Na_(3)V_(2)(PO_(4))_(3)(NVP)has garnered great attentions as a prospective cathode material for sodium-ion batteries(SIBs)by virtue of its decent theoretical capacity,superior ion conductivity and high structural stab...Na_(3)V_(2)(PO_(4))_(3)(NVP)has garnered great attentions as a prospective cathode material for sodium-ion batteries(SIBs)by virtue of its decent theoretical capacity,superior ion conductivity and high structural stability.However,the inherently poor electronic conductivity and sluggish sodium-ion diffusion kinetics of NVP material give rise to inferior rate performance and unsatisfactory energy density,which strictly confine its further application in SIBs.Thus,it is of significance to boost the sodium storage performance of NVP cathode material.Up to now,many methods have been developed to optimize the electrochemical performance of NVP cathode material.In this review,the latest advances in optimization strategies for improving the electrochemical performance of NVP cathode material are well summarized and discussed,including carbon coating or modification,foreign-ion doping or substitution and nanostructure and morphology design.The foreign-ion doping or substitution is highlighted,involving Na,V,and PO_(4)^(3−)sites,which include single-site doping,multiple-site doping,single-ion doping,multiple-ion doping and so on.Furthermore,the challenges and prospects of high-performance NVP cathode material are also put forward.It is believed that this review can provide a useful reference for designing and developing high-performance NVP cathode material toward the large-scale application in SIBs.展开更多
The electrochemical performance of layered O3-type NaCrO_(2)cathode material is significantly affected by the side reactions between NaCrO_(2)and electrolyte during sodium storage.A uniform Cr_(2)O_(3)coating layer wa...The electrochemical performance of layered O3-type NaCrO_(2)cathode material is significantly affected by the side reactions between NaCrO_(2)and electrolyte during sodium storage.A uniform Cr_(2)O_(3)coating layer was in situ constructed on the surface of NaCrO_(2)by controlling the excess ratio of sodium source.The structure,morphology,valence and electrochemical performance of the Cr_(2)O_(3)-coated NaCrO_(2)were characterized.The results indicate that the Cr_(2)O_(3)coating layer does not alter the crystal structure and morphology of NaCrO_(2),but effectively suppresses the side reactions between NaCrO_(2)and electrolyte,and improves the surface/interfacial stability of NaCrO_(2)material.The Cr_(2)O_(3)-coated NaCrO_(2)exhibits improved electrochemical performance with a capacity retention of 66.4%after 500 cycles at 10C.展开更多
Li[NixCoyMn2]O2（0.6≤x≤0.8） cathode materials with a typical hexagonal α-NaFeO2 structure were prepared utilizing a co-precipitation method.It is found that the ratio of peak intensities of（003） to（104） observ...Li[NixCoyMn2]O2（0.6≤x≤0.8） cathode materials with a typical hexagonal α-NaFeO2 structure were prepared utilizing a co-precipitation method.It is found that the ratio of peak intensities of（003） to（104） observed from X-ray diffraction（XRD）increases with decreasing the Ni content or increasing the Co content.The scanning electron microscopy（SEM） images reveal that the small primary particles are agglomerated to form the secondary ones.As the Mn content increases,the primary and secondary particles become larger and the resulted particle size for the Li[Ni（0.6）Co（0.2）Mn（0.2）]O2 is uniformly distributed in the range of100-300 nm.Although the initial discharge capacity of the Li/Li[NixCoyMn2]O2 cells reduces with decreasing the Ni content,the cyclic performance and rate capability are improved with higher Mn or Co content.The Li[Ni（0.6）Co（0.2）Mn（0.2）]O2 can deliver excellent cyclability with a capacity retention of 97.1%after 50 cycles.展开更多
The Li3V2（PO4）3/C composite cathode material was synthesized via sol-gel method using three different chelating agents （citric acid, salicylic acid and polyacrylic acid） at pH value of 3 or 7. The crystal structur...The Li3V2（PO4）3/C composite cathode material was synthesized via sol-gel method using three different chelating agents （citric acid, salicylic acid and polyacrylic acid） at pH value of 3 or 7. The crystal structure, morphology, specific surface area and electrochemical performance of the prepared samples were investigated by X-ray diffraction （XRD）, scanning electron microscopy （SEM）, cyclic voltammetry （CV）, electrochemical impedance spectroscopy （EIS） and galvanostatic charge/discharge test. The results show that the effects of pH value on the performance of the prepared materials are greatly related to the chelating agents. With salicylic acid or polyacrylic acid as the chelating reagent, the structure, morphology and electrochemical performance of the samples are greatly influenced by the pH values. However, the structure of the materials with citric acid as the chelating agent does not change as pH value changes, and the materials own uniform particle size distribution and good electrochemical performance. It delivers an initial discharge capacity of 113.58 mA·h/g at 10C, remaining as high as 108.48 mA·h/g after 900 cycles, with a capacity retention of 95.51%.展开更多
