High-capacity LiBH_(4)is a promising solid hydrogen storage material.However,the large electron cloud density between the B-H bonds in LiBH_(4)induces high dehydrogenation temperatures and sluggish dehydrogenation kin...High-capacity LiBH_(4)is a promising solid hydrogen storage material.However,the large electron cloud density between the B-H bonds in LiBH_(4)induces high dehydrogenation temperatures and sluggish dehydrogenation kinetics.To solve the above problems,it is proposed to enhance the hydrogen storage properties of LiBH_(4)through the synergistic effect of Brønsted and Lewis acid in Hβzeolite.Composite hydrogen storage systems with different mass ratios were prepared by simple ball-milling.At a LiBH_(4)-to-Hβmass ratio of 6:4,the 6LiBH_(4)-4Hβsystem released hydrogen at 190℃and achieved a hydrogen release capacity of 7.0 wt%H_(2)upon heating to 400℃.More importantly,the hydrogen release capacity of the system reached 6.02 wt%at 350℃under isothermal conditions after 100 min and 7.2 wt%at 400℃under isothermal conditions after 80 min,whereas the pristine LiBH_(4)only achieved 2.2 wt%.The improvement in hydrogen storage performance of the system was mainly attributed to two factors:(i)Lewis acid sites with acceptable electrons in the Hβweaken the electron density of B-H bonds in LiBH_(4),and(ii)the H+proton from the Brønsted acid sites and H−of LiBH_(4)undergo a H^(+)+H^(−)=H_(2)reaction.Theoretical calculations revealed that the Lewis and Brønsted acid sites in the Hβzeolite are conducive to the weakening of B-H bonds and that storage charge transfer occurs near the Lewis acid sites.The present work provides new insights into improving the hydrogen storage performance of LiBH_(4)by weakening the B-H bonds in the LiBH_(4).展开更多
The role of catalysts in enhancing the hydrogen storage kinetics of the Mg/MgH_(2)system is pivotal.However,the exploration of efficient catalysts and the underlying principles of their design remain both a prominent ...The role of catalysts in enhancing the hydrogen storage kinetics of the Mg/MgH_(2)system is pivotal.However,the exploration of efficient catalysts and the underlying principles of their design remain both a prominent focus and a significant challenge in current research.In this study,we present a bimetallic oxide of Bi_(2)Ti_(2)O_(7)hollow sphere as a highly effective catalyst for MgH_(2).As a result,the Bi_(2)Ti_(2)O_(7)-catalyzed Mg/MgH_(2)system lowers the hydrogen desorption initiation temperature to 194.3℃,reduces the peak desorption temperature to 245.6℃,decreases the dehydrogenation activation energy to 82.14 kJ·mol^(−1),and can absorb 5.4 wt.%of hydrogen within 60 s at 200℃,demonstrating outstanding hydrogen ab/desorption kinetics,compared to pure MgH_(2).Additionally,it can maintain a high hydrogen capacity of 5.2 wt.%,even after 50 dehydrogenation cycles,showing good cycle stability.The characterization results show that the high-valent Bi and Ti in Bi_(2)Ti_(2)O_(7)are reduced to their low-valent or even zero-valent metallic states during the dehydrogenation and hydrogenation process,thus establishing an in-situ multivalent and multi-element catalytic environment.Density functional theory calculations further reveal that the synergistic effects between Bi and Ti in the Bi-Ti mixed oxide facilitate the cleavage of Mg-H bonds and lower the kinetic barrier for the dissociation of hydrogen molecules,thereby substantially enhancing the kinetics of the Mg/MgH_(2)system.This study presents a strategic method for developing efficient catalysts for hydrogen storage materials by harnessing the synergistic effects of metal elements.展开更多
Lithium and manganese-rich layered oxides(LMROs)have attracted extensive attention and are promising cathode materials for next-generation lithium ion batteries due to their high capacities and high energy densities.H...Lithium and manganese-rich layered oxides(LMROs)have attracted extensive attention and are promising cathode materials for next-generation lithium ion batteries due to their high capacities and high energy densities.However,LMRO cathode suffers from severe capacity and voltage fading originating from irreversible surface oxygen evolution.Herein,we propose a facile redox couple strategy by introducing nitroxyl radicals species to regulate the surface anionic redox reaction of LMRO cathode.Differential electrochemical mass spectroscopy,X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy analyses demonstrate that during charge process,the peroxide ion O_(2)^(2−)on the surface generated from the oxidation of lattice O^(2-)could be reduced back to stable O^(2-)by redox couple in time,thus avoiding oxygen evolution and structure degradation,as well as enhancing bulk oxygen redox activity.The enhanced LMRO electrode delivers a high capacity of 220.3 mAh g^(−1)at 1 C.An excellent cycling stability with a capacity retention of 94.4%is achieved after 500 cycles,as well as a suppressed voltage decay with only 1.12 mV per cycle.展开更多
Hydrogen energy is expected to be an“ideal fuel”in the era of decarbonization.The discovery,de-velopment,and modification of high-performance hydrogen storage materials are the keys to the fu-ture development of sol...Hydrogen energy is expected to be an“ideal fuel”in the era of decarbonization.The discovery,de-velopment,and modification of high-performance hydrogen storage materials are the keys to the fu-ture development of solid-state hydrogen storage and hydrogen energy utilization.Magnesium hydride(MgH_(2)),with its high hydrogen storage capacity,abundant natural reserves,and environmental friend-liness,has been extensively researched.Herein,we briefly summarize the typical structure and hy-drogenation/dehydrogenation reaction mechanism of MgH_(2)and provide a comprehensive overview of strategies to effectively tune the thermodynamics and kinetics of Mg-based materials,such as alloy-ing,nanosizing,the introduction of additives,and composite modification.With substantial efforts,great achievements have been achieved,such as lower absorption/desorption temperatures and better cy-cling stability.Nonetheless,some pivotal issues remain to be addressed,such as unfavorable hydro-genation/dehydrogenation factors,harsh conditions,slow kinetics,incomplete dehydrogenation,low hy-drogen purity,expensive catalysts,and a lack of valid exploration of mechanisms in the hydrogena-tion/dehydrogenation process.Lastly,some future development prospects of MgH_(2)in energy-efficient conversion and storage have been presented,including advanced manufacturing ways,stabilization of nanostructures,the introduction of additives combined with structural modification,and utilization of advanced characterization techniques.展开更多
MgH_(2)is a promising solid-state hydrogen storage material.However,its high thermodynamics and sluggish kinetics hinder its practical application.Catalytic strategy is effective in improving its kinetic performance.N...MgH_(2)is a promising solid-state hydrogen storage material.However,its high thermodynamics and sluggish kinetics hinder its practical application.Catalytic strategy is effective in improving its kinetic performance.Nevertheless,the highly efficient catalysts or additives are normally of low-yield in fabrication with high cost.In this work,a novel structural LaVO_(4)fabricated by a low-cost method of spraying dry followed by a calcination is used as a catalytic additive for the hydrogen storage of MgH_(2).With an optimized addition of LaVO_(4),the overall hydrogen storage performances of MgH_(2)are significantly improved.An onset dehydrogenation temperature of only 183℃is obtained after an initial activation of dehydrogenation and hydrogenation.The system can desorb 5.7 wt%H_(2)at 250℃within 10 min and maintains a dehydrogenation capacity of 5.0 wt%H_(2)after 50 cycles.It is found that LaVO_(4)is transferred to lanthanum hydride and metallic vanadium in the initial dehydrogenation process,the former acts as a highly effective catalyst for the hydrogen storage of MgH_(2)and the latter undergoes reversible hydrogenation and dehydrogenation in the subsequent cycles.The structural design of the catalyst and its scalable fabrication are highly valuable in realizing the practical application of catalytic strategy for the hydrogen storage of MgH_(2).展开更多
