Lithium metal batteries(LMBs)have been regarded as one of the most promising alternatives in the post-lithium battery era due to their high energy density,which meets the needs of light-weight electronic devices and l...Lithium metal batteries(LMBs)have been regarded as one of the most promising alternatives in the post-lithium battery era due to their high energy density,which meets the needs of light-weight electronic devices and long-range electric vehicles.However,technical barriers such as dendrite growth and poor Li plating/stripping reversibility severely hinder the practical application of LMBs.However,lithium nitrate(LiNO_(3))is found to be able to stabilize the Li/electrolyte interface and has been used to address the above challenges.To date,considerable research efforts have been devoted toward understanding the roles of LiNO_(3) in regulating the surface properties of Li anodes and toward the development of many effective strategies.These research efforts are partially mentioned in some articles on LMBs and yet have not been reviewed systematically.To fill this gap,we discuss the recent advances in fundamental and technological research on LiNO_(3) and its derivatives for improving the performances of LMBs,particularly for Li-sulfur(S),Li-oxygen(O),and Li-Li-containing transition-metal oxide(LTMO)batteries,as well as LiNO_(3)-containing recipes for precursors in battery materials and interphase fabrication.This review pays attention to the effects of LiNO_(3) in lithium-based batteries,aiming to provide scientific guidance for the optimization of electrode/electrolyte interfaces and enrich the design of advanced LMBs.展开更多
Twisted multilayers of two-dimensional materials attract widespread research interest due to their intriguing electronic and optical properties related to their chiral symmetry breaking and moiréeffects.The two-d...Twisted multilayers of two-dimensional materials attract widespread research interest due to their intriguing electronic and optical properties related to their chiral symmetry breaking and moiréeffects.The two-dimensional transition metal dichalcogenide MoSe_(2) is a particularly promising material for twisted multilayers,capable of sustaining moiréexcitons.Here,we report on a rational bottomup synthesis approach for twisted MoSe_(2) flakes by chemical vapor transport(CVT).Screw dislocation-driven growth was forced by surface-fused SiO_(2)nanoparticles on the substrates that serve as potential nucleation points in low supersaturation condition.Thus,crystal growth by in-situ CVT under addition of MoCl_(5) leads to bulk 2H-MoSe_(2) in a temperature gradient from 900 to 820℃ with a dwell time of 96 h.Hexagonally shaped 2H-MoSe_(2) flakes were grown from 710 to 685℃ with a dwell time of 30 min on SiO_(2)@Al_(2)O_(3)(0001)substrates.Electron backscatter diffraction as well as electron microscopy reveals the screw dislocation-driven growth of triangular 3R-MoSe_(2) with individual step heights between 0.9 and 2.9 nm on SiO_(2)@Si(100)under the same conditions.Finally,twisted MoSe_(2) flakes exhibiting a twist angle of 19°with respect to the[010]zone axis could be synthesized.展开更多
Wide-temperature applications of sodium-ion batteries(SIBs)are severely limited by the sluggish ion insertion/diffusion kinetics of conversion-type anodes.Quantum-sized transition metal dichalcogenides possess unique ...Wide-temperature applications of sodium-ion batteries(SIBs)are severely limited by the sluggish ion insertion/diffusion kinetics of conversion-type anodes.Quantum-sized transition metal dichalcogenides possess unique advantages of charge delocalization and enrich uncoordinated electrons and short-range transfer kinetics,which are crucial to achieve rapid low-temperature charge transfer and high-temperature interface stability.Herein,a quantum-scale FeS_(2) loaded on three-dimensional Ti_(3)C_(2) MXene skeletons(FeS_(2) QD/MXene)fabricated as SIBs anode,demonstrating impressive performance under wide-temperature conditions(−35 to 65).The theoretical calculations combined with experimental characterization interprets that the unsaturated coordination edges of FeS_(2) QD can induce delocalized electronic regions,which reduces electrostatic potential and significantly