Nitrogen Doped/Carbon Tuning Yolk‐Like TiO2 and Its Remarkable Impact on Sodium Storage Performances

Yolk‐like TiO₂ are prepared through an asymmetric Ostwald ripening, which is simultaneously doped by nitrogen and wrapped by carbon from core to shell. It presents a high specific surface area (144.9 m² g^?1), well‐defined yolk‐like structure (600–700 nm), covered with interweaved nanosheets (3–5 nm) and tailored porosity (5–10 nm) configuration. When first utilized as anode material for sodium‐ion batteries (SIBs), it delivers a high reversible specific capacity of 242.7 mA h g^?1 at 0.5 C and maintains a considerable capacity of 115.9 mA h g^?1 especially at rate 20 C. Moreover, the reversible capacity can still reach 200.7 mA h g^?1 after 550 cycles with full capacity retention at 1 C. Even cycled at extremely high rate 25 C, the capacity retention of 95.5% after 3000 cycles is acquired. Notably, an ultrahigh initial coulombic efficiency of 59.1% is achieved. The incorporation of nitrogen with narrowing the band gap accompanied with carbon uniformly coating from core to shell make the NC TiO₂‐Y favor a bulk type conductor, resulting in fast electron transfer, which is beneficial to long‐term cycling stability and remarkable rate capability. It is of great significance to improve the energy‐storage properties through development of the bulk type conductor as anode materials in SIBs.     

Exploring Advanced Sandwiched Arrays by Vertical Graphene and N‐Doped Carbon for Enhanced Sodium Storage

Smart hybridization of active materials into tailored electrode structure is highly important for developing advanced electrochemical energy storage devices. With the help of sandwiched design, herein a powerful strategy is developed to fabricate three‐layer sandwiched composite core/shell arrays via combined hydrothermal and polymerization approaches. In such a unique architecture, wrinkled MoSe₂ nanosheets are sandwiched by vertical graphene (VG) core and N‐doped carbon (N‐C) shell forming sandwiched core/shell arrays. Interesting advantages including high electrical conductivity, strong mechanical stability, and large porosity are combined in the self‐supported VG/MoSe₂/N‐C sandwiched arrays. As a preliminary test, the sodium ion storage properties of VG/MoSe₂/N‐C sandwiched arrays are characterized and demonstrated with high capacity (540 mA h g^?1), enhanced high rate capability, and long‐term cycling stability (298 mA h g^?1 at 2.0 A g^?1 after 1000 cycles). The sandwiched core/shell structure plays positive roles in the enhancement of electrochemical performances due to dual conductive carbon networks, good volume accommodation, and highly porous structure with fast ion diffusion. The directional electrode design protocol provides a general method for synthesis of high‐performance ternary core/shell electrodes.     

Ultrafine MoO2‐Carbon Microstructures Enable Ultralong‐Life Power‐Type Sodium Ion Storage by Enhanced Pseudocapacitance

The achievement of the superior rate capability and cycling stability is always the pursuit of sodium‐ion batteries (SIBs). However, it is mainly restricted by the sluggish reaction kinetics and large volume change of SIBs during the discharge/charge process. This study reports a facile and scalable strategy to fabricate hierarchical architectures where TiO₂ nanotube clusters are coated with the composites of ultrafine MoO₂ nanoparticles embedded in carbon matrix (TiO₂@MoO₂‐C), and demonstrates the superior electrochemical performance as the anode material for SIBs. The ultrafine MoO₂ nanoparticles and the unique nanorod structure of TiO₂@MoO₂‐C help to decrease the Na⁺ diffusion length and to accommodate the accompanying volume expansion. The good integration of MoO₂ nanoparticles into carbon matrix and the cable core role of TiO₂ nanotube clusters enable the rapid electron transfer during discharge/charge process. Benefiting from these structure merits, the as‐made TiO₂@MoO₂‐C can deliver an excellent cycling stability up to 10 000 cycles even at a high current density of 10 A g^?1. Additionally, it exhibits superior rate capacities of 110 and 76 mA h g^?1 at high current densities of 10 and 20 A g^?1, respectively, which is mainly attributed to the high capacitance contribution.     

