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An integrated composite architecture composed of N/P codoped porous carbon sheets and embedded Ni2P NPs (Ni2P⊂N/P-CNS) was synthesized by a self-template strategy and demonstrated superior electrochemical performance as alkali ion battery anode.

Zn metal anode is believed to be a promising anode material for aqueous Zn-ion batteries (ZIBs) due to the merits such as low electrochemical potential, low cost, high theoretical specific capacity, high hydrogen evolution overpotential, less-reactive property, environmental friendliness and easy processing. However, issues including uncontrollable growth of Zn dendrites, corrosion by aqueous electrolyte, large volume change and unstable interface hinder its further development. Recently, multifunctional metal-organic frameworks (MOFs) and their derivatives have shown huge advantages in solving the issues facing Zn metal anode, and large advances have been achieved. MOFs and their derivatives can stabilize Zn metal anode by interface engineering, designing host, decorating separator, constructing solid-state electrolyte and so on. Here we carefully summarize and analyse these advances. Meanwhile, some perspectives and outlooks are put forward. This review can promote the development of MOFs, Zn metal anode as well as aqueous ZIBs.

Immobilizing primary electroactive nanomaterials in porous carbon matrix is an effective approach for boosting the electrochemical performance of potassium-ion batteries (PIBs) because of the synergy among functional components. Herein, an integrated hybrid architecture composed of ultrathin Cu3P nanoparticles (~20 nm) confined in porous carbon nanosheets (Cu3P⊂NPCSs) as a new anode material for PIBs is synthesized through a rational self-designed self-templating strategy. Benefiting from the unique structural advantages including more active heterointerfacial sites, intimate and stable electrical contact, effectively relieved volume change, and rapid K+ ion migration, the Cu3P⊂NPCSs indicate excellent potassium-storage performance involving high reversible capacity, exceptional rate capability, and cycling stability. Moreover, the strong adsorption of K+ ions and fast potassium-ion reaction kinetics in Cu3P⊂NPCSs is verified by the theoretical calculation investigation. Noted, the intercalation mechanism of Cu3P to store potassium ions is, for the first time, clearly confirmed during the electrochemical process by a series of advanced characterization techniques.

With the advantages of a high theoretical capacity, proper working voltage, and abundant reserves, silicon (Si) is regarded as a promising anode for lithium-ion batteries. However, huge volume expansion and low electronic conductivity impede the commercialization of Si anodes. We devised a one-step, vacuum-assisted reactive carbon coating technique to controllably produce micrometer-sized nanoporous silicon confined by homogeneous N-doped carbon nanosheet frameworks (NPSi@NCNFs), achieved by the solid state reaction of a commercial bulk precursor and the subsequent evaporation of byproducts. The graphitization degree, C and N contents of the carbon shell, as well as the porosity of Si can be regulated by adjusting the synthetic conditions. A rational structure can mitigate volume expansion to maintain structural integrity, enhance electronic conductivity to facilitate charge transport, and serve as a protected layer to stabilize the solid electrolyte interphase. The NPSi@NCNF anode enables a stable cycling performance with 95.68% capacity retention for 4000 cycles at 5 A g

The development of high-performance biocompatible batteries is pivotal in personalized health-care devices such as pacemakers and neuro-stimulators. We have for the first time developed a one-pot collagen-assisted biomineralization strategy to create hierarchical CuO nanostructures. Recombinant collagen has been demonstrated as an excellent biotemplate to delicately tune the morphologies of copper oxide mesocrystals. The initial formation of Cu(OH)2 nanoneedles gradually turned into leaf-like CuO nanostructures with branched edges and a compact middle during the biomineralization process. The as-prepared leaf-like CuO mesocrystals exhibited an attractive electrochemical performance, and may have great potential as a promising anode material for lithium-ion batteries. Notably, collagen also acts as an excellent functional agent to endow the CuO nanomaterials with high biocompatibility and bioactivity. The environmentally friendly method assisted by collagen provides novel opportunities for the construction of advanced CuO nanomaterials that have a well-controlled morphology, function and electrochemical performance, and which may have promising applications in implantable health-care electronics.

