking solution to these challenges consisting in the preparation of a Li₂TiO₃ (LT) layer that can be used to cover Li electrodes via a simple and scalable fabrication method, is suggested. Not only does this LT layer impede direct contact between electrode and electrolyte, thus avoiding side reactions, but it assists and expedites Li‐ion flux in batteries, thus suppressing Li dendrite growth. Other effects of the LT layer on electrochemical performance are investigated by scanning electron microscopy, electrochemical impedance spectroscopy, and galvanostatic intermittent titration technique analyses. Notably, LT layer‐incorporating Li cells comprising high‐capacity/voltage cathodes with reasonably high mass loading (LiNi_0.8Co_0.1Mn_0.1O₂, LiNi_0.5Mn_1.5O₄, and LiMn₂O₄) show highly stable cycling performance in a carbonate‐based electrolyte. Therefore, it is believed that the approach based on the LT layer can boost the realization of high energy density lithium metal batteries and next‐generation batteries.     

Highly‐Safe and Ultra‐Stable All‐Flexible Gel Polymer Lithium Ion Batteries Aiming for Scalable Applications

With the development of flexible electronics, flexible lithium ion batteries (LIBs) have received great attention. Previously, almost all reported flexible components had shortcomings related to poor mechanical flexibility, low energy density, and poor safety, which led to the failure of scalable applications. This study demonstrates a fully flexible lithium ion battery using LiCoO₂ as the cathode, Li₄Ti₅O₁₂ as the anode, and graphene film as the flexible current collector. The graphene oxide modified gel polymer electrolyte exhibits higher ionic conductivity than a conventional liquid electrolyte and improves the safety of the flexible battery. The optimum design of the flexible graphene battery exhibits super electrochemical performance, with a 2.3 V output voltage plateau and a satisfactory capacity of 143.0 mAh g^?1 at 1 C. The mass energy density and power density are both ≈1.4 times higher than a standard electrode using metal foils as current collectors. No capacity loss is observed after 100 thousand cycles of mechanical bending. More importantly, even in the clipping state, this flexible gel polymer battery can still demonstrate a stable and safe electrochemical performance. This work may lead to a promising strategy of high‐performance scalable LIBs for the next‐generation flexible electronics.     

High‐Performance Lithium‐Sulfur Batteries with a Self‐Supported, 3D Li2S‐Doped Graphene Aerogel Cathodes

Lithium‐sulfur (Li‐S) batteries are being considered as the next‐generation high‐energy‐storage system due to their high theoretical energy density. However, the use of a lithium‐metal anode poses serious safety concerns due to lithium dendrite formation, which causes short‐circuiting, and possible explosions of the cell. One feasible way to address this issue is to pair a fully lithiated lithium sulfide (Li₂S) cathode with lithium metal‐free anodes. However, bulk Li₂S particles face the challenges of having a large activation barrier during the initial charge, low active‐material utilization, poor electrical conductivity, and fast capacity fade, preventing their practical utility. Here, the development of a self‐supported, high capacity, long‐life cathode material is presented for Li‐S batteries by coating Li₂S onto doped graphene aerogels via a simple liquid infiltration–evaporation coating method. The resultant cathodes are able to lower the initial charge voltage barrier and attain a high specific capacity, good rate capability, and excellent cycling stability. The improved performance can be attributed to the (i) cross‐linked, porous graphene network enabling fast electron/ion transfer, (ii) coated Li₂S on graphene with high utilization and a reduced energy barrier, and (iii) doped heteroatoms with a strong binding affinity toward Li₂S/lithium polysulfides with reduced polysulfide dissolution based on first‐principles calculations.     

Constructing Multifunctional Interphase between Li1.4Al0.4Ti1.6(PO4)3 and Li Metal by Magnetron Sputtering for Highly Stable Solid‐State Lithium Metal Batteries

Due to high ionic conductivity and low cost, Li_1.4Al_0.4Ti_1.6(PO₄)₃ (LATP) has emerged as a promising solid‐state electrolyte for next‐generation lithium (Li) metal solid‐state batterie with high safety performance and energy density. However, the extremely high impedance and surface instability of LATP with Li metal retard its practical application. Herein, a novel method is proposed to construct an ultrathin ZnO layer that is tightly coated on the LATP pellets, surface (ZnO@LATP) via magnetron sputtering, which in situ reacts with Li to form a low electronic conductivity and multifunctional solid electrolyte interphase (SEI). The formed SEI can not only effectively lower the interfacial resistance, but also overcome the side reactions of LATP with the Li metal anode and suppress the Li dendrite growth. Specifically, the interface resistance decreases from 80 554 to 353 Ω and the overpotential reduces from 1 V to 20 mV. As a result, the Li/ZnO@LATP@ZnO/Li symmetric batteries can stably cycle for more than 2000 h without short circuit at 0.05 mA cm^?2 and Li/ZnO@LATP/LiFePO₄ batteries show excellent cycle stability for 200 cycles at 0.1 C. This work highlights the significance of multifunctional interphase between LATP and Li metal for improvement of interfacial impedance and instability.     

