Sodium-ion batteries(SIBs)are considered as a low-cost complementary or alternative system to prestigious lithium-ion batteries(LIBs)because of their similar working principle to LIBs,cost-effectiveness,and sustainabl...Sodium-ion batteries(SIBs)are considered as a low-cost complementary or alternative system to prestigious lithium-ion batteries(LIBs)because of their similar working principle to LIBs,cost-effectiveness,and sustainable availability of sodium resources,especially in large-scale energy storage systems(EESs).Among various cathode candidates for SIBs,Na-based layered transition metal oxides have received extensive attention for their relatively large specific capacity,high operating potential,facile synthesis,and environmental benignity.However,there are a series of fatal issues in terms of poor air stability,unstable cathode/electrolyte interphase,and irreversible phase transition that lead to unsatisfactory battery performance from the perspective of preparation to application,outside to inside of layered oxide cathodes,which severely limit their practical application.This work is meant to review these critical problems associated with layered oxide cathodes to understand their fundamental roots and degradation mechanisms,and to provide a comprehensive summary of mainstream modification strategies including chemical substitution,surface modification,structure modulation,and so forth,concentrating on how to improve air stability,reduce interfacial side reaction,and suppress phase transition for realizing high structural reversibility,fast Na+kinetics,and superior comprehensive electrochemical performance.The advantages and disadvantages of different strategies are discussed,and insights into future challenges and opportunities for layered oxide cathodes are also presented.展开更多
There are two types of temporally and spatially associated intrusions within the Emeishan large igneous province （LIP）; namely, small ultramafic subvolcanic sills that host magmatic Cu-Ni-Platinum Group Element （PG...There are two types of temporally and spatially associated intrusions within the Emeishan large igneous province （LIP）; namely, small ultramafic subvolcanic sills that host magmatic Cu-Ni-Platinum Group Element （PGE）-bearing sulfide deposits and large mafic layered intrusions that host giant Ti-V magnetite deposits in the Panxi region. However, except for their coeval ages, the genetic relations between the ore-bearing intrusions and extrusive rocks are poorly understood. Phase equilibria analysis （Q-PI-OI-Opx-Cpx system） has been carried out to elucidate whether ore-bearing Panzhihua, Xinjie and Limahe intrusions are co-magmatic with the picrites and flood basalts （including high-Ti, low-Ti and alkali basalts）, respectively. In this system, the parental magma can be classified as silica-undersaturated olivine basalt and silica-saturated tholeiite. The equivalents of the parental magma of the Xinjie and Limahe peridotites and picrites and low-Ti basalts are silica-undersaturated, whereas the Limahe gabbro-diorites and high-Ti basalts are silica-saturated. In contrast, the Panzhihua intrusion appears to be alkali character. Phase equilibria relations clearly show that the magmas that formed the Panzhihua intrusion and high-Ti basalts cannot be co-magmatic as there is no way to derive one liquid from another by fractional crystallization. On the other hand, the Panzhihua intrusion appears to be related to Permian alkali intrusions in the region, but does not appear to be related to the alkali basalts recognized in the Longzhoushan lava stratigraphy. Comparably, the Limahe intrusion appears to be a genetic relation to the picrites, whereas the Xinjie intrusion may be genetically related to be low-Ti basalts. Additionally, the gabbro-diorites and peridotites of the Limahe intrusion are not co-magmatic, and the former appears to be derived liquid from high-Ti basalts.展开更多
Sodium-ion batteries(SIBs),which are an alternative to lithium-ion batteries(LIBs),have attracted increasing attention due to their low cost of Na resources and similar Na storage mechanism to LIBs.Compared with anode...Sodium-ion batteries(SIBs),which are an alternative to lithium-ion batteries(LIBs),have attracted increasing attention due to their low cost of Na resources and similar Na storage mechanism to LIBs.Compared with anode materials and electrolytes,the development of cathode materials lags behind.Therefore,the key to improving the specific energy and promoting the application of SIBs is to develop high-performance sodium intercalation cathode materials.Transition-metal oxides are one of the most promising cathode materials for SIBs owing to their excellent energy density,high specific discharge capacity,and environmentally friendly nature.In the present work,the latest progress in the research of transition-metal oxides is summarized.Moreover,the existing challenges are discussed,and a series of strategies are proposed to overcome these drawbacks.This review aims at providing guidance for the development of metal oxides in the next stage.展开更多
Electrocatalysis can enable efficient energy storage and conversion and thus is an effective way to achieve carbon neutrality.The unique structure and function of organisms can offer many ideas for the design of elect...Electrocatalysis can enable efficient energy storage and conversion and thus is an effective way to achieve carbon neutrality.The unique structure and function of organisms can offer many ideas for the design of electrocatalysts,which has become one of the most promising research directions.Recently,the understanding of the mechanism of bio-inspired electrocatalysis has become clearer,which has promoted the design of bio-inspired catalysts and catalytic systems.Various bio-inspired catalysts(enzyme-like catalysts,layered porous catalysts,superhydrophobic/superhydrophilic surfaces,and so on)have been developed to enable efficient electrocatalytic reactions.Herein,we discuss the key advances in the field of bio-inspired electrocatalysts progressed in recent years.First,the role of bio-inspiration in increasing the intrinsic activity and number of active sites of catalysts is introduced.Then,the structure and mechanism of layered porous catalytic systems that mimic biological transport systems are comprehensively discussed.Subsequently,the design of three-phase interfaces from micro-nanoscale to atomic scale is highlighted,including the wettability of the electrode surface and the transport system near the electrode.We conclude the review by identifying challenges in bio-inspired electrocatalysts and providing insights into future prospects for the exciting research field.展开更多