Li3V2-2/3xMnx（PO4）3（0≤x≤0.12） powders were synthesized by sol-gel method. The effect of Mn2＋-doping on the structure and electrochemical performances of Li3V2（PO4）3/C was characterized by XRD, SEM, XPS, galva...Li3V2-2/3xMnx（PO4）3（0≤x≤0.12） powders were synthesized by sol-gel method. The effect of Mn2＋-doping on the structure and electrochemical performances of Li3V2（PO4）3/C was characterized by XRD, SEM, XPS, galvanostatic charge /discharge and electrochemical impedance spectroscopy（EIS）. The XRD study shows that a small amount of Mn2＋-doped does not alter the structure of Li3V2（PO4）3/C materials, and all Mn2＋-doped samples are of pure single phase with a monoclinic structure （space group P21/n）. The XPS analysis indicates that valences state of V and Mn are ＋3 and ＋2 in Li3V1.94Mn0.09（PO4）3/C, respectively, and the citric acid in raw materials was decomposed into carbon during calcination, and residual carbon exists in Li3V1.94Mn0.09（PO4）/C. The results of electrochemical measurements show that Mn2＋-doping can improve the cyclic stability and rate performance of these cathode materials. The Li3V1.94Mn0.09（PO4）3/C cathode material shows the best cyclic stability and rate performance. For example, at the discharge current density of 40 mA/g, after 100 cycles, the discharge capacity of Li3V1.94Mn0.09（PO4）3/C declines from initial 158.8 mA·h/g to 120.5 mA·h/g with a capacity retention of 75.9%; however, that of the Mn-undoed sample declines from 164.2 mA·h/g to 72.6 mA·h/g with a capacity retention of 44.2%. When the discharge current is increased up to 1C, the intial discharge capacity of Li3V1.94Mn0.09（PO4）3/C still reaches 146.4 mA·h/g, and the discharge capacity maintains at 107.5 mA·h/g after 100 cycles. The EIS measurement indicates that Mn2＋-doping with a appropriate amount of Mn2＋ decreases the charge transfer resistance, which is favorable for the insertion/extraction of Li＋.展开更多
Some compounds of LiCo 1- x RE x O 2 (RE=rare earth elements and x =0.01～0.03) were prepared by doping rare earth elements to LiCoO 2 via solid state synthesis. The microstructure characteristics of t...Some compounds of LiCo 1- x RE x O 2 (RE=rare earth elements and x =0.01～0.03) were prepared by doping rare earth elements to LiCoO 2 via solid state synthesis. The microstructure characteristics of the LiCo 1- x RE x O 2 were investigated by XRD. It was found that the lattice parameters c are increased and the lattice volumes are enlarged compared to that of LiCoO 2. Moreover, the performance of LiCo 1- x RE x O 2 as the cathode material in lithium ion battery is improved, especially LiCo 1- x Y x O 2 and LiCo 1- x La x O 2. The initial charge/discharge capacities of LiCo 0.99 Y 0.01 O 2 and LiCo 0.99 La 0.01 O 2 are 174/154 (mAh·g -1 ) and 159/149 (mAh·g -1 ) respectively, while those for LiCoO 2 working in the same way are only 139/131 (mAh·g -1 ).展开更多
Layered F-doped cathode materials 0.3 Li_2 MnO_3-0.7 LiMn_(1/3)Ni_(1/3)CO_(1/3))O_(2-x)F_x(x = 0, 0.01, 0.02, 0.03, 0.04,0.05) microspheres made up of nanosized primary grains were prepared through co-precipitation me...Layered F-doped cathode materials 0.3 Li_2 MnO_3-0.7 LiMn_(1/3)Ni_(1/3)CO_(1/3))O_(2-x)F_x(x = 0, 0.01, 0.02, 0.03, 0.04,0.05) microspheres made up of nanosized primary grains were prepared through co-precipitation method. The sample of x = 0.02 demonstrates a large discharge capacity of226 mAh g^(-1) over 100 cycles at 0.1 C and excellent rate performance with discharge capacity of 96 mAh g-1 at 5.0 C and room temperature. Particularly, this material shows much enhanced electrochemical performances even at high temperature of 55 ℃. It delivers a quite high discharge capacity of 233.7 mAh·g^(-1) at 1.0 C with capacity retention as high as 97.9% after 100 cycles. The results demonstrate that the fluorine incorporation stabilizes the cathode structure and maintains stable interfacial resistances.展开更多
A novel synthetic method of microwave processing to prepare Li2FeSiO4 cathode materials is adopted. The Li2FeSiO4 cathode material is prepared by mechanical ball-milling and subsequent microwave processing. Olivin-typ...A novel synthetic method of microwave processing to prepare Li2FeSiO4 cathode materials is adopted. The Li2FeSiO4 cathode material is prepared by mechanical ball-milling and subsequent microwave processing. Olivin-type Li2FeSiO4 sample with uniform and fine particle sizes is successfully and fast synthesized by microwave heating at 700 ℃ in 12 rain. And the obtained Li2FeSiO4 materials show better electrochemical performance and microstructure than those of Li2FeSiO4 sample by the conventional solidstate reaction. ？2009 Yan Bing Cao. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.展开更多
Spherical LiNi0.8Co0.15Al0.05O2 OOH precursor prepared by a co-oxidation-controlled crystallization method, was used to synthesize LiNi0.5Co0.15Al0.05O2. The obtained LiNi0.8Co0.15Al0.05O2 materials showed excellent e...Spherical LiNi0.8Co0.15Al0.05O2 OOH precursor prepared by a co-oxidation-controlled crystallization method, was used to synthesize LiNi0.5Co0.15Al0.05O2. The obtained LiNi0.8Co0.15Al0.05O2 materials showed excellent electrochemical performance, with an initial discharge capacity of 193.5 mAh/g and capacity retention of 95.1% after 50 cycles when cycled at 0.2 C rate between 2.8 and 4.3 V.展开更多
LiMn2O4 spinel cathode materials were modified with 2 wt.%Li-M-PO4（M=Co,Ni,Mn） by polyol synthesis method.The phosphate surface-modified LiMn2O4 cathode materials were physically characterized by X-ray diffraction（...LiMn2O4 spinel cathode materials were modified with 2 wt.%Li-M-PO4（M=Co,Ni,Mn） by polyol synthesis method.The phosphate surface-modified LiMn2O4 cathode materials were physically characterized by X-ray diffraction（XRD）,scanning electron microscopy（SEM） and energy dispersive X-ray spectroscopy（EDS）.The charge-discharge test showed that the cycling and rate capacities of LiMn2O4 cathode materials were significantly enhanced by stabilizing the electrode surface with phosphate.展开更多
