Recently,rechargeable aqueous zinc-based batteries using manganese oxide as the cathode(e.g.,MnO_(2))have gained attention due to their inherent safety,environmental friendliness,and low cost.Despite their potential,a...Recently,rechargeable aqueous zinc-based batteries using manganese oxide as the cathode(e.g.,MnO_(2))have gained attention due to their inherent safety,environmental friendliness,and low cost.Despite their potential,achieving high energy density in Zn||MnO_(2)batteries remains challenging,highlighting the need to understand the electrochemical reaction mechanisms underlying these batteries more deeply and optimize battery components,including electrodes and electrolytes.This review comprehensively summarizes the latest advancements for understanding the electrochemistry reaction mechanisms and designing electrodes and electrolytes for Zn||MnO_(2)batteries in mildly and strongly acidic environments.Furthermore,we highlight the key challenges hindering the extensive application of Zn||MnO_(2)batteries,including high-voltage requirements and areal capacity,and propose innovative solutions to overcome these challenges.We suggest that MnO_(2)/Mn^(2+)conversion in neutral electrolytes is a crucial aspect that needs to be addressed to achieve high-performance Zn||MnO_(2)batteries.These approaches could lead to breakthroughs in the future development of Zn||MnO_(2)batteries,off ering a more sustainable,costeff ective,and high-performance alternative to traditional batteries.展开更多
Lithium-oxygen batteries are a promising technology because they can greatly surpass the energy density of lithium-ion batteries.However,this theoretical characteristic has not yet been converted into a real device wi...Lithium-oxygen batteries are a promising technology because they can greatly surpass the energy density of lithium-ion batteries.However,this theoretical characteristic has not yet been converted into a real device with high cyclability.Problems with air contamination,metallic lithium reactivity,and complex discharge and charge reactions are the main issues for this technology.A fast and reversible oxygen reduction reaction(ORR)is crucial for good performance of secondary batteries',but the partial knowledge of its mechanisms,especially when devices are concerned,hinders further development.From this perspective,the present work uses operando Raman experiments and electrochemical impedance spectroscopy(EIS)to assess the first stages of the discharge processes in porous carbon electrodes,following their changes cycle by cycle at initial operation.A growth kinetic formation of the discharge product signal(Li_(2)O_(2))was observed with operando Raman,indicating a first-order reaction and enabling an analysis by a microkinetic model.The solution mechanism in the evaluated system was ascribed for an equivalent circuit with three time constants.While the time constant for the anode interface reveals to remain relatively constant after the first discharge,its surface seemed to be more non-uniform.The model indicated that the reaction occurs at the Li_(2)O_(2) surface,decreasing the associated resistance during the initial discharge phase.Furthermore,the growth of Li_(2)O_(2) forms a hetero-phase between Li_(2)O_(2)/electrolyte,while creating a more compact and homogeneous on the Li_(2)O_(2)/cathode surface.The methodology here described thus offers a way of directly probing changes in surface chemistry evolution during cycling from a device through EIS analysis.展开更多
Developing high-performance aqueous Zn-ion batteries from sustainable biomass becomes increasingly vital for large-scale energy storage in the foreseeable future.Therefore,γ-MnO_(2) uniformly loaded on N-doped carbon...Developing high-performance aqueous Zn-ion batteries from sustainable biomass becomes increasingly vital for large-scale energy storage in the foreseeable future.Therefore,γ-MnO_(2) uniformly loaded on N-doped carbon derived from grapefruit peel is successfully fabricated in this work,and particularly the composite cathode with carbon carrier quality percentage of 20 wt%delivers the specific capacity of 391.2 mAh g^(−1)at 0.1 A g^(−1),outstanding cyclic stability of 92.17%after 3000 cycles at 5 A g^(−1),and remarkable energy density of 553.12 Wh kg^(−1) together with superior coulombic efficiency of~100%.Additionally,the cathodic biosafety is further explored specifically through in vitro cell toxicity experiments,which verifies its tremendous potential in the application of clinical medicine.Besides,Zinc ion energy storage mechanism of the cathode is mainly discussed from the aspects of Jahn–Teller effect and Mn domains distribution combined with theoretical analysis and experimental data.Thus,a novel perspective of the conversion from biomass waste to biocompatible Mn-based cathode is successfully developed.展开更多
As a prevailing cathode material of lithium-ion batteries(LIBs),LiCoO_(2)(LCO)still encounters the tricky problems of structural collapse,whose morphological engineering and cation doping are crucial for surmounting t...As a prevailing cathode material of lithium-ion batteries(LIBs),LiCoO_(2)(LCO)still encounters the tricky problems of structural collapse,whose morphological engineering and cation doping are crucial for surmounting the mechanical strains and alleviating phase degradation upon cycling.Hereinafter,we propose a strategy using a zeolitic imidazolate framework(ZIF)as the self-sacrificing template to directionally prepare a series of LiNi_(0.1)Co_(0.9)O_(2)(LNCO)with tailorable electrochemical properties.The rational selection of sintering temperature imparts the superiority of the resultant products in lithium storage,during which the sample prepared at 700℃(LNCO-700)outperforms its counterparts in cyclability(156.8 mA h g^(-1)at 1 C for 200 cycles in half cells,1 C=275 mA g^(-1))and rate capability due to the expedited ion/electron transport and the strengthen mechanical robustness.The feasibility of proper Ni doping is also divulged by half/full cell tests and theoretical study,during which LNCO-700(167 mA h g^(-1)at 1 C for 100 cycles in full cells)surpasses LCO-700 in battery performance due to the mitigated phase deterioration,stabilized layered structu re,ameliorated electro nic co nductivity,a nd exalted lithium sto rage activity.This work systematically unveils tailorable electrochemical behaviors of LNCO to better direct their practical application.展开更多
Lithium-ion batteries(LIBs)featuring a Ni-rich cathode exhibit increased specific capacity,but the establishment of a stable interphase through the implementation of a functional electrolyte strategy remains challengi...Lithium-ion batteries(LIBs)featuring a Ni-rich cathode exhibit increased specific capacity,but the establishment of a stable interphase through the implementation of a functional electrolyte strategy remains challenging.Especially when the battery is operated under high temperature,the trace water present in the electrolyte will accelerate the hydrolysis of the electrolyte and the resulting HF will further erode the interphase.In order to enhance the long-term cycling performance of graphite/LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)LIBs,herein,Tolylene-2,4-diisocyanate(TDI)additive containing lone-pair electrons is employed to formulate a novel bifunctional electrolyte aimed at eliminating H_(2)O/HF generated at elevated temperature.After 1000 cycles at 25℃,the battery incorporating the TDI-containing electrolyte exhibits an impressive capacity retention of 94%at 1 C.In contrast,the battery utilizing the blank electrolyte has a lower capacity retention of only 78%.Furthermore,after undergoing 550 cycles at 1 C under45℃,the inclusion of TDI results in a notable enhancement of capacity,increasing it from 68%to 80%.This indicates TDI has a favorable influence on the cycling performance of LIBs,especially at elevated temperatures.The analysis of the film formation mechanism suggests that the lone pair of electrons of the isocyanate group in TDI play a crucial role in inhibiting the generation of H_(2)O and HF,which leads to the formation of a thin and dense interphase.The existence of this interphase is thought to substantially enhance the cycling performance of the LIBs.This work not only improves the performance of graphite/NCM811 batteries at room temperature and high temperature by eliminating H_(2)O/HF but also presents a novel strategy for advancing functional electrolyte development.展开更多