Among complex oxides containing rare earth and manganese BaLn_2Mn_2O_7 (Ln=rare earth) with the layered perovskite type and Ln_2(Mn, M)O_7 with pyrochlore-related structure were studied since these compounds show many...Among complex oxides containing rare earth and manganese BaLn_2Mn_2O_7 (Ln=rare earth) with the layered perovskite type and Ln_2(Mn, M)O_7 with pyrochlore-related structure were studied since these compounds show many kinds of phases and unique phase transitions. In BaLn_2Mn_2O_7 there appear many phases, depending on the synthetic conditions for each rare earth. The tetragonal phase of so-called Ruddlesden-Popper type is the fundamental structure and many kinds of deformed modification of this structure are obtained. For BaEu_2Mn_2O_7 at least five phases have been identified from the results of X-ray diffraction analysis with the space group P4_2/mnm, Fmmm, Immm and A2/m in addition to the fundamental tetragonal I4/mmm phase. In the pyrochlore-related type compounds, Ln_2Mn_(2-x)M_xO_7 (M=Ta, Nb, W etc), there also appear several phases with different crystal structures. With regard to every rare earth, Ln_2MnTaO_7 phase is stable only for excess Ta and can be obtained under high oxygen partial pressure process. This group has trigonal structure with zirkelite type (P3_121 space group). On the other hand Ln_2Mn_(2/3)Nb_(4/3)O_7 phase has monoclinic (C2/c space group) and zirconolite type structure. All of these structural models have the fundamental structure based on HTB (hexagonal tungsten bronze) layers formed by the arrangement of oxygen octahedra.展开更多
BA_(2)(MA)_(n-1)Pb_nI_(3n+1)series low-dimensional(2D)perovskites have been widely investigated for their re markable environmental stability,but still suffer the poor light absorption and disordered phase distri buti...BA_(2)(MA)_(n-1)Pb_nI_(3n+1)series low-dimensional(2D)perovskites have been widely investigated for their re markable environmental stability,but still suffer the poor light absorption and disordered phase distri bution,hindering their practical applications.In this work,we combine the introduction of FA and the addition of PbCl_(2)to optimize the film quality,strengthen the light absorption,regulate internal phase distribution,and promote carrier transport inside 2D perovskite films.The incorporation of FA promote sufficient light absorption and improve the film crystallinity.Furthermore,the addition of Pb Cl_(2)elimi nates the low n phase(n=1)and suppresses the forming of the low n phase of n=2,enhancing the film conductivity and diminishing carrier recombination.The synergistic of A-site cation engineering and phase manipulation achieves a high efficiency of 16.48%.Importantly,the synergistic prepared perovskite film does not show any changes after 60 days in the air with an average humidity of 57%±3%,and the corresponding solar cell maintains 85%of the original efficiency after more than 800 h,demonstrating remarkable environmental stability.The results indicate that the synergistic of A-site cation engineering and phase manipulation is promising for producing superior efficiency,along with satisfying humidity stability.展开更多
With the shortage of lithium resources,sodiumion batteries(SIBs)are considered one of the most promising candidates for lithium-ion batteries.P2-type and O3-type layered oxides are one of the few cathodes that can acc...With the shortage of lithium resources,sodiumion batteries(SIBs)are considered one of the most promising candidates for lithium-ion batteries.P2-type and O3-type layered oxides are one of the few cathodes that can access high energy density.However,they usually exhibit structural change,capacity decay,and slow Na ion kinetic.Herein,we present layered ternary-phase cathodes with P2,P3 and O3 phases by a lattice doping strategy,which is demonstrated by X-ray diffraction(XRD)refinement.Combining the characteristics of P2,P3 and O3 phases,the layered composites show performance improvement during long-term battery cycling.In particular,Na_(0.7)Li_(0.1)Co_(0.3-)Fe_(0.3)Mn_(0.3)O_(2)(NLCFM)delivers a reversible capacity of120.1 mAh·g^(-1)at 0.1C(1.0C=175 mA·g^(-1))with a superior capacity retention of 72.5%after 1000 cycles at10.0C.This work offers insights into the development of advanced cathode materials for SIBs.展开更多
Atomic intercalation in two-dimensional （2D） layered materials can be used to engineer the electronic structure at the atomic scale and generate tuneable physical and chemical properties which are quite distinct in ...Atomic intercalation in two-dimensional （2D） layered materials can be used to engineer the electronic structure at the atomic scale and generate tuneable physical and chemical properties which are quite distinct in comparison with the pristine material. Among them, electron-doped engineering induced by intercalation is an efficient route to modulate electronic states in 2D layers. Herein, we demonstrate a semiconducting to metallic phase transition in zirconium diselenide （ZrSe2） single crystals via controllable incorporation of copper （Cu） atoms. Our angle resolved photoemission spectroscopy （ARPES） measurements and first-principles density functional theory （DFT） calculations dearly revealed the emergence of conduction band dispersion at the M/L point of the Brillouin zone due to Cu-induced electron doping in ZrSe2 interlayers. Moreover, electrical measurements in ZrSe2 revealed semiconducting behavior, while the Cu-intercalated ZrSe2 exhibited a linear current-voltage curve with metallic character. The atomic intercalation approach may have high potential for realizing transparent electron-doping systems for many specific 2D-based nanoelectronic applications.展开更多