Toward High Energy Density All Solid‐State Sodium Batteries with Excellent Flexibility

All solid‐state sodium batteries (ASSBs) have attracted considerable attention due to their enhanced safety, long lifespan, and high energy density. However, several challenges have plagued the development of ASSBs, especially the relatively low ionic conductivity of solid‐state electrolytes (SSEs), large interfacial resistance, and low stability/compatibility between SSEs and electrodes. Here, a high‐performance all solid‐state sodium battery (NVP@C|PEGDMA‐NaFSI‐SPE|Na) is designed by employing carbon coated Na₃V₂(PO₄)₃ composite nanosheets (NVP@C) as the cathode, solvent‐free solid polymer electrolyte (PEGDMA‐NaFSI‐SPE) as the electrolyte and metallic sodium as the anode. The integrated electrolyte and cathode system prepared by the in situ polymerization process exhibits high ionic conductivity (≈10^?4 S cm^?1 at room temperature) and an outstanding electrolyte/electrode interface. Benefiting from these merits, the soft‐pack ASSB (NVP@C|PEGDMA‐NaFSI‐SPE|Na) delivers excellent cycling life over 740 cycles (capacity decay of only 0.007% per cycle) and maintains 95% of the initial reversible capacity with almost no self‐discharge even after resting for 3 months. Moreover, the bendable ASSB exhibits a high capacity of 106 mAh g^?1 (corresponds to energy density of ≈355 Wh kg^?1) at 0.5 C despite undergoing repeated bending for 535 cycles. This work offers a new strategy to fabricate high‐performance flexible ASSBs with a long lifespan and excellent flexibility.     

Highly Efficient Perovskite Solar Cell Photocharging of Lithium Ion Battery Using DC–DC Booster

Solar cells become a viable energy source to charge lithium ion batteries. Here a simple and efficient photocharging design approach is demonstrated, where a promising low cost single junction solar cell such as perovskite solar cell or dye sensitized solar cell efficiently charges a Li₄Ti₅O₁₂‐LiCoO₂ Li‐ion cell using a DC–DC voltage boost converter. The converter boosts the low input voltage of a single junction solar cell to charge a lithium ion cell and offers advantages including maximum power point tracking of solar photovoltaics and overvoltage protection for the lithium ion cell. This is the first demonstration of this technology. This approach leads to the highest reported overall efficiency of 9.36% and average storage efficiency of 77.2% at 0.5 C discharge for a perovskite solar cell‐converter charging. The high efficiency for the perovskite solar cell‐converter charging is attributed to maximum power harvesting along with high power conversion efficiency of the perovskite solar cell and low potential polarization between the charge and discharge voltage plateaus for the Li₄Ti₅O₁₂‐LiCoO₂ Li‐ion cell.     

Stack Pressure Considerations for Room‐Temperature All‐Solid‐State Lithium Metal Batteries

All‐solid‐state batteries are expected to enable batteries with high energy density with the use of lithium metal anodes. Although solid electrolytes are believed to be mechanically strong enough to prevent lithium dendrites from propagating, various reports today still show cell failure due to lithium dendrit growth at room temperature. While cell parameters such as current density, electrolyte porosity, and interfacial properties have been investigated, mechanical properties of lithium metal and the role of applied stack pressure on the shorting behavior are still poorly understood. Here, failure mechanisms of lithium metal are investigated in all‐solid‐state batteries as a function of stack pressure, and in situ characterization of the interfacial and morphological properties of the buried lithium is conducted in solid electrolytes. It is found that a low stack pressure of 5 MPa allows reliable plating and stripping in a lithium symmetric cell for more than 1000 h, and a Li | Li₆PS₅Cl | LiNi_0.80Co_0.15Al_0.05O₂ full cell, plating more than 4 µm of lithium per charge, is able to cycle over 200 cycles at room temperature. These results suggest the possibility of enabling the lithium metal anode in all‐solid‐state batteries at reasonable stack pressures.     

Metal Sulfide‐Decorated Carbon Sponge as a Highly Efficient Electrocatalyst and Absorbant for Polysulfide in High‐Loading Li2S Batteries

Owing to its high theoretical specific capacity (1166 mA h g^?1) and particularly its advantage to be paired with a lithium‐metal‐free anode, lithium sulfide (Li₂S) is regarded as a much safer cathode for next‐generation advanced lithium–sulfur (Li–S) batteries. However, the low conductivity of Li₂S and particularly the severe “polysulfide shuttle” of lithium polysulfide (LiPS) dramatically hinder their practical application in Li–S batteries. To address such issues, herein a bifuctional 3D metal sulfide‐decorated carbon sponge (3DTSC), which is constructed by 1D carbon nanowires cross‐linked with 2D graphene nanosheets with high conductivity and polar 0D metal sulfide nanodots with efficient electrocatalytic activity and strong chemical adsorption capability for LiPSs, is presented. Benefiting from the well‐designed multiscale, multidimensional 3D porous nanoarchitecture with high conductivity, and efficient electrocatalytic and absorption ability, the 3DTSC significantly mitigates LiPS shuttle, improves the utilization of Li₂S, and facilitates the transport of electrons and ions. As a result, even with a high Li₂S loading of 8 mg cm^?2, the freestanding 3DTSC‐Li₂S cathode without a polymer binder and metallic current collector delivers outstanding electrochemical performance with a high areal capacity of 8.44 mA h cm^?2.     