LiBH_(4) containing 18.5 wt.%H_(2) is an attractive high-capacity hydrogen storage material,however,it suffers from high operation temperature and poor reversibility.Herein,a novel and low-cost bifunctional additive,w...LiBH_(4) containing 18.5 wt.%H_(2) is an attractive high-capacity hydrogen storage material,however,it suffers from high operation temperature and poor reversibility.Herein,a novel and low-cost bifunctional additive,waxberry-like Fe_(3)O_(4) secondary nanospheres assembled from ultrafine primary Fe_(3)O_(4) nanoparticles,is synthesized,which exhibits significant destabilization and bidirectional catalyzation towards(de)hydrogenation of LiBH_(4).With an optimized addition of 30 wt.% waxberry-like Fe_(3)O_(4),the system initiated dehydrogenation below 100℃ and released a total of 8.1 wt.%H_(2) to 400℃.After 10 cycles,a capacity retention of 70% was achieved,greatly superior to previously reported oxides-modified systems.The destabilizing and catalyzing mechanisms of waxberry-like Fe_(3)O_(4) on LiBH_(4) were systematically analyzed by phase and microstructural evolutions during dehydrogenation and hydrogenation cycling as well as density functional theory(DFT)calculations.The present work provides new insights in developing advanced nano-additives with unique structural and multifunctional designs towards LiBH4 hydrogen storage.展开更多
Although MgH_(2)is widely deemed to be the most promising solid-state hydrogen storage materials for the medium-high temperature fuelcell applications expected in the near future,the high-temperature desorption and sl...Although MgH_(2)is widely deemed to be the most promising solid-state hydrogen storage materials for the medium-high temperature fuelcell applications expected in the near future,the high-temperature desorption and sluggish hydrogen absorption/desorption kinetics are the major challenges for its applications.Herein,reduced graphene oxide/patronite nanoparticle composite(rGO@VS_(4))is successfully synthesized using an ionic liquid(IL)-assisted hydrothermal method,and superior catalytic effects originated from the rGO@VS_(4)composite precursor towards the hydrogen storage reaction of MgH_(2)are systematically investigated.The VS_(4)reacts with MgH_(2)leads to the in-situ formed and uniformly scattered of metallic V and MgS during both ball-milling and the initial hydrogen desorption,and the synergic catalytic effect of metallic V and MgS facilitates the improved hydrogen desorption of MgH_(2).The MgH_(2)-15 wt%rGO@VS_(4)composite starts releasing hydrogen at 180℃and peaks at 220℃,which is 145℃and 128℃lower than that of the Pristine MgH_(2),respectively.The energy required for H_(2)desorption from MgH_(2)is decreased to 63.8 kJ mol^(-1),58.9 kJ mol^(-1)lower than that of the Pristine MgH_(2).Furthermore,the MgH_(2)-15 wt%rGO@VS_(4)composite shows excellent cycling stability,of which reversible hydrogen capacity can stabilize at about 5.9 wt%with capacity retention of 98.2%at 300℃for 100 cycles.This study provides a deeper insight into metallic V and MgS to enhance the hydrogen desorption of solid-state hydrogen storage materials and also offers a perspective for the construction of high-activity catalysts for solid-state hydrogen storage materials.展开更多
Lithium sulfide(Li_(2)S)is widely regarded as the next-generation cathode material for rechargeable batteries due to its satisfactory theoretical capacity and excellent compatibility with lithium-free anodes.However,t...Lithium sulfide(Li_(2)S)is widely regarded as the next-generation cathode material for rechargeable batteries due to its satisfactory theoretical capacity and excellent compatibility with lithium-free anodes.However,the large-scale applications of Li_(2)S cathodes are limited by the shuttle effect of soluble intermediate lithium polysulfides(LiPSs)and the sluggish redox kinetics of the interconversion between Li_(2)S and sulfur(S).Herein,we report novel nitrogen-doped carbon nanoflakes in-situ embedded with WN-Ni_(2)P heterostructures(WN-Ni_(2)P@NCN)as a multifunctional host to promote the cycling performance and reaction kinetics of Li_(2)S.After loading Li_(2)S,the WNNi_(2)P@NCN/Li_(2)S exhibits stable reversible capacity of 597mAh g^(-1)at 0.5 A g^(-1)over 150 cycles,and superior cycling stability over 800 cycles.The high reversible capacities,excellent cycling properties and superior reaction kinetics of WN-Ni_(2)P@NCN/Li_(2)S are attributed to the strong LiPSs fixation,remarkable catalytic activation and high electronic/ionic conductivity of the WN-Ni_(2)P@NCN framework,confirmed by the experiment and the density function theory calculation results.This work offers a new strategy for designing heterostructure nanoflakes with metal nitride and metal phosphide to facilitate the applications of advanced lithium-sulfur batteries.展开更多
The rapid advance of mild aqueous zinc-ion batteries(ZIBs)is driving the development of the energy storage system market.But the thorny issues of Zn anodes,mainly including dendrite growth,hydrogen evolution,and corro...The rapid advance of mild aqueous zinc-ion batteries(ZIBs)is driving the development of the energy storage system market.But the thorny issues of Zn anodes,mainly including dendrite growth,hydrogen evolution,and corrosion,severely reduce the performance of ZIBs.To commercialize ZIBs,researchers must overcome formidable challenges.Research about mild aqueous ZIBs is still developing.Various technical and scientific obstacles to designing Zn anodes with high stripping efficiency and long cycling life have not been resolved.Moreover,the performance of Zn anodes is a complex scientific issue determined by various parameters,most of which are often ignored,failing to achieve the maximum performance of the cell.This review proposes a comprehensive overview of existing Zn anode issues and the corresponding strategies,frontiers,and development trends to deeply comprehend the essence and inner connection of degradation mechanism and performance.First,the formation mechanism of dendrite growth,hydrogen evolution,corrosion,and their influence on the anode are analyzed.Furthermore,various strategies for constructing stable Zn anodes are summarized and discussed in detail from multiple perspectives.These strategies are mainly divided into interface modification,structural anode,alloying anode,intercalation anode,liquid electrolyte,non-liquid electrolyte,separator design,and other strategies.Finally,research directions and prospects are put forward for Zn anodes.This contribution highlights the latest developments and provides new insights into the advanced Zn anode for future research.展开更多
The conjugation of external species with twodimensional(2D)materials has broad application prospects.In this study,we have explored the potential of noble metal/2D MOF heterostructures in hydrogen storage.Specifically...The conjugation of external species with twodimensional(2D)materials has broad application prospects.In this study,we have explored the potential of noble metal/2D MOF heterostructures in hydrogen storage.Specifically,the MgH_(2)-Ni-MOF@Pd system has shown remarkable hydrogen desorption/sorption performances,starting to liberate hydrogen at 1810C,which is 2300C lower than that of pristine MgH2.Under the catalytic effect of Ni-MOF@Pd,the dehydrogenation apparent activation energy of MgH2 is noticeably decreased from(133.5±17.5)to(34.58±1.87)kJ·moL^(-1),and the hydrogenation apparent activation energy is reduced from(70.41±7.43)to(25.78±4.64)kJ·moL^(-1),which is lowered by 63.4%.The fully-dehydrogenated MgH2-NiMOF@Pd composite rapidly uptakes hydrogen,with 2.62wt%at 100℃and 6.06 wt%at 150℃within 300 s,respectively.The mechanism analysis of MgH2 catalyzed by Ni-MOF@Pd has revealed that the transformation of Mg_2Ni and Mg_2NiH_4 could act as a"hydrogen pump",providing numerous channels for fast diffusion and transport of hydrogen atoms.Moreover,in the dehydrogenation process,the element Pd reacts with MgH_(2)to form the MgPd alloy phase,which makes MgH_(2)take precedence to decompose through the Mg-Pd alloy rather than self-decomposition,further reducing thermal stability and improving de/hydrogenation kinetics.The synergistic effect of Mg-Pd,Mg_2Ni,and the special ultra-thin 2D sheet structure of the additive is the main reason for the good hydrogen storage property of MgH_(2)-Ni-MOF@Pd.Our findings provide inspiration for designing efficient multifunctional additives with unique morphologies to optimize the hydrogen desorption/sorption behaviors of hydrogen storage materials.展开更多