facilitates efficient Na+diffusion across a broad temperature range.Moreover,the Ti_(3)C_(2) skeleton reinforces structural integrity via Fe-O-Ti bonding,while enabling excellent dispersion of FeS_(2) QD.As expected,FeS_(2) QD/MXene anode harvests capacities of 255.2 and 424.9 mAh g^(−1) at 0.1 A g^(−1) under−35 and 65,and the energy density of FeS_(2) QD/MXene//NVP full cell can reach to 162.4 Wh kg^(−1) at−35,highlighting its practical potential for wide-temperatures conditions.This work extends the uncoordinated regions induced by quantum-size effects for exceptional Na^(+)ion storage and diffusion performance at wide-temperatures environment.展开更多
Micro-sized anatase TiO_(2) displays inferior capacity as cathode material for magnesium ion batteries because of the higher diffusion energy barrier of Mg^(2+)in anatase TiO_(2) lattice.Herein,we report that nanosize...Micro-sized anatase TiO_(2) displays inferior capacity as cathode material for magnesium ion batteries because of the higher diffusion energy barrier of Mg^(2+)in anatase TiO_(2) lattice.Herein,we report that nanosized anatase TiO_(2) exposed(001)facet doubles the capacity compared to the micro-sized sample ascribed to the interfacial Mg^(2+)ion storage.First-principles calculations reveal that the diffusion energy barrier of Mg^(2+)on the(001)facet is significantly lower than those in the bulk phase and on(100)facet,and the adsorption energy of Mg^(2+)on the(001)facet is also considerably lower than that on(100)facet,which guarantees superior interfacial Mg^(2+)storage of(001)facet.Moreover,anatase TiO_(2) exposed(001)facet displays a significantly higher capacity of 312.9 mAh g^(−1) in Mg-Li dual-salt electrolyte compared to 234.3 mAh g^(−1) in Li salt electrolyte.The adsorption energies of Mg^(2+)on(001)facet are much lower than the adsorption energies of Li+on(001)facet,implying that the Mg^(2+)ion interfacial storage is more favorable.These results highlight that controlling the crystal facet of the nanocrystals effectively enhances the interfacial storage of multivalent ions.This work offers valuable guidance for the rational design of high-capacity storage systems.展开更多
TiNb_(2)O_(7)represents an up-and-coming anode material for fast-charging lithium-ion batteries,but its practicalities are severely impeded by slow transfer rates of ionic and electronic especially at the low-temperat...TiNb_(2)O_(7)represents an up-and-coming anode material for fast-charging lithium-ion batteries,but its practicalities are severely impeded by slow transfer rates of ionic and electronic especially at the low-temperature conditions.Herein,we introduce crystallographic engineering to enhance structure stability and promote Li+diffusion kinetics of TiNb_(2)O_(7)(TNO).The density functional theory computation reveals that Ti^(4+)is replaced by Sb^(5+)and Nb^(5+)in crystal lattices,which can reduce the Li+diffusion impediment and improve electronic conductivity.Synchrotron radiation X-ray 3D nano-computed tomography and in situ X-ray diffraction measurement confirm the introduction of Sb/Nb alleviates volume expansion during lithiation and delithiation processes,contributing to enhancing structure stability.Extended X-ray absorption fine structure spectra results verify that crystallographic engineering also increases short Nb-O bond length in TNO-Sb/Nb.Accordingly,the TNO-Sb/Nb anode delivers an outstanding capacity retention rate of 89.8%at 10 C after 700 cycles and excellent rate performance(140.4 mAh g^(−1) at 20 C).Even at−30℃,TNO-Sb/Nb anode delivers a capacity of 102.6 mAh g^(−1) with little capacity degeneration for 500 cycles.This work provides guidance for the design of fast-charging batteries at low-temperature condition.展开更多