Iron‐based pyrophosphates are attractive cathodes for sodium‐ion batteries due to their large framework,cost‐effectiveness,and high energy density.However,the understanding of the crystal structure is scarce and on...Iron‐based pyrophosphates are attractive cathodes for sodium‐ion batteries due to their large framework,cost‐effectiveness,and high energy density.However,the understanding of the crystal structure is scarce and only a limited candidates have been reported so far.In this work,we found for the first time that a continuous solid solution,Na_(4−α)Fe_(2+α)_(2)(P_(2)O_(7))_(2)(0≤α≤1,could be obtained by mutual substitution of cations at center‐symmetric Na3 and Na4 sites while keeping the crystal building blocks of anionic P_(2)O_(7) unchanged.In particular,a novel off‐stoichiometric Na_(3)Fe(2.5)(P_(2)O_(7))_(2)is thus proposed,and its structure,energy storage mechanism,and electrochemical performance are extensively investigated to unveil the structure–function relationship.The as‐prepared off‐stoichiometric electrode delivers appealing performance with a reversible discharge capacity of 83 mAh g^(−1),a working voltage of 2.9 V(vs.Na^(+)/Na),the retention of 89.2%of the initial capacity after 500 cycles,and enhanced rate capability of 51 mAh g^(−1)at a current density of 1600 mA g^(−1).This research shows that sodium ferric pyrophosphate could form extended solid solution composition and promising phase is concealed in the range of Na_(4−α)Fe_(2+α)_(2)(P_(2)O_(7))_(2),offering more chances for exploration of new cathode materials for the construction of high‐performance SIBs.展开更多
Li–CO_(2)/O_(2)batteries,a promising energy storage technology,not only provide ultrahigh discharge capacity but also capture CO_(2)and turn it into renewable energy.Their electrochemical reaction pathways'ambigu...Li–CO_(2)/O_(2)batteries,a promising energy storage technology,not only provide ultrahigh discharge capacity but also capture CO_(2)and turn it into renewable energy.Their electrochemical reaction pathways'ambiguity,however,creates a hurdle for their practical application.This study used copper selenide(CuSe)nanosheets as the air cathode medium in an environmental transmission electron microscope to in situ study Li–CO_(2)/O_(2)(mix CO_(2)as well as O_(2)at a volume ratio of 1:1)and Li–O_(2)batteries as well as Li–CO_(2)batteries.Primary discharge reactions take place successively in the Li–CO_(2)/O_(2)–CuSe nanobattery:(I)4Li^(+)+O_(2)+4e^(−)→2Li_(2)O;(II)Li_(2)O+CO_(2)→Li_(2)CO_(3).The charge reaction proceeded via(III)2Li_(2)CO_(3)→4Li^(+)+2CO_(2)+O_(2)+4e^(−).However,Li–O_(2)and Li–CO_(2)nanobatteries showed poor cycling stability,suggesting the difficulty in the direct decomposition of the discharge product.The fluctuations of the Li–CO_(2)/O_(2)battery's electrochemistry were also shown to depend heavily on O_(2).The CuSe‐based Li–CO_(2)/O_(2)battery showed exceptional electrochemical performance.The Li^–CO_(2)/O_(2)battery offered a discharge capacity apex of 15,492 mAh g^(−1) and stable cycling 60 times at 100 mA g^(−1).Our research offers crucial insight into the electrochemical behavior of Li–CO_(2)/O_(2),Li–O_(2),and Li–CO_(2)nanobatteries,which may help the creation of high‐performance Li–CO_(2)/O_(2)batteries for energy storage applications.展开更多
SnO_(2) has been extensively investigated as an anode material for sodium-ion batteries(SIBs)and potassium-ion batteries(PIBs)due to its high Na/K storage capacity,high abundance,and low toxicity.However,the sluggish ...SnO_(2) has been extensively investigated as an anode material for sodium-ion batteries(SIBs)and potassium-ion batteries(PIBs)due to its high Na/K storage capacity,high abundance,and low toxicity.However,the sluggish reaction kinetics,low electronic conductivity,and large volume changes during charge and discharge hinder the practical applications of SnO_(2)-based electrodes for SIBs and PIBs.Engineering rational structures with fast charge/ion transfer and robust stability is important to overcoming these challenges.Herein,S-doped SnO_(2)(S-SnO_(2))quantum dots(QDs)(≈3 nm)encapsulated in an N,S codoped carbon fiber networks(S-SnO_(2)-CFN)are rationally fabricated using a sequential freeze-drying,calcination,and S-doping strategy.Experimental analysis and density functional theory calculations reveal that the integration of S-SnO_(2) QDs with N,S codoped carbon fiber network remarkably decreases the adsorption energies of Na/K atoms in the interlayer of SnO_(2)-CFN,and the S doping can increase the conductivity of SnO_(2),thereby enhancing the ion transfer kinetics.The synergistic interaction between S-SnO_(2) QDs and N,S codoped carbon fiber network results in a composite with fast Na+/K+storage and extraordinary long-term cyclability.Specifically,the S-SnO_(2)-CFN delivers high rate capacities of 141.0 mAh g^(−1) at 20 A g^(−1) in SIBs and 102.8 mAh g^(−1) at 10 A g^(−1) in PIBs.Impressively,it delivers ultra-stable sodium storage up to 10,000 cycles at 5 A g^(−1) and potassium storage up to 5000 cycles at 2 A g^(−1).This study provides insights into constructing metal oxide-based carbon fiber network structures for high-performance electrochemical energy storage and conversion devices.展开更多
Li–CO_(2) batteries are considered promising energy storage systems in extreme environments such as Mars;however,severe performance degradation will occur at a subzero temperature owning to the sluggish reaction kine...Li–CO_(2) batteries are considered promising energy storage systems in extreme environments such as Mars;however,severe performance degradation will occur at a subzero temperature owning to the sluggish reaction kinetics.Herein,a photo-energized strategy adopting sustainable solar energy in wide working temperature range Li–CO_(2) battery was achieved with a binder-free MoS_(2)/carbon nanotube(CNT)photo-electrode as cathode.The unique layered structure and excellent photoelectric properties of MoS_(2) facilitate the abundant generation and rapid transfer of photo-excited carriers,which accelerate the CO_(2) reduction and Li_(2)CO_(3) decomposition upon illumination.The illuminated battery at room temperature exhibited high discharge voltage of 2.95 V and mitigated charge voltage of 3.27 V,attaining superior energy efficiency of 90.2%and excellent cycling stability of over 120 cycles.Even at an extremely low temperature of−30℃,the battery with same electrolyte can still deliver a small polarization of 0.45 V by the photoelectric and photothermal synergistic mechanism of MoS_(2)/CNT cathode.This work demonstrates the promising potential of the photo-energized wide working temperature range Li–CO_(2) battery in addressing the obstacle of charge overpotential and energy efficiency.展开更多