Nickel-rich layered oxide LiNi_(x)Co_(y)MnzO_(2)(NCM,x+y+z=1)is the most promising cathode material for high-energy lithium-ion batteries.However,conventional synthesis methods are limited by the slow heating rate,slu...Nickel-rich layered oxide LiNi_(x)Co_(y)MnzO_(2)(NCM,x+y+z=1)is the most promising cathode material for high-energy lithium-ion batteries.However,conventional synthesis methods are limited by the slow heating rate,sluggish reaction dynamics,high energy consumption,and long reaction time.To overcome these chal-lenges,we first employed a high-temperature shock(HTS)strategy for fast synthesis of the NCM,and the approaching ultimate reaction rate of solid phase transition is deeply investigated for the first time.In the HTS process,ultrafast average reaction rate of phase transition from Ni_(0.6)Co_(0.2)Mn_(0.2)(OH)_(2) to Li-containing oxides is 66.7(%s^(-1)),that is,taking only 1.5 s.An ultrahigh heating rate leads to fast reaction kinetics,which induces the rapid phase transition of NCM cathodes.The HTS-synthesized nickel-rich layered oxides perform good cycling performances(94%for NCM523,94%for NCM622,and 80%for NCM811 after 200 cycles at 4.3 V).These findings might also assist to pave the way for preparing effectively Ni-rich layered oxides for lithium-ion batteries.展开更多
High nickel content worsens the thermal stability of layered cathodes for lithium-ion batteries,raising safety concerns for their applications.Thoroughly understanding the thermal failure process can offer valuable gu...High nickel content worsens the thermal stability of layered cathodes for lithium-ion batteries,raising safety concerns for their applications.Thoroughly understanding the thermal failure process can offer valuable guidance for material optimization on thermal stability and new opportunities in monitoring battery thermal runaway(TR).Herein,this work comprehensively investigates the thermal failure process of a single-crystal nickel-rich layered cathode and finds that the latent thermal failure starts at∼120℃far below the TR temperature(225℃).During this stage of heat accumulation,sequential structure transition is revealed by atomic resolution electron microscopy,which follows the layered→cation mixing layered→LiMn_(2)O_(4)-type spinel→disordered spinel→rock salt.This progression occurs as a result of the continuous migration and densification of transition metal cations.Phase transition generates gaseous oxygen,initially confined within the isolated closed pores,thereby not showing any thermal failure phenomena at the macro-level.Increasing temperature leads to pore growth and coalescence,and eventually to the formation of open pores,causing oxygen gas release and weight loss,which are the typical TR features.We highlight that latent thermal instability occurs before the macro-level TR,suggesting that suppressing phase transitions caused by early thermal instability is a crucial direction for material optimization.Our findings can also be used for early warning of battery thermal runaway.展开更多
The thermodynamic instability of zinc anodes in aqueous electrolytes leads to issues such as corrosion,hydrogen evolution reactions(HER), and dendrite growth, severely hindering the practical application of zinc-based...The thermodynamic instability of zinc anodes in aqueous electrolytes leads to issues such as corrosion,hydrogen evolution reactions(HER), and dendrite growth, severely hindering the practical application of zinc-based aqueous energy storage devices. To address these challenges, this work proposes a dualfunction zinc anode protective layer, composed of Zn-Al-In layered double oxides(ILDO) by rationally designing Zn-Al layered double hydroxides(Zn-Al LDHs) for the first time. Differing from previous works on the LDHs coatings, firstly, the ILDO layer accelerates zinc-ion desolvation and also captures and anchors SO_(4)^(2-). Secondly, the in-situ formation of the Zn-In alloy phase effectively lowers the nucleation energy barrier, thereby regulating zinc nucleation. Consequently, the zinc anode with the ILDO protective layer demonstrates long-term stability exceeding 1900 h and low voltage hysteresis of 7.5 m V at 0.5 m A cm^(-2) and 0.5 m A h cm^(-2). Additionally, it significantly enhances the rate capability and cycling performance of Zn@ILDO//MnO_(2) full batteries and Zn@ILDO//activated carbon zinc-ion hybrid capacitors.This simple and effective dual-function protective layer strategy offers a promising approach for achieving high-performance zinc-ion batteries.展开更多
Due to a high energy density,layered transition-metal oxides have gained much attention as the promising sodium-ion batteries cathodes.However,they readily suffer from multiple phase transitions during the Na extracti...Due to a high energy density,layered transition-metal oxides have gained much attention as the promising sodium-ion batteries cathodes.However,they readily suffer from multiple phase transitions during the Na extraction process,resulting in large lattice strains which are the origin of cycledstructure degradations.Here,we demonstrate that the Na-storage lattice strains of layered oxides can be reduced by pushing charge transfer on anions(O^(2-)).Specifically,the designed O3-type Ru-based model compound,which shows an increased charge transfer on anions,displays retarded O3-P3-O1 multiple phase transitions and obviously reduced lattice strains upon cycling as directly revealed by a combination of ex situ X-ray absorption spectroscopy,in situ X-ray diffraction and geometric phase analysis.Meanwhile,the stable Na-storage lattice structure leads to a superior cycling stability with an excellent capacity retention of 84%and ultralow voltage decay of 0.2 mV/cycle after 300 cycles.More broadly,our work highlights an intrinsically structure-regulation strategy to enable a stable cycling structure of layered oxides meanwhile increasing the materials’redox activity and Nadiffusion kinetics.展开更多
