Carbon materials for stable Li metal anodes: Challenges, solutions, and outlook

Lithium(Li)metal is regarded as the ultimate anode for next-generation Li-ion batteries due to its highest specific capacity and lowest electrochemical potential.However,the Li metal anode has limitations,including virtually infinite volume change,nonuniform Li deposition,and an unstable electrode-electrolyte interface,which lead to rapid capacity degradation and poor cycling stability,significantly hindering its practical application.To address these issues,intensive efforts have been devoted toward accommodating and guiding Li deposition as well as stabilizing the interface using various carbon materials,which have demonstrated excellent effectiveness,benefiting from their vast variety and excellent tunability of the structure-property relationship.This review is intended as a guide through the fundamental challenges of Li metal anodes to the corresponding solutions utilizing carbon materials.The specific functionalities and mechanisms of carbon materials for stabilizing Li metal anodes in these solutions are discussed in detail.Apart from the stabilization of the Li metal anode in liquid electrolytes,attention has also been paid to the review of anode-free Li metal batteries and solid-state batteries enabled by strategies based on carbon materials.Furthermore,we have reviewed the unresolved challenges and presented our outlook on the implementation of carbon materials for stabilizing Li metal anodes in practical applications.

Ultrasmall CoS nanoparticles embedded in heteroatom-doped carbon for sodium-ion batteries and mechanism explorations via synchrotron X-ray techniques

Transition metal sulfides have been regarded as promising anode materials for sodium-ion batteries(SIB).However,they face the challenges of poor electronic conductivity and large volume change,which result in capacity fade and low rate capability.In this work,a composite containing ultrasmall CoS(~7 nm)nanoparticles embedded in heteroatom(N,S,and O)-doped carbon was synthesized by an efficient one-step sulfidation process using a Co(Salen)precursor.The ultrasmall CoS nanoparticles are beneficial for mechanical stability and shortening Na-ions diffusion pathways.Furthermore,the N,S,and O-doped defect-rich carbon provides a robust and highly conductive framework enriched with active sites for sodium storage as well as mitigates volume expansion and polysulfide shuttle.As anode for SIB,CoS@HDC exhibits a high initial capacity of 906 mA h g^(-1)at 100 mA g^(-1)and a stable long-term cycling life with over 1000 cycles at 500 mA g^(-1),showing a reversible capacity of 330 mA h g^(-1).Meanwhile,the CoS@HDC anode is proven to maintain its structural integrity and compositional reversibility during cycling.Furthermore,Na-ion full batteries based on the CoS@HDC anode and Na_(3)V_(2)(PO_(4))_(3)cathode demonstrate a stable cycling behavior with a reversible specific capacity of~200 m A h g^(-1)at least for 100 cycles.Moreover,advanced synchrotron operando X-ray diffraction,ex-situ X-ray absorption spectroscopy,and comprehensive electrochemical tests reveal the structural transformation and the Co coordination chemistry evolution of the CoS@HDC during cycling,providing fundamental insights into the sodium storage mechanism.

Porous nitrogen-enriched hollow carbon nanofibers as freestanding electrode for enhanced lithium storage

Onedimensional porous carbons bearing high surface areas and sufficient heteroatom doped functionalities are essential for advanced electrochemical energy storage devices,especially for developing freestanding film electrodes.Here we develop a porous,nitrogenenriched,freestanding hollow carbon nanofiber(PNFHCF)electrode material via filtration of polypyrrole(PPy)hollow nanofibers formed by in situ selfdegraded templateassisted strategy,followed by NH3assisted carbonization.The PNFHCF retains the freestanding film morphology that is composed of threedimensional networks from the entanglement of 1D nanofiber and delivers 3.7fold increase in specific surface area(592 m^(2)g^(-1))compared to the carbon without NH_(3)treatment(FHCF).In spite of the enhanced specific surface area,PNFHCF still exhibits comparable high content of surface N functionalities(8.8%,atom fraction)to FHCF.Such developed hierarchical porous structure without sacrificing N doping functionalities together enables the achievement of high capacity,highrate property and good cycling stability when applied as selfsupporting anode in lithiumion batteries,superior to those of FHCF without NH3 treatment.