Lithium-oxygen(Li-O_(2))batteries have attracted significant attention due to their ultra-high theoretical energy density.However,serious challenges,such as potential lag,low-rate capability,round-trip efficiency,and ...Lithium-oxygen(Li-O_(2))batteries have attracted significant attention due to their ultra-high theoretical energy density.However,serious challenges,such as potential lag,low-rate capability,round-trip efficiency,and poor cycle stability,greatly limit their practical application.This review provides a comprehensive account of the development of Li-O_(2)batteries,elucidates the current discharge/charge mechanism,and highlights both the advantages and bottlenecks of this technology.In particular,recent research progress on various cathode materials,such as carbon-based materials,noble metals,and non-noble metals,for Li-O_(2)batteries is deeply reviewed,emphasizing the impact of design strategies,material structures,chemical compositions,and microphysical parameters on oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)kinetics,as well as discharge products and overall battery performance.This review will also shed light on future research directions for oxygen electrode catalysts and material construction to facilitate the development of Li-O_(2)batteries with maximized electrochemical performance.展开更多
Magnesium ion batteries(MIBs)are a potential field for the energy storage of the future but are restricted by insufficient rate capability and rapid capacity degradation.Magnesium-sodium hybrid ion batteries(MSHBs)are...Magnesium ion batteries(MIBs)are a potential field for the energy storage of the future but are restricted by insufficient rate capability and rapid capacity degradation.Magnesium-sodium hybrid ion batteries(MSHBs)are an effective way to address these problems.Here,we report a new type of MSHBs that use layered sodium vanadate((Na,Mn)V_(8)O_(20)·5H_(2)O,Mn-NVO)cathodes coupled with an organic 3,4,9,10-perylenetetracarboxylic diimide(PTCDI)anode in Mg^(2+)/Na^(+)hybrid electrolytes.During electrochemical cycling,Mg^(2+)and Na^(+)co-participate in the cathode reactions,and the introduction of Na^(+)promotes the structural stability of the Mn-NVO cathode,as cleared by several ex-situ characterizations.Consequently,the Mn-NVO cathode presents great specific capacity(249.9 mA h g^(−1)at 300 mA g^(−1))and cycling(1500 cycles at 1500 mA g^(−1))in the Mg^(2+)/Na^(+)hybrid electrolytes.Besides,full battery displays long lifespan with 10,000 cycles at 1000 mA g^(−1).The rate performance and cycling stability of MSHBs have been improved by an economical and scalable method,and the mechanism for these improvements is discussed.展开更多
3D hierarchical flowerlike WS_(2) microspheres were synthesized through a facile one-pot hydrothermal route.The as-synthesized samples were characterized by powder X-ray powder diffraction (XRD),energy-dispersive spec...3D hierarchical flowerlike WS_(2) microspheres were synthesized through a facile one-pot hydrothermal route.The as-synthesized samples were characterized by powder X-ray powder diffraction (XRD),energy-dispersive spectroscopy (EDS),scanning electron microscopy (SEM) and Raman.SEM images of the samples reveal that the hierarchical flowerlike WS_(2) microspheres with diameters of about 3-5μm are composed of a number of curled nanosheets.Electrochemical tests such as charge/discharge,cyclic voltammetry,cycle life and rate performance were carried out on the WS_(2) sample.As an anode material for lithium-ion batteries,hierarchical flowerlike WS_(2) microspheres show excellent electrochemical performance.At a current density of100 mA·g^(-1),a high specific capacity of 647.8 mA·h·g^(-1) was achieved after 120 discharge/charge cycles.The excellent electrochemical performance of WS_(2) as an anode material for lithium-ion batteries can be attributed to its special 3D hierarchical structure.展开更多
Ammonia plays a crucial role in contemporary society,impacting medicine,agriculture,and the chemical industry.The conventional industrial synthesis of NH_(3) through the Haber-Bosch technique,carried out under severe ...Ammonia plays a crucial role in contemporary society,impacting medicine,agriculture,and the chemical industry.The conventional industrial synthesis of NH_(3) through the Haber-Bosch technique,carried out under severe reaction conditions,leads to substantial energy consumption and environmental pollution.It is thus imperative for NH_(3) synthesis methods to be investigated under more favorable conditions.Synthesis of ammonia by electrocatalysis can effectively reduce the environmental damage and other urgent problems,which is a promising solution.Metal-nitrogen series batteries(M-N batteries),such as metal-nitrogen gas batteries,metal-nitrogen oxide batteries and metal-oxynitride batteries have been regarded recently as an exemplar of concurrent NH_(3) synthesis and energy production.Nonetheless,the large-scale application of these batteries is still limited by numerous challenges are currently existing in building high-efficiency M-N batteries,including poor Faradic efficiency and low NH_(3) yield.Therefore,a comprehensive overview of M-N batteries is offered,specifically focusing on advanced strategies for designing highly efficient cathode catalysts in anticipation of future developments.The metal anodes,cathodic electro-reduction reactions,and design principles are encompassed in the discussion,offering detailed insights to enhance understanding.Mechanisms,feasibility analyses,technoeconomic assessments,device combinations,and comparative evaluations are delved into in the review,contributing to a thorough comprehension of diverse systems and their application potential.Perspectives and opportunities for future research directions are also delineated.展开更多
The Li-CO_(2) battery has been under the spotlight of future battery technologies since it can achieve CO_(2)utilization and energy conversion simultaneously.However,its advancement is hampered by poor energy efficien...The Li-CO_(2) battery has been under the spotlight of future battery technologies since it can achieve CO_(2)utilization and energy conversion simultaneously.However,its advancement is hampered by poor energy efficiency and limited reversibility due to the sluggish kinetics of the CO_(2) reduction and evolution reactions.Herein,a multiscale nanoporous interpenetrating phase nanohybrid of RuAl intermetallic and Cu_(2)O(MP-Cu_(2)O/RuAl) was carved by driving synchronous phase and microstructure evolutions through dealloying of one RuCuAl master alloy.The built-in RuAl intermetallic and Cu_(2)O closely stack to form abundant nano-interfaces with revolutionized electronic structure,The theoretical simulations reveal that the Cu_(2)O/RuAl interface can distinctly reduce the energy barrier of the Li_(2)CO_(3) decomposition reaction,The interconnected pore channels with large surface area can enhance catalytic site accessibility,mass transfer,and uniform deposition of the discharge products.In situ differential electrochemical mass spectrometry discloses that the CO_(2)-to-electron ratio during charging coincides with the theoretical value of 3/4,demonstrating the high efficacy of MP-Cu_(2)O/RuAl in achieving the recycling of CO_(2).The dealloying protocol provides an affordable platform to empower transition metal oxides into high-efficiency electrocatalysts by hybridizing with metallic nano-sponge for advancing the application of Li-CO_(2)batteries.展开更多