To date, elemental sulfur has been considered as a prospective cathode material for exploring high-energy power systems with low cost and sustainability. However, its practical commercialization has been impeded by inherent drawbacks of notorious capacity decay, unsatisfied insulating nature, and sluggish conversion chemistry. To address these issues, for the first time, freestanding nanofibrous networks with hierarchical nanostructures are facilely constructed by inlaying electrocatalytic bimetallic chalcogenides (FexMn1-xS nanoparticles) into conductive graphene nanosheet (GN)-doped sulfurized polyacrylonitrile (SPAN) fiber matrices. Covalent-bonded SPAN featuring an insoluble mechanism serves as a reliable cathode substrate with enhanced electrostability and high sulfur utilization, while high-surface-area GN dopants promote conductivity improvement and rapid electron transfer. Meanwhile, the results prove that sulfiphilic FexMn1-xS nanoparticles with abundant electrochemically active sites facilitate construction of uniform deposition interfaces and efficient electrocatalysis conversion toward lithium polysufides. This feasible catalytic-insoluble cathode strategy drives the Li-S battery, which exhibits excellent electrochemical performances with a remarkable reversible discharge capacity of 967 mA h g-1 and a capacity retention of 623 mA h g-1 after 500 cycles. Moreover, the corresponding lithiation/delithiation mechanisms are systematically investigated through complementary morphological and spectral analyses, providing valuable insights into advanced metal-sulfur batteries.

Rechargeable zinc(Zn)-based batteries are promising power sources due to their low cost and safety characters. However, Zn dendrites and side reactions restrict the practical application of Zn metal anode. In this work, multifunctional uniform antimony (Sb) nanoarrays are designed and grown on Ti3C2Tx MXene paper. It is found that antimony can reversibly alloy with Zn to form ZnSb phase, which enable antimony as both alloying-type Zn storage material and zincophilic nucleation seed to regulate homogeneous Zn deposition. Optimized freestanding MXene@Sb electrode deliver 299.6 mAh g − 1 capacity over 200 cycles at 50 mA g − 1 based on the formation ZnSb phase and maintain 148.43 mAh g − 1 capacity after 1000 cycles at 500 mA g − 1, proving that zinc can alloy with antimony. Benefiting from the zincophilic antimony seeds and 3D MXene architecture, the MXene@Sb can significantly suppress Zn dendrite and achieve a long cycling life up to 1000 h. This study demonstrates the feasibility of antimony as alloying-type Zn storage anode and provides an effective approach to suppress Zn dendrites.

Owing to its high theoretical capacity, appropriate working potential, abundant resource, intrinsic safety, and low cost, zinc (Zn) metal is regarded as one of the most promising anode candidates for aqueous batteries. However, the hazards caused by dendrite growth and side reactions impede its practical applications. Herein, to solve these problems, a protective heterogeneous layer composed of electronic conductive sulfur-doped three-dimensional (3D) MXene and ionic conductive ZnS on Zn anode is designed and constructed. The sulfur doping and the creation of a 3D structure on MXene are simultaneously achieved during the generation of ZnS. The sulfur-doped 3D MXene can effectively homogenize distribution of electric field, decrease local current density, and alleviate volume change. The ZnS can inhibit side reactions, promote uniform Zn2+ distribution, and accelerate Zn2+ migration. Consequently, a stable and dendrite-free Zn anode is achieved with notable cycling stability up to 1600 h and rate performance. The relationship between structure of protective layer and performance of Zn anode is also probed. With the protected Zn anode and freestanding sulfur-doped 3D MXene@MnO2 cathode, a high-energy, long cycling life, and high-rate full cell is obtained. This work may provide a direction for the design of practical Zn anodes and other metal-based battery systems.

The exploitation of new sulfiphilic and catalytic materials is considered as the promising strategy to overcome severe shuttle effect and sluggish kinetics conversion of lithium polysulfides within lithium-sulfur batteries. Herein, we design and fabricate monodisperse VN ultrafine nanocrystals immobilized on nitrogen-doped carbon hybrid nanosheets (VN@NCSs) via an one-step in-situ self-template and self-reduction strategy, which simultaneously promotes the interaction with polysulfides and the kinetics of the sulfur conversion reactions demonstrated by experimental and theoretical results. By virtue of the multifunctional structural features of VN@NCSs, the cell with ultrathin VN@NCSs (only 5 µm thickness) modified separator indicates improved electrochemical performances with long cycling stability over 1,000 cycles at 2 C with only 0.041% capacity decay per cycle and excellent rate capability (787.6 mAh·g−1 at 10 C). Importantly, it delivers an areal reversible capacity of 3.71 mAh·cm−2 accompanied by robust cycling life.