To synergistically recover alumina and alkali from red mud(RM),the structural stability and conversion mechanism of hydroandradite(HA)from hydrogarnet(HG)were investigated via the First-principles,XRF,XRD,PSD and SEM ...To synergistically recover alumina and alkali from red mud(RM),the structural stability and conversion mechanism of hydroandradite(HA)from hydrogarnet(HG)were investigated via the First-principles,XRF,XRD,PSD and SEM methods,and a novel hydrothermal process based on the conversion principle was finally proposed.The crystal structure simulation shows that the HA with varied silicon saturation coefficients is more stable than HG,and the HA with a high iron substitution coefficient is more difficult to be converted from HG.The(110)plane of Fe_(2)O_(3) is easier to combine with HG to form HA,and the binding energy is 81.93 kJ/mol.The effects of raw material ratio,solution concentration and hydrothermal parameters on the conversion from HG to HA were revealed,and the optimal conditions for the alumina recovery were obtained.The recovery efficiencies of alumina and Na_(2)O from the RM are 63.06%and 97.34%,respectively,and the Na_(2)O content in the treated RM is only 0.13%.展开更多
Although intermediate temperature solid oxide fuel cells(IT-SOFCs)show great potential to address energy conversion challenges,the sluggish oxygen reduction reaction(ORR)kinetics of cathode materials has severely hind...Although intermediate temperature solid oxide fuel cells(IT-SOFCs)show great potential to address energy conversion challenges,the sluggish oxygen reduction reaction(ORR)kinetics of cathode materials has severely hindered extended applications.Herein,we have demonstrated that Bi^(3+)doping on the A-site synergistically regulates the phase transition and electron spin state in La_(0.3)Bi_(0.3)Ca_(0.4)FeO_(3-δ)(LBCF3)for improved performance.An orthorhombic to cubic phase transition occurred with Bi^(3+)doping increases oxygen vacancy concentration and thus increases oxygen ion migration capacity.Simultaneously,the change of Fe from low to medium electron spin state strengths O_(2)adsorption and improves catalytic performances.Consequently,a peak power density improvement up to 48%(from 1.21 to 1.79 W·cm^(-2))at 800℃ is realized in the anodesupported single cell using LBCF3 as cathode,which remains stable for over 270 h at 750℃.展开更多
Introduction of active centers,such as oxygen vacancy and metal single atoms,has emerged as a promising strategy to further improve the electrochemical properties of transition metal oxide electrodes for high-performa...Introduction of active centers,such as oxygen vacancy and metal single atoms,has emerged as a promising strategy to further improve the electrochemical properties of transition metal oxide electrodes for high-performance pseudocapacitors.Here,an unprecedented MoO_(3)with multiple active centers,Ni anchored reduced MoO_(3)with oxygen vacancy(NirMoO_(3-x)),was in situ synthesized via γ-ray radiationinduced one-pot strategy under ambient conditions.This approach leverages the synergistic effects of radiation activation,etching,and reduction.The characteristics of multiple valence states(Mo^(4+/5+/6+)and Ni^(0/2+)),oxygen vacancies,single atoms,and atomic clusters in NirMoO_(3-x) were determined by X-ray photoelectron spectroscopy(XPS),X-ray absorption fine structure spectroscopy(XAFS),and atomic-resolution aberrationcorrected high-angle annular dark-field scanning transmission electron microscopy(HAADF-STEM)measurements.Notably,Ni-rMoO_(3-x)exhibited exceptional pseudocapacitive performance,with ultrahigh specific charge(881.0 C·g^(-1)at 1 A·g^(-1),more than twice that of MoO_(3)),fast charge/discharge rates,and remarkable cycle life stability(98.5% capacitance retention after 10,000 cycles).Furthermore,a hybrid supercapacitor device(Ni-rMoO_(3-x)//activated carbon(AC))demonstrated a high energy density of 97.8 Wh·kg^(-1)at a power density of 0.90 kW·kg^(-1)and exhibited excellent mechanical flexibility for practical applications.展开更多
Layered vanadium oxides are desired cathode materials due to their multielectron redox reactions.However,their further development has been limited by the low electrical conductivity and unstable crystal structure.Her...Layered vanadium oxides are desired cathode materials due to their multielectron redox reactions.However,their further development has been limited by the low electrical conductivity and unstable crystal structure.Herein,we synthesize V_(2)O_(5)microspheres with oxygen-rich vacancies by Mo doping strategy.The oxygen vacancies provide preferential adsorption sites for Zn ions,thereby decreasing the ionic migration barrier within the host framework.The Zn//Mo-V_(2)O_(5)batteries achieve a specific capacity of 502.5 mAh·g^(-1)at 0.2 A·g^(-1)and retain 433.2 mAh·g^(-1)after 100 times cycling.Moreover,they possess 2000 times cycling life with a retention rate of 100% at a low temperature of 0℃(1 A·g^(-1)).It is believed that the reliable Mo-doping approach will provide new insights for high-performance energy storage systems.展开更多
