Walnut‐Like Multicore–Shell MnO Encapsulated Nitrogen‐Rich Carbon Nanocapsules as Anode Material for Long‐Cycling and Soft‐Packed Lithium‐Ion Batteries

Metal oxide‐based nanomaterials are widely studied because of their high‐energy densities as anode materials in lithium‐ion batteries. However, the fast capacity degradation resulting from the large volume expansion upon lithiation hinders their practical application. In this work, the preparation of walnut‐like multicore–shell MnO encapsulated nitrogen‐rich carbon nanocapsules (MnO@NC) is reported via a facile and eco‐friendly process for long‐cycling Li‐ion batteries. In this hybrid structure, MnO nanoparticles are uniformly dispersed inside carbon nanoshells, which can simultaneously act as a conductive framework and also a protective buffer layer to restrain the volume variation. The MnO@NC nanocapsules show remarkable electrochemical performances for lithium‐ion batteries, exhibiting high reversible capability (762 mAh g^?1 at 100 mA g^?1) and stable cycling life (624 mAh g^?1 after 1000 cycles at 1000 mA g^?1). In addition, the soft‐packed full batteries based on MnO@NC nanocapsules anodes and commercial LiFePO₄ cathodes present good flexibility and cycling stability.     

Enhancing Ultrafast Lithium Ion Storage of Li4Ti5O12 by Tailored TiC/C Core/Shell Skeleton Plus Nitrogen Doping

It is of great importance to reinforce electronic and ionic conductivity of Li₄Ti₅O₁₂ electrodes to achieve fast reaction kinetics and good high‐power capability. Herein, for the first time, a dual strategy of combing N‐doped Li₄Ti₅O₁₂ (N‐LTO) with highly conductive TiC/C skeleton to realize enhanced ultrafast Li ion storage is reported. Interlinked hydrothermal‐synthesized N‐LTO nanosheets are homogeneously decorated on the chemical vapor deposition (CVD) derived TiC/C nanowires forming binder‐free N‐LTO@TiC/C core–branch arrays. Positive advantages including large surface area, strong mechanical stability, and enhanced electronic/ionic conductivity are obtained in the designed integrated arrays and rooted upon synergistic TiC/C matrix and N doping. The above appealing features can effectively boost kinetic properties throughout the N‐LTO@TiC/C electrodes to realize outstanding high‐rate capability at different working temperatures (143 mAh g^?1/10 C at 25 °C and 122 mAh g^?1/50 C at 50 °C) and notable cycling stability with a capacity retention of 99.3% after 10 000 cycles at 10 C. Moreover, superior high‐rate cycling life is also demonstrated for the full cells with N‐LTO@TiC/C anode and LiFePO₄ cathode. The dual strategy may provoke wide interests in fast energy storage areas and motivate the further performance improvement of power‐type lithium ion batteries (LIBs).     

Template‐Assisted Formation of Rattle‐type V2O5 Hollow Microspheres with Enhanced Lithium Storage Properties

In this work, rattle‐type ball‐in‐ball V₂O₅ hollow microspheres are controllably synthesized with the assistance of carbon colloidal spheres as hard templates. Carbon spheres@vanadium‐precursor (CS@V) core–shell composite microspheres are first prepared through a one‐step solvothermal method. The composition of solvent for the solvothermal synthesis has great influence on the morphology and structure of the vanadium‐precursor shells. V₂O₅ hollow microspheres with various shell architectures can be obtained after removing the carbon microspheres by calcination in air. Moreover, the interior hollow shell can be tailored by varying the temperature ramping rate and calcination temperature. The rattle‐type V₂O₅ hollow microspheres are evaluated as a cathode material for lithium‐ion batteries, which manifest high specific discharge capacity, good cycling stability and rate capability.     