O3-type layered oxides have garnered great attention as cathode materials for sodium-ion batteries because of their abundant reserves and high theoretical capacity.However,challenges persist in the form of uncontrolla...O3-type layered oxides have garnered great attention as cathode materials for sodium-ion batteries because of their abundant reserves and high theoretical capacity.However,challenges persist in the form of uncontrollable phase transitions and intricate Na^(+)diffusion pathways during cycling,resulting in compromised structural stability and reduced capacity over cycles.This study introduces a special approach employing site-specific Ca/F co-substitution within the layered structure of O_(3)-NaNi_(0.5)Mn_(0.5)O_(2) to effectively address these issues.Herein,the strategically site-specific doping of Ca into Na sites and F into O sites not only expands the Na^(+)diffusion pathways but also orchestrates a mild phase transition by suppressing the Na^(+)/vacancy ordering and providing strong metal-oxygen bonding strength,respectively.The as-synthesized Na_(0.95)Ca_(0.05)Ni_(0.5)Mn_(0.5)O_(1.95)F_(0.05)(NNMO-CaF)exhibits a mild O3→O3+O'3→P3 phase transition with minimized interlayer distance variation,leading to enhanced structural integrity and stability over extended cycles.As a result,NNMO-CaF delivers a high specific capacity of 119.5 mA h g^(-1)at a current density of 120 mA g^(-1)with a capacity retention of 87.1%after 100 cycles.This study presents a promising strategy to mitigate the challenges posed by multiple phase transitions and augment Na^(+)diffusion kinetics,thus paving the way for high-performance layered cathode materials in sodium-ion batteries.展开更多
Ni-rich layered cathode is regarded as one of the most promising candidates to achieve lithium-ion batteries (LIBs) with high energy density. However, due to the irreversible phase transformation (IPT) and its eventua...Ni-rich layered cathode is regarded as one of the most promising candidates to achieve lithium-ion batteries (LIBs) with high energy density. However, due to the irreversible phase transformation (IPT) and its eventual propagation from surface to the bulk of the material, Ni-rich layered cathode typically suffers from severe capacity fading, structure failure, and thermal instability, which greatly hinders its mass adoption. Hence, achieving an in-depth understanding of the IPT propagation mechanism in Ni-rich layered cathode is crucial in addressing these issues. Herein, the triggering factor of IPT propagation in Ni-rich cathode is verified to be the initial surface disordered cation mixing domain covered by a thin rock-salt phase, instead of the rock-salt phase itself. According to the density functional theory (DFT) results, it is further illustrated that the metastable cation mixing domain possesses a lower Ni migration energy barrier, which facilitates the migration of Ni ions towards the Li slab, and thus driving the propagation of IPT from surface to the bulk of the material. This finding clarifies a prevailing debate regarding the surface impurity phases of Ni-rich cathode material and reveals the origin of IPT propagation, which implies the principle and its effectiveness of tuning the surface microstructure to address the structural and thermal instability issue of Ni-rich layered cathode materials.展开更多
Owing to the features(high safety,inexpensive and environmental friendliness)of aqueous rechargeable Mg-ion batteries(ARMIBs),they have drawn extensive attention in the future energy storage systems.However,the poor M...Owing to the features(high safety,inexpensive and environmental friendliness)of aqueous rechargeable Mg-ion batteries(ARMIBs),they have drawn extensive attention in the future energy storage systems.However,the poor Mg^(2+)migration kinetics during the Mg^(2+)intercalation/extraction still hinders the progress of developing suitable cathode materials.Herein,a layered buserite Mg-Mn oxide(MMO)material with large interlayer space(~9.70A)and low-crystalline structure is studied as a high-performance cathode in ARMIBs.Compared with the counterpart,the Mg^(2+)migration kinetics of the MMO cathode can be enhanced by its unique structure(bigger interlayer spacing and low-crystalline structure).The layered buserite MMO as a high-performance ARMIBs cathode exhibits high Mg storage capacity(50 mAg^(-1):169.3 mAh g^(-1)),excellent rate capability(1000 mAg^(-1):98.3 mAh g^(-1)),and fast Mg^(2+)migration(an average diffusion coefficient:~4.21×10-^(10)cm^(2)s^(-1))in 0.5 M MgCl_(2)aqueous electrolyte.Moreover,the MMO-1//AC full battery achieved a high discharge capacity(100 mAg^(-1):111 mAh g^(-1)),and an ignored fading over 5000 cycles(1000 mAg^(-1)).Therefore,layered Mg-Mn oxide with large interlayer space may break a new path to develop the promising ARMIBs.展开更多
基金This work was supported by the National Key Research and Development Programs(Grant No.2021YFB2400400)National Natural Science Foundation of China(Grant Nos.51772093,52202284)+5 种基金Major Science and Technology Innovation Project of Hunan Province(Grant No.2020GK1010-2020GK1014-4)Distinguished Youth Foun-dation of Hunan Province(Grant No.2019JJ20010)Zhejiang Natural Science Foundation(Grant No.LQ23E020002)Wenzhou Natural Science Foundation(Grant No.G20220019)Cooperation between industry and education project of Ministry of Education(Grant No.220601318235513)State Key Laboratory of Elec-trical Insulation and Power Equipment,Xi'an Jiaotong University(Grant No.EIPE22208).