In Situ Generation of Few‐Layer Graphene Coatings on SnO2‐SiC Core‐Shell Nanoparticles for High‐Performance Lithium‐Ion Storage

A simple ball‐milling method is used to synthesize a tin oxide‐silicon carbide/few‐layer graphene core‐shell structure in which nanometer‐sized SnO₂ particles are uniformly dispersed on a supporting SiC core and encapsulated with few‐layer graphene coatings by in situ mechanical peeling. The SnO₂‐SiC/G nanocomposite material delivers a high reversible capacity of 810 mA h g^?1 and 83% capacity retention over 150 charge/discharge cycles between 1.5 and 0.01 V at a rate of 0.1 A g^?1. A high reversible capacity of 425 mA h g^?1 also can be obtained at a rate of 2 A g^?1. When discharged (Li extraction) to a higher potential at 3.0 V (vs. Li/Li⁺), the SnO₂‐SiC/G nanocomposite material delivers a reversible capacity of 1451 mA h g^?1 (based on the SnO₂ mass), which corresponds to 97% of the expected theoretical capacity (1494 mA h g^?1, 8.4 equivalent of lithium per SnO₂), and exhibits good cyclability. This result suggests that the core‐shell nanostructure can achieve a completely reversible transformation from Li_4.4Sn to SnO₂ during discharging (i.e., Li extraction by dealloying and a reversible conversion reaction, generating 8.4 electrons). This suggests that simple mechanical milling can be a powerful approach to improve the stability of high‐performance electrode materials involving structural conversion and transformation.     

Three‐Dimensional Porous Core‐Shell Sn@Carbon Composite Anodes for High‐Performance Lithium‐Ion Battery Applications

A three‐dimensional porous core‐shell Sn@carbon anode on nickel foam substrate was fabricated by electrostatic spray deposition (ESD) technique followed by high temperature treatment. The carbon shell with a thickness of about 3.2 nm was formed on porous Sn structure at high temperature. 3D porous structure and carbon shell were designed to buffer volume expansion/shrinkage of Sn lattice upon cycling and increase the electrical conductivity. After 315 charge/discharge cycles Sn@carbon anode exhibited high specific capacity of 638 mAh g^?1 with the low capacity fade of average 0.11 mAh g^?1 per cycle. Sn@carbon based anodes was demonstrated to have promising potential for high performance lithium ion batteries application.     

High‐Rate and Long Cycle‐Life Alloy‐Type Magnesium‐Ion Battery Anode Enabled Through (De)magnesiation‐Induced Near‐Room‐Temperature Solid–Liquid Phase Transformation

Resources used in lithium‐ion batteries are becoming more expensive due to their high demand, and the global cobalt market heavily depends on supplies from countries with high geopolitical risks. Alternative battery technologies including magnesium‐ion batteries are therefore desirable. Progress toward practical magnesium‐ion batteries are impeded by an absence of suitable anodes that can operate with conventional electrolyte solvents. Although alloy‐type magnesium‐ion battery anodes are compatible with common electrolyte solvents, they suffer from severe failure associated with huge volume changes during cycling. Consequently, achieving more than 200 cycles in alloy‐type magnesium‐ion battery anodes remains a challenge. Here an unprecedented long‐cycle life of 1000 cycles, achieved at a relatively high (dis)charge rate of 3 C (current density: 922.5 mA g^?1) in Mg₂Ga₅ alloy‐type anode, taking advantage of near‐room‐temperatures solid–liquid phase transformation between Mg₂Ga₅ (solid) and Ga (liquid), is demonstrated. This concept should open the way to the development of practical anodes for next‐generation magnesium‐ion batteries.     

Li+ Pre‐Insertion Leads to Formation of Solid Electrolyte Interface on TiO2 Nanotubes That Enables High‐Performance Anodes for Sodium Ion Batteries

Recently, sodium ion batteries (SIBs) have been widely investigated as one of the most promising candidates for replacing lithium ion batteries (LIBs). For SIBs or LIBs, designing a stable and uniform solid electrolyte interphase (SEI) at the electrode–electrolyte interface is the key factor to provide high capacity, long‐term cycling, and high‐rate performance. In this paper, it is described how a remarkably enhanced SEI layer can be obtained on TiO₂ nanotube (TiO₂ NTs) arrays that allows for a strongly improved performance of sodium battery systems. Key is that a Li⁺ pre‐insertion in TiO₂ NTs can condition the SEI for Na⁺ replacement. SIBs constructed with Li‐pre‐inserted NTs deliver an exceptional Na⁺ cycling stability (e.g., 99.9 ± 0.1% capacity retention during 250 cycles at a current rate of 50 mA g^?1) and an excellent rate capability (e.g., 132 mA h g^?1 at a current rate of 1 A g^?1). The key factor in this outstanding performance is that Li‐pre‐insertion into TiO₂ NTs leads not only to an enhanced electronic conductivity in the tubes, but also expands the anatase lattice for facilitated subsequent Na⁺ cycling.     