A Self‐Standing and Flexible Electrode of Li4Ti5O12 Nanosheets with a N‐Doped Carbon Coating for High Rate Lithium Ion Batteries

Flexible energy‐storage devices have attracted growing attention with the fast development of bendable electronic systems. Thus, the search for reliable electrodes with both high mechanical flexibility and excellent electron and lithium‐ion conductivity has become an urgent task. Carbon‐coated nanostructures of Li₄Ti₅O₁₂ (LTO) have important applications in high‐performance lithium ion batteries (LIBs). However, these materials still need to be mixed with a binder and carbon black and pressed onto metal substrates or, alternatively, by be deposited onto a conductive substrate before they are assembled into batteries, which makes the batteries less flexible and have a low energy density. Herein, a simple and scalable process to fabricate LTO nanosheets with a N‐doped carbon coating is reported. This can be assembled into a film which can be used as a binder‐free and flexible electrode for LIBs that does not require any current collectors. Such a flexible electrode has a long life. More significantly, it exhibits an excellent rate capability due to the thin carbon coating and porous nanosheet structures, which produces a highly conductive pathway for electrons and fast transport channels for lithium ions.     

Template‐Based Engineering of Carbon‐Doped Co3O4 Hollow Nanofibers as Anode Materials for Lithium‐Ion Batteries

Co₃O₄ anode materials exhibit poor conductivity and a large volume change, rendering controlling of their nanostructure essential to optimize their lithium storage performance. Carbon‐doped Co₃O₄ hollow nanofibers (C‐doped Co₃O₄ HNFs), for the first time are synthesized using bifunctional polymeric nanofibers as template and carbon source. Compared with undoped Co₃O₄ HNFs and solid Co₃O₄ NFs, C‐doped Co₃O₄ HNFs feature a remarkably high specific capacity, excellent cycling stability, and superior rate capacity as anode materials for lithium‐ion batteries. The superior performance of C‐doped Co₃O₄ HNFs electrodes can be attributed to their structural features, which confer enhanced electron transportation and Li⁺ ion diffusion due to C‐doping, and tolerance for volume change due to the 1D hollow structure. Density functional theory calculations provide a good explanation of the observed enhanced conductivity in C‐doped Co₃O₄ HNFs.     

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

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

B‐doped Carbon Coating Improves the Electrochemical Performance of Electrode Materials for Li‐ion Batteries

An evolutionary modification approach, boron doped carbon coating, is initially used to improve the electrochemical properties of electrode materials of lithium‐ion batteries, such as Li₃V₂(PO₄)₃, and demonstrates apparent and significant modification effects. Based on the precise analysis of X‐ray photoemission spectroscopy results, Raman spectra, and electrochemical impedance spectroscopy results for various B‐doped carbon coated Li₃V₂(PO₄)₃ samples, it is found that, among various B‐doping types (B₄C, BC₃, BC₂O and BCO₂), the graphite‐like BC₃ dopant species plays a huge role on improving the electronic conductivity and electrochemical activity of the carbon coated layer on Li₃V₂(PO₄)₃ surface. As a result, when compared with the bare carbon coated Li₃V₂(PO₄)₃, the electrochemical performances of the B‐doped carbon coated Li₃V₂(PO₄)₃ electrode with a moderate doping amount are greatly improved. For example, when cycled under 1 C and 20 C in the potential range of 3.0–4.3 V, this sample shows an initial capacity of 122.5 and 118.4 mAh g^?1, respectively; after 200 cycles, nearly 100% of the initial capacity is retained. Moreover, the modification effects of B‐doped carbon coating approach are further validated on Li₄Ti₅O₁₂ anode material.     

Optimizing Main Materials for a Lithium‐Air Battery of High Cycle Life

By optimizing the main materials in lithium‐air batteries, namely sulfolane as electrolyte solvent, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) as electrolyte salt, carbon paper as current collector, and Li₂O₂–C hybrids as positive electrode materials, a performance of 800 cycles with a specific capacity of 1000 mAh g^?1 (based on the total mass of positive electrode materials) and an average energy efficiency of 74.72% has been achieved in this work and for the first time reported in the field of lithium‐air battery. Sulfolane‐based electrolyte and carbon paper current collector play the most critical role in building such a lithium‐air battery of high cycle life. The findings described here are expected to benefit the pursuit of green, sustainable, and high‐performance lithium‐air batteries.     

