Layered Li[Ni1/3Co1/3Mn1/3]O2 was synthesized with complex metal hydroxide precursors that were prepared by a co-precipitation method.The influence of coordination between ammonia and transition-metal cations on the s...Layered Li[Ni1/3Co1/3Mn1/3]O2 was synthesized with complex metal hydroxide precursors that were prepared by a co-precipitation method.The influence of coordination between ammonia and transition-metal cations on the structural and electrochemical properties of the Li[Ni1/3Co1/3Mn1/3]O2 materials was studied.It is found that when the molar ratio of ammonia to total transition-metal cations is 2.7：1,uniform particle size distribution of the complex metal hydroxide is observed via scanning electron microscopy.The average particle size of Li[Ni1/3Co1/3Mn1/3]O2 materials was measured to be about 500 nm,and the tap-density was measured to be approximately 2.37 g/cm3,which is comparable with that of commercialized LiCoO2.XRD analysis indicates that the presently synthesized Li[Ni1/3Co1/3Mn1/3]O2 has a hexagonal layered-structure.The initial discharge capacity of the Li[Ni1/3Co1/3Mn1/3]O2 positive-electrode material is determined to be 181.5 mA·h/g using a Li/Li[Ni1/3Co1/3Mn1/3]O2 cell operated at 0.1C in the voltage range of 2.8-4.5 V.The discharge capacity at the 50th cycle at 0.5C is 170.6 mA·h/g.展开更多
Sodium superionic conductor(NASICON)-type compounds have been regarded as promising cathodes for sodium-ion batteries(SIBs)due to their favorable ionic conductivity and robust structural stability.However,their high c...Sodium superionic conductor(NASICON)-type compounds have been regarded as promising cathodes for sodium-ion batteries(SIBs)due to their favorable ionic conductivity and robust structural stability.However,their high cost and relatively low energy density restrict their further practical application,which can be tailored by widening the operating voltages with earth-abundant elements such as Mn.Here,we propose a rational strategy of infusing Mn element in NASICON frameworks with sufficiently mobile sodium ions that enhances the redox voltage and ionic migration activity.The optimized structure of Na3.5Mn0.5V1.5(PO4)3/C is achieved and investigated systematically to be a durable cathode(76.6%capacity retention over 5,000 cycles at 20 C)for SIBs,which exhibits high reversible capacity(113.1 mAh·g^−1 at 0.5 C)with relatively low volume change(7.6%).Importantly,its high-areal-loading and temperature-resistant sodium ion storage properties are evaluated,and the full-cell configuration is demonstrated.This work indicates that this Na3.5Mn0.5V1.5(PO4)3/C composite could be a promising cathode candidate for SIBs.展开更多
Although lithium-sulfur batteries are one of the favorable candidates for next-generation energy storage devices,a few key challenges that have not been addressed have limited its commercialization.These challenges in...Although lithium-sulfur batteries are one of the favorable candidates for next-generation energy storage devices,a few key challenges that have not been addressed have limited its commercialization.These challenges include lithium dendrite growth in the anode side,volume change of the active material,poor electrical conductivity,dissolution and migration of poly sulfides,and slow rate of solid-state reactions in the cathode side.Since the electrochemical performance of lithium-sulfur batteries is greatly affected by the design of the cathode host material,it has also been widely discussed in addressing the abovementioned issues.In this paper,three design ideas of cathode host materials in terms of microstructure,crystal structure and electronic structure are introduced and summarized.Crucially,the current progress of these three structural design strategies and their effects on the electrochemical performance of lithium-sulfur batteries are discussed in detail.Finally,future directions in the structural design of cathode materials for lithium-sulfur batteries are discussed and further perspectives are provided.展开更多