Cobalt-free LiNiO_(2)(LNO)is considered a promising cathode for its high energy density and costeffectiveness.However,its structural instability under deep delithiation severely limits practical application in nextgen...Cobalt-free LiNiO_(2)(LNO)is considered a promising cathode for its high energy density and costeffectiveness.However,its structural instability under deep delithiation severely limits practical application in nextgeneration batteries.Herein,we propose a high-valence Mo6+doping strategy to simultaneously improve mechanical robustness and electrochemical stability.By stabilizing intergranular interfaces,this method effectively suppresses mechanical degradation induced by lattice strain under deep delithiation.The modified cathode exhibits exceptional electrochemical performance,achieving a specific capacity of 234 mAh·g^(-1)at 0.1 C with 83.4% retention over 100 cycles at 45℃ in lithium-ion batteries(LIBs).Notably,it maintains comparable efficacy in all-solid-state batteries(ASSBs),delivering 239 mAh·g^(-1)at 0.05 C and 82.8% retention after 300 cycles.Density functional theory(DFT)calculations demonstrate a pronounced rise in oxygen vacancy formation energy,increasing from 1.42 to 3.27 eV.These findings offer valuable insights into overcoming the kinetic performance limitations of cobalt-free LNO under deep delithiation conditions.展开更多
基金supported by the Yunnan Fundamental Research Projects(Grant Nos.202401AU070163 and 202501AT070298)the Yunnan Engineering Research Center Innovation Ability Construction and Enhancement Projects(Grant No.2023-XMDJ-00617107)+5 种基金the University Service Key Industry Project of Yunnan Province(Grant No.FWCY-ZD2024005)the Expert Workstation Support Project of Yunnan Province(Grant No.202405AF140069)the Scientific Research Foundation of Kunming University of Science and Technology(Grant No.20220122)the Analysis and Test Foundation of Kunming University of Science and Technology(Grant No.2023T20220122)the Natural Science Foundation of Inner Mongolia Autonomous Region of China(Grant No.2025QN02057)the Ordos City Strategic Pioneering Science and Technology Special Program for New Energy(Grant No.DC2400003365).
文摘Lithium metal batteries(LMBs)have been regarded as one of the most promising alternatives in the post-lithium battery era due to their high energy density,which meets the needs of light-weight electronic devices and long-range electric vehicles.However,technical barriers such as dendrite growth and poor Li plating/stripping reversibility severely hinder the practical application of LMBs.However,lithium nitrate(LiNO_(3))is found to be able to stabilize the Li/electrolyte interface and has been used to address the above challenges.To date,considerable research efforts have been devoted toward understanding the roles of LiNO_(3) in regulating the surface properties of Li anodes and toward the development of many effective strategies.These research efforts are partially mentioned in some articles on LMBs and yet have not been reviewed systematically.To fill this gap,we discuss the recent advances in fundamental and technological research on LiNO_(3) and its derivatives for improving the performances of LMBs,particularly for Li-sulfur(S),Li-oxygen(O),and Li-Li-containing transition-metal oxide(LTMO)batteries,as well as LiNO_(3)-containing recipes for precursors in battery materials and interphase fabrication.This review pays attention to the effects of LiNO_(3) in lithium-based batteries,aiming to provide scientific guidance for the optimization of electrode/electrolyte interfaces and enrich the design of advanced LMBs.
基金funding from SFB 1415 subproject B04(Deutsche Forschungsgemeinschaft,No.417590517)supported by the Deutsche Forschungsgemeinschaft through the Würzburg-Dresden Cluster of Excellence on Complexity and Topology in Quantum Matter-ct.qmat(EXC 2147,No.390858490)the support provided by the DRESDEN-concept alliance of research institutions.