文摘Sodium-ion batteries(SIBs)are considered as a low-cost complementary or alternative system to prestigious lithium-ion batteries(LIBs)because of their similar working principle to LIBs,cost-effectiveness,and sustainable availability of sodium resources,especially in large-scale energy storage systems(EESs).Among various cathode candidates for SIBs,Na-based layered transition metal oxides have received extensive attention for their relatively large specific capacity,high operating potential,facile synthesis,and environmental benignity.However,there are a series of fatal issues in terms of poor air stability,unstable cathode/electrolyte interphase,and irreversible phase transition that lead to unsatisfactory battery performance from the perspective of preparation to application,outside to inside of layered oxide cathodes,which severely limit their practical application.This work is meant to review these critical problems associated with layered oxide cathodes to understand their fundamental roots and degradation mechanisms,and to provide a comprehensive summary of mainstream modification strategies including chemical substitution,surface modification,structure modulation,and so forth,concentrating on how to improve air stability,reduce interfacial side reaction,and suppress phase transition for realizing high structural reversibility,fast Na+kinetics,and superior comprehensive electrochemical performance.The advantages and disadvantages of different strategies are discussed,and insights into future challenges and opportunities for layered oxide cathodes are also presented.
基金supported by the National Basic Research Program of China(2009CB421002)National Natural Science Foundation of China(Grant No.40473008,40273020,40572036)+1 种基金Program for New Century Excellent Talents in University(Grant No.NCET-04-0728)Project(B07011)and PCSIRT.
文摘There are two types of temporally and spatially associated intrusions within the Emeishan large igneous province （LIP）; namely, small ultramafic subvolcanic sills that host magmatic Cu-Ni-Platinum Group Element （PGE）-bearing sulfide deposits and large mafic layered intrusions that host giant Ti-V magnetite deposits in the Panxi region. However, except for their coeval ages, the genetic relations between the ore-bearing intrusions and extrusive rocks are poorly understood. Phase equilibria analysis （Q-PI-OI-Opx-Cpx system） has been carried out to elucidate whether ore-bearing Panzhihua, Xinjie and Limahe intrusions are co-magmatic with the picrites and flood basalts （including high-Ti, low-Ti and alkali basalts）, respectively. In this system, the parental magma can be classified as silica-undersaturated olivine basalt and silica-saturated tholeiite. The equivalents of the parental magma of the Xinjie and Limahe peridotites and picrites and low-Ti basalts are silica-undersaturated, whereas the Limahe gabbro-diorites and high-Ti basalts are silica-saturated. In contrast, the Panzhihua intrusion appears to be alkali character. Phase equilibria relations clearly show that the magmas that formed the Panzhihua intrusion and high-Ti basalts cannot be co-magmatic as there is no way to derive one liquid from another by fractional crystallization. On the other hand, the Panzhihua intrusion appears to be related to Permian alkali intrusions in the region, but does not appear to be related to the alkali basalts recognized in the Longzhoushan lava stratigraphy. Comparably, the Limahe intrusion appears to be a genetic relation to the picrites, whereas the Xinjie intrusion may be genetically related to be low-Ti basalts. Additionally, the gabbro-diorites and peridotites of the Limahe intrusion are not co-magmatic, and the former appears to be derived liquid from high-Ti basalts.
基金This study was supported by the National Natural Science Foundation of China(No.21471162)the Hunan Provincial Innovation Foundation for Post graduate(No.502211822).
文摘Sodium-ion batteries(SIBs),which are an alternative to lithium-ion batteries(LIBs),have attracted increasing attention due to their low cost of Na resources and similar Na storage mechanism to LIBs.Compared with anode materials and electrolytes,the development of cathode materials lags behind.Therefore,the key to improving the specific energy and promoting the application of SIBs is to develop high-performance sodium intercalation cathode materials.Transition-metal oxides are one of the most promising cathode materials for SIBs owing to their excellent energy density,high specific discharge capacity,and environmentally friendly nature.In the present work,the latest progress in the research of transition-metal oxides is summarized.Moreover,the existing challenges are discussed,and a series of strategies are proposed to overcome these drawbacks.This review aims at providing guidance for the development of metal oxides in the next stage.
基金supported by the National Basic Research Program of China(No.2018YFA0702001)the National Natural Science Foundation of China(Nos.22225901,21975237,and 22175162)+3 种基金the Anhui Provincial Research and Development Program(No.202004a05020073)the Fundamental Research Funds for the Central Universities(No.WK2340000101)the USTC Research Funds of the Double First-Class Initiative(No.YD2340002007)the Open Funds of the State Key Laboratory of Rare Earth Resource Utilization(No.RERU2022007).
文摘Electrocatalysis can enable efficient energy storage and conversion and thus is an effective way to achieve carbon neutrality.The unique structure and function of organisms can offer many ideas for the design of electrocatalysts,which has become one of the most promising research directions.Recently,the understanding of the mechanism of bio-inspired electrocatalysis has become clearer,which has promoted the design of bio-inspired catalysts and catalytic systems.Various bio-inspired catalysts(enzyme-like catalysts,layered porous catalysts,superhydrophobic/superhydrophilic surfaces,and so on)have been developed to enable efficient electrocatalytic reactions.Herein,we discuss the key advances in the field of bio-inspired electrocatalysts progressed in recent years.First,the role of bio-inspiration in increasing the intrinsic activity and number of active sites of catalysts is introduced.Then,the structure and mechanism of layered porous catalytic systems that mimic biological transport systems are comprehensively discussed.Subsequently,the design of three-phase interfaces from micro-nanoscale to atomic scale is highlighted,including the wettability of the electrode surface and the transport system near the electrode.We conclude the review by identifying challenges in bio-inspired electrocatalysts and providing insights into future prospects for the exciting research field.