Spinel phase LiMn2O4 was successfully embedded into monoclinic phase layered- structured Li2MnO3 nanorods, and these spineMayered integrate structured nanorods showed both high capacities and superior high-rate capabi...Spinel phase LiMn2O4 was successfully embedded into monoclinic phase layered- structured Li2MnO3 nanorods, and these spineMayered integrate structured nanorods showed both high capacities and superior high-rate capabilities as cathode material for lithium-ion batteries （LIBs）. Pristine Li2MnO3 nanorods were synthesized by a simple rheological phase method using α-MnO2 nanowires as precursors. The spinel-layered integrate structured nanorods were fabricated by a facile partial reduction reaction using stearic acid as the reductant. Both structural characterizations and electrochemical properties of the integrate structured nanorods verified that LiMn2O4 nanodomains were embedded inside the pristine Li2MnO3 nanorods. When used as cathode materials for LIBs, the spineMayered integrate structured Li2MnO3 nanorods （SL-Li2MnO3） showed much better performances than the pristine layered-structured Li2MnO3 nanorods （L-Li2MnO3）. When charge-discharged at 20 mA.g-1 in a voltage window of 2.0-4.8 V, the SL-Li2MnO3 showed discharge capacities of 272.3 and 228.4 mAh.g-1 in the first and the 60th cycles, respectively, with capacity retention of 83.8%. The SL-Li2MnO3 also showed superior high-rate performances. When cycled at rates of 1 C, 2 C, 5 C, and 10 C （1 C = 200 mA-g-1） for hundreds of cycles, the discharge capacities of the SL-Li2MnO3 reached 218.9, 200.5, 147.1, and 123.9 mAh-g-1, respectively. The superior performances of the SL-Li2MnO3 are ascribed to the spineMayered integrated structures. With large capacities and superior high-rate performances, these spinel-layered integrate structured materials are good candidates for cathodes of next-generation high-power LIBs.展开更多
Despite the high energy density of lithium-rich(Li-rich)cathodes,their implementation is hampered by the unsatisfied rate capacity and poor cycling performance accompanied with substantial voltage decay.To address the...Despite the high energy density of lithium-rich(Li-rich)cathodes,their implementation is hampered by the unsatisfied rate capacity and poor cycling performance accompanied with substantial voltage decay.To address these issues,the hierarchical yolk-shell structured Li_(1.2)Mn_(0.54)Ni_(0.13)Co_(0.13)O_(2)cathodes(YK-LMNCO)was proposed and synthesized through a facile glycerol assisted solvothermal approach and the following lithiation process.Benefitting from the shortened lithium diffusion lengths and the enhanced tolerance to the large volume variation upon lithium ions intercalation/de-intercalation,the unique structure reciprocates an initial coulombic efficiency of 85.8%,an outstanding capacity retention rate of 89.1%after cycling at 2.0 C for 200 cycles with a minor voltage drop,and a capacity retention rate of 93.8%after cycling at 10.0 C for 500 cycles,85.2%for 1,000 cycles.When assembled with graphite as anode,the YK-LMNCO//graphite full cell shows a remarkable capacity retention rate of 87.2%after cycling at 5.0 C for 50 cycles.Our facile strategy for constructing the yolk-shell structured Li-rich cathodes with high capacity and voltage stability sheds light on synthesizing other lithium storage materials.展开更多
Ni-rich oxides,LiNixMnyCozO2(NMC),are among leading candidates for cathode materials in Li-ion batteries.However,they are mostly fabricated by coprecipitation approach under complex conditions,which usually produces l...Ni-rich oxides,LiNixMnyCozO2(NMC),are among leading candidates for cathode materials in Li-ion batteries.However,they are mostly fabricated by coprecipitation approach under complex conditions,which usually produces large secondary particles composed of aggregated primary particles.Undesirable cation mixing and crack propagation upon cycling block ion and electron transport,result in fast capacity fading and poor rate capability.Herein,we present an ultrasound-triggered cation chelation and reassembly route for synthesizing one-dimensional precursor with homogeneous element distribution at the atomic level.This process is accomplished by the synergistic combination of ultrasound and surfactant,which can disperse reactants and remove hydration shells surrounding cations so as to accelerate chelating reaction,and then separate and assemble chelates into one dimensional structure.The whole synthesis time is only 20 min(8.9 min of ultrasonic working time)in an open vessel under natural ambient conditions.One-dimensional LiNi0.6Mn0.2Co0.2O2 has a high reversible capacity(184 mAh·g^−1 at 0.1 C)and long cycling stability(95.1%and 82.4%capacity retention for 100 and 1000 cycles,respectively).The short charging time of 76 s is realized at super high current rate of 20 C,which is very important to improve the competitiveness of electric vehicles relative to fuel vehicles.Our synthetic approach can provide a general strategy for the growth of mixed-metal-EDTA chelate precursors by changing the feeding ratio of Ni2+,Mn2+and Co2+cations in reaction for fabricating NMC cathode materials with other compositions.展开更多