文摘Twisted multilayers of two-dimensional materials attract widespread research interest due to their intriguing electronic and optical properties related to their chiral symmetry breaking and moiréeffects.The two-dimensional transition metal dichalcogenide MoSe_(2) is a particularly promising material for twisted multilayers,capable of sustaining moiréexcitons.Here,we report on a rational bottomup synthesis approach for twisted MoSe_(2) flakes by chemical vapor transport(CVT).Screw dislocation-driven growth was forced by surface-fused SiO_(2)nanoparticles on the substrates that serve as potential nucleation points in low supersaturation condition.Thus,crystal growth by in-situ CVT under addition of MoCl_(5) leads to bulk 2H-MoSe_(2) in a temperature gradient from 900 to 820℃ with a dwell time of 96 h.Hexagonally shaped 2H-MoSe_(2) flakes were grown from 710 to 685℃ with a dwell time of 30 min on SiO_(2)@Al_(2)O_(3)(0001)substrates.Electron backscatter diffraction as well as electron microscopy reveals the screw dislocation-driven growth of triangular 3R-MoSe_(2) with individual step heights between 0.9 and 2.9 nm on SiO_(2)@Si(100)under the same conditions.Finally,twisted MoSe_(2) flakes exhibiting a twist angle of 19°with respect to the[010]zone axis could be synthesized.
基金supported by the National Nature Science Foundation of China(Nos.52202335 and 52171227)Natural Science Foundation of Jiangsu Province(No.BK20221137)National Key R&D Program of China(2024YFE0108500).
文摘Wide-temperature applications of sodium-ion batteries(SIBs)are severely limited by the sluggish ion insertion/diffusion kinetics of conversion-type anodes.Quantum-sized transition metal dichalcogenides possess unique advantages of charge delocalization and enrich uncoordinated electrons and short-range transfer kinetics,which are crucial to achieve rapid low-temperature charge transfer and high-temperature interface stability.Herein,a quantum-scale FeS_(2) loaded on three-dimensional Ti_(3)C_(2) MXene skeletons(FeS_(2) QD/MXene)fabricated as SIBs anode,demonstrating impressive performance under wide-temperature conditions(−35 to 65).The theoretical calculations combined with experimental characterization interprets that the unsaturated coordination edges of FeS_(2) QD can induce delocalized electronic regions,which reduces electrostatic potential and significantly facilitates efficient Na+diffusion across a broad temperature range.Moreover,the Ti_(3)C_(2) skeleton reinforces structural integrity via Fe-O-Ti bonding,while enabling excellent dispersion of FeS_(2) QD.As expected,FeS_(2) QD/MXene anode harvests capacities of 255.2 and 424.9 mAh g^(−1) at 0.1 A g^(−1) under−35 and 65,and the energy density of FeS_(2) QD/MXene//NVP full cell can reach to 162.4 Wh kg^(−1) at−35,highlighting its practical potential for wide-temperatures conditions.This work extends the uncoordinated regions induced by quantum-size effects for exceptional Na^(+)ion storage and diffusion performance at wide-temperatures environment.
基金supported by the National Key R&D Program of China(No.2023YFB3809500)the Fundamental Research Funds for the Central Universities(No.2024CDJXY003)+1 种基金the Venture&Innovation Support Program for Chongqing Overseas Returnees(cx2023087)The Chongqing Technology Innovation and Application Development Project(No.2024TIAD-KPX0003).
文摘Micro-sized anatase TiO_(2) displays inferior capacity as cathode material for magnesium ion batteries because of the higher diffusion energy barrier of Mg^(2+)in anatase TiO_(2) lattice.Herein,we report that nanosized anatase TiO_(2) exposed(001)facet doubles the capacity compared to the micro-sized sample ascribed to the interfacial Mg^(2+)ion storage.First-principles calculations reveal that the diffusion energy barrier of Mg^(2+)on the(001)facet is significantly lower than those in the bulk phase and on(100)facet,and the adsorption energy of Mg^(2+)on the(001)facet is also considerably lower than that on(100)facet,which guarantees superior interfacial Mg^(2+)storage of(001)facet.Moreover,anatase TiO_(2) exposed(001)facet displays a significantly higher capacity of 312.9 mAh g^(−1) in Mg-Li dual-salt electrolyte compared to 234.3 mAh g^(−1) in Li salt electrolyte.The adsorption energies of Mg^(2+)on(001)facet are much lower than the adsorption energies of Li+on(001)facet,implying that the Mg^(2+)ion interfacial storage is more favorable.These results highlight that controlling the crystal facet of the nanocrystals effectively enhances the interfacial storage of multivalent ions.This work offers valuable guidance for the rational design of high-capacity storage systems.
