Inducing the Preferential Growth of Zn (002) Plane for Long Cycle Aqueous Zn-Ion Batteries

Uncontrolled growth of Zn dendrites is the main reason for the short-circuit failure of aqueous Zn-ion batteries. Using electrolyte additives to manipulate the crystal growth is one of the most convenient strategies to mitigate the dendrite issue. However, most additives would be unstable during cycling due to the structural reconstruction of the deposition layer. Herein, it is proposed to use 1-butyl-3-methylimidazolium cation (BMIm⁺ ion) as an electrolyte additive, which could steadily induce the preferential growth of (002) plane and inhibit the formation of Zn dendrites. Specifically, BMIm⁺ ion will be preferentially adsorbed on (100) and (101) planes of Zn anodes, forcing Zn²⁺ ion to deposit on the (002) plane, thus inducing the preferential growth of the (002) plane and forming a flat and compact deposition layer. As a result, the Zn anode cycles for 1000 h at10 mA cm⁻² and 10 mAh cm⁻² as well as a high Coulombic efficiency of 99.8%. Meanwhile, the NH₄V₄O₁₀||Zn pouch cell can operate stably for 240 cycles at 0.4 A g⁻¹. The BMIm⁺ ion additive keeps a stable effect on the structural reconstruction of the Zn anode during the prolonged cycling.     

High Polarity Poly(vinylidene difluoride) Thin Coating for Dendrite‐Free and High‐Performance Lithium Metal Anodes

The high‐polarity β‐phase poly(vinylidene difluoride) (β‐PVDF), which has all trans conformation with F and H atoms located on the opposite sides of the polymer backbone, is demonstrated to be a promising artificial solid‐electrolyte interphase coating on both Cu and Li metal anodes for dendrite‐free Li deposition/stripping and enhanced cycling performance. A thin (≈4 µm) β‐PVDF coating on Cu enables uniform Li deposition/stripping at high current densities up to 5 mA cm^?2, Li‐plating capacity loadings of up to 4 mAh cm^?2, and excellent cycling stability over hundreds of cycles under practical conditions (1 mA cm^?2 with 2 mAh cm^?2). Full cells containing an LiFePO₄ cathode and an anode of either β‐PVDF coated Cu or Li also exhibit excellent cycling stability. The profound effects of the high‐polarity PVDF coating on dendrite suppression are attributed to the electronegative F‐rich interface that favors layer‐by‐layer Li deposition. This study offers a new strategy for the development of dendrite‐free metal anode technology.     

Unveiling The Mechanism of The Dendrite Nucleation and Growth in Aqueous Zinc Ion Batteries

Aqueous zinc ion batteries (ZIBs) exhibit great potential for next-generation energy storage devices. However, significant challenges exist, including the uncontrollable formation of Zn dendrite and side reactions during zinc stripping and plating. The mechanism of Zn dendrite nucleation has yet to be fully understood. In this work, the first principles simulations are used to investigate the Zn dendrite formation process. The unintentionally adsorbed O²⁻ and OH⁻ ions are the inducing factors for Zn dendrite nucleation and growth on the Zn (0001) plane due to significantly increased Zn diffusion barriers. A top-down method is demonstrated to suppress the dendrite using delaminated V₂CT_x to capture O²⁻ and OH⁻ ions thanks to reduced Zn diffusion barriers. The experimental results revealed significantly suppressed Zn dendrite nucleation and growth, resulting in a layer-by-layer deposit/stripping of Zn. Based on the electrochemical evaluations, the V₂CT_x-coated Zn composite delivers a high coulombic efficiency of 99.3% at 1.0 mAh cm⁻². Furthermore, the full cell achieves excellent cyclic performance of 93.6% capacity retention after 2000 cycles at 1 A g⁻¹. This strategy has broad scalability and can be widely applied in designing metallic anodes for rechargeable batteries.     