Rechargeable zinc (Zn)-ion batteries are regarded as highly prospective candidates for next-generation renewable and safe energy storage systems. However, the uncontrolled dendrite growth of the Zn anode impedes their practical application. Here, a scalable and controllable approach is developed for converting commercial titanium (Ti) foil to 3D porous Ti, which retains good resistance to corrosion, high electrical conductivity, and excellent mechanical properties. Benefiting from a spontaneous ultrathin zincophilic titanium dioxide (TiO2) interfacial layer and continuous 3D structure, the 3D porous Ti can act as an effective host to achieve a 3D Ti/Zn metal anode. By ensuring homogeneous nucleation, uniform current distribution, and volume change accommodation, the dendritic growth of 3D Ti/Zn metal anode is effectively inhibited with stable Zn plating/stripping up to 2000 h with low polarization. When conjugated with a 3D sulfur-doped Ti3C2Tx MXene@MnO2 nanotube cathode, a high rate and stable Zn cell is achieved with 95.46% capacity retention after 500 cycles at a high rate of 5 A g-1. This work may also be interesting for researches in porous metals and other battery systems.

The employment of catalytic materials is regarded as the most desirable strategy to cope with sluggish kinetics of lithium polysulfides (LiPSs) transformation and severe shuttle effect within lithium-sulfur batteries (LSBs). Single-atom catalysts (SACs) with 100% atom-utilization possess competitive advantages to serve as both anchoring and electrocatalytic centers for LiPSs. However, it's still a great challenge due to the insufficiency of facile synthetic strategy and ambiguity of the structure-property relationships. Herein, a novel kind of tungsten (W) SAC immobilized on nitrogen-doped graphene (W/NG) with a unique W-O2N2-C coordination configuration and a high W loading of 8.6 wt% is first proposed via a self-template and self-reduction strategy. The special local coordination environment of W atom endows the W/NG with elevated LiPSs adsorption ability and catalytic activity evidenced by combination of experimental and theoretical studies. Impressively, LSBs equipped with W/NG modified separator manifest greatly improved electrochemical performances with high cycling stability over 1000 cycles and ultrahigh rate capability. Moreover, it indicates high areal capacity of 6.24 mAh cm-2 with robust cycling life at a high sulfur mass loading of 8.3 mg cm-2 .

Rechargeable aqueous zinc-ion batteries (AZIBs) have captured a surge of interest in recent years as a promising alternative for scalable energy storage applications owing to the intrinsic safety, affordability, environmental benignity, and impressive electrochemical performance. Despite the facilitated development of this technology by many investigations, however, its smooth implementation is still plagued by inadequate energy density and undesirable life span, which calls for an efficient and controllable cathode storage chemistry. Here, this review focuses on the key bottlenecks by offering a comprehensive summary of representative cathode materials and comparatively analyzing their structural features and electrochemical properties. Then, we critically present several feasible electrode design strategies to guide future research activities from a fundamental perspective for high-energy-density and durable cathode materials mainly in terms of interlayer regulation, defect engineering, multiple redox reactions, activated two-electron reactions, and electrochemical activation and conversion. Finally, we outline the remaining challenges and future perspectives of developing high-performance AZIBs.

Lithium (Li) metal is a “superstar” among all the anode materials for lithium-ion batteries (LIBs) owing to its low electrochemical potential, high theoretical specific capacity, low density, etc. The inherent issues of Li-metal anodes including high chemical activity, uncontrollable growth of Li dendrites, large volume changes, and unstable solid electrolyte interphase (SEI) have been gradually improved in the past several years. However, most of the previous study on Li-metal anodes is performed at room temperature under inert atmosphere. The stability and behavior of Li-metal anode in extreme conditions such as air, water, and high/low temperatures are easy to be ignored. Improving the stability of Li-metal anodes in extreme conditions is meaningful for constructing safe, long-cycling, low-cost, and high-energy Li-metal batteries in all working conditions. Tremendous work has been conducted to enable stable Li-metal anodes in extreme conditions recently. Here we carefully present a review for stable Li-metal anodes in extreme conditions. The backgrounds of Li-metal anodes and strategies for achieving stable Li-metal anodes in extreme conditions are carefully summarized. Meanwhile, we proposed some outlooks and perspectives. We hope this review can make more researchers pay attention to Li-metal anodes in extreme conditions.