Architecture engineering of carbonaceous anodes for high-rate potassium-ion batteries

The limited lithium resource in earth's crust has stimulated the pursuit of alternative energy storage technologies to lithium-ion battery.Potassium-ion batteries(KIBs)are regarded as a kind of promising candidate for large-scale energy storage owing to the high abundance and low cost of potassium resources.Nevertheless,further development and wide application of KIBs are still challenged by several obstacles,one of which is their fast capacity deterioration at high rates.A considerable amount of effort has recently been devoted to address this problem by developing advanced carbonaceous anode materials with diverse structures and morphologies.This review presents and highlights how the architecture engineering of carbonaceous anode materials gives rise to high-rate performances for KIBs,and also the beneficial conceptions are consciously extracted from the recent progress.Particularly,basic insights into the recent engineering strategies,structural innovation,and the related advances of carbonaceous anodes for high-rate KIBs are under specific concerns.Based on the achievements attained so far,a perspective on the foregoing,and proposed possible directions,and avenues for designing high-rate anodes,are presented finally.

Mixed phase sodium manganese oxide as cathode for enhanced aqueous zinc-ion storage

Aqueous zinc-ion batteries have been regarded as a promising alternative to large-scale energy storage, due to associated low-cost, improved safety and environmental friendliness. However, a high-performance cathode material for both rate capability and specific capacity is still a challenge. One kind of the more promising candidates are sodium manganese oxide(NMO) materials, although they suffer from individual issues and need to be further improved. Herein, we present a novel mixed phase NMO material composed of nearly equal amounts of Na(0.55)Mn2O4 and Na(0.7)MnO(2.05). The structured configuration with particle size of 200–500 nm is found to be beneficial towards improving the ion diffusion rate during the charge/discharge process. Compared with Na(0.7)MnO(2.05) and Na(0.55)Mn2O4, the mixed phase NMO demonstrates an enhanced rate capability and excellent long-term cycling stability with a capacity retention of 83% after 800 cycles. More importantly, the system also delivers an impressive energy density and power density, as 378 W·h·kg^-1 at 68.7 W·kg^-1, or 172 W·h·kg^-1 at 1705 W·kg^-1. The superior electrochemical performance is ascribed to the fast Zn^2+ diffusion rate because of a large ratio of capacitive contribution(63.9% at 0.9 m V·s^-1). Thus, the mixed phase route provides a novel strategy to enhance electrochemical performance, enabling mixed phase NMO as very promising material towards large-scale energy-storage applications.

Vanadium oxide cathode with synergistic engineering of calcium-ion intercalation and polyaniline coating for high performance zinc-ion batteries

Vanadium oxides as cathode for zinc-ion batteries have attracted much attention because of their high theoretical capacity,flexible layered structure and abundant resources.However,cathodes are susceptible to the collapse of their layered structure and the dissolution of vanadium after repeated long cycles,which worsen their capacities and cycling stabilities.Herein,a synergistic engineering of calcium-ion intercalation and polyaniline coating was developed to achieve the superior electrochemical performance of vanadium pentoxide for zinc-ion batteries.The pre-intercalation of calcium-ion between vanadium pentoxide layers as pillars increase the crystal structure’s stability,while the polyaniline coating on the cathodes improves the conductivity and inhibits the dissolution of vanadium.This synergistic engineering enables that the battery system based-on the polyaniline coated calcium vanadate cathode to deliver a high capacity of 406.4 mAh·g^(−1)at 1 A·g^(−1),an ultralong cycle life over 6000 cycles at 10 A·g^(−1)with 93%capacity retention and high-rate capability.The vanadium oxide cathode with synergistic engineering of calcium-ion intercalation and polyaniline coating was verified to effectively improve the electrochemical performance of zinc-ion batteries.