A Novel Dendrite‐Free Mn2+/Zn2+ Hybrid Battery with 2.3 V Voltage Window and 11000‐Cycle Lifespan

With the increasing energy crisis and environmental pollution, rechargeable aqueous Zn‐based batteries (AZBs) are receiving unprecedented attention due to their list of merits, such as low cost, high safety, and nontoxicity. However, the limited voltage window, Zn dendrites, and relatively low specific capacity are still great challenges. In this work, a new reaction mechanism of reversible Mn²⁺ ion oxidation deposition is introduced to AZBs. The assembled Mn²⁺/Zn²⁺ hybrid battery (Mn²⁺/Zn²⁺ HB) based on a hybrid storage mechanism including Mn²⁺ ion deposition, Zn²⁺ ion insertion, and conversion reaction of MnO₂ can achieve an ultrawide voltage window (0–2.3 V) and high capacity (0.96 mAh cm^?2). Furthermore, the carbon nanotubes coated Zn anode is proved to effectively inhibit Zn dendrites and control side reaction, hence exhibiting an ultrastable cycling (33 times longer than bare Zn foil) without obvious polarization. Benefiting from the optimal Zn anode and highly reversible Mn²⁺/Zn²⁺ hybrid storage mechanism, the Mn²⁺/Zn²⁺ HB shows an excellent cycling performance over 11 000 cycles with a 100% capacity retention. To the best of the authors' knowledge, it is the highest reported cycling performance and wide voltage window for AZBs with mild electrolyte, which may inspire a great insight into designing high‐performance aqueous batteries.     

Coordination Engineering of N,O Co-Doped Cu Single Atom on Porous Carbon for High Performance Zinc Metal Anodes

Traditional challenges of poor cycling stability and low Coulombic efficiency in Zinc (Zn) metal anodes have limited their practical application. To overcome these issues, this work introduces a single metal-atom design featuring atomically dispersed single copper (Cu) atoms on 3D nitrogen (N) and oxygen (O) co-doped porous carbon (CuNOC) as a highly reversible Zn host. The CuNOC structure provides highly active sites for initial Zn nucleation and further promotes uniform Zn deposition. The 3D porous architecture further mitigates the volume changes during the cycle with homogeneous Zn²⁺ flux. Consequently, CuNOC demonstrates exceptional reversibility in Zn plating/stripping processes over 1000 cycles at 2 and 5 mA cm⁻² with a fixed capacity of 1 mAh cm⁻², while achieving stable operation and low voltage hysteresis over 700 h at 5 mA cm⁻² and 5 mAh cm⁻². Furthermore, density functional theory calculations show that co-doping N and O on porous carbon with atomically dispersed single Cu atoms creates an efficient zincophilic site for stable Zn nucleation. A full cell with the CuNOC host anode and high loading V₂O₅ cathode exhibits outstanding rate-capability up to 5 A g⁻¹ and a stable cycle life over 400 cycles at 0.5 A g⁻¹.     

Tailoring Lithium Deposition via an SEI‐Functionalized Membrane Derived from LiF Decorated Layered Carbon Structure

Lithium (Li) metal is a key anode material for constructing next generation high energy density batteries. However, dendritic Li deposition and unstable solid electrolyte interphase (SEI) layers still prevent practical application of Li metal anodes. In this work, it is demonstrated that an uniform Li coating can be achieved in a lithium fluoride (LiF) decorated layered structure of stacked graphene (SG), leading to the formation of an SEI‐functionalized membrane that retards electron transfer by three orders of magnitude to avoid undesirable Li deposition on the top surface, and ameliorates Li⁺ ion migration to enable uniform and dendrite‐free Li deposition beneath such an interlayer. Surface chemistry analysis and density functional theory calculations demonstrate that these beneficial features arise from the formation of C–F_x surface components on the SG sheets during the Li coating process. Based on such an SEI‐functionalized membrane, stable cycling at high current densities up to 3 mA cm^?2 and Li plating capacities up to 4 mAh cm^?2 can be realized in LiPF₆/carbonate electrolytes. This work elucidates the promising strategy of modifying Li plating behavior through the SEI‐functionalized carbon structure, with significantly improved cycling stability of rechargeable Li metal anodes.     

Toward a Reversible Mn4+/Mn2+ Redox Reaction and Dendrite‐Free Zn Anode in Near‐Neutral Aqueous Zn/MnO2 Batteries via Salt Anion Chemistry