Aqueous zinc-sulfur batteries at room temperature hold great potential for next-generation energy storage technology due to their low cost,safety and high energy density.However,slow reaction kinetics and high activat...Aqueous zinc-sulfur batteries at room temperature hold great potential for next-generation energy storage technology due to their low cost,safety and high energy density.However,slow reaction kinetics and high activation energy at the sulfur cathode pose great challenges for the practical applications.Herein,biomass-derived carbon with single-atomic cobalt sites(MMPC-Co)is synthesized as the cathode in Zn-S batteries.The catalysis of single-atom Co sites greatly promotes the transform of cathode electrolyte interface(CEI)on the cathode surface,while offering accelerated charge transfer rate for high conversion reversibility and large electrochemical surface area(ECSA)for high electrocatalytic current.Furthermore,the rich pore structure not only physically limits sulfur loss,but also accelerates the transport of zinc ions.In addition,the large pore volume of MMPC-Co is able to relieve the stress effect caused by the volume expansion of Zn S during charge/discharge cycles,thereby maintaining the stability of electrode structure.Consequently,the sulfur cathode maintains a high specific capacity of 729.96 m A h g^(-1)after 500 cycles at4 A g^(-1),which is much better than most cathode materials reported in the literature.This work provides new insights into the design and development of room-temperature aqueous Zn-S batteries.展开更多
Organic carbonyl compounds are considered as promising candidates for lithium batteries due to theirhigh capacity and environmental friendliness, However, they suffer from serious dissolution in the elec-trolyte, lead...Organic carbonyl compounds are considered as promising candidates for lithium batteries due to theirhigh capacity and environmental friendliness, However, they suffer from serious dissolution in the elec-trolyte, leading to fast capacity decay. Here we report core-shell structured 1,4-benzoquinone@titaniumdioxide （BQ@TiO2） composite as cathode for lithium batteries. The composite cathode can deliver a highdischarge capacity of 441.2 mA h/g at 50 mA/g and a high capacity retention of 80.7% after 100 cycles. Thegood cycling performance of BQ@TiO2 composite can be attributed to the suppressed dissolution of BQ,which results from the physical confinement effect of Ti02 shell and the strong interactions between BQand Ti02. Moreover, the combination of ex situ infrared spectra and density functional theory calculationsreveals that the active redox sites of BQ are carbonyl groups. This work provides an alternative way tomitigate the dissolution of small carbonyl compounds and thus enhance their cycling stability.展开更多
The cathode materials LiMn2O4 and rare earth elements La-doped or La and F dual-doped spinel lithium manganese oxides.were synthesized by the citric acid-assisted sol-gel method. The synthesized samples were investiga...The cathode materials LiMn2O4 and rare earth elements La-doped or La and F dual-doped spinel lithium manganese oxides.were synthesized by the citric acid-assisted sol-gel method. The synthesized samples were investigated by differential thermal analysis （DTA） and thermogravimetry （TG） measurements, X-ray diffraction （XRD）, scanning electronic microscope （SEM）, cyclic voltammetry （CV）, and charge-discharge test. XRD data shows that all the samples exhibit the same pure spinel phase, and the LiLa0.01Mn1.99O3.99F0.01 and LiLao.olMnl.9904 samples have smaller lattice parameters and unit cell volume than LiMn2O4. SEM indicates that LiLa0.01Mn1.99O3.99F0.01 has a slightly smaller particle size and a more regular morphology structure with narrow size distribution. The charge-discharge test reveals that the initial capacities of LiMn2O4, LiLa0.01Mn1.99O4, and LiLa0.01Mn1.99O3.99F0.01 are 129.9, 122.8, and 126.4 mAh·g^-1, and the capacity losses of the initial values after 50 cycles are 14.5%, 7.6%, and 8.0%, respectively The CVs show that the La and F dual-doped spinel displays a better reversibility than LiMn2O4.展开更多