Freestanding MXene-based macroforms for electrochemical energy storage applications

Freestanding MXene-based macroforms have gained significant attention as versatile components in electrochemical energy storage applications owing to their interconnected conductive network,strong mechanical strength,and customizable surface chemistries derived from MXene nanosheets.This comprehensive review article encompasses key aspects related to the synthesis of MXene nanosheets,strategies for structure design and surface medication,surface modification,and the diverse fabrication methods employed to create freestanding MXene-based macroform architectures.The review also delves into the recent advancements in utilizing freestanding MXene macroforms for electrochemical energy storage applications,offering a detailed discussion on the significant progress achieved thus far.Notably,the correlation between the macroform’s structural attributes and its performance characteristics is thoroughly explored,shedding light on the critical factors influencing efficiency and durability.Despite the remarkable development,the review also highlights the existing challenges and presents future perspectives for freestanding MXenebased macroforms in the realms of high-performance energy storage devices.By addressing these challenges and leveraging emerging opportunities,the potential of freestanding MXene-based macroforms can be harnessed to enable groundbreaking advancements in the field of energy storage.

自支撑碳基柔性超级电容器电极材料研究进展

为了驱动柔性电子设备和传感器工作,急需探索具有高电化学性能和优异力学性能的柔性超级电容器。自支撑电极在柔性超级电容器中起着至关重要的作用。独立自支撑碳基电极因其高导电性、重量轻、孔隙率可调、表面积可调、易于功能化和优异的力学性能而被广泛应用于柔性超级电容器。此外,碳基电极还具有来源丰富,成本低廉等优势。本综述系统总结了基于各种炭材料的独立自支撑碳基电极在柔性超级电容器中的最新进展,并讨论了独立自支撑碳基电极在柔性超级电容器商业化过程中的挑战和未来机遇。

Freestanding strontium vanadate/carbon nanotube films for long-life aqueous zinc-ion batteries

Aqueous rechargeable zinc-ion battery(ZIB)is considered to be a potential energy storage system for large-scale applications due to its environmental friendliness,high safety,and low cost.However,it remains challenging to develop suitable cathode materials with high specific capacity and long-term cyclic stability.Herein,we have fabricated freestanding Sr0.19V2O51.3H2O/carbon nanotubes(SrVO/CNTs)composite films with different mass ratios by incorporating SrVO into CNTs network.The synthesized SrVO possesses a large interlayer spacing of 1.31 nm,which facilitates Zn(2+)diffusion.Furthermore,the SrVO/CNTs composite film with conductive network structure promotes electron transfer and ensures good contact between SrVO and CNTs during the long-term cycling process.As a result,the battery based on the SrVO/CNTs composite cathode with a mass ratio of 7:3 delivers a specific capacity of 326 mAh·g^(-1)at 0.1 A·g^(-1)and 145 mAh·g^(-1)at 5 A·g^(-1),demonstrating a high capacity and excellent rate capability.Remarkably,the assembled ZIB shows good capacity retention of 91%even after ultra-long cycling for 7500 cycles at a high current rate of 5 Ag^(-1).More importantly,the battery also delivers a high energy density and power density,as 290 Wh·kg^(-1)at 125 W·kg^(-1)(0.1 A·g^(-1)),or 115 Wh·kg^(-1)at 6078 W·kg^(-1)(5 Ag^(-1)).The results demonstrate that the SrVO/CNTs composite is a promising cathode toward large-scale energy storage applications.