P2-type Na_(2/3)Fe_(1/2)Mn_(1/2)O_(2) was synthesized by a facile sol−gel method,and the effect of calcination temperature on the structure,morphology and electrochemical performance of samples was investigated.The re...P2-type Na_(2/3)Fe_(1/2)Mn_(1/2)O_(2) was synthesized by a facile sol−gel method,and the effect of calcination temperature on the structure,morphology and electrochemical performance of samples was investigated.The results show that the sample obtained at 900℃ is pure P2-type Na_(2/3)Fe_(1/2)Mn_(1/2)O_(2) phase with good crystallization,which consists of hexagon plate-shaped particles with the size and thickness of 2−4μm and 200−400 nm,respectively.The sample exhibits an initial specific discharge capacity of 243 mA·h/g at a current density of 26 mA/g with good cycling stability.The high specific capacity indicates that P2-type Na_(2/3)Fe_(1/2)Mn_(1/2)O_(2) is a promising cathode material for sodiumion batteries.展开更多
Y-doped Li3V2（PO4）3 cathode materials were prepared by a carbothermal reduction（CTR） process.The properties of the Y-doped Li3V2（PO4）3 were investigated by X-ray diffraction（XRD） and electrochemical measuremen...Y-doped Li3V2（PO4）3 cathode materials were prepared by a carbothermal reduction（CTR） process.The properties of the Y-doped Li3V2（PO4）3 were investigated by X-ray diffraction（XRD） and electrochemical measurements.XRD studies showed that the Y-doped Li3V2（PO4）3 had the same monoclinic structure as the undoped Li3V2（PO4）3.The Y-doped Li3V2（PO4）3 samples were investigated on the Li extraction/insertion performances through charge/discharge, cyclic voltammogram（CV）, and electrochemical impedance spectra（EIS）.The optimal doping content of Y was x=0.03 in Li3V2-xYx（PO4）3 system.The Y-doped Li3V2（PO4）3 samples showed a better cyclic ability.The electrode reaction reversibility was enhanced, and the charge transfer resistance was decreased through the Y-doping.The improved electrochemical perormances of the Y-doped Li3V2（PO4）3 cathode materials were attributed to the addition of Y3＋ ion by stabilizing the monoclinic structure.展开更多
In this paper,we report on the preparation of Li2FeSiO4,sintered Li2FeSiO4,and Li2FeSiO4-C composite with spindle-like morphologies and their application as cathode materials of lithium-ion batteries.Spindle-like Li2F...In this paper,we report on the preparation of Li2FeSiO4,sintered Li2FeSiO4,and Li2FeSiO4-C composite with spindle-like morphologies and their application as cathode materials of lithium-ion batteries.Spindle-like Li2FeSi04 was synthesized by a facile hydrothermal method with（NH4）2Fe（SO4）2 as the iron source.The spindle-like Li2FeSiO4 was sintered at 600 ℃ for 6 h in Ar atmosphere.Li2FeSiO4-C composite was obtained by the hydrothermal treatment of spindle-like Li2FeSiO4 in glucose solution at 190 ℃ for 3 h.Electrochemical measurements show that after carbon coating,the electrode performances such as discharge capacity and high-rate capability are greatly enhanced.In particular.Li2FeSiO4-C with carbon content of 7.21 wt%delivers the discharge capacities of 160.9 mAh·g-1 at room temperature and 213 mAh·g-1 at45℃（0.1 C）,revealing the potential application in lithium-ion batteries.展开更多
Spherical Ni(OH)2 powder coated with Co(OH)2 as raw material was mixed with LiOH to synthesize cathode material for lithium ion battery by using solid-state reaction. After sintered at temperature above 600 ℃, a soli...Spherical Ni(OH)2 powder coated with Co(OH)2 as raw material was mixed with LiOH to synthesize cathode material for lithium ion battery by using solid-state reaction. After sintered at temperature above 600 ℃, a solid solution with layer structure was formed. The result of XPS shows that it is a concentration gradient material with higher cobalt content at the surface, and the gradient decreases with increasing sintering temperature from 650 to 750 ℃. This new gradient material, called as Co-coated LiNiO2, exhibits excellent electrochemical performances for the cathode of Li-ion batteries in comparison with LiNiO2 and Co-doping LiNiO2. The discharge capacity of Co-coated LiNiO2 is over 180 mA·h/g and capacity decay per cycle is less than 0.07% when Co-coated LiNiO2 consisting of 92% nickel and 8% cobalt was sintered at the temperatures between 650-670 ℃. Though initial discharge capacity could be increased with higher sintering temperature, the cycle life would be reduced.展开更多
Li2FeSiO4 is deemed to be a potential candidate for large-scale applications because of its abundance,low cost and high safety,etc.Unfortunately,its low conductivity,resulting in poor rate performance,has become a mai...Li2FeSiO4 is deemed to be a potential candidate for large-scale applications because of its abundance,low cost and high safety,etc.Unfortunately,its low conductivity,resulting in poor rate performance,has become a main obstacle to its applications in power battery and energy storage system.In this work,C-Ag coated Li2FeSiO4 is introduced to improve the innate electronic conductivity and Li-ion diffusion ability.The results demonstrate that Li2FeSiO4/C/Ag composite exhibits better electrochemical performance.It possesses a specific discharge capacity of 152,121,108 mA.h/g at 0.2C,5C and 10C,respectively.At the same time,the Li2FeSiO4/C/Ag composite shows good cycle stability and a capacity retention ratio of 97.9%after 100 cycles at 1C.展开更多