Lithium is considered to be the ‘‘holy grail” for the application of energy storage due to its highest theoretical capacity and lowest anode potential. However, one of the grand difficulties in the development of l...Lithium is considered to be the ‘‘holy grail” for the application of energy storage due to its highest theoretical capacity and lowest anode potential. However, one of the grand difficulties in the development of lithium-based batteries is the lithium dendrite growth that leads to capacity fading and electrode degradation over long-term cycling. Compared with conventional electrolyte modifications, artificial solid electrolyte interfaces(SEI) synthesis and framework designing approaches, tuning surface morphology of lithium anode is the direct route to induce homogeneous Li ion deposition. Due to the high chemical activity of lithium metal, however, controllable growth of lithium micro/nanostructures by traditionally chemical approaches is still a big challenge. Herein, we have developed a facile compression route to fabricate lithium anode with abundant stepped lithium structures. The electrochemical results demonstrate that the dendritic growth issue is effectively suppressed by orderly arranged stepped lithium structures. After 90 cycles, a high discharge capacity of 954 mAh g^(-1) is achieved, which is 2.7times that of the uncompressed lithium anode(342 mAh g). First-principles calculations reveal that the orderly arranged stepped lithium structures are lithiophilic active sites to adsorb Li ion, which contributes to homogeneous deposition of Li ion on lithium anode, eventually solving the lithium dendrite issue. This work paves a new road to suppress dendritic growth, which will provide some new ideas to design long recycling sodium, potassium and zinc, and other metal anode batteries.展开更多
The development of high-performance binders is a simple but effective approach to address the rapid capacity decay of high-capacity anodes caused by large volume change upon lithiation/delithiation.Herein,we demonstra...The development of high-performance binders is a simple but effective approach to address the rapid capacity decay of high-capacity anodes caused by large volume change upon lithiation/delithiation.Herein,we demonstrate a unique organic/inorganic hybrid binder system that enables an efficient in situ crosslinking of aqueous binders(e.g.,sodium alginate(SA)and carboxymethyl cellulose(CMC))by reacting with an inorganic crosslinker(sodium metaborate hydrate(SMH))upon vacuum drying.The resultant 3D interconnected networks endow the binders with strong adhesion and outstanding self-healing capability,which effectively improve the electrode integrity by preventing fracturing and exfoliation during cycling and facilitate Li^(+)ion transfer.SiO anodes fabricated from the commercial microsized powders with the SA/0.2SMH binder maintain 1470 mAh g^(-1)of specific capacity at 100 mA g^(-1)after 200 cycles,which is 5 times higher than that fabricated with SA binder alone(293 mAh g^(-1)).Nearly,no capacity loss was observed over 500 cycles when limiting discharge capacity at 1500 mAh g^(-1).The new binders also dramatically improved the performance of Fe_(2)O_(3),Fe_(3)O_(4),NiO,and Si electrodes,indicating the excellent applicability.This finding represents a novel strategy in developing high-performance aqueous binders and improves the prospect of using high-capacity anode materials in Li-ion batteries.展开更多
TiFe alloys are AB-based hydrogen storage materials with unique characteristics and a wide range of applications.However,the presence of impurity gases(such as O_(2),CO,CO_(2),and CH4)has a considerable impact on the ...TiFe alloys are AB-based hydrogen storage materials with unique characteristics and a wide range of applications.However,the presence of impurity gases(such as O_(2),CO,CO_(2),and CH4)has a considerable impact on the hydrogen storage capacity and kinetics of TiFe alloys,drastically limiting their practical application in hydrogen storage.Consequently,in this study,we investigated the hydrogen absorption kinetics and cycling performance of the TiFe_(0.9) alloy in the presence of common impurity gases(including CH4,CO,CO_(2),and O_(2))and determined the corresponding poisoning mechanisms.Specifically,we found that CH4 did not react with the alloy but acted through physical coverage.In contrast,CO and CO_(2) occupy the active sites for H_(2),significantly impeding the dissociation and absorption of H_(2).In addition,O_(2) reacts directly with the alloy to form a passivating layer that prevents hydrogen absorption.These findings were fur-ther corroborated by in situ Fourier transform infrared spectrometry(FTIR)and density functional theory(DFT).The relationship between the adsorption energies of the impurity gases and hydrogen obtained through DFT calculations complements the experimental results.Un-derstanding these poisoning behaviors is crucial for designing Ti-based high-entropy hydrogen storage alloy alloys with enhanced resist-ance to poisoning.展开更多
A novel poly(ether block amide)(PEBA)based solid-state polymer electrolyte(SPE)was prepared using a casting method,in which 20wt%lithium(Li)bis-(trifluoromethanesulfonyl)imide(LiTFSI)and aluminum oxide(Al_(2)O_(3))nan...A novel poly(ether block amide)(PEBA)based solid-state polymer electrolyte(SPE)was prepared using a casting method,in which 20wt%lithium(Li)bis-(trifluoromethanesulfonyl)imide(LiTFSI)and aluminum oxide(Al_(2)O_(3))nanoparticles were used as the Li salt and solid plasticizer,respectively.In the case of addition of 3wt%Al_(2)O_(3) nanoparticles,ion conductivity of the obtained PEBA 2533-20wt%LiTFSI-3wt%Al_(2)O_(3) SPE was 3.57×10^(−5) S cm^(−1) at 25°C.Furthermore,the Li symmetrical battery assembled with it showed excellent cycling stability(1000 h)at 0.1 mA cm^(−2).While,the assembled all-solid-state Li/PEBA 2533-20%LiTFSI-3wt%Al_(2)O_(3)/LiFePO 4(areal capacity:0.15 mAh cm^(−2))battery maintained 94.9%of the maximal capacity(133.9 mAh g^(−1@0.1) mA cm^(−2))at 60°C even after 650 cycles with a superior average coulombic efficiency(CE)of 99.84%.By using X-ray photoelectron spectroscope(XPS),self-aggregation layer(SAL)of polyamide 12(PA12)of PEBA 2533 was discovered,which should contribute to promoting the robustness of lithium fluoride(LiF)enriched solid-electrolyte interphase(SEI)layer.In addition,it is considered that the state of interface between SPE and cathode should be the cause of voltage polarization of the full cell.展开更多
Solid-state batteries(SSBs) are highly attractive on account of their high energy density and good safety.In high-voltage and high-current conditions,however,the interface reactions,structural changes,and decompositio...Solid-state batteries(SSBs) are highly attractive on account of their high energy density and good safety.In high-voltage and high-current conditions,however,the interface reactions,structural changes,and decomposition of the electrolyte impede the transmission of lithium ions in all-solid-state lithium batteries(ASSLBs),significantly reducing the charging and discharging capacity and cycling stability of the battery and therefore restricting its practical applications.The main content of review is to conduct an in-depth analysis of the existing problems of solid-state batteries from the aspects of interface reactions,material failure,ion migration,and dendrite growth,and points out the main factors influencing the electrochemical performance of ASSLBs.Additionally,the compatibility and ion conduction mechanisms between polymer electrolytes,inorganic solid electrolytes,and composite electrolytes and the electrode materials are discussed.Furthermore,the perspectives of electrode materials,electrolyte properties,and interface modification are summarized and prospected,providing new optimization directions for the future commercialization of high-voltage solid-state electrolytes.展开更多
In the realm of sodium-ion batteries(SIBs),Mn-based layered oxide cathodes have garnered considerable attention owing to their anionic redox reactions(ARRs).Compared to other types of popular sodium-ion cathodes,Mn-ba...In the realm of sodium-ion batteries(SIBs),Mn-based layered oxide cathodes have garnered considerable attention owing to their anionic redox reactions(ARRs).Compared to other types of popular sodium-ion cathodes,Mn-based layered oxide cathodes with ARRs exhibit outstanding specific capacity and energy density,making them promising for SIB applications.However,these cathodes still face some scientific challenges that need to be addressed.This review systematically summarizes the composition,structure,oxygen-redox mechanism,and performance of various types of Mn-based cathodes with ARRs,as well as the main scientific challenges they face,including sluggish ion diffusion,cationic migration,O_(2) release,and element dissolution.Currently,to resolve these challenges,efforts mainly focus on six aspects:synthesis methods,structural design,doped modification,electrolyte design,and surface engineering.Finally,this review provides new insights for future direction,encompassing both fundamental research,such as novel cathode types,interface optimization,and interdisciplinary research,and considerations from an industrialization perspective,including scalability,stability,and safety.展开更多