Ultra‐High Capacity Lithium‐Ion Batteries with Hierarchical CoO Nanowire Clusters as Binder Free Electrodes

Although transition metal oxide electrodes have large lithium storage capacity, they often suffer from low rate capability, poor cycling stability, and unclear additional capacity. In this paper, CoO nanowire clusters (NWCs) composed of ultra‐small nanoparticles (≈10 nm) directly grown on copper current collector are fabricated and evaluated as an anode of binder‐free lithium‐ion batteries, which exhibits an ultra‐high capacity and good rate capability. At a rate of 1 C (716 mA g^?1), a reversible capacity as high as 1516.2 mA h g^?1 is obtained, and even when the current density is increased to 5 C, a capacity of 1330.5 mA h g^?1 could still be maintained. Importantly, the origins of the additional capacity are investigated in detail, with the results suggesting that pseudocapacitive charge and the higher‐oxidation‐state products are jointly responsible for the large additional capacity. In addition, nanoreactors for the CoO nanowires are fabricated by coating the CoO nanowires with amorphous silica shells. This hierarchical core–shell CoO@SiO₂ NWC electrode achieves an improved cycling stability without degrading the high capacity and good rate capability compared to the uncoated CoO NWCs electrode.     

Binary Li4Ti5O12‐Li2Ti3O7 Nanocomposite as an Anode Material for Li‐Ion Batteries

Li₄Ti₅O₁₂ typically shows a flat charge/discharge curve, which usually leads to difficulty in the voltage‐based state of charge (SOC) estimation. In this study, a facile quench‐assisted solid‐state method is used to prepare a highly crystalline binary Li₄Ti₅O₁₂‐Li₂Ti₃O₇ nanocomposite. While Li₄Ti₅O₁₂ exhibits a sudden voltage rise/drop near the end of its charge/discharge curve, this binary nanocomposite has a tunable sloped voltage profile. The nanocomposite exhibits a unique lamellar morphology consisting of interconnected nanograins of ≈20 nm size with a hierarchical nanoporous structure, contributing to an enhanced rate capability with a capacity of 128 mA h g^?1 at a high C‐rate of 10 C, and excellent cycling stability.     

Empowering Metal Phosphides Anode with Catalytic Attribute toward Superior Cyclability for Lithium‐Ion Storage

Due to high capacity, moderate redox voltage, and relatively low polarization, metal phosphides (MPs) attract much attention as viable anode materials for lithium‐ion storage. However, severe capacity decay induced by the poor reversibility of discharge product (Li₃P) in these anodes suppresses their practical applications. Herein, it is first revealed that N‐doped carbon can effectively catalyze the oxidation of Li₃P by density functional theory calculations and activation experiments. By anchoring Ni₂P nanoparticles on N‐doped carbon sheets (Ni₂P@N‐C) via a facile method, an MP‐based anode rendered with a catalytic attribute is successfully fabricated for improving the reversibility of Li₃P during lithium‐ion storage. Benefiting from this design, not only can high capacity and rate performance be reached, but also an extraordinary cyclability and capacity retention be realized, which is the best among all other phosphides reported so far. By employing such a Ni₂P@N‐C composite and a commercialized active carbon as the anode and cathode, respectively, hybrid lithium‐ion capacitors can be fabricated with an ultrahigh energy density of 80 Wh kg^?1 at a power density of 12.5 kW kg^?1. This strategy of designing electrodes may be generalized to other energy storage systems whose cycling performance needs to be improved.     