Ti-doped Li3V2(PO4)3/C cathode materials were synthesized by a solid-state method. The properties of the samples were characterized by X-ray diffraction(XRD), scanning electronic microscopic(SEM), and electrochemical ...Ti-doped Li3V2(PO4)3/C cathode materials were synthesized by a solid-state method. The properties of the samples were characterized by X-ray diffraction(XRD), scanning electronic microscopic(SEM), and electrochemical tests. XRD results indicate that Ti-doping and carbon coating do not alter the structure of Li3V2(PO4)3.SEM images show that Ti-doping could reduce the particle size of Li3V2(PO4)3. Electrochemical tests reveal that Li3V1.95Ti0.05(PO4)3/C possesses the best electrochemical performances. It delivers the first discharge specific capacities of 124.4, 123.5, 120.9, and 114.9 m Ahág-1at0.1C, 1.0C, 2.0C, and 3.0C rates, respectively, and shows excellent cycling performance. The improved electrochemical performances are attributed to the Ti-doping,which increases the electronic and ionic conductivities of the cathode material.展开更多
The effect of Al-substitution on the electrochemical performances of Li3V2(PO4)3 cathode materials was studied.Samples with stoichiometric proportion of Li3AlxV2-x(PO4)3(x=0,0.05,0.10)were prepared by adding Al(NO3)3 ...The effect of Al-substitution on the electrochemical performances of Li3V2(PO4)3 cathode materials was studied.Samples with stoichiometric proportion of Li3AlxV2-x(PO4)3(x=0,0.05,0.10)were prepared by adding Al(NO3)3 in the raw materials of Li3V2(PO4)3.The XRD analysis shows that the Al-substituted Li3V2(PO4)3 has the same monoclinic structure as the un-substituted Li3V2(PO4)3.The SEM images show that Al-substituted Li3V2(PO4)3 has regular and uniform particles.The electrochemical measurements show that Al-substitution can improve the rate capability of cathode materials.The Li3Al0.05V1.95(PO4)3 sample shows the best high-rate performance.The discharge capacity at 1C rate is 119 mA·h/g with 30th capacity retention rate about 92.97%.The electrode reaction reversibility and electronic conductivity are enhanced,and the charge transfer resistance decreases through Al-substitution.The improved electrochemical performances of Al-substituted Li3V2(PO4)3 cathode materials offer some favorable properties for their commercial application.展开更多
Transition metal fluorides(TMFs)cathode materials have shown extraordinary promises for electrochemical energy storage,but the understanding of their electrochemical reaction mechanisms is still a matter of debate due...Transition metal fluorides(TMFs)cathode materials have shown extraordinary promises for electrochemical energy storage,but the understanding of their electrochemical reaction mechanisms is still a matter of debate due to the complicated and continuous changing in the battery internal environment.Here,we design a novel iron fluoride(FeF_(2))aggregate assembled with cylindrical nanoparticles as cathode material to build FeF_(2) lithium-ion batteries(LIBs)and employ advanced in situ magnetometry to detect their intrinsic electronic structure during cycling in real time.The results show that FeF_(2) cannot be involved in complete conversion reactions when the FeF_(2) LIBs operate between the conventional voltage range of 1.0–4.0 V,and that the corresponding conversion ratio of FeF_(2) can be further estimated.Importantly,we first demonstrate that the spin-polarized surface capacitance exists in the FeF_(2) cathode by monitoring the magnetic responses over various voltage ranges.The research presents an original and insightful method to examine the conversion mechanism of TMFs and significantly provides an important reference for the future artificial design of energy systems based on spinpolarized surface capacitance.展开更多
At present,metal ions from spent lithium-ion batteries are mostly recovered by the acid leaching procedure,which unavoidably introduces potential pollutants to the environment.Therefore,it is necessary to develop more...At present,metal ions from spent lithium-ion batteries are mostly recovered by the acid leaching procedure,which unavoidably introduces potential pollutants to the environment.Therefore,it is necessary to develop more direct and effective green recycling methods.In this research,a method for the direct regeneration of anode materials is reported,which includes the particles size reduction of recovered raw materials by jet milling and ball milling,followed by calcination at high temperature after lithium supplementation.The regenerated LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2) single-crystal cathode material possessed a relatively ideal layered structure and a complete surface morphology when the lithium content was n(Ni+Co+Mn):n(Li)=1:1.10 at a sintering temperature of 920 0 C,and a sintering time of 12 h.The first discharge specific capacity was 154.87 mA·h·g^(-1) between 2.75 V and 4.2 V,with a capacity retention rate of 90% after 100 cycles.展开更多
The micro-single crystal material spinel LiMn2-xAlxO4 was prepared by a sol-gel procedure and modified by alumina; the electrochemical measurements show that the performances and characteristics of modified LiMn2-xAlx...The micro-single crystal material spinel LiMn2-xAlxO4 was prepared by a sol-gel procedure and modified by alumina; the electrochemical measurements show that the performances and characteristics of modified LiMn2-xAlxO4 electrode material are better than those of LiMn204. Hence, the modified LiMn2- AlxO4 is a good cathode material for lithium batteries. This can be explained that the size of the modified particle is larger than that of unmodified material, so electrons can be easily transported between the particles.展开更多
基金partly supported by the National Natural Science Foundation of China(Grant No.52272225).