Owing to anionic redox,cathode materials containing layered Li-rich Mn-based oxides(LLOs)are promising for the development of next-generation lithium-ion batteries(LIBs)with a large energy density(~500–600 Wh·kg...Owing to anionic redox,cathode materials containing layered Li-rich Mn-based oxides(LLOs)are promising for the development of next-generation lithium-ion batteries(LIBs)with a large energy density(~500–600 Wh·kg^(−1)).However,these LLOs are easily degraded during cycling,which limits their lifespan.So far,the degradation mechanism is still under debate.Herein,LLOs are post-treated through implantation with energetic Ti ion flux(Ti-LLO),which modifies the structure of LLOs both at the surface and within the bulk.Unlike the dominant R3m phase(73.24%)observed in LLOs,the phase structure of Ti-LLO is altered,with Li-rich C2/m accounting for 67.72%in the bulk,alongside the formation of a thin(approximately 2 nm),uniform,and continuous Li-Ti-O spinel layer at the surface.Apart from phase structure changes,chemical valence states of transition metals and O,as well as their evolution,are analyzed and compared to charge transport kinetics to elucidate their contributions to the enhanced discharge capacity in Ti-LLOs.Besides,the role of the Li-Ti-O spinel layer at the surface in providing anticorrosion protection at the interface of LLOs/electrolyte during cycling is evaluated.As a result,we demonstrate that a superhigh discharge capacity(335.3 mAh·g^(−1))at 0.1 C can be achieved,along with prolonged cycling stability(showing capacity retention of approximately 80%after 500 cycles at 1 C)through these modifications.Moreover,we confirmed the universality of the strategy by implanting other ions,which offers practical strategies for achieving high performance in LLO cathode materials through thermodynamics and kinetics pathways.展开更多
The electric double layer(EDL)at the electrochemical interface is crucial for ion transport,charge transfer,and surface reactions in aqueous rechargeable zinc batteries(ARZBs).However,Zn anodes routinely encounter per...The electric double layer(EDL)at the electrochemical interface is crucial for ion transport,charge transfer,and surface reactions in aqueous rechargeable zinc batteries(ARZBs).However,Zn anodes routinely encounter persistent dendrite growth and parasitic reactions,driven by the inhomogeneous charge distribution and water-dominated environment within the EDL.Compounding this,classical EDL theory,rooted in meanfield approximations,further fails to resolve molecular-scale interfacial dynamics under battery-operating conditions,limiting mechanistic insights.Herein,we established a multiscale theoretical calculation framework from single molecular characteristics to interfacial ion distribution,revealing the EDL’s structure and interactions between different ions and molecules,which helps us understand the parasitic processes in depth.Simulations demonstrate that water dipole and sulfate ion adsorption at the inner Helmholtz plane drives severe hydrogen evolution and by-product formation.Guided by these insights,we engineered a“water-poor and anion-expelled”EDL using 4,1’,6’-trichlorogalactosucrose(TGS)as an electrolyte additive.As a result,Zn||Zn symmetric cells with TGS exhibited stable cycling for over 4700 h under a current density of 1 mA cm^(−2),while NaV_(3)O_(8)·1.5H_(2)O-based full cells kept 90.4%of the initial specific capacity after 800 cycles at 5 A g^(−1).This work highlights the power of multiscale theoretical frameworks to unravel EDL complexities and guide high-performance ARZB design through integrated theory-experiment approaches.展开更多
Nanoscaled catalysts have attracted much more attention due to their more abundant active sites and better dispersion than their bulky counterparts.In this work,VH_(x) nanoparticles smaller than 10 nm in average size ...Nanoscaled catalysts have attracted much more attention due to their more abundant active sites and better dispersion than their bulky counterparts.In this work,VH_(x) nanoparticles smaller than 10 nm in average size are successfully synthesized by a simple solid-state ball milling coupled with THF washing process,which are proved to be highly effective in enhancing the hydrogen absorption/desorption kinetics of MgH_(2) at moderate temperatures.The nano-VH_(x)-modified MgH_(2) releases hydrogen from 182℃,which is 88℃ lower than additive-free MgH_(2).The release of hydrogen amounts to 6.3 wt%H within 10 min at 230℃ and 5.6 wt%H after 30 min at 215℃ with initial vacuum.More importantly,the dehydro-genated MgH_(2)+10 wt.%nano-VH_(x) rapidly absorbs 5.2 wt%H within 3 min at 50℃ under 50 bar H_(2).It even takes up 4.3 wt%H within 30 min at room temperature(25℃)under 10 bar H_(2),exhibiting supe-rior hydrogenation kinetics to most of the previous reports.Mechanistic analyzes disclose the reversible transformation between V and V-H species during the hydrogen desorption-absorption process.The ho-mogeneously distributed V-based species is believed to act as hydrogen pump and nucleation sites for MgH_(2) and Mg,respectively,thus triggering fast hydrogenation/dehydrogenation kinetics.展开更多
The practical application of lithium-sulfur batteries is severely hampered by the poor conductivity,polysulfide shuttle effect and sluggish reaction kinetics of sulfur cathodes.Herein,a hierarchi-cally porous three-di...The practical application of lithium-sulfur batteries is severely hampered by the poor conductivity,polysulfide shuttle effect and sluggish reaction kinetics of sulfur cathodes.Herein,a hierarchi-cally porous three-dimension(3D)carbon architecture assembled by cross-linked carbon leaves with implanted atomic Co-N4 has been deli-cately developed as an advanced sulfur host through a SiO_(2)-mediated zeolitic imidazolate framework-L(ZIF-L)strategy.The unique 3D architectures not only provide a highly conductive network for fast electron transfer and buffer the volume change upon lithiation-delithi-ation process but also endow rich interface with full exposure of Co-N4 active sites to boost the lithium polysulfides adsorption and conversion.Owing to the accelerated kinetics and suppressed shuttle effect,the as-prepared sulfur cathode exhibits a superior electrochemical perfor-mance with a high reversible specific capacity of 695 mAh g^(−1) at 5 C and a low capacity fading rate of 0.053%per cycle over 500 cycles at 1 C.This work may provide a promising solution for the design of an advanced sulfur-based cathode toward high-performance Li-S batteries.展开更多
基金supported by the National Natural Science Foundation of China(No.52201274)the Project of Education Department of Shanxi Province(No.22JK0419).
文摘High-capacity LiBH_(4)is a promising solid hydrogen storage material.However,the large electron cloud density between the B-H bonds in LiBH_(4)induces high dehydrogenation temperatures and sluggish dehydrogenation kinetics.To solve the above problems,it is proposed to enhance the hydrogen storage properties of LiBH_(4)through the synergistic effect of Brønsted and Lewis acid in Hβzeolite.Composite hydrogen storage systems with different mass ratios were prepared by simple ball-milling.At a LiBH_(4)-to-Hβmass ratio of 6:4,the 6LiBH_(4)-4Hβsystem released hydrogen at 190℃and achieved a hydrogen release capacity of 7.0 wt%H_(2)upon heating to 400℃.More importantly,the hydrogen release capacity of the system reached 6.02 wt%at 350℃under isothermal conditions after 100 min and 7.2 wt%at 400℃under isothermal conditions after 80 min,whereas the pristine LiBH_(4)only achieved 2.2 wt%.The improvement in hydrogen storage performance of the system was mainly attributed to two factors:(i)Lewis acid sites with acceptable electrons in the Hβweaken the electron density of B-H bonds in LiBH_(4),and(ii)the H+proton from the Brønsted acid sites and H−of LiBH_(4)undergo a H^(+)+H^(−)=H_(2)reaction.Theoretical calculations revealed that the Lewis and Brønsted acid sites in the Hβzeolite are conducive to the weakening of B-H bonds and that storage charge transfer occurs near the Lewis acid sites.The present work provides new insights into improving the hydrogen storage performance of LiBH_(4)by weakening the B-H bonds in the LiBH_(4).