文摘Among complex oxides containing rare earth and manganese BaLn_2Mn_2O_7 (Ln=rare earth) with the layered perovskite type and Ln_2(Mn, M)O_7 with pyrochlore-related structure were studied since these compounds show many kinds of phases and unique phase transitions. In BaLn_2Mn_2O_7 there appear many phases, depending on the synthetic conditions for each rare earth. The tetragonal phase of so-called Ruddlesden-Popper type is the fundamental structure and many kinds of deformed modification of this structure are obtained. For BaEu_2Mn_2O_7 at least five phases have been identified from the results of X-ray diffraction analysis with the space group P4_2/mnm, Fmmm, Immm and A2/m in addition to the fundamental tetragonal I4/mmm phase. In the pyrochlore-related type compounds, Ln_2Mn_(2-x)M_xO_7 (M=Ta, Nb, W etc), there also appear several phases with different crystal structures. With regard to every rare earth, Ln_2MnTaO_7 phase is stable only for excess Ta and can be obtained under high oxygen partial pressure process. This group has trigonal structure with zirkelite type (P3_121 space group). On the other hand Ln_2Mn_(2/3)Nb_(4/3)O_7 phase has monoclinic (C2/c space group) and zirconolite type structure. All of these structural models have the fundamental structure based on HTB (hexagonal tungsten bronze) layers formed by the arrangement of oxygen octahedra.
基金supported by the Chengdu Science and Technology Program(No.2021GH0200032HZ)Sichuan Engineering Technology Research Center of Basalt Fiber Composites Development and Application(No.2022SCXWYXWFC006)Natural Science Foundation of Sichuan Province(No.2022NSFSC0356)。
文摘BA_(2)(MA)_(n-1)Pb_nI_(3n+1)series low-dimensional(2D)perovskites have been widely investigated for their re markable environmental stability,but still suffer the poor light absorption and disordered phase distri bution,hindering their practical applications.In this work,we combine the introduction of FA and the addition of PbCl_(2)to optimize the film quality,strengthen the light absorption,regulate internal phase distribution,and promote carrier transport inside 2D perovskite films.The incorporation of FA promote sufficient light absorption and improve the film crystallinity.Furthermore,the addition of Pb Cl_(2)elimi nates the low n phase(n=1)and suppresses the forming of the low n phase of n=2,enhancing the film conductivity and diminishing carrier recombination.The synergistic of A-site cation engineering and phase manipulation achieves a high efficiency of 16.48%.Importantly,the synergistic prepared perovskite film does not show any changes after 60 days in the air with an average humidity of 57%±3%,and the corresponding solar cell maintains 85%of the original efficiency after more than 800 h,demonstrating remarkable environmental stability.The results indicate that the synergistic of A-site cation engineering and phase manipulation is promising for producing superior efficiency,along with satisfying humidity stability.
基金financially supported by Guangxi Natural Science Foundation(No.2021GXNSFDA075012)the National Natural Science Foundation of China(Nos.U20A20249 and 22169004)+2 种基金the Natural Science Fund of Huanggang Normal University for Young Scholars(No.2014019203)the Special Fund for Guangxi Distinguished Expertthe Innovation Project of Guangxi Graduate Education(No.JGY2022031)。
文摘With the shortage of lithium resources,sodiumion batteries(SIBs)are considered one of the most promising candidates for lithium-ion batteries.P2-type and O3-type layered oxides are one of the few cathodes that can access high energy density.However,they usually exhibit structural change,capacity decay,and slow Na ion kinetic.Herein,we present layered ternary-phase cathodes with P2,P3 and O3 phases by a lattice doping strategy,which is demonstrated by X-ray diffraction(XRD)refinement.Combining the characteristics of P2,P3 and O3 phases,the layered composites show performance improvement during long-term battery cycling.In particular,Na_(0.7)Li_(0.1)Co_(0.3-)Fe_(0.3)Mn_(0.3)O_(2)(NLCFM)delivers a reversible capacity of120.1 mAh·g^(-1)at 0.1C(1.0C=175 mA·g^(-1))with a superior capacity retention of 72.5%after 1000 cycles at10.0C.This work offers insights into the development of advanced cathode materials for SIBs.
文摘Atomic intercalation in two-dimensional （2D） layered materials can be used to engineer the electronic structure at the atomic scale and generate tuneable physical and chemical properties which are quite distinct in comparison with the pristine material. Among them, electron-doped engineering induced by intercalation is an efficient route to modulate electronic states in 2D layers. Herein, we demonstrate a semiconducting to metallic phase transition in zirconium diselenide （ZrSe2） single crystals via controllable incorporation of copper （Cu） atoms. Our angle resolved photoemission spectroscopy （ARPES） measurements and first-principles density functional theory （DFT） calculations dearly revealed the emergence of conduction band dispersion at the M/L point of the Brillouin zone due to Cu-induced electron doping in ZrSe2 interlayers. Moreover, electrical measurements in ZrSe2 revealed semiconducting behavior, while the Cu-intercalated ZrSe2 exhibited a linear current-voltage curve with metallic character. The atomic intercalation approach may have high potential for realizing transparent electron-doping systems for many specific 2D-based nanoelectronic applications.