High Reversible Pseudocapacity in Mesoporous Yolk–Shell Anatase TiO2/TiO2(B) Microspheres Used as Anodes for Li‐Ion Batteries

As an anode material for lithium‐ion batteries, titanium dioxide (TiO₂) shows good gravimetric performance (336 mAh g^?1 for LiTiO₂) and excellent cyclability. To address the poor rate behavior, slow lithium‐ion (Li⁺) diffusion, and high irreversible capacity decay, TiO₂ nanomaterials with tuned phase compositions and morphologies are being investigated. Here, a promising material is prepared that comprises a mesoporous “yolk–shell” spherical morphology in which the core is anatase TiO₂ and the shell is TiO₂(B). The preparation employs a NaCl‐assisted solvothermal process and the electrochemical results indicate that the mesoporous yolk–shell microspheres have high specific reversible capacity at moderate current (330.0 mAh g^?1 at C/5), excellent rate performance (181.8 mAh g^?1 at 40C), and impressive cyclability (98% capacity retention after 500 cycles). The superior properties are attributed to the TiO₂(B) nanosheet shell, which provides additional active area to stabilize the pseudocapacity. In addition, the open mesoporous morphology improves diffusion of electrolyte throughout the electrode, thereby contributing directly to greatly improved rate capacity.     

Gallium Sulfide–Single‐Walled Carbon Nanotube Composites: High‐Performance Anodes for Lithium‐Ion Batteries

Metal sulfides are an important class of functional materials possessing exceptional electrochemical performance and thus hold great promise for rechargeable secondary batteries. In this work, we deposited gallium sulfide (GaS_x, x = 1.2) thin films by atomic layer deposition (ALD) onto single‐walled carbon nanotube (SWCNT) powders. The ALD GaS_x was performed at 150 °C, and produced uniform and conformal amorphous films. The resulting core‐shell, nanostructured SWCNT‐GaS_x composite exhibited excellent electrochemical performance as an anode material for lithium‐ion batteries (LIBs), yielding a stable capacity of ≈575 mA g^–1 at a current density of 120 mA g^–1 in the voltage window of 0.01–2 V, and an exceptional columbic efficiency of >99.7%. The GaS_x component of the composite produced a specific capacity of 766 mA g^–1, a value two times that of conventional graphite anodes. We attribute the excellent electrochemical performance of the composite to four synergistic effects: 1) the uniform and conformal ALD GaS_x coating offers short electronic and Li‐ion pathways during cycling; 2) the amorphous structure of the ALD GaS_x accommodates stress during lithiation‐delithiation processes; 3) the mechanically robust SWCNT framework also accommodates stress from cycling; 4) the SWCNT matrix provides a continuous, high conductivity network.     

A Mixed Lithium‐Ion Conductive Li2S/Li2Se Protection Layer for Stable Lithium Metal Anode

Constructing artificial solid‐electrolyte interphase (SEI) on the surface of Li metal is an effective approach to improve ionic conductivity of surface SEI and buffer Li dendrite growth of Li metal anode. However, constructing of homogenous ideal artificial SEI is still a great challenge. Here, a mixed lithium‐ion conductive Li₂S/Li₂Se (denoted as LSSe) protection layer, fabricated by a facile and inexpensive gas–solid reaction, is employed to construct stable surface SEI with high ionic conductivity. The Li₂S/Li₂Se‐protected Li metal (denoted as LSSe@Li) exhibits a stable dendrite‐free cycling behavior over 900 h with a high lithium stripping/plating capacity of 3 mAh cm^?2 at 1.5 mA cm^?2 in the symmetrical cell. Compared to bare Li anode, full batteries paired with LiFePO₄, sulfur/carbon, and LiNi_0.6Co_0.2Mn_0.2O₂ cathodes all present better battery cycling and rate performance when LSSe@Li anode is used. Moreover, Li₂Se exhibits a lower lithium‐ion migration energy barrier in comparison with Li₂S which is proved by density functional theory calculation.     