基金supported by the National Key Research and Development Program of China(No.2024YFB4007204,2022YFB4004301)the National Natural Science Founda-tion of China(Grant Nos.52477220,52301287,22005353)+2 种基金the Two-chain Integration Key Project of Shaanxi Province(2021LLRH-09)the Key Research and Development Program of Shaanxi Province(No.2024CY2-GJHX-44,2024CY2-GJHX-53,2024GX-ZDCYL-04-06)the Key Industrial Chain Technology Research Program of Xi’an city(23LL-RHZDZX0017).
文摘The role of catalysts in enhancing the hydrogen storage kinetics of the Mg/MgH_(2)system is pivotal.However,the exploration of efficient catalysts and the underlying principles of their design remain both a prominent focus and a significant challenge in current research.In this study,we present a bimetallic oxide of Bi_(2)Ti_(2)O_(7)hollow sphere as a highly effective catalyst for MgH_(2).As a result,the Bi_(2)Ti_(2)O_(7)-catalyzed Mg/MgH_(2)system lowers the hydrogen desorption initiation temperature to 194.3℃,reduces the peak desorption temperature to 245.6℃,decreases the dehydrogenation activation energy to 82.14 kJ·mol^(−1),and can absorb 5.4 wt.%of hydrogen within 60 s at 200℃,demonstrating outstanding hydrogen ab/desorption kinetics,compared to pure MgH_(2).Additionally,it can maintain a high hydrogen capacity of 5.2 wt.%,even after 50 dehydrogenation cycles,showing good cycle stability.The characterization results show that the high-valent Bi and Ti in Bi_(2)Ti_(2)O_(7)are reduced to their low-valent or even zero-valent metallic states during the dehydrogenation and hydrogenation process,thus establishing an in-situ multivalent and multi-element catalytic environment.Density functional theory calculations further reveal that the synergistic effects between Bi and Ti in the Bi-Ti mixed oxide facilitate the cleavage of Mg-H bonds and lower the kinetic barrier for the dissociation of hydrogen molecules,thereby substantially enhancing the kinetics of the Mg/MgH_(2)system.This study presents a strategic method for developing efficient catalysts for hydrogen storage materials by harnessing the synergistic effects of metal elements.
基金support from the National Key Research and Development Program of China(No.2022YFB2502000)the National Natural Science Foundation of China(Grant Nos.52201277)+1 种基金the key program of the National Natural Science Foundation of China(Grant Nos.51831009)the National Outstanding Youth Foundation of China(No.52125104).
文摘Lithium and manganese-rich layered oxides(LMROs)have attracted extensive attention and are promising cathode materials for next-generation lithium ion batteries due to their high capacities and high energy densities.However,LMRO cathode suffers from severe capacity and voltage fading originating from irreversible surface oxygen evolution.Herein,we propose a facile redox couple strategy by introducing nitroxyl radicals species to regulate the surface anionic redox reaction of LMRO cathode.Differential electrochemical mass spectroscopy,X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy analyses demonstrate that during charge process,the peroxide ion O_(2)^(2−)on the surface generated from the oxidation of lattice O^(2-)could be reduced back to stable O^(2-)by redox couple in time,thus avoiding oxygen evolution and structure degradation,as well as enhancing bulk oxygen redox activity.The enhanced LMRO electrode delivers a high capacity of 220.3 mAh g^(−1)at 1 C.An excellent cycling stability with a capacity retention of 94.4%is achieved after 500 cycles,as well as a suppressed voltage decay with only 1.12 mV per cycle.
基金supported by the National Natu-ral Science Foundation of China(Nos.U20A20237,51863005,52271205,51871065,51971068,and 52101245)the Scientific Research and Technology Development Program of Guangxi(Nos.AA19182014,AD17195073,AA17202030-1,AB21220027,and 2021AB17045)+2 种基金National Natural Science Foundation of Guangxi Province(Nos.2021GXNSFBA075057,2018GXNSFDA281051,2014GXNSFAA118401,and 2013GXNSFBA019244)the Scientific Research and Technology Development Program of Guilin(Nos.20210102-4 and 20210216-1)Guangxi Bagui Scholar Founda-tion,Guilin Lijiang Scholar Foundation,Guangxi Collaborative Innovation centre of Structure and Property for New Energy and Materials,Guangxi Advanced Functional Materials Foundation and Application Talents Small Highlands,Chinesisch-Deutsche Kooperationsgruppe(No.GZ1528).
文摘Hydrogen energy is expected to be an“ideal fuel”in the era of decarbonization.The discovery,de-velopment,and modification of high-performance hydrogen storage materials are the keys to the fu-ture development of solid-state hydrogen storage and hydrogen energy utilization.Magnesium hydride(MgH_(2)),with its high hydrogen storage capacity,abundant natural reserves,and environmental friend-liness,has been extensively researched.Herein,we briefly summarize the typical structure and hy-drogenation/dehydrogenation reaction mechanism of MgH_(2)and provide a comprehensive overview of strategies to effectively tune the thermodynamics and kinetics of Mg-based materials,such as alloy-ing,nanosizing,the introduction of additives,and composite modification.With substantial efforts,great achievements have been achieved,such as lower absorption/desorption temperatures and better cy-cling stability.Nonetheless,some pivotal issues remain to be addressed,such as unfavorable hydro-genation/dehydrogenation factors,harsh conditions,slow kinetics,incomplete dehydrogenation,low hy-drogen purity,expensive catalysts,and a lack of valid exploration of mechanisms in the hydrogena-tion/dehydrogenation process.Lastly,some future development prospects of MgH_(2)in energy-efficient conversion and storage have been presented,including advanced manufacturing ways,stabilization of nanostructures,the introduction of additives combined with structural modification,and utilization of advanced characterization techniques.
基金supported by the National Natural Science Foundation of PR China(Nos.52071287,52125104 and 52072342)Natural Science Foundation of Zhejiang Province,PR China(No.LZ23E010002).
文摘MgH_(2)is a promising solid-state hydrogen storage material.However,its high thermodynamics and sluggish kinetics hinder its practical application.Catalytic strategy is effective in improving its kinetic performance.Nevertheless,the highly efficient catalysts or additives are normally of low-yield in fabrication with high cost.In this work,a novel structural LaVO_(4)fabricated by a low-cost method of spraying dry followed by a calcination is used as a catalytic additive for the hydrogen storage of MgH_(2).With an optimized addition of LaVO_(4),the overall hydrogen storage performances of MgH_(2)are significantly improved.An onset dehydrogenation temperature of only 183℃is obtained after an initial activation of dehydrogenation and hydrogenation.The system can desorb 5.7 wt%H_(2)at 250℃within 10 min and maintains a dehydrogenation capacity of 5.0 wt%H_(2)after 50 cycles.It is found that LaVO_(4)is transferred to lanthanum hydride and metallic vanadium in the initial dehydrogenation process,the former acts as a highly effective catalyst for the hydrogen storage of MgH_(2)and the latter undergoes reversible hydrogenation and dehydrogenation in the subsequent cycles.The structural design of the catalyst and its scalable fabrication are highly valuable in realizing the practical application of catalytic strategy for the hydrogen storage of MgH_(2).
基金supported by the National Natural Science Foundation of China(No.52071287)the Natural Science Foundation of Zhejiang Province(No.LZ23E010002)the Basic and Applied Basic Research Foundation of Guangdong Province(Nos.2021A1515110676,2022A1515011832).
文摘LiBH_(4) containing 18.5 wt.%H_(2) is an attractive high-capacity hydrogen storage material,however,it suffers from high operation temperature and poor reversibility.Herein,a novel and low-cost bifunctional additive,waxberry-like Fe_(3)O_(4) secondary nanospheres assembled from ultrafine primary Fe_(3)O_(4) nanoparticles,is synthesized,which exhibits significant destabilization and bidirectional catalyzation towards(de)hydrogenation of LiBH_(4).With an optimized addition of 30 wt.% waxberry-like Fe_(3)O_(4),the system initiated dehydrogenation below 100℃ and released a total of 8.1 wt.%H_(2) to 400℃.After 10 cycles,a capacity retention of 70% was achieved,greatly superior to previously reported oxides-modified systems.The destabilizing and catalyzing mechanisms of waxberry-like Fe_(3)O_(4) on LiBH_(4) were systematically analyzed by phase and microstructural evolutions during dehydrogenation and hydrogenation cycling as well as density functional theory(DFT)calculations.The present work provides new insights in developing advanced nano-additives with unique structural and multifunctional designs towards LiBH4 hydrogen storage.