基金the financial support from the National Natural Science Foundation of China(Grant Nos.92372107 and 52171219).
文摘Nickel-rich layered oxide LiNi_(x)Co_(y)MnzO_(2)(NCM,x+y+z=1)is the most promising cathode material for high-energy lithium-ion batteries.However,conventional synthesis methods are limited by the slow heating rate,sluggish reaction dynamics,high energy consumption,and long reaction time.To overcome these chal-lenges,we first employed a high-temperature shock(HTS)strategy for fast synthesis of the NCM,and the approaching ultimate reaction rate of solid phase transition is deeply investigated for the first time.In the HTS process,ultrafast average reaction rate of phase transition from Ni_(0.6)Co_(0.2)Mn_(0.2)(OH)_(2) to Li-containing oxides is 66.7(%s^(-1)),that is,taking only 1.5 s.An ultrahigh heating rate leads to fast reaction kinetics,which induces the rapid phase transition of NCM cathodes.The HTS-synthesized nickel-rich layered oxides perform good cycling performances(94%for NCM523,94%for NCM622,and 80%for NCM811 after 200 cycles at 4.3 V).These findings might also assist to pave the way for preparing effectively Ni-rich layered oxides for lithium-ion batteries.
基金the National Natural Science Foundation of China(12174015)the Natural Science Foundation of Beijing,China(2212003)+1 种基金the China National Petroleum Corporation Innovation Found(2021DQ02-1004)the National Natural Science Foundation of China(12074017,12274010).
文摘High nickel content worsens the thermal stability of layered cathodes for lithium-ion batteries,raising safety concerns for their applications.Thoroughly understanding the thermal failure process can offer valuable guidance for material optimization on thermal stability and new opportunities in monitoring battery thermal runaway(TR).Herein,this work comprehensively investigates the thermal failure process of a single-crystal nickel-rich layered cathode and finds that the latent thermal failure starts at∼120℃far below the TR temperature(225℃).During this stage of heat accumulation,sequential structure transition is revealed by atomic resolution electron microscopy,which follows the layered→cation mixing layered→LiMn_(2)O_(4)-type spinel→disordered spinel→rock salt.This progression occurs as a result of the continuous migration and densification of transition metal cations.Phase transition generates gaseous oxygen,initially confined within the isolated closed pores,thereby not showing any thermal failure phenomena at the macro-level.Increasing temperature leads to pore growth and coalescence,and eventually to the formation of open pores,causing oxygen gas release and weight loss,which are the typical TR features.We highlight that latent thermal instability occurs before the macro-level TR,suggesting that suppressing phase transitions caused by early thermal instability is a crucial direction for material optimization.Our findings can also be used for early warning of battery thermal runaway.
基金Natural Science Foundation of Hunan Province (No.2020JJ4734)High Performance Computing Center of Central South University。
文摘The thermodynamic instability of zinc anodes in aqueous electrolytes leads to issues such as corrosion,hydrogen evolution reactions(HER), and dendrite growth, severely hindering the practical application of zinc-based aqueous energy storage devices. To address these challenges, this work proposes a dualfunction zinc anode protective layer, composed of Zn-Al-In layered double oxides(ILDO) by rationally designing Zn-Al layered double hydroxides(Zn-Al LDHs) for the first time. Differing from previous works on the LDHs coatings, firstly, the ILDO layer accelerates zinc-ion desolvation and also captures and anchors SO_(4)^(2-). Secondly, the in-situ formation of the Zn-In alloy phase effectively lowers the nucleation energy barrier, thereby regulating zinc nucleation. Consequently, the zinc anode with the ILDO protective layer demonstrates long-term stability exceeding 1900 h and low voltage hysteresis of 7.5 m V at 0.5 m A cm^(-2) and 0.5 m A h cm^(-2). Additionally, it significantly enhances the rate capability and cycling performance of Zn@ILDO//MnO_(2) full batteries and Zn@ILDO//activated carbon zinc-ion hybrid capacitors.This simple and effective dual-function protective layer strategy offers a promising approach for achieving high-performance zinc-ion batteries.
基金supported by the National Natural Science Foundation of China(Grant No.12105197 and 52088101)Guangdong Basic and Applied Basic Research Foundation(Grant No.2022A1515010319)+1 种基金the open research fund of Songshan Lake Materials Laboratory(No.2022SLABFK04)Large Scientific Facility Open Subject of Songshan Lake,Dongguan,Guangdong
文摘Due to a high energy density,layered transition-metal oxides have gained much attention as the promising sodium-ion batteries cathodes.However,they readily suffer from multiple phase transitions during the Na extraction process,resulting in large lattice strains which are the origin of cycledstructure degradations.Here,we demonstrate that the Na-storage lattice strains of layered oxides can be reduced by pushing charge transfer on anions(O^(2-)).Specifically,the designed O3-type Ru-based model compound,which shows an increased charge transfer on anions,displays retarded O3-P3-O1 multiple phase transitions and obviously reduced lattice strains upon cycling as directly revealed by a combination of ex situ X-ray absorption spectroscopy,in situ X-ray diffraction and geometric phase analysis.Meanwhile,the stable Na-storage lattice structure leads to a superior cycling stability with an excellent capacity retention of 84%and ultralow voltage decay of 0.2 mV/cycle after 300 cycles.More broadly,our work highlights an intrinsically structure-regulation strategy to enable a stable cycling structure of layered oxides meanwhile increasing the materials’redox activity and Nadiffusion kinetics.