Tailored Plum Pudding‐Like Co2P/Sn Encapsulated with Carbon Nanobox Shell as Superior Anode Materials for High‐Performance Sodium‐Ion Capacitors

Sodium‐ion capacitors (SICs) are emerging energy storage devices with high energy, high power, and durable life. Sn is a promising anode material for lithium storage, but the poor conductivity of the a‐NaSn phase upon sodaition hinders its implementation in SICs. Herein, a superior Sn‐based anode material consisting of plum pudding‐like Co₂P/Sn yolk encapsulated with nitrogen‐doped carbon nanobox (Co₂P/Sn@NC) for high‐performance SICs is reported. The 8–10 nm metallic nanoparticles produced in situ are uniformly dispersed in the amorphous Sn matrix serving as conductive fillers to facilitate electron transfer in spite of the formation of electrically resistive a‐NaSn phase during cycling. Meanwhile, the carbon shell buffers the large expansion of active Sn and provides a stable electrode–electrolyte interface. Owing to these merits, the yolk–shell Co₂P/Sn@NC demonstrates a large capacity of 394 mA h g^?1 at 100 mA g^?1, high rate capability of 168 mA h g^?1 at 5000 mA g^?1, and excellent cyclability with 87% capacity retention after 10 000 cycles. By integrating the Co₂P/Sn@NC anode with a peanut shell‐derived carbon cathode in the SIC, high energy densities of 112.3 and 43.7 Wh kg^?1 at power densities of 100 and 10 000 W kg^?1 are achieved.     

A High‐Rate and Ultrastable Sodium Ion Anode Based on a Novel Sn4P3‐P@Graphene Nanocomposite

Phosphorus and tin phosphide based materials that are extensively researched as the anode for Na‐ion batteries mostly involve complexly synthesized and sophisticated nanocomposites limiting their commercial viability. This work reports a Sn₄P₃‐P (Sn:P = 1:3) @graphene nanocomposite synthesized with a novel and facile mechanochemical method, which exhibits unrivalled high‐rate capacity retentions of >550 and 371 mA h g^?1 at 1 and 2 A g^?1, respectively, over 1000 cycles and achieves excellent rate capability (>815, ≈585 and ≈315 mA h g^?1 at 0.1, 2, and 10 A g^?1, respectively).     

Revealing Pseudocapacitive Mechanisms of Metal Dichalcogenide SnS2/Graphene‐CNT Aerogels for High‐Energy Na Hybrid Capacitors

SnS₂ nanoplatelet electrodes can offer an exceptionally high pseudocapacitance in an organic Na⁺ ion electrolyte system, but their underlying mechanisms are still largely unexplored, hindering the practical applications of pseudocapacitive SnS₂ anodes in Na‐ion batteries (SIBs) and Na hybrid capacitors (SHCs). Herein, SnS₂ nanoplatelets are grown directly on SnO₂/C composites to synthesize SnS₂/graphene‐carbon nanotube aerogel (SnS₂/GCA) by pressurized sulfidation where the original morphology of carbon framework is preserved. The composite electrode possessing a large surface area delivers a remarkable specific capacity of 600.3 mA h g^?1 at 0.2 A g^?1 and 304.8 mA h g^?1 at an ultrahigh current density of 10 A g^?1 in SIBs. SHCs comprising a SnS₂/GCA composite anode and an activated carbon cathode present exceptional energy densities of 108.3 and 26.9 W h kg^?1 at power densities of 130 and 6053 W kg^?1, respectively. The in situ transmission electron microscopy and the density functional theory calculations reveal that the excellent pseudocapacitance originates from the combination of Na adsorption on the surface/Sn edge of SnS₂ nanoplatelets and ultrafast Na⁺ ion intercalation into the SnS₂ layers.     