文摘Na_(3)V_(2)(PO_(4))_(3)(NVP)has garnered great attentions as a prospective cathode material for sodium-ion batteries(SIBs)by virtue of its decent theoretical capacity,superior ion conductivity and high structural stability.However,the inherently poor electronic conductivity and sluggish sodium-ion diffusion kinetics of NVP material give rise to inferior rate performance and unsatisfactory energy density,which strictly confine its further application in SIBs.Thus,it is of significance to boost the sodium storage performance of NVP cathode material.Up to now,many methods have been developed to optimize the electrochemical performance of NVP cathode material.In this review,the latest advances in optimization strategies for improving the electrochemical performance of NVP cathode material are well summarized and discussed,including carbon coating or modification,foreign-ion doping or substitution and nanostructure and morphology design.The foreign-ion doping or substitution is highlighted,involving Na,V,and PO_(4)^(3−)sites,which include single-site doping,multiple-site doping,single-ion doping,multiple-ion doping and so on.Furthermore,the challenges and prospects of high-performance NVP cathode material are also put forward.It is believed that this review can provide a useful reference for designing and developing high-performance NVP cathode material toward the large-scale application in SIBs.
基金supported by the Scientific Research Fund of Hunan Provincial Education Department,China(No.22B0741)。
文摘The electrochemical performance of layered O3-type NaCrO_(2)cathode material is significantly affected by the side reactions between NaCrO_(2)and electrolyte during sodium storage.A uniform Cr_(2)O_(3)coating layer was in situ constructed on the surface of NaCrO_(2)by controlling the excess ratio of sodium source.The structure,morphology,valence and electrochemical performance of the Cr_(2)O_(3)-coated NaCrO_(2)were characterized.The results indicate that the Cr_(2)O_(3)coating layer does not alter the crystal structure and morphology of NaCrO_(2),but effectively suppresses the side reactions between NaCrO_(2)and electrolyte,and improves the surface/interfacial stability of NaCrO_(2)material.The Cr_(2)O_(3)-coated NaCrO_(2)exhibits improved electrochemical performance with a capacity retention of 66.4%after 500 cycles at 10C.
基金Project(21473258)supported by the National Natural Science Foundation of ChinaProject(13JJ1004)supported by the Distinguished Young Scientists of Hunan Province,ChinaProject(NCET-11-0513)supported by the New Century Excellent Talents in University,China
文摘Li[NixCoyMn2]O2（0.6≤x≤0.8） cathode materials with a typical hexagonal α-NaFeO2 structure were prepared utilizing a co-precipitation method.It is found that the ratio of peak intensities of（003） to（104） observed from X-ray diffraction（XRD）increases with decreasing the Ni content or increasing the Co content.The scanning electron microscopy（SEM） images reveal that the small primary particles are agglomerated to form the secondary ones.As the Mn content increases,the primary and secondary particles become larger and the resulted particle size for the Li[Ni（0.6）Co（0.2）Mn（0.2）]O2 is uniformly distributed in the range of100-300 nm.Although the initial discharge capacity of the Li/Li[NixCoyMn2]O2 cells reduces with decreasing the Ni content,the cyclic performance and rate capability are improved with higher Mn or Co content.The Li[Ni（0.6）Co（0.2）Mn（0.2）]O2 can deliver excellent cyclability with a capacity retention of 97.1%after 50 cycles.
基金Project(2007BAQ01055)supported by the National Key Technology R&D Program of ChinaProject(2011SCU11081)supported by the Sichuan University Funds for Young Scientists,ChinaProject(20120181120103)supported by Ph.D.Programs Foundation of the Ministry of Education of China
文摘The Li3V2（PO4）3/C composite cathode material was synthesized via sol-gel method using three different chelating agents （citric acid, salicylic acid and polyacrylic acid） at pH value of 3 or 7. The crystal structure, morphology, specific surface area and electrochemical performance of the prepared samples were investigated by X-ray diffraction （XRD）, scanning electron microscopy （SEM）, cyclic voltammetry （CV）, electrochemical impedance spectroscopy （EIS） and galvanostatic charge/discharge test. The results show that the effects of pH value on the performance of the prepared materials are greatly related to the chelating agents. With salicylic acid or polyacrylic acid as the chelating reagent, the structure, morphology and electrochemical performance of the samples are greatly influenced by the pH values. However, the structure of the materials with citric acid as the chelating agent does not change as pH value changes, and the materials own uniform particle size distribution and good electrochemical performance. It delivers an initial discharge capacity of 113.58 mA·h/g at 10C, remaining as high as 108.48 mA·h/g after 900 cycles, with a capacity retention of 95.51%.