基金supported by the Science and Technology Program of Suzhou(ST202304)the National Natural Science Foundation of China(12275189)+1 种基金the Collaborative Innovation Center of Suzhou Nano Science&Technologythe 111 project。
文摘O3-type layered oxides have garnered great attention as cathode materials for sodium-ion batteries because of their abundant reserves and high theoretical capacity.However,challenges persist in the form of uncontrollable phase transitions and intricate Na^(+)diffusion pathways during cycling,resulting in compromised structural stability and reduced capacity over cycles.This study introduces a special approach employing site-specific Ca/F co-substitution within the layered structure of O_(3)-NaNi_(0.5)Mn_(0.5)O_(2) to effectively address these issues.Herein,the strategically site-specific doping of Ca into Na sites and F into O sites not only expands the Na^(+)diffusion pathways but also orchestrates a mild phase transition by suppressing the Na^(+)/vacancy ordering and providing strong metal-oxygen bonding strength,respectively.The as-synthesized Na_(0.95)Ca_(0.05)Ni_(0.5)Mn_(0.5)O_(1.95)F_(0.05)(NNMO-CaF)exhibits a mild O3→O3+O'3→P3 phase transition with minimized interlayer distance variation,leading to enhanced structural integrity and stability over extended cycles.As a result,NNMO-CaF delivers a high specific capacity of 119.5 mA h g^(-1)at a current density of 120 mA g^(-1)with a capacity retention of 87.1%after 100 cycles.This study presents a promising strategy to mitigate the challenges posed by multiple phase transitions and augment Na^(+)diffusion kinetics,thus paving the way for high-performance layered cathode materials in sodium-ion batteries.
基金This work was supported by the National Key R&D Program of China(2016YFB0100301)National Natural Science Foundation of China(21875022,51802020)+2 种基金the Natural Science Foundation of Chongqing,China(cstc2020jcyj-msxmX0654,cstc2020jcyj-msxm X0589)the Science and Technology Innovation Foundation of Beijing Institute of Technology Chongqing Innovation Center(2020CX5100006)the Young Elite Scientists Sponsorship Program by CAST(2018QNRC001).L.Chen,N.Li and D.Y.Cao acknowledge the support from Beijing Institute of Technology Research Fund Program for Young Scholars.
文摘Ni-rich layered cathode is regarded as one of the most promising candidates to achieve lithium-ion batteries (LIBs) with high energy density. However, due to the irreversible phase transformation (IPT) and its eventual propagation from surface to the bulk of the material, Ni-rich layered cathode typically suffers from severe capacity fading, structure failure, and thermal instability, which greatly hinders its mass adoption. Hence, achieving an in-depth understanding of the IPT propagation mechanism in Ni-rich layered cathode is crucial in addressing these issues. Herein, the triggering factor of IPT propagation in Ni-rich cathode is verified to be the initial surface disordered cation mixing domain covered by a thin rock-salt phase, instead of the rock-salt phase itself. According to the density functional theory (DFT) results, it is further illustrated that the metastable cation mixing domain possesses a lower Ni migration energy barrier, which facilitates the migration of Ni ions towards the Li slab, and thus driving the propagation of IPT from surface to the bulk of the material. This finding clarifies a prevailing debate regarding the surface impurity phases of Ni-rich cathode material and reveals the origin of IPT propagation, which implies the principle and its effectiveness of tuning the surface microstructure to address the structural and thermal instability issue of Ni-rich layered cathode materials.
基金financially supported by the Fundamental Research Funds for the Central Universities(NO.2021CDJXDJH003)Guangdong National Technology Co.,Ltd.
文摘Owing to the features(high safety,inexpensive and environmental friendliness)of aqueous rechargeable Mg-ion batteries(ARMIBs),they have drawn extensive attention in the future energy storage systems.However,the poor Mg^(2+)migration kinetics during the Mg^(2+)intercalation/extraction still hinders the progress of developing suitable cathode materials.Herein,a layered buserite Mg-Mn oxide(MMO)material with large interlayer space(~9.70A)and low-crystalline structure is studied as a high-performance cathode in ARMIBs.Compared with the counterpart,the Mg^(2+)migration kinetics of the MMO cathode can be enhanced by its unique structure(bigger interlayer spacing and low-crystalline structure).The layered buserite MMO as a high-performance ARMIBs cathode exhibits high Mg storage capacity(50 mAg^(-1):169.3 mAh g^(-1)),excellent rate capability(1000 mAg^(-1):98.3 mAh g^(-1)),and fast Mg^(2+)migration(an average diffusion coefficient:~4.21×10-^(10)cm^(2)s^(-1))in 0.5 M MgCl_(2)aqueous electrolyte.Moreover,the MMO-1//AC full battery achieved a high discharge capacity(100 mAg^(-1):111 mAh g^(-1)),and an ignored fading over 5000 cycles(1000 mAg^(-1)).Therefore,layered Mg-Mn oxide with large interlayer space may break a new path to develop the promising ARMIBs.