Inactive elemental doping is commonly used to improve the structural stability of high-voltage layered transition-metal oxide cathodes.However,the one-step co-doping strategy usually results in small grain size since ...Inactive elemental doping is commonly used to improve the structural stability of high-voltage layered transition-metal oxide cathodes.However,the one-step co-doping strategy usually results in small grain size since the low diffusivity ions such as Ti^(4+)will be concentrated on grain boundaries,which hinders the grain growth.In order to synthesize large single-crystal layered oxide cathodes,considering the different diffusivities of different dopant ions,we propose a simple two-step multi-element co-doping strategy to fabricate core–shell structured LiCoO_(2)(CS-LCO).In the current work,the high-diffusivity Al^(3+)/Mg^(2+)ions occupy the core of single-crystal grain while the low diffusivity Ti^(4+)ions enrich the shell layer.The Ti^(4+)-enriched shell layer(~12 nm)with Co/Ti substitution and stronger Ti–O bond gives rise to less oxygen ligand holes.In-situ XRD demonstrates the constrained contraction of c-axis lattice parameter and mitigated structural distortion.Under a high upper cut-off voltage of 4.6 V,the single-crystal CS-LCO maintains a reversible capacity of 159.8 mAh g^(−1)with a good retention of~89%after 300 cycles,and reaches a high specific capacity of 163.8 mAh g^(−1)at 5C.The proposed strategy can be extended to other pairs of low-(Zr^(4+),Ta^(5+),and W6+,etc.)and high-diffusivity cations(Zn^(2+),Ni^(2+),and Fe^(3+),etc.)for rational design of advanced layered oxide core–shell structured cathodes for lithium-ion batteries.展开更多
The widespread interest in layered P2-type Mn-based cathode materials for sodium-ion batteries(SIBs)stems from their cost-effectiveness and abundant resources.However,the inferior cycle stability and mediocre rate per...The widespread interest in layered P2-type Mn-based cathode materials for sodium-ion batteries(SIBs)stems from their cost-effectiveness and abundant resources.However,the inferior cycle stability and mediocre rate performance impede their further development in practical applications.Herein,we devised a wet chemical precipitation method to deposit an amorphous aluminum phosphate(AlPO_(4),denoted as AP)protective layer onto the surface of P2-type Na_(0.55)Ni_(0.1)Co_(0.7)Mn_(0.8)O_(2)(NCM@AP).The resulting NCM@5AP electrode,with a 5 wt%coating,exhibits extended cycle life(capacity retention of78.4%after 200 cycles at 100 mA g^(-1))and superior rate performance(98 mA h g^(-1)at 500 mA g^(-1))compared to pristine NCM.Moreover,our investigation provides comprehensive insights into the phase stability and active Na^(+)ion kinetics in the NCM@5AP composite electrode,shedding light on the underlying mechanisms responsible for the enhanced performance observed in the coated electrode.展开更多
Bromine has attracted significant attention as a cathode material for aqueous batteries due to its high reduction potential of 1.05 V(Br_(3)^(-)+2e~-■3Br~-),impressive theoretical specific capacity of 223 mA h g^(-1)...Bromine has attracted significant attention as a cathode material for aqueous batteries due to its high reduction potential of 1.05 V(Br_(3)^(-)+2e~-■3Br~-),impressive theoretical specific capacity of 223 mA h g^(-1),and rapid reaction kinetics in the electrolyte.However,searching for compatible anode materials to match with bromine has posed a challenge due to its highly corrosive nature.In this study,we developed oxygen-deficient MoO_(3) with TiO_(2) coating(referred to as MoO_(3-x)@TiO_(2))as an anode material to pair with a bromine cathode in static full batteries.The oxygen deficiency contributes to enhanced electronic and protonic diffusion within the MoO_(3-x)lattice,while the TiO_(2) coating mitigates structural dissolution and proton trapping during cycling.The MoO_(3-x)@TiO_(2) demonstrates fast charge storage kinetics and excellent resistance to bromine corrosion.The impressive compatibility between MoO_(3-x)@TiO_(2) and bromine enables the construction of membrane-less full batteries with exceptional rate capability and cyclic stability.The MoO_(3-x)@TiO_(2)-bromine battery achieves an energy density of70.8 W h kg^(-1)at a power density of 328.1 W kg^(-1),showcasing an impressive long-term cyclic life of 20,000 cycles.Our study provides valuable insights for the development of high-performance aqueous secondary batteries.展开更多
Although biomass-derived carbon(biochar)has been widely used in the energy field,the relation between the carbonization condition and the physical/chemical property of the product remains elusive.Here,we revealed the ...Although biomass-derived carbon(biochar)has been widely used in the energy field,the relation between the carbonization condition and the physical/chemical property of the product remains elusive.Here,we revealed the carbonization condition's effect on the morphology,surface property,and electrochemical performance of the obtained carbon.An open slit pore structure with shower-puff-like nanoparticles can be obtained by finely tuning the carbonization temperature,and its unique pore structure and surface properties enable the Li–O_(2) battery with cycling longevity(221 cycles with 99.8%Coulombic efficiency at 0.2 mA cm^(−2) and controlled discharge–charge depths of 500 mAh g^(−1))and high capacity(16,334 mAh g^(−1) at 0.02 mA cm^(−2)).This work provides a greater understanding of the mechanism of the biochar carbonization procedure under various pyrolysis conditions,paving the way for future study of energy storage devices.展开更多
The Sabatier principle has been widely used for designing electrocatalysts for energy conversion applications,but it is rarely mentioned in the research of cathode catalyst of Li-CO_(2) batteries.In our work,the"...The Sabatier principle has been widely used for designing electrocatalysts for energy conversion applications,but it is rarely mentioned in the research of cathode catalyst of Li-CO_(2) batteries.In our work,the"volcanic"relationship between the catalytic activity and the adsorption energy of the catalyst to the intermediates is first demonstrated based on the first-principles calculation,which meets the Sabatier principle and can be used to design the cathode catalysts.The increases in the number of nitrogenvacancy in WN shift the d-band center and increase the interaction with the reactants.The catalytic activity increases first and then decreases with the increase of adsorption energy,which was proved in the experiment.The optimal catalyst for moderate adsorption of intermediate makes the thin LiaCO_(3) distribute evenly.It exhibits a median voltage difference of 0.68 V and an energy efficiency of 84.33%at20μA cm^(-2)with a limited capacity of 200μA h cm^(-2).展开更多
文摘Recently,rechargeable aqueous zinc-based batteries using manganese oxide as the cathode(e.g.,MnO_(2))have gained attention due to their inherent safety,environmental friendliness,and low cost.Despite their potential,achieving high energy density in Zn||MnO_(2)batteries remains challenging,highlighting the need to understand the electrochemical reaction mechanisms underlying these batteries more deeply and optimize battery components,including electrodes and electrolytes.This review comprehensively summarizes the latest advancements for understanding the electrochemistry reaction mechanisms and designing electrodes and electrolytes for Zn||MnO_(2)batteries in mildly and strongly acidic environments.Furthermore,we highlight the key challenges hindering the extensive application of Zn||MnO_(2)batteries,including high-voltage requirements and areal capacity,and propose innovative solutions to overcome these challenges.We suggest that MnO_(2)/Mn^(2+)conversion in neutral electrolytes is a crucial aspect that needs to be addressed to achieve high-performance Zn||MnO_(2)batteries.These approaches could lead to breakthroughs in the future development of Zn||MnO_(2)batteries,off ering a more sustainable,costeff ective,and high-performance alternative to traditional batteries.