Chemical Synthesis of 3D Graphene‐Like Cages for Sodium‐Ion Batteries Applications

Sodium (Na) super ion conductor structured Na₃V₂(PO₄)₃ (NVP) is extensively explored as cathode material for sodium‐ion batteries (SIBs) due to its large interstitial channels for Na⁺ migration. The synthesis of 3D graphene‐like structure coated on NVP nanoflakes arrays via a one‐pot, solid‐state reaction in molten hydrocarbon is reported. The NVP nanoflakes are uniformly coated by the in situ generated 3D graphene‐like layers with the thickness of 3 nm. As a cathode material, graphene covered NVP nanoflakes exhibit excellent electrochemical performances, including close to theoretical reversible capacity (115.2 mA h g^?1 at 1 C), superior rate capability (75.9 mA h g^?1 at 200 C), and excellent cyclic stability (62.5% of capacity retention over 30000 cycles at 50 C). Furthermore, the 3D graphene‐like cages after removing NVP also serve as a good anode material and deliver a specific capacity of 242.5 mA h g^?1 at 0.1 A g^?1. The full SIB using these two cathode and anode materials delivers a high specific capacity (109.2 mA h g^?1 at 0.1 A g^?1) and good cycling stability (77.1% capacity retention over 200 cycles at 0.1 A g^?1).     

A Novel Aluminum‐Ion Battery: Al/AlCl3‐[EMIm]Cl/Ni3S2@Graphene

Due to an ever‐increasing demand for electronic devices, rechargeable batteries are attractive for energy storage systems. A novel rechargeable aluminum‐ion battery based on Al³⁺ intercalation and deintercalation is fabricated with Ni₃S₂/graphene microflakes composite as cathode material and high‐purity Al foil as anode. This kind of aluminum‐ion battery comprises of an electrolyte containing AlCl₃ in an ionic liquid of 1‐ethyl‐3‐methylimidazolium chloride ([EMIm]Cl). Galvanostatic charge/discharge measurements have been performed in a voltage range of 0.1–2.0 V versus Al/AlCl₄ ^?. An initial discharge specific capacity of 350 mA h g^?1 at a current density of 100 mA g^?1 is achieved, and the discharge capacity remains over 60 mA h g^?1 and coulombic efficiency of 99% after 100 cycles. Typically, for the current density at 200 mA g^?1, the initial charge and discharge capacities are 300 and 235 mA h g^?1, respectively. More importantly, it should be emphasized that the battery has a high discharge voltage plateau (≈1.0 V vs Al/AlCl₄ ^?). These meaningful results represent a significant step forward in the development of aluminum‐ion batteries.     

Electrospun NaVPO4F/C Nanofibers as Self‐Standing Cathode Material for Ultralong Cycle Life Na‐Ion Batteries

NaVPO₄F has received a great deal of attention as cathode material for Na‐ion batteries due to its high theoretical capacity (143 mA h g^?1), high voltage platform, and structural stability. Novel NaVPO₄F/C nanofibers are successfully prepared via a feasible electrospinning method and subsequent heat treatment as self‐standing cathode for Na‐ion batteries. Based on the morphological and microstructural characterization, it can be seen that the NaVPO₄F/C nanofibers are smooth and continuous with NaVPO₄F nanoparticles (≈6 nm) embedded in porous carbon matrix. For Na‐storage, this electrode exhibits extraordinary electrochemical performance: a high capacity (126.3 mA h g^?1 at 1 C), a superior rate capability (61.2 mA h g^?1 at 50 C), and ultralong cyclability (96.5% capacity retention after 1000 cycles at 2 C). 1D NaVPO₄F/C nanofibers that interlink into 3D conductive network improve the conductivity of NaVPO₄F, and effectively restrain the aggregation of NaVPO₄F particles during charge/discharge process, leading to the high performance.     

One‐Step In Situ Formation of N‐doped Carbon Nanosheet 3D Porous Networks/TiO2 Hybrids with Ultrafast Sodium Storage

In spite of the satisfactory advancement in preparing TiO₂‐based hybrid structures, most methods rely on additional template‐based multistep reactions for engineering the given structure. Herein, a unique self‐template and in situ recrystallization strategy is explored to synthesize uniform flowerlike multicompositional structures of nitrogen‐doped porous carbon nanosheet networks immobilizing TiO₂ nanoparticles (TiO₂∩NPCSs) via a self‐prepared single precursor and subsequent thermal treatment. Depending on the unique coordination ability of 2,4‐dihydroxybenzoic acid with metal ions under alkaline conditions to form a flowerlike network, a self‐produced single precursor can be achieved. Careful investigations of the self‐prepared precursor reveal a high practicability of the present synthetic scheme. Because of the novel structural and compositional features, these TiO₂∩NCSN flowers indicate superior sodium storage properties when evaluated as anodes for sodium‐ion batteries. Impressively, the TiO₂∩NCSN flowers deliver high reversible capacities of 152 mAh g^?1 at 2C for 3000 cycles and 114 mAh g^?1 at 10C for 10000 cycles, as well as an ultrahigh rate capability up to 50C with a capacity of 101 mAh g^?1. The facile method could stimulate further capability in precise construction of complex architectures with complicated compositions for different device applications.     