基金Project (20771100) supported by the National Natural Science Foundation of China
文摘Li3V2-2/3xMnx（PO4）3（0≤x≤0.12） powders were synthesized by sol-gel method. The effect of Mn2＋-doping on the structure and electrochemical performances of Li3V2（PO4）3/C was characterized by XRD, SEM, XPS, galvanostatic charge /discharge and electrochemical impedance spectroscopy（EIS）. The XRD study shows that a small amount of Mn2＋-doped does not alter the structure of Li3V2（PO4）3/C materials, and all Mn2＋-doped samples are of pure single phase with a monoclinic structure （space group P21/n）. The XPS analysis indicates that valences state of V and Mn are ＋3 and ＋2 in Li3V1.94Mn0.09（PO4）3/C, respectively, and the citric acid in raw materials was decomposed into carbon during calcination, and residual carbon exists in Li3V1.94Mn0.09（PO4）/C. The results of electrochemical measurements show that Mn2＋-doping can improve the cyclic stability and rate performance of these cathode materials. The Li3V1.94Mn0.09（PO4）3/C cathode material shows the best cyclic stability and rate performance. For example, at the discharge current density of 40 mA/g, after 100 cycles, the discharge capacity of Li3V1.94Mn0.09（PO4）3/C declines from initial 158.8 mA·h/g to 120.5 mA·h/g with a capacity retention of 75.9%; however, that of the Mn-undoed sample declines from 164.2 mA·h/g to 72.6 mA·h/g with a capacity retention of 44.2%. When the discharge current is increased up to 1C, the intial discharge capacity of Li3V1.94Mn0.09（PO4）3/C still reaches 146.4 mA·h/g, and the discharge capacity maintains at 107.5 mA·h/g after 100 cycles. The EIS measurement indicates that Mn2＋-doping with a appropriate amount of Mn2＋ decreases the charge transfer resistance, which is favorable for the insertion/extraction of Li＋.
文摘Some compounds of LiCo 1- x RE x O 2 (RE=rare earth elements and x =0.01～0.03) were prepared by doping rare earth elements to LiCoO 2 via solid state synthesis. The microstructure characteristics of the LiCo 1- x RE x O 2 were investigated by XRD. It was found that the lattice parameters c are increased and the lattice volumes are enlarged compared to that of LiCoO 2. Moreover, the performance of LiCo 1- x RE x O 2 as the cathode material in lithium ion battery is improved, especially LiCo 1- x Y x O 2 and LiCo 1- x La x O 2. The initial charge/discharge capacities of LiCo 0.99 Y 0.01 O 2 and LiCo 0.99 La 0.01 O 2 are 174/154 (mAh·g -1 ) and 159/149 (mAh·g -1 ) respectively, while those for LiCoO 2 working in the same way are only 139/131 (mAh·g -1 ).
基金financially supported by the National Natural Science Foundation of China (No. 51372136)the NSFC-Guangdong United Fund (No. U1401246)
文摘Layered F-doped cathode materials 0.3 Li_2 MnO_3-0.7 LiMn_(1/3)Ni_(1/3)CO_(1/3))O_(2-x)F_x(x = 0, 0.01, 0.02, 0.03, 0.04,0.05) microspheres made up of nanosized primary grains were prepared through co-precipitation method. The sample of x = 0.02 demonstrates a large discharge capacity of226 mAh g^(-1) over 100 cycles at 0.1 C and excellent rate performance with discharge capacity of 96 mAh g-1 at 5.0 C and room temperature. Particularly, this material shows much enhanced electrochemical performances even at high temperature of 55 ℃. It delivers a quite high discharge capacity of 233.7 mAh·g^(-1) at 1.0 C with capacity retention as high as 97.9% after 100 cycles. The results demonstrate that the fluorine incorporation stabilizes the cathode structure and maintains stable interfacial resistances.
基金supported by National Key Technology R&D Program of China(No.2007BAE12B01-1)Science and Technology Planning Program of Hunan Province,China(No.2008GK3015)
文摘A novel synthetic method of microwave processing to prepare Li2FeSiO4 cathode materials is adopted. The Li2FeSiO4 cathode material is prepared by mechanical ball-milling and subsequent microwave processing. Olivin-type Li2FeSiO4 sample with uniform and fine particle sizes is successfully and fast synthesized by microwave heating at 700 ℃ in 12 rain. And the obtained Li2FeSiO4 materials show better electrochemical performance and microstructure than those of Li2FeSiO4 sample by the conventional solidstate reaction. ？2009 Yan Bing Cao. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.
基金supported by National Natural Science Foundation of China(No.50604018)National Key Technology R&D Program of China(No.2007BAE12B01)
文摘Spherical LiNi0.8Co0.15Al0.05O2 OOH precursor prepared by a co-oxidation-controlled crystallization method, was used to synthesize LiNi0.5Co0.15Al0.05O2. The obtained LiNi0.8Co0.15Al0.05O2 materials showed excellent electrochemical performance, with an initial discharge capacity of 193.5 mAh/g and capacity retention of 95.1% after 50 cycles when cycled at 0.2 C rate between 2.8 and 4.3 V.