基金supported by the S?o Paulo Research Foundation (FAPESP) (2017/11958-1)the strategic importance of the support given by ANP (Brazil's National Oil,Natural Gas and Biofuels Agency)through the R&D levy regulation and the support from the Brazilian Coordination for the Improvement of Higher Education and Personnel (CAPES)CNPq (PQ-2 grant:Process 304442/2019-4 and UFMT STI-Server for access to their computing resources)。
文摘Lithium-oxygen batteries are a promising technology because they can greatly surpass the energy density of lithium-ion batteries.However,this theoretical characteristic has not yet been converted into a real device with high cyclability.Problems with air contamination,metallic lithium reactivity,and complex discharge and charge reactions are the main issues for this technology.A fast and reversible oxygen reduction reaction(ORR)is crucial for good performance of secondary batteries',but the partial knowledge of its mechanisms,especially when devices are concerned,hinders further development.From this perspective,the present work uses operando Raman experiments and electrochemical impedance spectroscopy(EIS)to assess the first stages of the discharge processes in porous carbon electrodes,following their changes cycle by cycle at initial operation.A growth kinetic formation of the discharge product signal(Li_(2)O_(2))was observed with operando Raman,indicating a first-order reaction and enabling an analysis by a microkinetic model.The solution mechanism in the evaluated system was ascribed for an equivalent circuit with three time constants.While the time constant for the anode interface reveals to remain relatively constant after the first discharge,its surface seemed to be more non-uniform.The model indicated that the reaction occurs at the Li_(2)O_(2) surface,decreasing the associated resistance during the initial discharge phase.Furthermore,the growth of Li_(2)O_(2) forms a hetero-phase between Li_(2)O_(2)/electrolyte,while creating a more compact and homogeneous on the Li_(2)O_(2)/cathode surface.The methodology here described thus offers a way of directly probing changes in surface chemistry evolution during cycling from a device through EIS analysis.
基金supported by the National Natural Science Foundation of China[Grant no.51821004].
文摘Developing high-performance aqueous Zn-ion batteries from sustainable biomass becomes increasingly vital for large-scale energy storage in the foreseeable future.Therefore,γ-MnO_(2) uniformly loaded on N-doped carbon derived from grapefruit peel is successfully fabricated in this work,and particularly the composite cathode with carbon carrier quality percentage of 20 wt%delivers the specific capacity of 391.2 mAh g^(−1)at 0.1 A g^(−1),outstanding cyclic stability of 92.17%after 3000 cycles at 5 A g^(−1),and remarkable energy density of 553.12 Wh kg^(−1) together with superior coulombic efficiency of~100%.Additionally,the cathodic biosafety is further explored specifically through in vitro cell toxicity experiments,which verifies its tremendous potential in the application of clinical medicine.Besides,Zinc ion energy storage mechanism of the cathode is mainly discussed from the aspects of Jahn–Teller effect and Mn domains distribution combined with theoretical analysis and experimental data.Thus,a novel perspective of the conversion from biomass waste to biocompatible Mn-based cathode is successfully developed.
基金the financial support from the Special Funds for the Cultivation of Guangdong College Students’Scientific and Technological Innovation(“Climbing Program”Special Funds,pdjh2023b0145)Guangdong Provincial International Joint Research Center for Energy Storage Materials(2023A0505090009)。
文摘As a prevailing cathode material of lithium-ion batteries(LIBs),LiCoO_(2)(LCO)still encounters the tricky problems of structural collapse,whose morphological engineering and cation doping are crucial for surmounting the mechanical strains and alleviating phase degradation upon cycling.Hereinafter,we propose a strategy using a zeolitic imidazolate framework(ZIF)as the self-sacrificing template to directionally prepare a series of LiNi_(0.1)Co_(0.9)O_(2)(LNCO)with tailorable electrochemical properties.The rational selection of sintering temperature imparts the superiority of the resultant products in lithium storage,during which the sample prepared at 700℃(LNCO-700)outperforms its counterparts in cyclability(156.8 mA h g^(-1)at 1 C for 200 cycles in half cells,1 C=275 mA g^(-1))and rate capability due to the expedited ion/electron transport and the strengthen mechanical robustness.The feasibility of proper Ni doping is also divulged by half/full cell tests and theoretical study,during which LNCO-700(167 mA h g^(-1)at 1 C for 100 cycles in full cells)surpasses LCO-700 in battery performance due to the mitigated phase deterioration,stabilized layered structu re,ameliorated electro nic co nductivity,a nd exalted lithium sto rage activity.This work systematically unveils tailorable electrochemical behaviors of LNCO to better direct their practical application.
基金financially supported by the Scientific and Technological Plan Projects of Guangzhou City(202103040001),P.R.Chinathe Project of Science and Technology Department of Henan Province(222102240074)the Key Research Programs of Higher Education Institutions of Henan Province(24B150009)。
文摘Lithium-ion batteries(LIBs)featuring a Ni-rich cathode exhibit increased specific capacity,but the establishment of a stable interphase through the implementation of a functional electrolyte strategy remains challenging.Especially when the battery is operated under high temperature,the trace water present in the electrolyte will accelerate the hydrolysis of the electrolyte and the resulting HF will further erode the interphase.In order to enhance the long-term cycling performance of graphite/LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)LIBs,herein,Tolylene-2,4-diisocyanate(TDI)additive containing lone-pair electrons is employed to formulate a novel bifunctional electrolyte aimed at eliminating H_(2)O/HF generated at elevated temperature.After 1000 cycles at 25℃,the battery incorporating the TDI-containing electrolyte exhibits an impressive capacity retention of 94%at 1 C.In contrast,the battery utilizing the blank electrolyte has a lower capacity retention of only 78%.Furthermore,after undergoing 550 cycles at 1 C under45℃,the inclusion of TDI results in a notable enhancement of capacity,increasing it from 68%to 80%.This indicates TDI has a favorable influence on the cycling performance of LIBs,especially at elevated temperatures.The analysis of the film formation mechanism suggests that the lone pair of electrons of the isocyanate group in TDI play a crucial role in inhibiting the generation of H_(2)O and HF,which leads to the formation of a thin and dense interphase.The existence of this interphase is thought to substantially enhance the cycling performance of the LIBs.This work not only improves the performance of graphite/NCM811 batteries at room temperature and high temperature by eliminating H_(2)O/HF but also presents a novel strategy for advancing functional electrolyte development.