Rechargeable aqueous Zn/MnO₂ batteries are very attractive large‐scale energy storage technologies, but still suffer from limited cycle life and low capacity. Here the novel adoption of a near‐neutral acetate‐based electrolyte (pH ≈ 6) is presented to promote the two‐electron Mn⁴⁺/Mn²⁺ redox reaction and simultaneously enable a stable Zn anode. The acetate anion triggers a highly reversible MnO₂/Mn²⁺ reaction, which ensures high capacity and avoids the issue of structural collapse of MnO₂. Meanwhile, the anode‐friendly electrolyte enables a dendrite‐free Zn anode with outstanding stability and high plating/stripping Coulombic efficiency (99.8%). Hence, a high capacity of 556 mA h g^?1, a lifetime of 4000 cycles without decay, and excellent rate capability up to 70 mA cm^?2 are demonstated in this new near‐neutral aqueous Zn/MnO₂ battery by simply manipulating the salt anion in the electrolyte. The acetate anion not only modifies the surface properties of MnO₂ cathode but also creates a highly compatible environment for the Zn anode. This work provides a new opportunity for developing high‐performance Zn/MnO₂ and other aqueous batteries based on the salt anion chemistry.     

Boosting Ion Diffusion and Charge Transfer by Zincophilic Accordion Arrays to Achieve Ultrafast Aqueous Zinc Metal Batteries

A key challenge to apply aqueous zinc metal batteries (AZMBs) as next-generation energy storage device is to improve the rechargeability at high current densities, which is needed to circumvent slowly ion diffusion in anode and sluggish charge transfer of Zn²⁺. Herein, a zincophilic accordion array derived from MOF is developed as zinc host for simultaneously boosted ion diffusion and charge transfer. The designed host is prepared by etching and disproportionation reactions, the abundant zincophilic Sn sites with nano-size uniform disperse on accordion arrays nanosheets (Sn-AA). Then a composite Zn anode (Sn-AA@Zn) is obtained by compacting Sn-AA host with zinc power (Zn-P). The Sn-AA@Zn anode has an ultra-low activation energy (37.1 kJ mol⁻¹) and nucleation overpotential (10 mV), achieving fast charge transfer of Zinc deposition. In addition, the cycle life of the symmetric cell with Sn-AA@Zn anode exceeds 13 000 cycles at 50 mA cm⁻², which is 32 times than that of the Zn-P anode. And the full cell with Sn-AA@Zn anode and MnO₂ cathode maintains a capacity of 122 mAh g⁻¹ after 5000 cycles at 5 Ag⁻¹. Hopefully, the 3D anode based on Sn-AA@Zn accordion array and Zn-P has significantly improved the rechargeability of AZMB at high current density.     

In Situ Generation of Artificial Solid‐Electrolyte Interphases on 3D Conducting Scaffolds for High‐Performance Lithium‐Metal Anodes

Rational structure design of the current collector along with further engineering of the solid‐electrolyte interphases (SEI) layer is one of the most promising strategies to achieve uniform Li deposition and inhibit uncontrolled growth of Li dendrites. Here, a Li₂S layer as an artificial SEI with high compositional uniformity and high lithium ion conductivity is in situ generated on the surface of the 3D porous Cu current collector to regulate homogeneous Li plating/stripping. Both simulations and experiments demonstrate that the Li₂S protective layer can passivate the porous Cu skeleton and balance the transport rate of lithium ions and electrons, thereby alleviating the agglomerated Li deposition at the top of the electrode or at the defect area of the SEI layer. As a result, the modified current collector exhibits long‐term cycling of 500 cycles at 1 mA cm^?2 and stable electrodeposition capabilities of 4 mAh cm^?2 at an ultrahigh current density of 4 mA cm^?2. Furthermore, full batteries (LiFePO₄ as cathode) paired with this designed 3D anode with only ≈200% extra lithium show superior stability and rate performance than the batteries paired with lithium foil (≈3000% extra lithium). These explorations provide new strategies for developing high‐performance Li metal anodes.     

Solvation Modulation and Reversible SiO2-Enriched Interphase Enabled by Deep Eutectic Sol Electrolytes for Low-Temperature Zinc Metal Batteries