基金supported by the National Key Research and Development Program of China(2022YFB3803801)National Natural Science Foundation of China(Grant No.52201275,52301287,52307250)+1 种基金Two-chain integration key project of Shaanxi Province(Grant No.2021LLRH-09)Young Talent Fund of Association for Science and Technology in Shaanxi,China(No.20220456).
文摘Although MgH_(2)is widely deemed to be the most promising solid-state hydrogen storage materials for the medium-high temperature fuelcell applications expected in the near future,the high-temperature desorption and sluggish hydrogen absorption/desorption kinetics are the major challenges for its applications.Herein,reduced graphene oxide/patronite nanoparticle composite(rGO@VS_(4))is successfully synthesized using an ionic liquid(IL)-assisted hydrothermal method,and superior catalytic effects originated from the rGO@VS_(4)composite precursor towards the hydrogen storage reaction of MgH_(2)are systematically investigated.The VS_(4)reacts with MgH_(2)leads to the in-situ formed and uniformly scattered of metallic V and MgS during both ball-milling and the initial hydrogen desorption,and the synergic catalytic effect of metallic V and MgS facilitates the improved hydrogen desorption of MgH_(2).The MgH_(2)-15 wt%rGO@VS_(4)composite starts releasing hydrogen at 180℃and peaks at 220℃,which is 145℃and 128℃lower than that of the Pristine MgH_(2),respectively.The energy required for H_(2)desorption from MgH_(2)is decreased to 63.8 kJ mol^(-1),58.9 kJ mol^(-1)lower than that of the Pristine MgH_(2).Furthermore,the MgH_(2)-15 wt%rGO@VS_(4)composite shows excellent cycling stability,of which reversible hydrogen capacity can stabilize at about 5.9 wt%with capacity retention of 98.2%at 300℃for 100 cycles.This study provides a deeper insight into metallic V and MgS to enhance the hydrogen desorption of solid-state hydrogen storage materials and also offers a perspective for the construction of high-activity catalysts for solid-state hydrogen storage materials.
基金financially supported by the National Key R&D Program of China(No.2022YFB2502000)the National Natural Science Foundation of China(Nos.51902079,52072342,52377216 and 52102324)+3 种基金Anhui Provincial Natural Science Foundation(Nos.2008085QE271 and 2208085ME108)Excellent Research and Innovation Team of Anhui Universities(No.2022AH010096)Natural Science Research Project for Anhui Universities(No.2024AH051519)Hefei Institutes of Physical Science,Chinese Academy of Sciences Director's Fund(Nos.BJPY2023B04,YZJJ-GGZX-2022-01 and YZJJ202102)
文摘Lithium sulfide(Li_(2)S)is widely regarded as the next-generation cathode material for rechargeable batteries due to its satisfactory theoretical capacity and excellent compatibility with lithium-free anodes.However,the large-scale applications of Li_(2)S cathodes are limited by the shuttle effect of soluble intermediate lithium polysulfides(LiPSs)and the sluggish redox kinetics of the interconversion between Li_(2)S and sulfur(S).Herein,we report novel nitrogen-doped carbon nanoflakes in-situ embedded with WN-Ni_(2)P heterostructures(WN-Ni_(2)P@NCN)as a multifunctional host to promote the cycling performance and reaction kinetics of Li_(2)S.After loading Li_(2)S,the WNNi_(2)P@NCN/Li_(2)S exhibits stable reversible capacity of 597mAh g^(-1)at 0.5 A g^(-1)over 150 cycles,and superior cycling stability over 800 cycles.The high reversible capacities,excellent cycling properties and superior reaction kinetics of WN-Ni_(2)P@NCN/Li_(2)S are attributed to the strong LiPSs fixation,remarkable catalytic activation and high electronic/ionic conductivity of the WN-Ni_(2)P@NCN framework,confirmed by the experiment and the density function theory calculation results.This work offers a new strategy for designing heterostructure nanoflakes with metal nitride and metal phosphide to facilitate the applications of advanced lithium-sulfur batteries.
基金supported by the National Natural Science Foundation of China(No.52071171)Liaoning Revitalization Talents Program-Pan Deng Scholars(XLYC1802005)+5 种基金Liaoning BaiQianWan Talents Program(LNBQW2018B0048)Natural Science Fund of Liaoning Province for Excellent Young Scholars(2019-YQ-04)Key Project of Scientific Research of the Education Department of Liaoning Province(LZD201902)Foundation for Young Scholars of Liaoning University(a252102001)Australian Research Council(ARC)Future Fellowship(FT210100298)CSIRO Energy Centre,Kick-Start Project and the Victorian Government’s support through the provision of a grant from veski-Study Melbourne Research Partnerships(SMRP)project.
文摘The rapid advance of mild aqueous zinc-ion batteries(ZIBs)is driving the development of the energy storage system market.But the thorny issues of Zn anodes,mainly including dendrite growth,hydrogen evolution,and corrosion,severely reduce the performance of ZIBs.To commercialize ZIBs,researchers must overcome formidable challenges.Research about mild aqueous ZIBs is still developing.Various technical and scientific obstacles to designing Zn anodes with high stripping efficiency and long cycling life have not been resolved.Moreover,the performance of Zn anodes is a complex scientific issue determined by various parameters,most of which are often ignored,failing to achieve the maximum performance of the cell.This review proposes a comprehensive overview of existing Zn anode issues and the corresponding strategies,frontiers,and development trends to deeply comprehend the essence and inner connection of degradation mechanism and performance.First,the formation mechanism of dendrite growth,hydrogen evolution,corrosion,and their influence on the anode are analyzed.Furthermore,various strategies for constructing stable Zn anodes are summarized and discussed in detail from multiple perspectives.These strategies are mainly divided into interface modification,structural anode,alloying anode,intercalation anode,liquid electrolyte,non-liquid electrolyte,separator design,and other strategies.Finally,research directions and prospects are put forward for Zn anodes.This contribution highlights the latest developments and provides new insights into the advanced Zn anode for future research.
基金financially supported by the National Natural Science Foundation of China(Nos.U20A20237,51863005,52271205,51871065,52371218,51863005,52271205,51871065,52371218,51971068,52101245 and 52201206)the Scientific Research and Technology Development Program of Guangxi(Nos.AA19182014,AD17195073,AA17202030-1,AB21220027 and 2021AB17045)+6 种基金the National Natural Science Foundation of Guangxi Province(Nos.2018GXNSFDA281051,2014GXNSFAA118401,2013GXNSFBA019244,2021GXNSFBA075057 and 2022GXNSFB A035632)the Scientific Research and Technology Development Program of Guilin(Nos.20210102-4 and 20210216-1)Guangxi B agui Scholar FoundationGuilin Lijiang Scholar FoundationGuangxi Collaborative Innovation Centre of Structure and Property for New Energy and MaterialsGuangxi Advanced Functional Materials FoundationApplication Talents Small Highlands and Chinesisch Deutsche Kooperationsgruppe(No.GZ1528)。
文摘The conjugation of external species with twodimensional(2D)materials has broad application prospects.In this study,we have explored the potential of noble metal/2D MOF heterostructures in hydrogen storage.Specifically,the MgH_(2)-Ni-MOF@Pd system has shown remarkable hydrogen desorption/sorption performances,starting to liberate hydrogen at 1810C,which is 2300C lower than that of pristine MgH2.Under the catalytic effect of Ni-MOF@Pd,the dehydrogenation apparent activation energy of MgH2 is noticeably decreased from(133.5±17.5)to(34.58±1.87)kJ·moL^(-1),and the hydrogenation apparent activation energy is reduced from(70.41±7.43)to(25.78±4.64)kJ·moL^(-1),which is lowered by 63.4%.The fully-dehydrogenated MgH2-NiMOF@Pd composite rapidly uptakes hydrogen,with 2.62wt%at 100℃and 6.06 wt%at 150℃within 300 s,respectively.The mechanism analysis of MgH2 catalyzed by Ni-MOF@Pd has revealed that the transformation of Mg_2Ni and Mg_2NiH_4 could act as a"hydrogen pump",providing numerous channels for fast diffusion and transport of hydrogen atoms.Moreover,in the dehydrogenation process,the element Pd reacts with MgH_(2)to form the MgPd alloy phase,which makes MgH_(2)take precedence to decompose through the Mg-Pd alloy rather than self-decomposition,further reducing thermal stability and improving de/hydrogenation kinetics.The synergistic effect of Mg-Pd,Mg_2Ni,and the special ultra-thin 2D sheet structure of the additive is the main reason for the good hydrogen storage property of MgH_(2)-Ni-MOF@Pd.Our findings provide inspiration for designing efficient multifunctional additives with unique morphologies to optimize the hydrogen desorption/sorption behaviors of hydrogen storage materials.