基金Project(50721003)supported by the National Natural Science Foundation of ChinaProject(07JJ6082)supported by the Natural Science Foundation of Hunan Province,ChinaProject supported by the Open Project of State Key Laboratory of Powder Metallurgy in Central South University,China
文摘Layered Li[Ni1/3Co1/3Mn1/3]O2 was synthesized with complex metal hydroxide precursors that were prepared by a co-precipitation method.The influence of coordination between ammonia and transition-metal cations on the structural and electrochemical properties of the Li[Ni1/3Co1/3Mn1/3]O2 materials was studied.It is found that when the molar ratio of ammonia to total transition-metal cations is 2.7：1,uniform particle size distribution of the complex metal hydroxide is observed via scanning electron microscopy.The average particle size of Li[Ni1/3Co1/3Mn1/3]O2 materials was measured to be about 500 nm,and the tap-density was measured to be approximately 2.37 g/cm3,which is comparable with that of commercialized LiCoO2.XRD analysis indicates that the presently synthesized Li[Ni1/3Co1/3Mn1/3]O2 has a hexagonal layered-structure.The initial discharge capacity of the Li[Ni1/3Co1/3Mn1/3]O2 positive-electrode material is determined to be 181.5 mA·h/g using a Li/Li[Ni1/3Co1/3Mn1/3]O2 cell operated at 0.1C in the voltage range of 2.8-4.5 V.The discharge capacity at the 50th cycle at 0.5C is 170.6 mA·h/g.
基金This work was supported by the National Natural Science Foundation of China(Nos.51872334 and 51932011)the Innovation-Driven Project of Central South University(No.2020CX024).
文摘Sodium superionic conductor(NASICON)-type compounds have been regarded as promising cathodes for sodium-ion batteries(SIBs)due to their favorable ionic conductivity and robust structural stability.However,their high cost and relatively low energy density restrict their further practical application,which can be tailored by widening the operating voltages with earth-abundant elements such as Mn.Here,we propose a rational strategy of infusing Mn element in NASICON frameworks with sufficiently mobile sodium ions that enhances the redox voltage and ionic migration activity.The optimized structure of Na3.5Mn0.5V1.5(PO4)3/C is achieved and investigated systematically to be a durable cathode(76.6%capacity retention over 5,000 cycles at 20 C)for SIBs,which exhibits high reversible capacity(113.1 mAh·g^−1 at 0.5 C)with relatively low volume change(7.6%).Importantly,its high-areal-loading and temperature-resistant sodium ion storage properties are evaluated,and the full-cell configuration is demonstrated.This work indicates that this Na3.5Mn0.5V1.5(PO4)3/C composite could be a promising cathode candidate for SIBs.
基金financially supported by the National Natural Science Foundation of China(Nos.52075351 and 51604177)the National Key Research and Development Program of China(No.2019YFA0705701)+4 种基金the Major S&T Infrastructure Construction Project of Sichuan Province(No.2020-510000-73-01-441847)the International S&T Innovation Cooperation Program of Sichuan Province(No.2020YFH0039)Chengdu International S&T Cooperation Funded Project(Nos.2020-GH02-00006-HZ and 2022-GH02-00027-HZ)the"1000 Talents Plan"of Sichuan Provincethe Talent Introduction Program of Sichuan University(No.YJ201410)。
文摘Although lithium-sulfur batteries are one of the favorable candidates for next-generation energy storage devices,a few key challenges that have not been addressed have limited its commercialization.These challenges include lithium dendrite growth in the anode side,volume change of the active material,poor electrical conductivity,dissolution and migration of poly sulfides,and slow rate of solid-state reactions in the cathode side.Since the electrochemical performance of lithium-sulfur batteries is greatly affected by the design of the cathode host material,it has also been widely discussed in addressing the abovementioned issues.In this paper,three design ideas of cathode host materials in terms of microstructure,crystal structure and electronic structure are introduced and summarized.Crucially,the current progress of these three structural design strategies and their effects on the electrochemical performance of lithium-sulfur batteries are discussed in detail.Finally,future directions in the structural design of cathode materials for lithium-sulfur batteries are discussed and further perspectives are provided.