Zinc metal batteries (ZMBs) hold great promise for large-scale energy storage in renewable solar and wind farms. However, their widespread application is hindered by poor stability and unsatisfactory low-temperature performance, attributed to issues such as dendrite formation, strong Zn²⁺-H₂O coordination, and electrolyte freezing. Herein, a deep eutectic sol electrolyte (DESE) is proposed by mixing SiO₂ nanoparticles with a solution composed of 1,3-dioxolane (DOL) and Zn(ClO₄)₂·6H₂O for stable low-temperature ZMBs. By substituting the strong Zn²⁺- H₂O coordination with favorable Zn²⁺-DOL coordination, the DESE exhibits exceptional antifreezing capability at temperatures beyond −40 °C. The formation of Si-O-Zn²⁺ bond near SiO₂ nanoparticles further improves the low-temperature performance of the DESE by decreasing Zn²⁺ desolvation energy. Moreover, the SiO₂ nanoparticles co-plating/co-stripping with Zn metal, forming a reversible and homogeneous SiO₂-enriched interphase to protect the Zn anode from dendrite growth and interfacial side reactions. Remarkably, the DESE-based ZMB full cells exhibit significantly prolonged cycle life of 8000 cycles at 1 A g⁻¹ at 25 °C and 700 cycles at 0.2 A g⁻¹ at -40 °C. This work provides a promising strategy to design advanced electrolytes for practical low-temperature ZMBs.     

Nonwoven rGO Fiber‐Aramid Separator for High‐Speed Charging and Discharging of Li Metal Anode

Li metal, which has a high theoretical specific capacity and low redox potential, is considered to the most promising anode material for next‐generation Li ion‐based batteries. However, it also exhibits a disadvantageous solid electrolyte interphase (SEI) layer problem that needs to be resolved. Herein, an advanced separator composed of reduced graphene oxide fiber attached to aramid paper (rGOF‐A) is introduced. When rGOF‐A is applied, F^? anions, generated from the decomposition of the LiPF₆ electrolyte during the SEI layer formation process form semi‐ionic C? F bonds along the surface of rGOF. As Li⁺ ions are plated, the “F‐doped” rGO surface induces the formation of LiF, which is known as a component of a chemically stable SEI, therefore it helps the Li metal anode to operate stably at a high current of 20 mA cm^?2 with a high capacity of 20 mAh cm^?2. The proposed rGOF‐A separator successfully achieves a stable SEI layer that could resolve the interfacial issues of the Li metal anode.     

A Room‐Temperature Molten Hydrate Electrolyte for Rechargeable Zinc–Air Batteries

Aqueous Zn‐based batteries are attracting extensive interest because of their economic feasibility and potentially high energy density. However, poor rechargeability of Zn anode in conventional electrolytes resulting from dendrite formation and self‐corrosion hinders their practical implementation. Herein, a Zn molten hydrate composed of inorganic Zn salt and water is demonstrated as an advantageous electrolyte for solving these issues. In this electrolyte, dendrite‐free Zn deposition/dissolution reaction with a high Coulombic efficiency (≈99%) as well as long‐term stability, free from CO₂ poisoning are realized. The resultant Zn–air cell exhibits a reversible capacity of 1000 mAh g_(catalyst)^?1 over 100 cycles at 30 °C. Combined with the intrinsic safety associated with aqueous chemistry and cost benefit of the raw material, the present Zn–air battery makes a strong candidate for large‐scale energy storage.     

Highly Stable Operation of Lithium Metal Batteries Enabled by the Formation of a Transient High‐Concentration Electrolyte Layer

Lithium (Li) metal has been extensively investigated as an anode for rechargeable battery applications due to its ultrahigh theoretical specific capacity and the lowest redox potential. However, significant challenges including dendrite growth and low Coulombic efficiency are still hindering the practical applications of rechargeable Li metal batteries. It is demonstrated that long‐term cycling of Li metal batteries can be realized by the formation of a transient high‐concentration electrolyte layer near the surface of Li metal anode during high rate discharge process. The highly concentrated Li⁺ ions in this transient layer will immediately be solvated by the available solvent molecules and facilitate the formation of a stable and flexible solid electrolyte interphase (SEI) layer composed of a poly(ethylene carbonate) framework integrated with other organic/inorganic lithium salts. This SEI layer largely suppresses the corrosion of Li metal anode attacked by free organic solvents and enables the long‐term operation of Li metal batteries. The fundamental findings in this work provide a new direction for the development of Li metal batteries that could be operated at high current densities for a wide range of applications.     