基金financially supported by the National High-Tech Research and Development(863) Program of China(No.2006AA11A160)the National Natural Science Foundation of China(No.50604018)
文摘LiMn2O4 spinel cathode materials were modified with 2 wt.%Li-M-PO4（M=Co,Ni,Mn） by polyol synthesis method.The phosphate surface-modified LiMn2O4 cathode materials were physically characterized by X-ray diffraction（XRD）,scanning electron microscopy（SEM） and energy dispersive X-ray spectroscopy（EDS）.The charge-discharge test showed that the cycling and rate capacities of LiMn2O4 cathode materials were significantly enhanced by stabilizing the electrode surface with phosphate.
基金the financial supports from the Natural Science Foundation of Hunan Province,China(No.2020JJ5102)the Scientific Research Fund of Hunan Provincial Education Department,China(No.19A111).
文摘P2-type Na_(2/3)Fe_(1/2)Mn_(1/2)O_(2) was synthesized by a facile sol−gel method,and the effect of calcination temperature on the structure,morphology and electrochemical performance of samples was investigated.The results show that the sample obtained at 900℃ is pure P2-type Na_(2/3)Fe_(1/2)Mn_(1/2)O_(2) phase with good crystallization,which consists of hexagon plate-shaped particles with the size and thickness of 2−4μm and 200−400 nm,respectively.The sample exhibits an initial specific discharge capacity of 243 mA·h/g at a current density of 26 mA/g with good cycling stability.The high specific capacity indicates that P2-type Na_(2/3)Fe_(1/2)Mn_(1/2)O_(2) is a promising cathode material for sodiumion batteries.
基金supported by Guangxi Natural Science Foundation (0832259)Program to Sponsor Teams for Innovation in the Construction of Talent Highlands in Guangxi Institutions of Higher Learning (GuiJiaoRen [2007]71)Research Funds of the Guangxi Key Laboratory of Environmental Engineering, Protection and Assessment
文摘Y-doped Li3V2（PO4）3 cathode materials were prepared by a carbothermal reduction（CTR） process.The properties of the Y-doped Li3V2（PO4）3 were investigated by X-ray diffraction（XRD） and electrochemical measurements.XRD studies showed that the Y-doped Li3V2（PO4）3 had the same monoclinic structure as the undoped Li3V2（PO4）3.The Y-doped Li3V2（PO4）3 samples were investigated on the Li extraction/insertion performances through charge/discharge, cyclic voltammogram（CV）, and electrochemical impedance spectra（EIS）.The optimal doping content of Y was x=0.03 in Li3V2-xYx（PO4）3 system.The Y-doped Li3V2（PO4）3 samples showed a better cyclic ability.The electrode reaction reversibility was enhanced, and the charge transfer resistance was decreased through the Y-doping.The improved electrochemical perormances of the Y-doped Li3V2（PO4）3 cathode materials were attributed to the addition of Y3＋ ion by stabilizing the monoclinic structure.
基金supported by the Programs of National 973(2011CB935900)NSFC(21231005)+1 种基金MOE(B12015 and 113016A)the Fundamental Research Funds for the Central Universities
文摘In this paper,we report on the preparation of Li2FeSiO4,sintered Li2FeSiO4,and Li2FeSiO4-C composite with spindle-like morphologies and their application as cathode materials of lithium-ion batteries.Spindle-like Li2FeSi04 was synthesized by a facile hydrothermal method with（NH4）2Fe（SO4）2 as the iron source.The spindle-like Li2FeSiO4 was sintered at 600 ℃ for 6 h in Ar atmosphere.Li2FeSiO4-C composite was obtained by the hydrothermal treatment of spindle-like Li2FeSiO4 in glucose solution at 190 ℃ for 3 h.Electrochemical measurements show that after carbon coating,the electrode performances such as discharge capacity and high-rate capability are greatly enhanced.In particular.Li2FeSiO4-C with carbon content of 7.21 wt%delivers the discharge capacities of 160.9 mAh·g-1 at room temperature and 213 mAh·g-1 at45℃（0.1 C）,revealing the potential application in lithium-ion batteries.
文摘Spherical Ni(OH)2 powder coated with Co(OH)2 as raw material was mixed with LiOH to synthesize cathode material for lithium ion battery by using solid-state reaction. After sintered at temperature above 600 ℃, a solid solution with layer structure was formed. The result of XPS shows that it is a concentration gradient material with higher cobalt content at the surface, and the gradient decreases with increasing sintering temperature from 650 to 750 ℃. This new gradient material, called as Co-coated LiNiO2, exhibits excellent electrochemical performances for the cathode of Li-ion batteries in comparison with LiNiO2 and Co-doping LiNiO2. The discharge capacity of Co-coated LiNiO2 is over 180 mA·h/g and capacity decay per cycle is less than 0.07% when Co-coated LiNiO2 consisting of 92% nickel and 8% cobalt was sintered at the temperatures between 650-670 ℃. Though initial discharge capacity could be increased with higher sintering temperature, the cycle life would be reduced.