High ionic conductive protection layer on Zn metal anode for enhanced aqueous zinc-ion batteries

Aqueous zinc-ion batteries(ZIBs)has been regarded as a promising energy storage system for large-scale application due to the advantages of low cost and high safety.However,the growth of Zn dendrite,hydrogen evolution and passivation issues induce the poor electrochemical performance of ZIBs.Herein,a Na_(3)Zr_(2)Si_(2)PO_(12)(NZSP)protection layer with high ionic conductivity of 2.94 m S/cm on Zn metal anode was fabricated by drop casting approach.The protection layer prevents Zn dendrites formation,hydrogen evolution as well as passivation,and facilitates a fast Zn~(2+)transport.As a result,the symmetric cells based on NZSP-coated Zn show a stable cycling over 1360 h at 0.5 m A/cm^(2)with 0.5 m Ah/cm^(2) and 1000 h even at a high current density of 5 m A/cm^(2) with 2 m Ah/cm^(2).Moreover,the full cells combined with V_(2)O_(5)-based cathode displays high capacities and high rate capability.This work offers a facile and effective approach to stabilizing Zn metal anode for enhanced ZIBs.

From non-carbon host toward carbon-free lithium-sulfur batteries

Lithium-sulfur(Li-S)batteries with advantages of high energy densities(2600 Wh·kg^(-1)/2800 Wh·L^(-1))and sulfur abundance are regarded as promising candidates for next-generation high-energy batteries.However,the conventional carbon host used in sulfur cathodes suffers from poor chemical adsorption towards Li-polysulfides(LPS)in liquid electrolyte and sluggish redox kinetics,leading to low capacity and rate capability.Besides,carbon host used in Li metal anode with the intrinsic property of poor lithiophilicity and high Li-nucleation barrier gives rise to uncontrollable dendrite growth and further battery failure.Therefore,non-carbon hosts with chemical adsorption toward LPS and catalytic activity for accelerating LPS redox conversion as well as lithiophilic property for guiding uniform Li deposition are proposed and demonstrated a high efficiency in both sulfur cathodes and Li metal anodes.In this review,the principle and challenges of Li-S batteries are first presented,then recent work using non-carbon hosts in Li-S batteries is summarized comprehensively,and the mechanism of non-carbon host in improving sulfur utilization and stabilizing Li metal anode is discussed in detail.Furthermore,remaining challenges and outlook on the implementation of non-carbon host for practical carbon-free Li-S batteries are also provided.

Achieving exceptional wear resistance in a crack-free high-carbon tool steel fabricated by laser powder bed fusion without pre-heating

Laser powder bed fusion(LPBF)for the fabrication of dense components used for tooling applications,is highly challenging.Residual stresses,which evolve in the additively manufactured part,are inherent to LPBF processing.An additional stress contribution in high-carbon steels arises from the austenite-to-martensite phase transformation,which may eventually lead to cracking or even delamination.As an alternative to pre-heating the base plate,which is not striven by industry,lowering the martensite content which forms in the part,is essential for the fabrication of dense parts by LPBF of high-carbon tool steels which are then adapted to LPBF.In this study,a successful strategy demonstrates the processing of the Fe85Cr4Mo1V1W8C1(wt%)high-carbon steel by LPBF into dense parts(99.8%).The hierarchical microstructure consists of austenitic and martensitic grains separated by elemental segregations in which nanoscopic carbide particles form a network.A high density of microsegregation was observed at the molten pool boundary ultimately forming a superstructure.The LPBF-fabricated steel shows a yield strength,ultimate compressive stress,and total strain of 1210 MPa,3556 MPa,and 27.4%,respectively.The mechanical and wear performance is rated against the industrially employed and highly wear-resistant 1.2379 tool steel taken as the reference.Despite its lower macro-hardness,the LPBF steel(58.6 HRC,0.0061 mm^(3) Nm^(-1))shows a higher wear resistance than the reference steel(62.6 HRC,0.0078 mm^(3) Nm^(-1)).This behavior results from the wear-induced formation of martensite in a microscale thick layer directly at the worn surface,as it was proven via high-energy X-ray diffraction mapping.