Uniform High Ionic Conducting Lithium Sulfide Protection Layer for Stable Lithium Metal Anode

Artificial solid‐electrolyte interphase (SEI) is one of the key approaches in addressing the low reversibility and dendritic growth problems of lithium metal anode, yet its current effect is still insufficient due to insufficient stability. Here, a new principle of “simultaneous high ionic conductivity and homogeneity” is proposed for stabilizing SEI and lithium metal anodes. Fabricated by a facile, environmentally friendly, and low‐cost lithium solid‐sulfur vapor reaction at elevated temperature, a designed lithium sulfide protective layer successfully maintains its protection function during cycling, which is confirmed by both simulations and experiments. Stable dendrite‐free cycling of lithium metal anode is realized even at a high areal capacity of 5 mAh cm^?2, and prototype Li–Li₄Ti₅O₁₂ cell with limited lithium also achieves 900 stable cycles. These findings give new insight into the ideal SEI composition and structure and provide new design strategies for stable lithium metal batteries.     

Ultrathin Reed Membranes: Nature's Intimate Ion-Regulation Skins Safeguarding Zinc Metal Anodes in Aqueous Batteries

The practical realization of aqueous zinc-ion batteries relies crucially on effective interphases governing Zn electrodeposition chemistry. In this study, an innovative solution by introducing an ultrathin (≈2 µm) biomass membrane as an intimate artificial interface, functioning as nature's ion-regulation skin to protect zinc metal anodes is proposed. Capitalizing on the inherent properties of natural reed membrane, including multiscale ion transport tunnels, abundant ─OH groups, and remarkable mechanical integrity, the reed membrane demonstrates efficacy in regulating uniform and rapid Zn²⁺ transport, promoting desolvation, and governing Zn (002) plane electrodeposition. Importantly, a unique in situ electrochemical Zn─O bond formation mechanism between the reed membrane and Zn electrode upon cycling is elucidated, resulting in a robustly adhered interface covering on the zinc anode surface, ultimately ensuring remarkable dendrite-free and highly reversible Zn anodes. Consequently, the approach achieves a prolonged cycle life for over 1450 h at 3 mA cm⁻²/1.5 mAh cm⁻² in symmetric Zn//Zn cells. Moreover, exceptional cyclic performance (88.95%, 4000 cycles) is obtained in active carbon-based cells with an active mass loading of 5.8 mg cm⁻². The approach offers a cost-effective and environmentally friendly strategy for achieving stable and reversible zinc anodes for aqueous batteries.     

An Anion‐Tuned Solid Electrolyte Interphase with Fast Ion Transfer Kinetics for Stable Lithium Anodes

The spatial distribution and transport characteristics of lithium ions (Li⁺) in the electrochemical interface region of a lithium anode in a lithium ion battery directly determine Li⁺ deposition behavior. The regulation of the Li⁺ solvation sheath on the solid electrolyte interphase (SEI) by electrolyte chemistry is key but challenging. Here, 1 m lithium trifluoroacetate (LiTFA) is induced to the electrolyte to regulate the Li⁺ solvation sheath, which significantly suppresses Li dendrite formation and enables a high Coulombic efficiency of 98.8% over 500 cycles. With its strong coordination between the carbonyl groups (C?O) and Li⁺, TFA^? modulates the environment of the Li⁺ solvation sheath and facilitates fast desolvation kinetics. In addition, due to relatively smaller lowest unoccupied molecular orbital energy than solvents, TFA^? has a preferential reduction to produce a stable SEI with uniform distribution of LiF and Li₂O. Such stable SEI effectively reduces the energy barrier for Li⁺ diffusion, contributing to low nucleation overpotential, fast ion transfer kinetics, and uniform Li⁺ deposition with high cycling stability. This work provides an alternative insight into the design of interface chemistry in terms of regulating anions in the Li⁺ solvation sheath. It is anticipated that this anion‐tuned strategy will pave the way to construct stable SEIs for other battery systems.     

Suppressing Li Dendrite Formation in Li2S‐P2S5 Solid Electrolyte by LiI Incorporation

Solid electrolytes have been considered as a promising approach for Li dendrite prevention because of their high mechanical strength and high Li transference number. However, recent reports indicate that Li dendrites also form in Li₂S‐P₂S₅ based sulfide electrolytes at current densities much lower than that in the conventional liquid electrolytes. The methods of suppressing dendrite formation in sulfide electrolytes have rarely been reported because the mechanism for the “unexpected” dendrite formation is unclear, limiting the successful utilization of high‐energy Li anode with these electrolytes. Herein, the authors demonstrate that the Li dendrite formation in Li₂S‐P₂S₅ glass can be effectively suppressed by tuning the composition of the solid electrolyte interphase (SEI) at the Li/electrolyte interface through incorporating LiI into the electrolyte. This approach introduces high ionic conductivity but electronic insulation of LiI in the SEI, and more importantly, improves the mobility of Li atoms, promoting the Li depositon at the interface and thus suppresses dendrite growth. It is shown that the critical current density is improved significantly after incorporating LiI into Li₂S‐P₂S₅ glass, reaching 3.90 mA cm^?2 at 100 °C after adding 30 mol% LiI. Stable cycling of the Li‐Li cells for 200 h is also achieved at 1.50 mA cm^?2 at 100 °C.     