Nanostructured Li2MnSiO4/C Cathodes with Hierarchical Macro‐/Mesoporosity for Lithium‐Ion Batteries

Li₂MnSiO₄/C nanocomposite with hierarchical macroporosity is prepared with poly(methyl methacrylate) (PMMA) colloidal crystals as a sacrificial hard‐template and water‐soluble phenol‐formaldehyde (PF) resin as the carbon source. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) analyses confirm that the periodic macropores are ≈400 nm in diameter with 20–40 nm walls comprising Li₂MnSiO₄/C nanocrystals that produce additional large mesopores (< 30 nm) between the nanocrystals. The nanostructured Li₂MnSiO₄/C cathode exhibits a high reversible discharge capacity of 200 mAh g^?1 at C/10 (16 mA g^?1) rate at 1.5–4.8 V at 45 °C. Although the discharge capacity can be further increased on operating at 55 °C, the sample exhibits a relatively fast capacity fade at 55 °C, which can be partially solved by simply narrowing the voltage window to avoid side reactions of the electrolyte. The good performance of the Li₂MnSiO₄/C cathodes is attributed to the unique macro‐/mesostructure of the silicate coupled with uniform carbon coating.     

Fe3O4 Nanoparticles Confined in Mesocellular Carbon Foam for High Performance Anode Materials for Lithium‐Ion Batteries

Fe₃O₄ nanocrystals confined in mesocellular carbon foam (MSU‐F‐C) are synthesized by a “ host–guest ” approach and tested as an anode material for lithium‐ion batteries (LIBs). Briefly, an iron oxide precursor, Fe(NO₃)₃·9H₂O, is impregnated in MSU‐F‐C having uniform cellular pores ～30 nm in dia­meter, followed by heat‐treatment at 400 °C for 4 h under Ar. Magnetite Fe₃O₄ nanocrystals with sizes between 13–27 nm are then successfully fabricated inside the pores of the MSU‐F‐C, as confirmed by transmission electron microscopy (TEM), dark‐field scanning transmission electron microscopy (STEM), energy dispersive X‐ray spectroscopy (EDS), X‐ray diffraction (XRD), and nitrogen sorption isotherms. The presence of the carbon most likely allows for reduction of some of the Fe³⁺ ions to Fe²⁺ ions via a carbothermoreduction process. A Fe₃O₄/MSU‐F‐C nanocomposite with 45 wt% Fe₃O₄ exhibited a first charge capacity of 1007 mA h g^?1 (Li⁺ extraction) at 0.1 A g^?1 (～0.1 C rate) with 111% capacity retention at the 150^th cycle, and retained 37% capacity at 7 A g^?1 (～7 C rate). Because the three dimensionally interconnected open pores are larger than the average nanosized Fe₃O₄ particles, the large volume expansion of Fe₃O₄ upon Li‐insertion is easily accommodated inside the pores, resulting in excellent electrochemical performance as a LIB anode. Furthermore, when an ultrathin Al₂O₃ layer (<4 Å) was deposited on the composite anode using atomic layer deposition (ALD), the durability, rate capability and undesirable side reactions are significantly improved.     

Quaternary Diamond‐Like Chalcogenidometalate Networks as Efficient Anode Material in Lithium‐Ion Batteries

An improvement of lithium‐ion batteries with regard to their reversible capacity, cycling stability, rate performance, and safety under repetitive charge and discharge still requires considerable research activity. However, graphite has remained the unexcelled material for the anode so far. Here, it is shown that two novel quaternary lithium‐chalcogenidometalate phases, Li₄MnGe₂S₇ ( 1 ) and Li₄MnSn₂Se₇ ( 2 ), represent very promising new anode materials for lithium‐ion cells in that they achieve specific lithium storage capacities higher than that of the commercially used graphite, and display an excellent stability during cycling. These properties are based on the structural peculiarities of the phases, which adopt Wurtzite‐related topologies and provide high structural flexibility of the metal sulfide or selenide bonds as advantageous pre‐requisitions for a large ion accessible volume.     