文摘Spinel phase LiMn2O4 was successfully embedded into monoclinic phase layered- structured Li2MnO3 nanorods, and these spineMayered integrate structured nanorods showed both high capacities and superior high-rate capabilities as cathode material for lithium-ion batteries （LIBs）. Pristine Li2MnO3 nanorods were synthesized by a simple rheological phase method using α-MnO2 nanowires as precursors. The spinel-layered integrate structured nanorods were fabricated by a facile partial reduction reaction using stearic acid as the reductant. Both structural characterizations and electrochemical properties of the integrate structured nanorods verified that LiMn2O4 nanodomains were embedded inside the pristine Li2MnO3 nanorods. When used as cathode materials for LIBs, the spineMayered integrate structured Li2MnO3 nanorods （SL-Li2MnO3） showed much better performances than the pristine layered-structured Li2MnO3 nanorods （L-Li2MnO3）. When charge-discharged at 20 mA.g-1 in a voltage window of 2.0-4.8 V, the SL-Li2MnO3 showed discharge capacities of 272.3 and 228.4 mAh.g-1 in the first and the 60th cycles, respectively, with capacity retention of 83.8%. The SL-Li2MnO3 also showed superior high-rate performances. When cycled at rates of 1 C, 2 C, 5 C, and 10 C （1 C = 200 mA-g-1） for hundreds of cycles, the discharge capacities of the SL-Li2MnO3 reached 218.9, 200.5, 147.1, and 123.9 mAh-g-1, respectively. The superior performances of the SL-Li2MnO3 are ascribed to the spineMayered integrated structures. With large capacities and superior high-rate performances, these spinel-layered integrate structured materials are good candidates for cathodes of next-generation high-power LIBs.
基金The authors acknowledge the financial support from Natural Science Foundation of Guangdong Province(No.2018A030313721)the National Key Research and Development Program of China(No.2018YFB0703500)the National Natural Science Foundation of China(No.91963113).
文摘Despite the high energy density of lithium-rich(Li-rich)cathodes,their implementation is hampered by the unsatisfied rate capacity and poor cycling performance accompanied with substantial voltage decay.To address these issues,the hierarchical yolk-shell structured Li_(1.2)Mn_(0.54)Ni_(0.13)Co_(0.13)O_(2)cathodes(YK-LMNCO)was proposed and synthesized through a facile glycerol assisted solvothermal approach and the following lithiation process.Benefitting from the shortened lithium diffusion lengths and the enhanced tolerance to the large volume variation upon lithium ions intercalation/de-intercalation,the unique structure reciprocates an initial coulombic efficiency of 85.8%,an outstanding capacity retention rate of 89.1%after cycling at 2.0 C for 200 cycles with a minor voltage drop,and a capacity retention rate of 93.8%after cycling at 10.0 C for 500 cycles,85.2%for 1,000 cycles.When assembled with graphite as anode,the YK-LMNCO//graphite full cell shows a remarkable capacity retention rate of 87.2%after cycling at 5.0 C for 50 cycles.Our facile strategy for constructing the yolk-shell structured Li-rich cathodes with high capacity and voltage stability sheds light on synthesizing other lithium storage materials.
基金This work was financially supported by the National Natural Science Foundation of China(No.51772337)Free Exploration Fund of State Key Laboratory of Optoelectronic Materials and Technologies of China(No.OEMT-2017-ZY-09).
文摘Ni-rich oxides,LiNixMnyCozO2(NMC),are among leading candidates for cathode materials in Li-ion batteries.However,they are mostly fabricated by coprecipitation approach under complex conditions,which usually produces large secondary particles composed of aggregated primary particles.Undesirable cation mixing and crack propagation upon cycling block ion and electron transport,result in fast capacity fading and poor rate capability.Herein,we present an ultrasound-triggered cation chelation and reassembly route for synthesizing one-dimensional precursor with homogeneous element distribution at the atomic level.This process is accomplished by the synergistic combination of ultrasound and surfactant,which can disperse reactants and remove hydration shells surrounding cations so as to accelerate chelating reaction,and then separate and assemble chelates into one dimensional structure.The whole synthesis time is only 20 min(8.9 min of ultrasonic working time)in an open vessel under natural ambient conditions.One-dimensional LiNi0.6Mn0.2Co0.2O2 has a high reversible capacity(184 mAh·g^−1 at 0.1 C)and long cycling stability(95.1%and 82.4%capacity retention for 100 and 1000 cycles,respectively).The short charging time of 76 s is realized at super high current rate of 20 C,which is very important to improve the competitiveness of electric vehicles relative to fuel vehicles.Our synthetic approach can provide a general strategy for the growth of mixed-metal-EDTA chelate precursors by changing the feeding ratio of Ni2+,Mn2+and Co2+cations in reaction for fabricating NMC cathode materials with other compositions.