Low‐Temperature Solution‐Based Phosphorization Reaction Route to Sn4P3/Reduced Graphene Oxide Nanohybrids as Anodes for Sodium Ion Batteries

Different from previously reported mechanical alloying route to synthesize Sn _x P₃, novel Sn₄P₃/reduced graphene oxide (RGO) hybrids are synthesized for the first time through an in situ low‐temperature solution‐based phosphorization reaction route from Sn/RGO. Sn₄P₃ nanoparticles combining with advantages of high conductivity of Sn and high capacity of P are homogenously loaded on the RGO nanosheets, interconnecting to form 3D mesoporous architecture nanostructures. The Sn₄P₃/RGO hybrid architecture materials exhibit significantly improved electrochemical performance of high reversible capacity, high‐rate capability, and excellent cycling performance as sodium ion batteries (SIBs) anode materials, showing an excellent reversible capacity of 656 mA h g^?1 at a current density of 100 mA g^?1 over 100 cycles, demonstrating a greatly enhanced rate capability of a reversible capacity of 391 mA h g^?1 even at a high current density of 2.0 A g^?1. Moreover, Sn₄P₃/RGO SIBs anodes exhibit a superior long cycling life, delivering a high capacity of 362 mA h g^?1 after 1500 cycles at a high current density of 1.0 A g^?1. The outstanding cycling performance and rate capability of these porous hierarchical Sn₄P₃/RGO hybrid anodes can be attributed to the advantage of porous structure, and the synergistic effect between Sn₄P₃ nanoparticles and RGO nanosheets.     

V2O5 Nano‐Electrodes with High Power and Energy Densities for Thin Film Li‐Ion Batteries

Nanostructured V₂O₅ thin films have been prepared by means of cathodic deposition from an aqueous solution made from V₂O₅ and H₂O₂ directly on fluorine‐doped tin oxide coated (FTO) glasses followed by annealing at 500°C in air, and studied as film electrodes for lithium ion batteries. XPS results show that the as‐deposited films contained 15% V⁴⁺, however after annealing all the vanadium is oxidized to V⁵⁺. The crystallinity, surface morphology, and microstructures of the films have been investigated by means of XRD, SEM, and AFM. The V₂O₅ thin film electrodes show excellent electrochemical properties as cathodes for lithium ion intercalation: a high initial discharge capacity of 402 mA h g^?1 and 240 mA h g^?1 is retained after over 200 cycles with a discharging rate of 200 mA g^?1 (1.3 C). The specific energy density is calculated as 900 W h kg^?1 for the 1^st cycle and 723 W h kg^?1 for the 180^th cycle when the films are tested at 200 mA g^?1 (1.3 C). When discharge/charge is carried out at a high current density of 10.5 A g^?1 (70 C), the thin film electrodes retain a good discharge capacity of 120 mA h g^?1, and the specific power density is over 28 kW kg^?1.     

Hydrogenated Core–Shell MAX@K2Ti8O17 Pseudocapacitance with Ultrafast Sodium Storage and Long‐Term Cycling

Sodium‐ion batteries are considered alternatives to lithium‐ion batteries for energy storage devices due to their competitive cost and source abundance. However, the development of electrode materials with long‐term stability and high capacity remains a great challenge. Here, this paper describes for the first time the synthesis of a new class of core–shell MAX@K₂Ti₈O₁₇ by alkaline hydrothermal reaction and hydrogenation of MAX, which grants high sodium ion‐intercalation pseudocapacitance. This composite electrode displays extraordinary reversible capacities of 190 mA h g^?1 at 200 mA g^?1 (0.9 C, theoretical value of ≈219 mA h g^?1) and 150 mA h g^?1 at 1000 mA g^?1 (4.6 C). More importantly, a reversible capacity of 75 mA h g^?1 at 10 000 mA g^?1 (46 C) is retained without any apparent capacity decay even after more than 10 000 cycles. Experimental tests and first‐principle calculations confirm that the increase in Ti³⁺ on the surface layers of MAX@K₂Ti₈O₁₇ by hydrogenation increases its conductivity in addition to enhancing the sodium‐ion intercalation pseudocapacitive process. Furthermore, the distorted dodecahedrons between Ti and O layers not only provide abundant sites for sodium‐ion accommodation but also act as wide tunnels for sodium‐ion transport.     