基金National Natural Science Foundation of China,Grant/Award Numbers:21972108,U20A20249,U22A20438Changzhou Science and Technology Bureau,Grant/Award Number:CM20223017Innovation and Technology Commission(ITC)of Hong Kong,The Innovation&Technology Fund(ITF)with Project No.ITS/126/21。
文摘Iron‐based pyrophosphates are attractive cathodes for sodium‐ion batteries due to their large framework,cost‐effectiveness,and high energy density.However,the understanding of the crystal structure is scarce and only a limited candidates have been reported so far.In this work,we found for the first time that a continuous solid solution,Na_(4−α)Fe_(2+α)_(2)(P_(2)O_(7))_(2)(0≤α≤1,could be obtained by mutual substitution of cations at center‐symmetric Na3 and Na4 sites while keeping the crystal building blocks of anionic P_(2)O_(7) unchanged.In particular,a novel off‐stoichiometric Na_(3)Fe(2.5)(P_(2)O_(7))_(2)is thus proposed,and its structure,energy storage mechanism,and electrochemical performance are extensively investigated to unveil the structure–function relationship.The as‐prepared off‐stoichiometric electrode delivers appealing performance with a reversible discharge capacity of 83 mAh g^(−1),a working voltage of 2.9 V(vs.Na^(+)/Na),the retention of 89.2%of the initial capacity after 500 cycles,and enhanced rate capability of 51 mAh g^(−1)at a current density of 1600 mA g^(−1).This research shows that sodium ferric pyrophosphate could form extended solid solution composition and promising phase is concealed in the range of Na_(4−α)Fe_(2+α)_(2)(P_(2)O_(7))_(2),offering more chances for exploration of new cathode materials for the construction of high‐performance SIBs.
基金Natural Science Foundation of Hebei Province,Grant/Award Number:F2021203097China Postdoctoral Science Foundation,Grant/Award Numbers:2021M702756,2023T160551National Natural Science Foundation of China,Grant/Award Numbers:51971245,52022088。
文摘Li–CO_(2)/O_(2)batteries,a promising energy storage technology,not only provide ultrahigh discharge capacity but also capture CO_(2)and turn it into renewable energy.Their electrochemical reaction pathways'ambiguity,however,creates a hurdle for their practical application.This study used copper selenide(CuSe)nanosheets as the air cathode medium in an environmental transmission electron microscope to in situ study Li–CO_(2)/O_(2)(mix CO_(2)as well as O_(2)at a volume ratio of 1:1)and Li–O_(2)batteries as well as Li–CO_(2)batteries.Primary discharge reactions take place successively in the Li–CO_(2)/O_(2)–CuSe nanobattery:(I)4Li^(+)+O_(2)+4e^(−)→2Li_(2)O;(II)Li_(2)O+CO_(2)→Li_(2)CO_(3).The charge reaction proceeded via(III)2Li_(2)CO_(3)→4Li^(+)+2CO_(2)+O_(2)+4e^(−).However,Li–O_(2)and Li–CO_(2)nanobatteries showed poor cycling stability,suggesting the difficulty in the direct decomposition of the discharge product.The fluctuations of the Li–CO_(2)/O_(2)battery's electrochemistry were also shown to depend heavily on O_(2).The CuSe‐based Li–CO_(2)/O_(2)battery showed exceptional electrochemical performance.The Li^–CO_(2)/O_(2)battery offered a discharge capacity apex of 15,492 mAh g^(−1) and stable cycling 60 times at 100 mA g^(−1).Our research offers crucial insight into the electrochemical behavior of Li–CO_(2)/O_(2),Li–O_(2),and Li–CO_(2)nanobatteries,which may help the creation of high‐performance Li–CO_(2)/O_(2)batteries for energy storage applications.
基金National Natural Science Foundation of China,Grant/Award Number:51971065Innovation Program of Shanghai Municipal Education Commission,Grant/Award Number:2019-01-07-00-07-E00028。
文摘SnO_(2) has been extensively investigated as an anode material for sodium-ion batteries(SIBs)and potassium-ion batteries(PIBs)due to its high Na/K storage capacity,high abundance,and low toxicity.However,the sluggish reaction kinetics,low electronic conductivity,and large volume changes during charge and discharge hinder the practical applications of SnO_(2)-based electrodes for SIBs and PIBs.Engineering rational structures with fast charge/ion transfer and robust stability is important to overcoming these challenges.Herein,S-doped SnO_(2)(S-SnO_(2))quantum dots(QDs)(≈3 nm)encapsulated in an N,S codoped carbon fiber networks(S-SnO_(2)-CFN)are rationally fabricated using a sequential freeze-drying,calcination,and S-doping strategy.Experimental analysis and density functional theory calculations reveal that the integration of S-SnO_(2) QDs with N,S codoped carbon fiber network remarkably decreases the adsorption energies of Na/K atoms in the interlayer of SnO_(2)-CFN,and the S doping can increase the conductivity of SnO_(2),thereby enhancing the ion transfer kinetics.The synergistic interaction between S-SnO_(2) QDs and N,S codoped carbon fiber network results in a composite with fast Na+/K+storage and extraordinary long-term cyclability.Specifically,the S-SnO_(2)-CFN delivers high rate capacities of 141.0 mAh g^(−1) at 20 A g^(−1) in SIBs and 102.8 mAh g^(−1) at 10 A g^(−1) in PIBs.Impressively,it delivers ultra-stable sodium storage up to 10,000 cycles at 5 A g^(−1) and potassium storage up to 5000 cycles at 2 A g^(−1).This study provides insights into constructing metal oxide-based carbon fiber network structures for high-performance electrochemical energy storage and conversion devices.
基金supported by the National Natural Science Foundation of China(52072173)the International Science and Technology Cooperation Program of Jiangsu Province(SBZ2022000084).
文摘Li–CO_(2) batteries are considered promising energy storage systems in extreme environments such as Mars;however,severe performance degradation will occur at a subzero temperature owning to the sluggish reaction kinetics.Herein,a photo-energized strategy adopting sustainable solar energy in wide working temperature range Li–CO_(2) battery was achieved with a binder-free MoS_(2)/carbon nanotube(CNT)photo-electrode as cathode.The unique layered structure and excellent photoelectric properties of MoS_(2) facilitate the abundant generation and rapid transfer of photo-excited carriers,which accelerate the CO_(2) reduction and Li_(2)CO_(3) decomposition upon illumination.The illuminated battery at room temperature exhibited high discharge voltage of 2.95 V and mitigated charge voltage of 3.27 V,attaining superior energy efficiency of 90.2%and excellent cycling stability of over 120 cycles.Even at an extremely low temperature of−30℃,the battery with same electrolyte can still deliver a small polarization of 0.45 V by the photoelectric and photothermal synergistic mechanism of MoS_(2)/CNT cathode.This work demonstrates the promising potential of the photo-energized wide working temperature range Li–CO_(2) battery in addressing the obstacle of charge overpotential and energy efficiency.