Ultrathin Bilayer of Graphite/SiO2 as Solid Interface for Reviving Li Metal Anode

Lithium metal anodes are expected to drive practical applications that require high energy‐density storage. However, the direct use of metallic lithium causes safety concerns, low rate capabilities, and poor cycling performance due to unstable solid electrolyte interphase (SEI) and undesired lithium dendrite growth. To address these issues, a radio frequency sputtered graphite‐SiO₂ ultrathin bilayer on a Li metal chips is demonstrated, for the first time, as an effective SEI layer. This leads to a dendrite free uniform Li deposition to achieve a stable voltage profile and outstanding long hours plating/stripping compared to the bare Li. Compared to a bare Li anode, the graphite‐SiO₂ bilayer modified Li anode coupled with lithium nickel cobalt manganese oxide cathode (NMC111) and lithium titanate shows improved capacity retention, higher capacity at higher rates, longer cycling stability, and lower voltage hysteresis. Graphite acts as an electrical bridge between the plated Li and Li electrode, which lowers the impedance and buffers the volume expansion during Li plating/stripping. Adding an ultrathin SiO₂ layer facilitates Li‐ion diffusion and lithiation/delithiation, provides higher electrolyte affinity, higher chemical stability, and higher Young's modulus to suppress the Li dendrite growth.     

Electrokinetic Phenomena Enhanced Lithium‐Ion Transport in Leaky Film for Stable Lithium Metal Anodes

The application of lithium (Li) metal anodes in Li metal batteries has been hindered by growth of Li dendrites, which lead to short cycling life. Here a Li‐ion‐affinity leaky film as a protection layer is reported to promote a dendrite‐free Li metal anode. The leaky film induces electrokinetic phenomena to enhance Li‐ion transport, leading to a reduced Li‐ion concentration polarization and homogeneous Li‐ion distribution. As a result, the dendrite‐free Li metal anode during Li plating/stripping is demonstrated even at an extremely high deposition capacity (6 mAh cm^?2) and current density (40 mA cm^?2) with improved Coulombic efficiencies. A full cell battery with the leaky‐film protected Li metal as the anode and high‐areal‐capacity LiNi_0.8Co_0.1Mn_0.1O₂ (NCM‐811) (≈4.2 mAh cm^?2) or LiFePO₄ (≈3.8 mAh cm^?2) as the cathode shows improved cycling stability and capacity retention, even at lean electrolyte conditions.     

SiO2 Hollow Nanosphere‐Based Composite Solid Electrolyte for Lithium Metal Batteries to Suppress Lithium Dendrite Growth and Enhance Cycle Life

The low Coulombic efficiency and serious security issues of lithium (Li) metal anode caused by uncontrollable Li dendrite growth have permanently prevented its practical application. A novel SiO₂ hollow nanosphere‐based composite solid electrolyte (SiSE) for Li metal batteries is reported. This hierarchical electrolyte is fabricated via in situ polymerizing the tripropylene gycol diacrylate (TPGDA) monomer in the presence of liquid electrolyte, which is absorbed in a SiO₂ hollow nanosphere layer. The polymerized TPGDA framework keeps the prepared SiSE in a quasi‐solid state without safety risks caused by electrolyte leakage, meanwhile the SiO₂ layer not only acts as a mechanics‐strong separator but also provides the SiSE with high room‐temperature ionic conductivity (1.74 × 10^?3 S cm^?1) due to the high pore volume (1.49 cm³ g^?1) and large liquid electrolyte uptake of SiO₂ hollow nanospheres. When the SiSE is in situ fabricated on the cathode and applied to LiFePO₄/SiSE/Li batteries, the obtained cells show a significant improvement in cycling stability, mainly attributed to the stable electrode/electrolyte interface and remarkable suppression for Li dendrite growth by the SiSE. This work can extend the application of hollow nanooxide and enable a safe, efficient operation of Li anode in next generation energy storage systems.