基金financially supported by the National Natural Science Foundation of China(22075035)the Key Research Project of Liaoning Province(2020JH2/1070008)。
文摘Lithium is considered to be the ‘‘holy grail” for the application of energy storage due to its highest theoretical capacity and lowest anode potential. However, one of the grand difficulties in the development of lithium-based batteries is the lithium dendrite growth that leads to capacity fading and electrode degradation over long-term cycling. Compared with conventional electrolyte modifications, artificial solid electrolyte interfaces(SEI) synthesis and framework designing approaches, tuning surface morphology of lithium anode is the direct route to induce homogeneous Li ion deposition. Due to the high chemical activity of lithium metal, however, controllable growth of lithium micro/nanostructures by traditionally chemical approaches is still a big challenge. Herein, we have developed a facile compression route to fabricate lithium anode with abundant stepped lithium structures. The electrochemical results demonstrate that the dendritic growth issue is effectively suppressed by orderly arranged stepped lithium structures. After 90 cycles, a high discharge capacity of 954 mAh g^(-1) is achieved, which is 2.7times that of the uncompressed lithium anode(342 mAh g). First-principles calculations reveal that the orderly arranged stepped lithium structures are lithiophilic active sites to adsorb Li ion, which contributes to homogeneous deposition of Li ion on lithium anode, eventually solving the lithium dendrite issue. This work paves a new road to suppress dendritic growth, which will provide some new ideas to design long recycling sodium, potassium and zinc, and other metal anode batteries.
基金support from the National Outstanding Youth Foundation of China(52125104)the National Natural Science Foundation of China(52071285 and 51831009)+1 种基金the Fundamental Research Funds for the Central Universities(2021FZZX001-09)the National Youth Top-Notch Talent Support Program.Z.H.acknowledges support under the Australian Research Council's Future Fellowship(FT190100658).
文摘The development of high-performance binders is a simple but effective approach to address the rapid capacity decay of high-capacity anodes caused by large volume change upon lithiation/delithiation.Herein,we demonstrate a unique organic/inorganic hybrid binder system that enables an efficient in situ crosslinking of aqueous binders(e.g.,sodium alginate(SA)and carboxymethyl cellulose(CMC))by reacting with an inorganic crosslinker(sodium metaborate hydrate(SMH))upon vacuum drying.The resultant 3D interconnected networks endow the binders with strong adhesion and outstanding self-healing capability,which effectively improve the electrode integrity by preventing fracturing and exfoliation during cycling and facilitate Li^(+)ion transfer.SiO anodes fabricated from the commercial microsized powders with the SA/0.2SMH binder maintain 1470 mAh g^(-1)of specific capacity at 100 mA g^(-1)after 200 cycles,which is 5 times higher than that fabricated with SA binder alone(293 mAh g^(-1)).Nearly,no capacity loss was observed over 500 cycles when limiting discharge capacity at 1500 mAh g^(-1).The new binders also dramatically improved the performance of Fe_(2)O_(3),Fe_(3)O_(4),NiO,and Si electrodes,indicating the excellent applicability.This finding represents a novel strategy in developing high-performance aqueous binders and improves the prospect of using high-capacity anode materials in Li-ion batteries.
基金supported by the National Key Research&Development Program of China(No.2022YFB4004301)the National Natural Science Foundation of China(Nos.52201274 and 52307250)the Shaanxi Province key research and development plan,China(No.2024CY2-GJHX-53).
文摘TiFe alloys are AB-based hydrogen storage materials with unique characteristics and a wide range of applications.However,the presence of impurity gases(such as O_(2),CO,CO_(2),and CH4)has a considerable impact on the hydrogen storage capacity and kinetics of TiFe alloys,drastically limiting their practical application in hydrogen storage.Consequently,in this study,we investigated the hydrogen absorption kinetics and cycling performance of the TiFe_(0.9) alloy in the presence of common impurity gases(including CH4,CO,CO_(2),and O_(2))and determined the corresponding poisoning mechanisms.Specifically,we found that CH4 did not react with the alloy but acted through physical coverage.In contrast,CO and CO_(2) occupy the active sites for H_(2),significantly impeding the dissociation and absorption of H_(2).In addition,O_(2) reacts directly with the alloy to form a passivating layer that prevents hydrogen absorption.These findings were fur-ther corroborated by in situ Fourier transform infrared spectrometry(FTIR)and density functional theory(DFT).The relationship between the adsorption energies of the impurity gases and hydrogen obtained through DFT calculations complements the experimental results.Un-derstanding these poisoning behaviors is crucial for designing Ti-based high-entropy hydrogen storage alloy alloys with enhanced resist-ance to poisoning.
文摘A novel poly(ether block amide)(PEBA)based solid-state polymer electrolyte(SPE)was prepared using a casting method,in which 20wt%lithium(Li)bis-(trifluoromethanesulfonyl)imide(LiTFSI)and aluminum oxide(Al_(2)O_(3))nanoparticles were used as the Li salt and solid plasticizer,respectively.In the case of addition of 3wt%Al_(2)O_(3) nanoparticles,ion conductivity of the obtained PEBA 2533-20wt%LiTFSI-3wt%Al_(2)O_(3) SPE was 3.57×10^(−5) S cm^(−1) at 25°C.Furthermore,the Li symmetrical battery assembled with it showed excellent cycling stability(1000 h)at 0.1 mA cm^(−2).While,the assembled all-solid-state Li/PEBA 2533-20%LiTFSI-3wt%Al_(2)O_(3)/LiFePO 4(areal capacity:0.15 mAh cm^(−2))battery maintained 94.9%of the maximal capacity(133.9 mAh g^(−1@0.1) mA cm^(−2))at 60°C even after 650 cycles with a superior average coulombic efficiency(CE)of 99.84%.By using X-ray photoelectron spectroscope(XPS),self-aggregation layer(SAL)of polyamide 12(PA12)of PEBA 2533 was discovered,which should contribute to promoting the robustness of lithium fluoride(LiF)enriched solid-electrolyte interphase(SEI)layer.In addition,it is considered that the state of interface between SPE and cathode should be the cause of voltage polarization of the full cell.
基金financial support received from the National Key R&D Program of China (2023YFB2504000)the financial support from the National Outstanding Youth Foundation of China (52125104)+2 种基金the National Natural Science Foundation of China (52071285)the Fundamental Research Funds for the Central Universities (226-2024-00075)the National Youth Top-Notch Talent Support Program。
文摘Solid-state batteries(SSBs) are highly attractive on account of their high energy density and good safety.In high-voltage and high-current conditions,however,the interface reactions,structural changes,and decomposition of the electrolyte impede the transmission of lithium ions in all-solid-state lithium batteries(ASSLBs),significantly reducing the charging and discharging capacity and cycling stability of the battery and therefore restricting its practical applications.The main content of review is to conduct an in-depth analysis of the existing problems of solid-state batteries from the aspects of interface reactions,material failure,ion migration,and dendrite growth,and points out the main factors influencing the electrochemical performance of ASSLBs.Additionally,the compatibility and ion conduction mechanisms between polymer electrolytes,inorganic solid electrolytes,and composite electrolytes and the electrode materials are discussed.Furthermore,the perspectives of electrode materials,electrolyte properties,and interface modification are summarized and prospected,providing new optimization directions for the future commercialization of high-voltage solid-state electrolytes.