基金supported by the National Natural Science Foundation of China(22279026,2247090373)the Natural Science Foundation of Chongqing(CSTB2022NSCQ-MSX1401)+2 种基金the China Postdoctoral Science Foundation(2024M764198)the National Natural Science Foundation of China(22509044)the Fundamental Research Funds for the Central Universities(grant no.HIT.OCEF.2022017).
文摘TiNb_(2)O_(7)represents an up-and-coming anode material for fast-charging lithium-ion batteries,but its practicalities are severely impeded by slow transfer rates of ionic and electronic especially at the low-temperature conditions.Herein,we introduce crystallographic engineering to enhance structure stability and promote Li+diffusion kinetics of TiNb_(2)O_(7)(TNO).The density functional theory computation reveals that Ti^(4+)is replaced by Sb^(5+)and Nb^(5+)in crystal lattices,which can reduce the Li+diffusion impediment and improve electronic conductivity.Synchrotron radiation X-ray 3D nano-computed tomography and in situ X-ray diffraction measurement confirm the introduction of Sb/Nb alleviates volume expansion during lithiation and delithiation processes,contributing to enhancing structure stability.Extended X-ray absorption fine structure spectra results verify that crystallographic engineering also increases short Nb-O bond length in TNO-Sb/Nb.Accordingly,the TNO-Sb/Nb anode delivers an outstanding capacity retention rate of 89.8%at 10 C after 700 cycles and excellent rate performance(140.4 mAh g^(−1) at 20 C).Even at−30℃,TNO-Sb/Nb anode delivers a capacity of 102.6 mAh g^(−1) with little capacity degeneration for 500 cycles.This work provides guidance for the design of fast-charging batteries at low-temperature condition.
基金the financial support from the National Key R&D Program of China(No.2022YFC2904405)the National Natural Science Foundation of China(Nos.22078055,51774079)。
文摘To synergistically recover alumina and alkali from red mud(RM),the structural stability and conversion mechanism of hydroandradite(HA)from hydrogarnet(HG)were investigated via the First-principles,XRF,XRD,PSD and SEM methods,and a novel hydrothermal process based on the conversion principle was finally proposed.The crystal structure simulation shows that the HA with varied silicon saturation coefficients is more stable than HG,and the HA with a high iron substitution coefficient is more difficult to be converted from HG.The(110)plane of Fe_(2)O_(3) is easier to combine with HG to form HA,and the binding energy is 81.93 kJ/mol.The effects of raw material ratio,solution concentration and hydrothermal parameters on the conversion from HG to HA were revealed,and the optimal conditions for the alumina recovery were obtained.The recovery efficiencies of alumina and Na_(2)O from the RM are 63.06%and 97.34%,respectively,and the Na_(2)O content in the treated RM is only 0.13%.
基金supported by the Xinjiang Autonomous Region Key Research Project(No.2022D01D31)the Start-up Grant of Xinjiang University,the Basic Research Fund for Autonomous Region Universities(No.XJEDU2024P015)the Natural Science Foundation of Xinjiang Uygur Autonomous Region(No.2022D01C668).
文摘Although intermediate temperature solid oxide fuel cells(IT-SOFCs)show great potential to address energy conversion challenges,the sluggish oxygen reduction reaction(ORR)kinetics of cathode materials has severely hindered extended applications.Herein,we have demonstrated that Bi^(3+)doping on the A-site synergistically regulates the phase transition and electron spin state in La_(0.3)Bi_(0.3)Ca_(0.4)FeO_(3-δ)(LBCF3)for improved performance.An orthorhombic to cubic phase transition occurred with Bi^(3+)doping increases oxygen vacancy concentration and thus increases oxygen ion migration capacity.Simultaneously,the change of Fe from low to medium electron spin state strengths O_(2)adsorption and improves catalytic performances.Consequently,a peak power density improvement up to 48%(from 1.21 to 1.79 W·cm^(-2))at 800℃ is realized in the anodesupported single cell using LBCF3 as cathode,which remains stable for over 270 h at 750℃.