Hierarchical NiCo2S4@NiO Core–Shell Heterostructures as Catalytic Cathode for Long‐Life Li‐O2 Batteries

The critical challenges of Li‐O₂ batteries lie in sluggish oxygen redox kinetics and undesirable parasitic reactions during the oxygen reduction reaction and oxygen evolution reaction processes, inducing large overpotential and inferior cycle stability. Herein, an elaborately designed 3D hierarchical heterostructure comprising NiCo₂S₄@NiO core–shell arrays on conductive carbon paper is first reported as a freestanding cathode for Li‐O₂ batteries. The unique hierarchical array structures can build up multidimensional channels for oxygen diffusion and electrolyte impregnation. A built‐in interfacial potential between NiCo₂S₄ and NiO can drastically enhance interfacial charge transfer kinetics. According to density functional theory calculations, intrinsic LiO₂‐affinity characteristics of NiCo₂S₄ and NiO play an importantly synergistic role in promoting the formation of large peasecod‐like Li₂O₂, conducive to construct a low‐impedance Li₂O₂/cathode contact interface. As expected, Li‐O₂ cells based on NiCo₂S₄@NiO electrode exhibit an improved overpotential of 0.88 V, a high discharge capacity of 10 050 mAh g^?1 at 200 mA g^?1, an excellent rate capability of 6150 mAh g^?1 at 1.0 A g^?1, and a long‐term cycle stability under a restricted capacity of 1000 mAh g^?1 at 200 mA g^?1. Notably, the reported strategy about heterostructure accouplement may pave a new avenue for the effective electrocatalyst design for Li‐O₂ batteries.     

Nanowire‐Based Three‐Dimensional Transparent Conducting Oxide Electrodes for Extremely Fast Charge Collection

A 3D transparent conducting oxide (3D‐TCO) has been fabricated by growing Sn‐doped indium oxide (ITO) nanowire arrays on glass substrates via a vapor transport method. The 3D TCO charge‐collection properties have been compared to those of conventional two‐dimensional TCO (2D‐TCO) thin films. For use as a photoelectrode in dye‐sensitized solar cells, ITO‐TiO₂ core‐shell nanowire arrays were prepared by depositing a 45 nm‐thick mesoporous TiO₂ shell layer consisting of ～6 nm anatase nanoparticles using TiCl₄ treatments. Dye‐sensitized solar cells fabricated using these ITO‐TiO₂ core‐shell nanowire arrays show extremely fast charge collection owing to the shorter electron paths across the 45 nm‐thick TiO₂ shell compared to the 2D TCO. Interestingly, the charge‐collection time does not increase with the overall electrode thickness, which is counterintuitive to conventional diffusion models. This result implies that, in principle, maximum light harvesting can be achieved without hindering the charge collection. The proposed new 3D TCO should also be attractive for other photovoltaic applications where the active layer thickness is limited by poor charge collection.     

3D TiC/C Core/Shell Nanowire Skeleton for Dendrite‐Free and Long‐Life Lithium Metal Anode

Construction of stable dendrite‐free Li metal anode is crucial for the development of advanced Li–S and Li–air batteries. Herein, self‐supported TiC/C core/shell nanowire arrays as skeletons and confined hosts of molten Li forming integrated trilayer TiC/C/Li anode are described. The TiC/C core/shell nanowires with diameters of 400–500 nm exhibit merits of good lithiophilicity, high electrical conductivity, and abundant porosity. The as‐prepared TiC/C/Li anode exhibits prominent electrochemical performance with a small hysteresis of less than 85 mV beyond 200 cycles (3.0 mA cm^?2) as well as a very high Coulombic efficiency up to 98.5% for 100 cycles at 1.0 mA cm^?2. When the structured anode is coupled with lithium iron phosphate or sulfur cathode, the assembled full cells with trilayer TiC/C/Li anodes display enhanced capability retention and improved Coulombic efficiency. This is ascribed to the unique TiC/C matrix, which can not only provide interspace for accommodating “hostless” Li, but also afford interconnected rapid transfer paths for electrons and ions with low local current densities, leading to effective inhabitation growth of Li dendrites and lower interfacial resistance. A fresh way for construction of advanced stable Li metal anodes is provided in this work.