基金Project(21771062)supported by the National Natural Science Foundation of ChinaProject(2016JJ2092)supported by the Hunan Provincial Natural Science Foundation,ChinaProject(2019013)supported by the Open Project Program of Key Laboratory of Preparation and Application of Environmental Friendly Materials,Ministry of Education,Jilin Normal University,China
文摘Li2FeSiO4 is deemed to be a potential candidate for large-scale applications because of its abundance,low cost and high safety,etc.Unfortunately,its low conductivity,resulting in poor rate performance,has become a main obstacle to its applications in power battery and energy storage system.In this work,C-Ag coated Li2FeSiO4 is introduced to improve the innate electronic conductivity and Li-ion diffusion ability.The results demonstrate that Li2FeSiO4/C/Ag composite exhibits better electrochemical performance.It possesses a specific discharge capacity of 152,121,108 mA.h/g at 0.2C,5C and 10C,respectively.At the same time,the Li2FeSiO4/C/Ag composite shows good cycle stability and a capacity retention ratio of 97.9%after 100 cycles at 1C.
基金financially supported by the National Natural Science Foundation of China (Nos. 51164007 and 51204114)
文摘Ti-doped Li3V2(PO4)3/C cathode materials were synthesized by a solid-state method. The properties of the samples were characterized by X-ray diffraction(XRD), scanning electronic microscopic(SEM), and electrochemical tests. XRD results indicate that Ti-doping and carbon coating do not alter the structure of Li3V2(PO4)3.SEM images show that Ti-doping could reduce the particle size of Li3V2(PO4)3. Electrochemical tests reveal that Li3V1.95Ti0.05(PO4)3/C possesses the best electrochemical performances. It delivers the first discharge specific capacities of 124.4, 123.5, 120.9, and 114.9 m Ahág-1at0.1C, 1.0C, 2.0C, and 3.0C rates, respectively, and shows excellent cycling performance. The improved electrochemical performances are attributed to the Ti-doping,which increases the electronic and ionic conductivities of the cathode material.
基金Project(GuiJiaoRen[2007]71)supported by the Research Funds of the Guangxi Key Laboratory of Environmental Engineering,Protection and Assessment Program to Sponsor Teams for Innovation in the Construction of Talent Highlands in Guangxi Institutions of Higher Learning,China
文摘The effect of Al-substitution on the electrochemical performances of Li3V2(PO4)3 cathode materials was studied.Samples with stoichiometric proportion of Li3AlxV2-x(PO4)3(x=0,0.05,0.10)were prepared by adding Al(NO3)3 in the raw materials of Li3V2(PO4)3.The XRD analysis shows that the Al-substituted Li3V2(PO4)3 has the same monoclinic structure as the un-substituted Li3V2(PO4)3.The SEM images show that Al-substituted Li3V2(PO4)3 has regular and uniform particles.The electrochemical measurements show that Al-substitution can improve the rate capability of cathode materials.The Li3Al0.05V1.95(PO4)3 sample shows the best high-rate performance.The discharge capacity at 1C rate is 119 mA·h/g with 30th capacity retention rate about 92.97%.The electrode reaction reversibility and electronic conductivity are enhanced,and the charge transfer resistance decreases through Al-substitution.The improved electrochemical performances of Al-substituted Li3V2(PO4)3 cathode materials offer some favorable properties for their commercial application.
基金National Natural Science Foundation of China,Grant/Award Number:51804173。
文摘Transition metal fluorides(TMFs)cathode materials have shown extraordinary promises for electrochemical energy storage,but the understanding of their electrochemical reaction mechanisms is still a matter of debate due to the complicated and continuous changing in the battery internal environment.Here,we design a novel iron fluoride(FeF_(2))aggregate assembled with cylindrical nanoparticles as cathode material to build FeF_(2) lithium-ion batteries(LIBs)and employ advanced in situ magnetometry to detect their intrinsic electronic structure during cycling in real time.The results show that FeF_(2) cannot be involved in complete conversion reactions when the FeF_(2) LIBs operate between the conventional voltage range of 1.0–4.0 V,and that the corresponding conversion ratio of FeF_(2) can be further estimated.Importantly,we first demonstrate that the spin-polarized surface capacitance exists in the FeF_(2) cathode by monitoring the magnetic responses over various voltage ranges.The research presents an original and insightful method to examine the conversion mechanism of TMFs and significantly provides an important reference for the future artificial design of energy systems based on spinpolarized surface capacitance.
文摘At present,metal ions from spent lithium-ion batteries are mostly recovered by the acid leaching procedure,which unavoidably introduces potential pollutants to the environment.Therefore,it is necessary to develop more direct and effective green recycling methods.In this research,a method for the direct regeneration of anode materials is reported,which includes the particles size reduction of recovered raw materials by jet milling and ball milling,followed by calcination at high temperature after lithium supplementation.The regenerated LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2) single-crystal cathode material possessed a relatively ideal layered structure and a complete surface morphology when the lithium content was n(Ni+Co+Mn):n(Li)=1:1.10 at a sintering temperature of 920 0 C,and a sintering time of 12 h.The first discharge specific capacity was 154.87 mA·h·g^(-1) between 2.75 V and 4.2 V,with a capacity retention rate of 90% after 100 cycles.
基金the Science and Research Reward Fund Program of Shandong Excellent Young Scientist of China (No. 2007BS04044)
文摘The micro-single crystal material spinel LiMn2-xAlxO4 was prepared by a sol-gel procedure and modified by alumina; the electrochemical measurements show that the performances and characteristics of modified LiMn2-xAlxO4 electrode material are better than those of LiMn204. Hence, the modified LiMn2- AlxO4 is a good cathode material for lithium batteries. This can be explained that the size of the modified particle is larger than that of unmodified material, so electrons can be easily transported between the particles.