Lithium metal (Li) is believed to be the ultimate anode for lithium-ion batteries (LIBs) owing to the advantages of high theoretical capacity, the lowest electrochemical potential, and light weight. Nevertheless, issues such as uncontrollable growth of Li dendrites, large volume changes, high chemical reactivity, and unstable solid electrolyte interphase (SEI) hinder its rapid development and practical application. Herein a stable and dendrite-free Li-metal anode is obtained by designing a flexible and freestanding MXene/COF framework for metallic Li. COF-LZU1 microspheres are distributed among the MXene film framework. Lithiophilic COF-LZU1 microspheres as nucleation seeds can promote uniform Li nucleation by homogenizing the Li+ flux and lowering the nucleation barrier, finally resulting in dense and dendrite-free Li deposition. Under the regulation of the COF-LZU1 seeds, the Coulombic efficiency of the MXene/COF-LZU1 framework and electrochemical stability of corresponding symmetric cells are obviously enhanced. Li-S full cells with the modified Li-metal anode and sulfurized polyacrylonitrile (S@PAN) cathode also exhibited a superior electrochemical performance.

To maintain the tendency towards lower cost and sustainability of innovative battery technologies, one challenge is the development of high-energy ecofriendly devices based on the potassium–sulfur (K–S) system using efficient sulfur-based cathodes. A free-standing flexible carbon nanotube/sulfur (CNT/S) composite cathode based on CNT film to form a conductive network on a sulfur substrate is proposed herein. The synthesized CNT/S composite takes advantages of the intercrossing microchannels of the conductive CNT networks, which clearly favors rapid charge transfer and enhanced active mass loading as well as the surface electrocatalytic effect in K–S batteries. The resulting self-supported CNT/S film cathode with high flexibility achieved high initial capacity of 585 mAh g−1 at current density of 50 mA g−1. The proposed CNT/S cathode system could thus be a promising candidate for further advancement of next-generation K–S power systems for practical applications.

The high reactivity between lithium metal and traditional carbonate electrolytes is a great obstacle to realize the long-term cycling ability of lithium metal batteries. Ether-based electrolytes have good stability toward lithium metal anodes. However, the oxidation stability of ether-based electrolytes is generally lower than 4 V, which limits the application of high-voltage (>4 V) cathodes and restricts the energy density. The high flammability of ether is another key issue that hinders the commercialization of ether-based electrolytes. To address these issues, herein, we report a high-voltage, nonflammable ether-based electrolyte with F-, N-, and P-rich hexafluorocyclotriphosphazene (HFPN) as a cosolvent. HFPN can not only act as a highly efficient flame-retarding agent but also form a dense and homogeneous solid electrolyte interphase (SEI) layer rich in LiF and Li3N on the lithium metal anode, which stabilizes the lithium/electrolyte interface and inhibits the formation of lithium dendrites. Moreover, the HFPN-based electrolyte has a wider potential window than 4 V. As a result, with this electrolyte, high-voltage lithium metal batteries exhibit a capacity retention of ∼95% after 100 cycles. This study may provide a new pathway for developing safe, high-energy, and dendrite-free lithium metal batteries.

Lithium (Li) metal is a promising anode for next-generation high-energy-density lithium-ion batteries (LIBs). Nevertheless, the stability of Li-metal anode is poor due to the severe corrosion by liquid electrolyte, uncontrollable growth of Li dendrites, huge volume expansion, and unstable solid electrolyte interphase (SEI). The high chemical reactivity of Li metal is the main inducement for the unstability of Li-metal anode. Herein, the stability of Li-metal anode is improved by passivating its surface with 3°C GaInSnZn liquid metal (LM). A Li-based alloy framework with submicron-scale grains is formed on the surface of Li metal through the spontaneous reaction between metallic Li and LM at room temperature. The Li-based alloy framework is tightly attached on Li metal without exfoliation and mechanical rupture even under bending and folding. The framework has higher Li+ diffusion coefficient, lower chemical reactivity, and better lithiophilicity than pure Li. Under the regulation of the multifunctional framework, the corrosion, uneven Li deposition, and unstable interface are effectively relieved even in a more corrosive carbonate-based electrolyte. When paired with 5 V-class cathodes, the full cells with passivated Li-metal anodes exhibit superior electrochemical performances. This passivation strategy also shows great potentials for high-reactive Na-metal and K-metal anodes.