Sustainable Separators for High‐Performance Lithium Ion Batteries Enabled by Chemical Modifications

Natural polymer nanofibers are attractive sustainable raw materials to fabricate separators for high‐performance lithium ion batteries (LIBs). Unfortunately, complicated pore‐forming processes, low ionic conductivity, and relatively low mechanical strength of previously reported natural polymer nanofiber‐based separators severely limit their performances and applications. Here, a chemical modification strategy to endow high performance to natural polymer nanofiber‐based separators is demonstrated by grafting cyanoethyl groups on the surface of chitin nanofibers. The fabricated cyanoethyl‐chitin nanofiber (CCN) separators not only exhibit much higher ionic conductivity but also retain excellent mechanical strength in comparison to unmodified chitin nanofiber separators. Through density function theory calculations, the mechanism of high Li⁺ ion transport in the CCN separator is unraveled as weakening of the binding of Li⁺ ions over that of PF₆^? ions with chitin, via the cyanoethyl modification. The LiFePO₄/Li₄Ti₅O₁₂ full cells using CCN separators show much better rate capability and enhanced capacity retention compared to the cell using commercial polypropylene (PP) separators. Beyond this, the CCN separator can work very well even at an elevated temperature of 120 °C in the LiFePO₄/Li cell. The proposed strategy chemical modification of natural polymer nanofibers will open a new avenue to fabricate sustainable separators for LIBs with superior performance.     

A Molecular‐Cage Strategy Enabling Efficient Chemisorption–Electrocatalytic Interface in Nanostructured Li2S Cathode for Li Metal‐Free Rechargeable Cells with High Energy

Using high‐capacity and metallic Li‐free lithium sulfide (Li₂S) cathodes offers an alternative solution to address serious safety risks and performance decay caused by uncontrolled dendrite hazards of Li metal anodes in next‐generation Li metal batteries. Practical applications of such a cathode, however, still suffer from low redox activity, unaffordable cost, and poor processability of infusible and moisture‐sensitive Li₂S. Herein, these difficulties are addressed by developing a molecular cage–engaged strategy that enables low‐cost production and interfacial engineering of Li₂S cathodes for rechargeable Li₂S//Si cells. An efficient chemisorption–electrocatalytic interface is built in extremely nanostructured Li₂S cathodes by harnessing the confinement/separation effect of metal–organic molecular cages on ionic clusters of air‐stable, soluble, and low‐cost Li salt and their chemical transformation. It effectively boosts the redox activity toward Li₂S activation/dissociation and polysulfide chemisorption–conversion in Li‐S batteries, leading to low activation voltage barrier, stable cycle life of 1000 cycles, ultrafast current rate up to 8 C, and high areal capacities of Li₂S cathodes with high mass loading. Encouragingly, this highly active Li₂S cathode can be applied for constructing truly workable Li₂S//Si cells with a high specific energy of 673 Wh kg^?1 and stable performance for 200 cycles at high rates against hollow nanostructured Si anode.     

Enhanced Interfacial Stability of Hybrid‐Electrolyte Lithium‐Sulfur Batteries with a Layer of Multifunctional Polymer with Intrinsic Nanoporosity

The use of lithium‐ion conductive solid electrolytes offers a promising approach to address the polysulfide shuttle and the lithium‐dendrite problems in lithium‐sulfur (Li‐S) batteries. One critical issue with the development of solid‐electrolyte Li‐S batteries is the electrode–electrolyte interfaces. Herein, a strategic approach is presented by employing a thin layer of a polymer with intrinsic nanoporosity (PIN) on a Li⁺‐ion conductive solid electrolyte, which significantly enhances the ionic interfaces between the electrodes and the solid electrolyte. Among the various types of Li⁺‐ion solid electrolytes, NASICON‐type Li_1+xAl_xTi_2‐x(PO₄)₃ (LATP) offers advantages in terms of Li⁺‐ion conductivity, stability in ambient environment, and practical viability. However, LATP is susceptible to reaction with both the Li‐metal anode and polysulfides in Li‐S batteries due to the presence of easily reducible Ti⁴⁺ ions in it. The coating with a thin layer of PIN presented in this study overcomes the above issues. At the negative‐electrode side, the PIN layer prevents the direct contact of Li‐metal with the LATP solid electrolyte, circumventing the reduction of LATP by Li metal. At the positive electrode side, the PIN layer prevents the migration of polysulfides to the surface of LATP, preventing the reduction of LATP by polysulfides.