基金the financial support from the National Natural Science Foundation of China,China(No.52172058)。
文摘Aqueous zinc-sulfur batteries at room temperature hold great potential for next-generation energy storage technology due to their low cost,safety and high energy density.However,slow reaction kinetics and high activation energy at the sulfur cathode pose great challenges for the practical applications.Herein,biomass-derived carbon with single-atomic cobalt sites(MMPC-Co)is synthesized as the cathode in Zn-S batteries.The catalysis of single-atom Co sites greatly promotes the transform of cathode electrolyte interface(CEI)on the cathode surface,while offering accelerated charge transfer rate for high conversion reversibility and large electrochemical surface area(ECSA)for high electrocatalytic current.Furthermore,the rich pore structure not only physically limits sulfur loss,but also accelerates the transport of zinc ions.In addition,the large pore volume of MMPC-Co is able to relieve the stress effect caused by the volume expansion of Zn S during charge/discharge cycles,thereby maintaining the stability of electrode structure.Consequently,the sulfur cathode maintains a high specific capacity of 729.96 m A h g^(-1)after 500 cycles at4 A g^(-1),which is much better than most cathode materials reported in the literature.This work provides new insights into the design and development of room-temperature aqueous Zn-S batteries.
基金supported by the National Programs for NanoKey Project (2017YFA0206700)the National Natural Science Foundation of China (51231003)the Ministry of Education of China (B12015)
文摘Organic carbonyl compounds are considered as promising candidates for lithium batteries due to theirhigh capacity and environmental friendliness, However, they suffer from serious dissolution in the elec-trolyte, leading to fast capacity decay. Here we report core-shell structured 1,4-benzoquinone@titaniumdioxide （BQ@TiO2） composite as cathode for lithium batteries. The composite cathode can deliver a highdischarge capacity of 441.2 mA h/g at 50 mA/g and a high capacity retention of 80.7% after 100 cycles. Thegood cycling performance of BQ@TiO2 composite can be attributed to the suppressed dissolution of BQ,which results from the physical confinement effect of Ti02 shell and the strong interactions between BQand Ti02. Moreover, the combination of ex situ infrared spectra and density functional theory calculationsreveals that the active redox sites of BQ are carbonyl groups. This work provides an alternative way tomitigate the dissolution of small carbonyl compounds and thus enhance their cycling stability.
文摘The cathode materials LiMn2O4 and rare earth elements La-doped or La and F dual-doped spinel lithium manganese oxides.were synthesized by the citric acid-assisted sol-gel method. The synthesized samples were investigated by differential thermal analysis （DTA） and thermogravimetry （TG） measurements, X-ray diffraction （XRD）, scanning electronic microscope （SEM）, cyclic voltammetry （CV）, and charge-discharge test. XRD data shows that all the samples exhibit the same pure spinel phase, and the LiLa0.01Mn1.99O3.99F0.01 and LiLao.olMnl.9904 samples have smaller lattice parameters and unit cell volume than LiMn2O4. SEM indicates that LiLa0.01Mn1.99O3.99F0.01 has a slightly smaller particle size and a more regular morphology structure with narrow size distribution. The charge-discharge test reveals that the initial capacities of LiMn2O4, LiLa0.01Mn1.99O4, and LiLa0.01Mn1.99O3.99F0.01 are 129.9, 122.8, and 126.4 mAh·g^-1, and the capacity losses of the initial values after 50 cycles are 14.5%, 7.6%, and 8.0%, respectively The CVs show that the La and F dual-doped spinel displays a better reversibility than LiMn2O4.