γ-MnO2 nanomaterials play an essential role in the development of advanced electrochemical energy storage and conversion devices with versatile industrial applications. Herein, novel dandelion-like hollow microspheres of γ-MnO2 mesocrystals have been fabricated for the first time by a one-pot biomineralization route. Recombinant collagen with unique rod-like structure has been demonstrated as a robust template to tune the morphologies of γ-MnO2 mesocrystals, and a very low concentration of collagen can alter the nanostructures of γ-MnO2 from nanorods to microspheres. The as-prepared γ-MnO2 mesocrystals formed well-ordered hollow microspheres composed of delicate nanoneedle-like units. Among all the reported γ-MnO2 with various nanostructures, the γ-MnO2 microspheres showed the most prowess to maintain high discharge capacities after 100+ cycles. The superior electrochemical performance of γ-MnO2 likely results from its unique hierarchical micro-nano structure. Notably, the γ-MnO2 mesocrystals display high biocompatibility and cellular activity. Collagen plays a key dual role in mediating the morphology as well as endowing the biofunction of the γ-MnO2 mesocrystals. This environmentally friendly biomineralization approach using rod-like collagen as the template, provides unprecedented opportunity for the production of novel nanostructured metal oxides with superior biocompatibility and electrochemical performance, which have great potential in advanced implantable and wearable health-care electronic devices.

Lithium–sulfur batteries (LSBs) are regarded as a competitive next-generation energy storage device. However, their practical performance is seriously restricted due to the undesired polysulfides shuttling. Herein, a multifunctional interlayer composed of paper-derived carbon (PC) scaffold, Fe3O4 nanoparticles, graphene, and graphite sheets is designed for applications in LSBs. The porous PC skeleton formed by the interweaving long-fibers not only facilitates fast transfer of Li ions and electrons but also provides a physical barrier for the polysulfide shuttling. The secondary Fe3O4@graphene component can reduce the polarization, boost the attachment of polysulfides, and promote the charging-discharging kinetics. The outer graphitic sheets layers benefit the interfacial electrochemistry and the utilization of S-containing species. The efficient obstruction of polysulfides diffusion is further witnessed via in situ ultraviolet-visible characterization and first-principles simulations. When 73% sulfur/commercial acetylene black is used as the cathode, the cell exhibits excellent capacity retention with high capacities at 0.5 C for 1000 cycles and even up to 10 C for 500 cycles, an ultrahigh rate capability up to 10 C (478 mAh g−1), and a high areal-sulfur loading of 8.05 mg cm−2. The strategy paves the way for developing multifunctional composites for LSBs with superior performance.

Silicon has been considered as the most promising anode candidate for next-generation lithium-ion batteries. However, the fast capacity decay caused by huge volume expansion and low electronic conductivity limit the electrochemical performance. Herein, atomic distributed, air-stable, layer-by-layer-assembled Si/C (L-Si/C) is designed and in situ constructed from commercial micron-sized layered CaSi2 alloy with the greenhouse gas CO2. The inner structure of Si as well as the content and graphitization of C can be regulated by simply adjusting the reaction conditions. The rationally designed layered structure can enhance electronic conductivity and mitigate volume change without disrupting the carbon layer or destroying the solid electrolyte interface. Moreover, the single-layer Si and C can enhance lithium-ion transport in active materials. With these advantages, L-Si/C anode delivers an 82.85% capacity retention even after 3200 cycles and superior rate performance. The battery-capacitance dual-model mechanism is certified via quantitative kinetics measurement. Besides, the self-standing architecture is designed via assembling L-Si/C and MXene. Lithiophilic L-Si/C can guide homogeneous Li deposition with alleviated volume change. With the MXene/L-Si/C host for lithium-metal batteries, an ultralong life span up to 500 h in a carbonate-based electrolyte is achieved. A full cell with a high-energy 5 V LiNi0.5Mn1.5O4 cathode is constructed to verify the practicality of L-Si/C and MXene/L-Si/C. The rational design of a special layer structure may propose a strategy for other materials and energy storage systems.