基金supported by the National Natural Science Foundation of China(U1663225,22293020 and 22293022)the National Key R&D Program of China(2021YFE0115800)+2 种基金the Program for Changjiang Scholars and Innovative Research Team in University(IRT_15R52)of the Chinese Ministry of Educationthe Program of Introducing Talents of Discipline to Universities-Plan 111(B20002)from the Ministry of Science and Technology and the Ministry of Education of Chinathe Belgium-China Governmental Key Cooperation Program WBI-MOST(SUB/2021/IND493971/524448)。
文摘Lithium-oxygen(Li-O_(2))batteries have attracted significant attention due to their ultra-high theoretical energy density.However,serious challenges,such as potential lag,low-rate capability,round-trip efficiency,and poor cycle stability,greatly limit their practical application.This review provides a comprehensive account of the development of Li-O_(2)batteries,elucidates the current discharge/charge mechanism,and highlights both the advantages and bottlenecks of this technology.In particular,recent research progress on various cathode materials,such as carbon-based materials,noble metals,and non-noble metals,for Li-O_(2)batteries is deeply reviewed,emphasizing the impact of design strategies,material structures,chemical compositions,and microphysical parameters on oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)kinetics,as well as discharge products and overall battery performance.This review will also shed light on future research directions for oxygen electrode catalysts and material construction to facilitate the development of Li-O_(2)batteries with maximized electrochemical performance.
基金the financial support from the National Natural Science Foundation of China, China (22005207, 52261160384)the Guangdong Basic and Applied Basic Research Foundation, Guangdong Province, China (2019A1515011819)+2 种基金the Outstanding Youth Basic Research Project of Shenzhen, Shenzhen, China (RCYX20221008092934093)the Joint Funds of the National Natural Science Foundation of China, China (U22A20140)the Science and Technology Development Fund, Macao SAR (0090/2021/A2 and 0049/2021/AGJ)
文摘Magnesium ion batteries(MIBs)are a potential field for the energy storage of the future but are restricted by insufficient rate capability and rapid capacity degradation.Magnesium-sodium hybrid ion batteries(MSHBs)are an effective way to address these problems.Here,we report a new type of MSHBs that use layered sodium vanadate((Na,Mn)V_(8)O_(20)·5H_(2)O,Mn-NVO)cathodes coupled with an organic 3,4,9,10-perylenetetracarboxylic diimide(PTCDI)anode in Mg^(2+)/Na^(+)hybrid electrolytes.During electrochemical cycling,Mg^(2+)and Na^(+)co-participate in the cathode reactions,and the introduction of Na^(+)promotes the structural stability of the Mn-NVO cathode,as cleared by several ex-situ characterizations.Consequently,the Mn-NVO cathode presents great specific capacity(249.9 mA h g^(−1)at 300 mA g^(−1))and cycling(1500 cycles at 1500 mA g^(−1))in the Mg^(2+)/Na^(+)hybrid electrolytes.Besides,full battery displays long lifespan with 10,000 cycles at 1000 mA g^(−1).The rate performance and cycling stability of MSHBs have been improved by an economical and scalable method,and the mechanism for these improvements is discussed.
基金Funded by the Jiangsu Province Industry-University-Research Cooperation Project (No.BY2018314)the Scientific Research Foundation of Jiangsu University of Technology (No.KYY18030)Jiangsu Overseas Visiting Scholar Program for University Prominent Young&Middle-aged Teachers and Presidents。
文摘3D hierarchical flowerlike WS_(2) microspheres were synthesized through a facile one-pot hydrothermal route.The as-synthesized samples were characterized by powder X-ray powder diffraction (XRD),energy-dispersive spectroscopy (EDS),scanning electron microscopy (SEM) and Raman.SEM images of the samples reveal that the hierarchical flowerlike WS_(2) microspheres with diameters of about 3-5μm are composed of a number of curled nanosheets.Electrochemical tests such as charge/discharge,cyclic voltammetry,cycle life and rate performance were carried out on the WS_(2) sample.As an anode material for lithium-ion batteries,hierarchical flowerlike WS_(2) microspheres show excellent electrochemical performance.At a current density of100 mA·g^(-1),a high specific capacity of 647.8 mA·h·g^(-1) was achieved after 120 discharge/charge cycles.The excellent electrochemical performance of WS_(2) as an anode material for lithium-ion batteries can be attributed to its special 3D hierarchical structure.
基金National Natural Science Foundation of China (22179065)Tianjin Graduate Research and Innovation Project (2022BKY018)。
文摘Ammonia plays a crucial role in contemporary society,impacting medicine,agriculture,and the chemical industry.The conventional industrial synthesis of NH_(3) through the Haber-Bosch technique,carried out under severe reaction conditions,leads to substantial energy consumption and environmental pollution.It is thus imperative for NH_(3) synthesis methods to be investigated under more favorable conditions.Synthesis of ammonia by electrocatalysis can effectively reduce the environmental damage and other urgent problems,which is a promising solution.Metal-nitrogen series batteries(M-N batteries),such as metal-nitrogen gas batteries,metal-nitrogen oxide batteries and metal-oxynitride batteries have been regarded recently as an exemplar of concurrent NH_(3) synthesis and energy production.Nonetheless,the large-scale application of these batteries is still limited by numerous challenges are currently existing in building high-efficiency M-N batteries,including poor Faradic efficiency and low NH_(3) yield.Therefore,a comprehensive overview of M-N batteries is offered,specifically focusing on advanced strategies for designing highly efficient cathode catalysts in anticipation of future developments.The metal anodes,cathodic electro-reduction reactions,and design principles are encompassed in the discussion,offering detailed insights to enhance understanding.Mechanisms,feasibility analyses,technoeconomic assessments,device combinations,and comparative evaluations are delved into in the review,contributing to a thorough comprehension of diverse systems and their application potential.Perspectives and opportunities for future research directions are also delineated.
基金financially National Natural Science Foundation of China (52201254)Natural Science Foundation of Shandong Province (ZR2023ME155, ZR2023ME085)+4 种基金project of “20 Items of University” of Jinan (202228046)Taishan Scholar Project of Shandong Province (tsqn202306226)Scientific Research Foundation for New Talents in University of Jinan (16010089104)Introducing Major Universities and Research Institutions to Jointly Build Innovative Carrier Project of Jining City (2023DYDS022)support provided by the Shandong Province Laboratory of Technology and Equipment for Molecular Diagnosis。
文摘The Li-CO_(2) battery has been under the spotlight of future battery technologies since it can achieve CO_(2)utilization and energy conversion simultaneously.However,its advancement is hampered by poor energy efficiency and limited reversibility due to the sluggish kinetics of the CO_(2) reduction and evolution reactions.Herein,a multiscale nanoporous interpenetrating phase nanohybrid of RuAl intermetallic and Cu_(2)O(MP-Cu_(2)O/RuAl) was carved by driving synchronous phase and microstructure evolutions through dealloying of one RuCuAl master alloy.The built-in RuAl intermetallic and Cu_(2)O closely stack to form abundant nano-interfaces with revolutionized electronic structure,The theoretical simulations reveal that the Cu_(2)O/RuAl interface can distinctly reduce the energy barrier of the Li_(2)CO_(3) decomposition reaction,The interconnected pore channels with large surface area can enhance catalytic site accessibility,mass transfer,and uniform deposition of the discharge products.In situ differential electrochemical mass spectrometry discloses that the CO_(2)-to-electron ratio during charging coincides with the theoretical value of 3/4,demonstrating the high efficacy of MP-Cu_(2)O/RuAl in achieving the recycling of CO_(2).The dealloying protocol provides an affordable platform to empower transition metal oxides into high-efficiency electrocatalysts by hybridizing with metallic nano-sponge for advancing the application of Li-CO_(2)batteries.
