Optimization Strategies of Na_(3)V_(2)(PO_(4))_(3) Cathode Materials for Sodium‑Ion Batteries

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.

Difficulties, strategies, and recent research and development of layered sodium transition metal oxide cathode materials for high-energy sodium-ion batteries

Energy-storage systems and their production have attracted significant interest for practical applications.Batteries are the foundation of sustainable energy sources for electric vehicles(EVs),portable electronic devices(PEDs),etc.In recent decades,Lithium-ion batteries(LIBs) have been extensively utilized in largescale energy storage devices owing to their long cycle life and high energy density.However,the high cost and limited availability of Li are the two main obstacles for LIBs.In this regard,sodium-ion batteries(SIBs) are attractive alternatives to LIBs for large-scale energy storage systems because of the abundance and low cost of sodium materials.Cathode is one of the most important components in the battery,which limits cost and performance of a battery.Among the classified cathode structures,layered structure materials have attracted attention because of their high ionic conductivity,fast diffusion rate,and high specific capacity.Here,we present a comprehensive review of the classification of layered structures and the preparation of layered materials.Furthermore,the review article discusses extensively about the issues of the layered materials,namely(1) electrochemical degradation,(2) irreversible structural changes,and(3) structural instability,and also it provides strategies to overcome the issues such as elemental phase composition,a small amount of elemental doping,structural design,and surface alteration for emerging SIBs.In addition,the article discusses about the recent research development on layered unary,binary,ternary,quaternary,quinary,and senary-based O3-and P2-type cathode materials for high-energy SIBs.This review article provides useful information for the development of high-energy layered sodium transition metal oxide P2 and O3-cathode materials for practical SIBs.

Influences of transition metal on structural and electrochemical properties of Li[Ni_xCo_yMn_z]O_2(0.6≤x≤0.8) cathode materials for lithium-ion batteries

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.

Influence of pH value and chelating reagent on performance of Li_3V_2(PO_4)3/C cathode material

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%.

Effect of Mn-doping on performance of Li_3V_2(PO_4)_3/C cathode material for lithium ion batteries

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＋.

Rare Earth Elements-Doped LiCoO_2 Cathode Material for Lithium-Ion Batteries

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 ).

Microwave synthesis of Li_2FeSiO_4 cathode materials for lithium-ion batteries

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.

Influence of Doping Rare Earth on Performance of Lithium Manganese Oxide Spinels as Cathode Materials for Lithium-Ion Batteries

Some rare earth doping spinel LiMn_(2-x)RE_xO_4 (RE=La, Ce, Nd) cathode materials for lithium ion batteries were synthesized by the solid-state reaction method. The structure characteristics of these produced samples were investigated by XRD, SEM, and particle size distribution analysis. According to the microstructure and charge-discharge testing, the effect of doping rare earth on stabilizing the spinel structure was analyzed. Through a series of doping experiments, it is shown that when the doping content x within the range of 0.01～0.02 the cycle performance of the materials is greatly improved. The discharge capacity of the sample LiMn_(1.98)La_(0.02)O_4, LiMn_(1.98)Ce_(0.02)O_4 and LiMn_(1.98)Nd_(0.02)O_4 remain 119.1, 114.2 and 117.5 mAh·g^(-1) after 50 cycles.

Synthesis and characterization of phosphate-modified LiMn_2O_4 cathode materials for Li-ion battery

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.

Preparation and electrochemical properties of Y-doped Li_3V_2(PO_4)_3 cathode materials for lithium batteries

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.

Facile synthesis of high capacity P2-type Na_(2/3)Fe_(1/2)Mn_(1/2)O_(2) cathode material for sodium-ion batteries

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.

Hydrothermal synthesis of spindle-like Li_2FeSiO_4-C composite as cathode materials for lithium-ion batteries

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.

Characteristics and electrochemical performance of cathode material Co-coated LiNiO_2 for Li-ion batteries

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.

Synthesis and Performance of LiMnO_2 as Cathodes for Li-ion Batteries

Two structure types of LiMnO 2 were synthesized by sol gel method and ion exchange method respectively.The results indicate that orthorhombic phase LiMnO 2 is more stable than layered LiMnO 2,o LiMnO 2 can be synthesized directly by sol gel methods followed by heat treated in argon,but layered LiMnO 2 was obtained only by indirect methods such as ion exchange method.In this paper,we first synthesized layered NaMnO 2 by the sol gel method,and then obtained layered LiMnO 2 by the ion exchange method.The phase constitution,chemical composition,and images of the products were tested by XRD,AAS (atomic absorption spectroscopy) and SEM.The electrochemical performances of the two structural types of LiMnO 2 are obviously different during the initial few cycles,but later they both have a good capacity retaining ability.The capacity of layered structure LiMnO 2 is higher than that of o LiMnO 2.

Synthesis and electrochemical properties of Li2FeSiO4/C/Ag composite as a cathode material for Li-ion battery

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.

Structure and electrochemical properties of La, F dual-doped LiLa_(0.01)Mn_(1.99)O_(3.99)F_(0.01) cathode materials

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.

Synthesis and electrochemical performance of VO/NaVO nanocomposites as cathode materials for sodium-ion batteries

V2O5/NaV6O15 nanocomposites were synthesized by a facile hydrothermal method using VO2(B)nanoarrays as the precursor.X-ray diffraction,scanning electron microscopy and transmission electron microscopy,and galvanostatic charge-discharge test were used to evaluate the structures,morphologies and electrochemical performance of samples,respectively.The results show that the nanocomposites are composed of one-dimensional nanobelts,preserving the morphology of the precursor well,and the hydrothermal reaction time has a significant effect on the phase contents and electrochemical performance of the composites.Compared with pure V2O5,V2O5/NaV6O15 nanocomposites exhibit enhanced electrochemical performance as cathode for sodium-ion batteries.It should be ascribed to the synergistic effect between V2O5 with high capacity and NaV6O15 with good cycling performance,and the introduced massive interfacial areas which can provide additional ion storage sites and improve the electronic and ionic conductivities.

Electrochemical performance of Al-substituted Li_3V_2(PO_4)_3 cathode materials synthesized by sol-gel method

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.

Direct regeneration of LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2) cathode material from spent lithium-ion batteries

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.

Synthesis and Properties of the Modification of Micro-Crystal LiMn_(2-x)Al_xO_4 Cathode Material for Li-Ion Batteries

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.