High‐Capacity All‐Solid‐State Sodium Metal Battery with Hybrid Polymer Electrolytes

All‐solid‐state sodium metal batteries (SSMBs) are of great interest for their high theoretical capacity, nonflammability, and relatively low cost owing partially to the abundance of sodium recourses. However, it is challenging to fabricate SSMBs because compared with their counterparts, which contain lithium metal, sodium metal is mechanically softer and more reactive toward the electrolyte. Herein, the synthesis and electrochemical properties of newly designed sodium‐containing hybrid network solid polymer electrolytes (SPEs) and their application in SSMBs are reported. The hybrid network is synthesized by controlled crosslinking of octakis(3‐glycidyloxypropyldimethylsiloxy)octasilsesquioxane and amine‐terminated polyethylene glycol in existence with sodium perchlorate (NaClO₄). Plating and stripping experiments using symmetric cells show prolonged cycle life of the SPEs, >5150 and 3550 h at current density of 0.1 and 0.5 mA cm^?2, respectively. The results for the first time show that the SPE|sodium metal interface migrates into the SPE phase upon cycling. SSMBs fabricated with the hybrid SPE sandwiched between sodium metal anode and bilayered δ‐Na_xV₂O₅ cathode exhibit record‐high specific capacity for solid sodium‐ion batteries of 305 mAh g^?1 and excellent Coulombic efficiency. This work demonstrates that the hybrid network SPEs are promising for SSMB applications.     

Ultrahigh‐Energy‐Density Lithium‐Ion Batteries Based on a High‐Capacity Anode and a High‐Voltage Cathode with an Electroconductive Nanoparticle Shell

The combination of high‐capacity anodes and high‐voltage cathodes has garnered a great deal of attention in the pursuit of high‐energy‐density lithium‐ion batteries. As a facile and scalable electrode‐architecture strategy to achieve this goal, a direct one‐pot decoration of high‐capacity silicon (Si) anode materials and of high‐voltage LiCoO₂ (LCO) cathode materials is demonstrated with colloidal nanoparticles composed of electroconductive antimony‐doped tin oxide (ATO). The unusual ATO nanoparticle shells enhance electronic conduction in the LCO and Si electrode materials and mitigate unwanted interfacial side reactions between the electrode materials and liquid electrolytes. The ATO‐coated LCO materials (ATO‐LCO) enable the construction of a high‐mass‐loading cathode and suppress the dissolution of cobalt and the generation of by‐products during high‐voltage cycling. In addition, the ATO‐coated Si (ATO‐Si) anodes exhibit highly stable capacity retention upon cycling. Integration of the high‐voltage ATO‐LCO cathode and high‐capacity ATO‐Si anode into a full cell configuration brings unprecedented improvements in the volumetric energy density and in the cycling performance compared to a commercialized cell system composed of LCO/graphite.     

Sodium Plating from Na‐β″‐Alumina Ceramics at Room Temperature,Paving the Way for Fast‐Charging All‐Solid‐State Batteries

All‐solid‐state batteries with an alkali metal anode have the potential to achieve high energy density. However, the onset of dendrite formation limits the maximum plating current density across the solid electrolyte and prevents fast charging. It is shown that the maximum plating current density is related to the interfacial resistance between the solid electrolyte and the metal anode. Due to their high ionic conductivity, low electronic conductivity, and stability against sodium metal, Na‐β″‐alumina ceramics are excellent candidates as electrolytes for room‐temperature all‐solid‐state batteries. Here, it is demonstrated that a heat treatment of Na‐β″‐alumina ceramics in argon atmosphere enables an interfacial resistance <10 Ω cm² and current densities up to 12 mA cm^?2 at room temperature. The current density obtained for Na‐β″‐alumina is ten times higher than that measured on a garnet‐type Li₇La₃Zr₂O₁₂ electrolyte under equivalent conditions. X‐ray photoelectron spectroscopy shows that eliminating hydroxyl groups and carbon contaminations at the interface between Na‐β″‐alumina and sodium metal is key to reach such values. By comparing the temperature‐dependent stripping/plating behavior of Na‐β″‐alumina and Li₇La₃Zr₂O₁₂, the role of the alkali metal in governing interface kinetics is discussed. This study provides new insights into dendrite formation and paves the way for fast‐charging all‐solid‐state batteries.