基金the Hong Kong Polytechnic University(Q-CDBG),the Science and Technology Program of Guangdong Province of China(2020A0505090001)the Research Grants Council of the Hong Kong Special Administrative Region,China(Project No.PolyU152178/20E)+2 种基金the National Natural Science Foundation of China(22379052)the Natural Science Foundation of Guangdong(No.2022A1515011667)China Postdoctoral Science Foundation(2021T140268).
文摘Inactive elemental doping is commonly used to improve the structural stability of high-voltage layered transition-metal oxide cathodes.However,the one-step co-doping strategy usually results in small grain size since the low diffusivity ions such as Ti^(4+)will be concentrated on grain boundaries,which hinders the grain growth.In order to synthesize large single-crystal layered oxide cathodes,considering the different diffusivities of different dopant ions,we propose a simple two-step multi-element co-doping strategy to fabricate core–shell structured LiCoO_(2)(CS-LCO).In the current work,the high-diffusivity Al^(3+)/Mg^(2+)ions occupy the core of single-crystal grain while the low diffusivity Ti^(4+)ions enrich the shell layer.The Ti^(4+)-enriched shell layer(~12 nm)with Co/Ti substitution and stronger Ti–O bond gives rise to less oxygen ligand holes.In-situ XRD demonstrates the constrained contraction of c-axis lattice parameter and mitigated structural distortion.Under a high upper cut-off voltage of 4.6 V,the single-crystal CS-LCO maintains a reversible capacity of 159.8 mAh g^(−1)with a good retention of~89%after 300 cycles,and reaches a high specific capacity of 163.8 mAh g^(−1)at 5C.The proposed strategy can be extended to other pairs of low-(Zr^(4+),Ta^(5+),and W6+,etc.)and high-diffusivity cations(Zn^(2+),Ni^(2+),and Fe^(3+),etc.)for rational design of advanced layered oxide core–shell structured cathodes for lithium-ion batteries.
基金financially supported by the Australian Research Council(ARC) through the Future Fellowship(FT180100705)the financial support from China Scholarship Council+3 种基金the support from UTS-HUST Key Technology Partner Seed Fundthe support from Open Project of State Key Laboratory of Advanced Special Steel,the Shanghai Key Laboratory of Advanced Ferrometallurgy,Shanghai University(SKLASS 2021-04)the Science and Technology Commission of Shanghai Municipality(22010500400)“Joint International Laboratory on Environmental and Energy Frontier Materials”and“Innovation Research Team of High–Level Local Universities in Shanghai”in Shanghai University。
文摘The widespread interest in layered P2-type Mn-based cathode materials for sodium-ion batteries(SIBs)stems from their cost-effectiveness and abundant resources.However,the inferior cycle stability and mediocre rate performance impede their further development in practical applications.Herein,we devised a wet chemical precipitation method to deposit an amorphous aluminum phosphate(AlPO_(4),denoted as AP)protective layer onto the surface of P2-type Na_(0.55)Ni_(0.1)Co_(0.7)Mn_(0.8)O_(2)(NCM@AP).The resulting NCM@5AP electrode,with a 5 wt%coating,exhibits extended cycle life(capacity retention of78.4%after 200 cycles at 100 mA g^(-1))and superior rate performance(98 mA h g^(-1)at 500 mA g^(-1))compared to pristine NCM.Moreover,our investigation provides comprehensive insights into the phase stability and active Na^(+)ion kinetics in the NCM@5AP composite electrode,shedding light on the underlying mechanisms responsible for the enhanced performance observed in the coated electrode.
基金the financial support from the National Key Research and Development Program of China(2022YFB2502003)the Guangdong Basic and Applied Basic Research Foundation(2023B1515040011)。
文摘Bromine has attracted significant attention as a cathode material for aqueous batteries due to its high reduction potential of 1.05 V(Br_(3)^(-)+2e~-■3Br~-),impressive theoretical specific capacity of 223 mA h g^(-1),and rapid reaction kinetics in the electrolyte.However,searching for compatible anode materials to match with bromine has posed a challenge due to its highly corrosive nature.In this study,we developed oxygen-deficient MoO_(3) with TiO_(2) coating(referred to as MoO_(3-x)@TiO_(2))as an anode material to pair with a bromine cathode in static full batteries.The oxygen deficiency contributes to enhanced electronic and protonic diffusion within the MoO_(3-x)lattice,while the TiO_(2) coating mitigates structural dissolution and proton trapping during cycling.The MoO_(3-x)@TiO_(2) demonstrates fast charge storage kinetics and excellent resistance to bromine corrosion.The impressive compatibility between MoO_(3-x)@TiO_(2) and bromine enables the construction of membrane-less full batteries with exceptional rate capability and cyclic stability.The MoO_(3-x)@TiO_(2)-bromine battery achieves an energy density of70.8 W h kg^(-1)at a power density of 328.1 W kg^(-1),showcasing an impressive long-term cyclic life of 20,000 cycles.Our study provides valuable insights for the development of high-performance aqueous secondary batteries.
基金supported by the National Natural Science Foundation of China(NSFC No.22179005)the BIT Research and Innovation Promoting Project(Grant No.2022YCXY008)supported by Cunzhong Zhang at the Beijing Institute of Technology.
文摘Although biomass-derived carbon(biochar)has been widely used in the energy field,the relation between the carbonization condition and the physical/chemical property of the product remains elusive.Here,we revealed the carbonization condition's effect on the morphology,surface property,and electrochemical performance of the obtained carbon.An open slit pore structure with shower-puff-like nanoparticles can be obtained by finely tuning the carbonization temperature,and its unique pore structure and surface properties enable the Li–O_(2) battery with cycling longevity(221 cycles with 99.8%Coulombic efficiency at 0.2 mA cm^(−2) and controlled discharge–charge depths of 500 mAh g^(−1))and high capacity(16,334 mAh g^(−1) at 0.02 mA cm^(−2)).This work provides a greater understanding of the mechanism of the biochar carbonization procedure under various pyrolysis conditions,paving the way for future study of energy storage devices.
基金supported by the National Natural Science Foundation of China (51972225)。
文摘The Sabatier principle has been widely used for designing electrocatalysts for energy conversion applications,but it is rarely mentioned in the research of cathode catalyst of Li-CO_(2) batteries.In our work,the"volcanic"relationship between the catalytic activity and the adsorption energy of the catalyst to the intermediates is first demonstrated based on the first-principles calculation,which meets the Sabatier principle and can be used to design the cathode catalysts.The increases in the number of nitrogenvacancy in WN shift the d-band center and increase the interaction with the reactants.The catalytic activity increases first and then decreases with the increase of adsorption energy,which was proved in the experiment.The optimal catalyst for moderate adsorption of intermediate makes the thin LiaCO_(3) distribute evenly.It exhibits a median voltage difference of 0.68 V and an energy efficiency of 84.33%at20μA cm^(-2)with a limited capacity of 200μA h cm^(-2).