基金supported by the National Natural Science Foundation of China(Nos.22176194,22206016,and 12305397)the Natural Science Foundation of Jiangsu Province(No.BK20230511)+2 种基金Science Challenge Project(No.TZ2018004)Suzhou Fundamental Research Project(No.SJC2023001)Key Scientific Research Foundation of the Education Department of Province Anhui(No.2022AH051835).
文摘Introduction of active centers,such as oxygen vacancy and metal single atoms,has emerged as a promising strategy to further improve the electrochemical properties of transition metal oxide electrodes for high-performance pseudocapacitors.Here,an unprecedented MoO_(3)with multiple active centers,Ni anchored reduced MoO_(3)with oxygen vacancy(NirMoO_(3-x)),was in situ synthesized via γ-ray radiationinduced one-pot strategy under ambient conditions.This approach leverages the synergistic effects of radiation activation,etching,and reduction.The characteristics of multiple valence states(Mo^(4+/5+/6+)and Ni^(0/2+)),oxygen vacancies,single atoms,and atomic clusters in NirMoO_(3-x) were determined by X-ray photoelectron spectroscopy(XPS),X-ray absorption fine structure spectroscopy(XAFS),and atomic-resolution aberrationcorrected high-angle annular dark-field scanning transmission electron microscopy(HAADF-STEM)measurements.Notably,Ni-rMoO_(3-x)exhibited exceptional pseudocapacitive performance,with ultrahigh specific charge(881.0 C·g^(-1)at 1 A·g^(-1),more than twice that of MoO_(3)),fast charge/discharge rates,and remarkable cycle life stability(98.5% capacitance retention after 10,000 cycles).Furthermore,a hybrid supercapacitor device(Ni-rMoO_(3-x)//activated carbon(AC))demonstrated a high energy density of 97.8 Wh·kg^(-1)at a power density of 0.90 kW·kg^(-1)and exhibited excellent mechanical flexibility for practical applications.
基金the National Natural Science Foundation of China(No.52472227).
文摘Layered vanadium oxides are desired cathode materials due to their multielectron redox reactions.However,their further development has been limited by the low electrical conductivity and unstable crystal structure.Herein,we synthesize V_(2)O_(5)microspheres with oxygen-rich vacancies by Mo doping strategy.The oxygen vacancies provide preferential adsorption sites for Zn ions,thereby decreasing the ionic migration barrier within the host framework.The Zn//Mo-V_(2)O_(5)batteries achieve a specific capacity of 502.5 mAh·g^(-1)at 0.2 A·g^(-1)and retain 433.2 mAh·g^(-1)after 100 times cycling.Moreover,they possess 2000 times cycling life with a retention rate of 100% at a low temperature of 0℃(1 A·g^(-1)).It is believed that the reliable Mo-doping approach will provide new insights for high-performance energy storage systems.
基金the Guangxi New Energy Vehicle Laboratory Special Project(No.GuikeAA23062079)the Special Project for Central Guidance of Local Science and Technology Development in Sichuan Province(No.2024ZYD0302).
文摘Cobalt-free LiNiO_(2)(LNO)is considered a promising cathode for its high energy density and costeffectiveness.However,its structural instability under deep delithiation severely limits practical application in nextgeneration batteries.Herein,we propose a high-valence Mo6+doping strategy to simultaneously improve mechanical robustness and electrochemical stability.By stabilizing intergranular interfaces,this method effectively suppresses mechanical degradation induced by lattice strain under deep delithiation.The modified cathode exhibits exceptional electrochemical performance,achieving a specific capacity of 234 mAh·g^(-1)at 0.1 C with 83.4% retention over 100 cycles at 45℃ in lithium-ion batteries(LIBs).Notably,it maintains comparable efficacy in all-solid-state batteries(ASSBs),delivering 239 mAh·g^(-1)at 0.05 C and 82.8% retention after 300 cycles.Density functional theory(DFT)calculations demonstrate a pronounced rise in oxygen vacancy formation energy,increasing from 1.42 to 3.27 eV.These findings offer valuable insights into overcoming the kinetic performance limitations of cobalt-free LNO under deep delithiation conditions.