基金National Key Research and Development Program of China,Grant/Award Number:2022YFB2502000National Natural Science Foundation of China,Grant/Award Number:52207244。
文摘In the realm of sodium-ion batteries(SIBs),Mn-based layered oxide cathodes have garnered considerable attention owing to their anionic redox reactions(ARRs).Compared to other types of popular sodium-ion cathodes,Mn-based layered oxide cathodes with ARRs exhibit outstanding specific capacity and energy density,making them promising for SIB applications.However,these cathodes still face some scientific challenges that need to be addressed.This review systematically summarizes the composition,structure,oxygen-redox mechanism,and performance of various types of Mn-based cathodes with ARRs,as well as the main scientific challenges they face,including sluggish ion diffusion,cationic migration,O_(2) release,and element dissolution.Currently,to resolve these challenges,efforts mainly focus on six aspects:synthesis methods,structural design,doped modification,electrolyte design,and surface engineering.Finally,this review provides new insights for future direction,encompassing both fundamental research,such as novel cathode types,interface optimization,and interdisciplinary research,and considerations from an industrialization perspective,including scalability,stability,and safety.
基金supported by the National Key Research and Development Program of China(2022YFB2502000)the National Natural Science Foundation of China(52201277,52207244,52207245)+1 种基金the Xi'an Young Talent Lifting Program(959202413060)the National Outstanding Youth Foundation of China(52125104).
文摘Owing to anionic redox,cathode materials containing layered Li-rich Mn-based oxides(LLOs)are promising for the development of next-generation lithium-ion batteries(LIBs)with a large energy density(~500–600 Wh·kg^(−1)).However,these LLOs are easily degraded during cycling,which limits their lifespan.So far,the degradation mechanism is still under debate.Herein,LLOs are post-treated through implantation with energetic Ti ion flux(Ti-LLO),which modifies the structure of LLOs both at the surface and within the bulk.Unlike the dominant R3m phase(73.24%)observed in LLOs,the phase structure of Ti-LLO is altered,with Li-rich C2/m accounting for 67.72%in the bulk,alongside the formation of a thin(approximately 2 nm),uniform,and continuous Li-Ti-O spinel layer at the surface.Apart from phase structure changes,chemical valence states of transition metals and O,as well as their evolution,are analyzed and compared to charge transport kinetics to elucidate their contributions to the enhanced discharge capacity in Ti-LLOs.Besides,the role of the Li-Ti-O spinel layer at the surface in providing anticorrosion protection at the interface of LLOs/electrolyte during cycling is evaluated.As a result,we demonstrate that a superhigh discharge capacity(335.3 mAh·g^(−1))at 0.1 C can be achieved,along with prolonged cycling stability(showing capacity retention of approximately 80%after 500 cycles at 1 C)through these modifications.Moreover,we confirmed the universality of the strategy by implanting other ions,which offers practical strategies for achieving high performance in LLO cathode materials through thermodynamics and kinetics pathways.
基金supported by the National Natural Science Foundation of China(52471240)the Natural Science Foundation of Zhejiang Province(LZ23B030003)+2 种基金the Fundamental Research Funds for the Central Universities(226-2024-00075)support from the Engineering and Physical Sciences Research Council(EPSRC,UK)RiR grant-RIR18221018-1EU COST CA23155。
文摘The electric double layer(EDL)at the electrochemical interface is crucial for ion transport,charge transfer,and surface reactions in aqueous rechargeable zinc batteries(ARZBs).However,Zn anodes routinely encounter persistent dendrite growth and parasitic reactions,driven by the inhomogeneous charge distribution and water-dominated environment within the EDL.Compounding this,classical EDL theory,rooted in meanfield approximations,further fails to resolve molecular-scale interfacial dynamics under battery-operating conditions,limiting mechanistic insights.Herein,we established a multiscale theoretical calculation framework from single molecular characteristics to interfacial ion distribution,revealing the EDL’s structure and interactions between different ions and molecules,which helps us understand the parasitic processes in depth.Simulations demonstrate that water dipole and sulfate ion adsorption at the inner Helmholtz plane drives severe hydrogen evolution and by-product formation.Guided by these insights,we engineered a“water-poor and anion-expelled”EDL using 4,1’,6’-trichlorogalactosucrose(TGS)as an electrolyte additive.As a result,Zn||Zn symmetric cells with TGS exhibited stable cycling for over 4700 h under a current density of 1 mA cm^(−2),while NaV_(3)O_(8)·1.5H_(2)O-based full cells kept 90.4%of the initial specific capacity after 800 cycles at 5 A g^(−1).This work highlights the power of multiscale theoretical frameworks to unravel EDL complexities and guide high-performance ARZB design through integrated theory-experiment approaches.
基金supported by the National Out-standing Youth Foundation of China (No.52125104)the Natural Science Foundation of Zhejiang Province (No.LD21E010002)+2 种基金the National Natural Science Foundation of China (No.52001277)the Fundamental Research Funds for the Central Universities (No.2021FZZX001-09)the National Youth Top-Notch Talent Support Program.
文摘Nanoscaled catalysts have attracted much more attention due to their more abundant active sites and better dispersion than their bulky counterparts.In this work,VH_(x) nanoparticles smaller than 10 nm in average size are successfully synthesized by a simple solid-state ball milling coupled with THF washing process,which are proved to be highly effective in enhancing the hydrogen absorption/desorption kinetics of MgH_(2) at moderate temperatures.The nano-VH_(x)-modified MgH_(2) releases hydrogen from 182℃,which is 88℃ lower than additive-free MgH_(2).The release of hydrogen amounts to 6.3 wt%H within 10 min at 230℃ and 5.6 wt%H after 30 min at 215℃ with initial vacuum.More importantly,the dehydro-genated MgH_(2)+10 wt.%nano-VH_(x) rapidly absorbs 5.2 wt%H within 3 min at 50℃ under 50 bar H_(2).It even takes up 4.3 wt%H within 30 min at room temperature(25℃)under 10 bar H_(2),exhibiting supe-rior hydrogenation kinetics to most of the previous reports.Mechanistic analyzes disclose the reversible transformation between V and V-H species during the hydrogen desorption-absorption process.The ho-mogeneously distributed V-based species is believed to act as hydrogen pump and nucleation sites for MgH_(2) and Mg,respectively,thus triggering fast hydrogenation/dehydrogenation kinetics.
基金financially supported by the National Natural Science Foundation of China(Grant Nos.51871060,52071084 and 51831009)Recruit Program of Global Youth Experts and Fudan’s Undergraduate Research Opportunities Program(FDUROP)。
文摘The practical application of lithium-sulfur batteries is severely hampered by the poor conductivity,polysulfide shuttle effect and sluggish reaction kinetics of sulfur cathodes.Herein,a hierarchi-cally porous three-dimension(3D)carbon architecture assembled by cross-linked carbon leaves with implanted atomic Co-N4 has been deli-cately developed as an advanced sulfur host through a SiO_(2)-mediated zeolitic imidazolate framework-L(ZIF-L)strategy.The unique 3D architectures not only provide a highly conductive network for fast electron transfer and buffer the volume change upon lithiation-delithi-ation process but also endow rich interface with full exposure of Co-N4 active sites to boost the lithium polysulfides adsorption and conversion.Owing to the accelerated kinetics and suppressed shuttle effect,the as-prepared sulfur cathode exhibits a superior electrochemical perfor-mance with a high reversible specific capacity of 695 mAh g^(−1) at 5 C and a low capacity fading rate of 0.053%per cycle over 500 cycles at 1 C.This work may provide a promising solution for the design of an advanced sulfur-based cathode toward high-performance Li-S batteries.
