With the rapid development of consumer electronics and electric vehicles(EV), a large number of spent lithium-ion batteries(LIBs) have been generated worldwide. Thus, effective recycling technologies to recapture a si...With the rapid development of consumer electronics and electric vehicles(EV), a large number of spent lithium-ion batteries(LIBs) have been generated worldwide. Thus, effective recycling technologies to recapture a significant amount of valuable metals contained in spent LIBs are highly desirable to prevent the environmental pollution and resource depletion. In this work, a novel recycling technology to regenerate a LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 cathode material from spent LIBs with different cathode chemistries has been developed. By dismantling, crushing,leaching and impurity removing, the LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2(selected as an example of LiNi_xCo_yMn_(1-x-y)O_2) powder can be directly prepared from the purified leaching solution via co-precipitation followed by solid-state synthesis. For comparison purposes, a fresh-synthesized sample with the same composition has also been prepared using the commercial raw materials via the same method. X-ray diffraction(XRD), scanning electron microscopy(SEM) and electrochemical measurements have been carried out to characterize these samples. The electrochemical test result suggests that the re-synthesized sample delivers cycle performance and low rate capability which are comparable to those of the freshsynthesized sample. This novel recycling technique can be of great value to the regeneration of a pure and marketable LiNi_xCo_yMn_(1-x-y)O_2 cathode material with low secondary pollution.展开更多
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 ...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.展开更多
Al-doped LiVPO4F cathode materials LiAlxV1-xPO4F were prepared by two-step reactions based on a car-bothermal reduction (CTR) process. The properties of the Al-doped LiVPO4F were investigated by X-ray diffraction (...Al-doped LiVPO4F cathode materials LiAlxV1-xPO4F were prepared by two-step reactions based on a car-bothermal reduction (CTR) process. The properties of the Al-doped LiVPO4F were investigated by X-ray diffraction (XRD),scanning electron microscopy (SEM),and electrochemical measurements. XRD studies show that the Al-doped LiVPO4F has the same triclinic structure (space group p-↑1 ) as the undoped LiVPO4F. The SEM images exhibit that the particle size of Al-doped LiVPO4F is smaller than that of the undoped LiVPO4F and that the smallest particle size is only about 1 μm. The Al-doped LiVPO4F was evaluated as a cathode material for secondary lithium batteries,and exhibited an improved reversibility and cycleability,which may be attributed to the addition of Al^3+ ion by stabilizing the triclinic structure.展开更多
LiFePO4/Carbon composite cathode material was prepared using starch as carbon source by spray-pelleting and subsequent pyrolysis in N2. The samples were characterized by XRD, SEM, Raman, and their electrochemical perf...LiFePO4/Carbon composite cathode material was prepared using starch as carbon source by spray-pelleting and subsequent pyrolysis in N2. The samples were characterized by XRD, SEM, Raman, and their electrochemical performance was investigated in terms of cycling behavior. There has a special micro-morphology via the process, which is favorable to electrochemical properties. The discharge capacity of the LiFePO4.C composite was 170 mAh g-1, equal to the theoretical specific capacity at 0.1 C rate. At 4 C current density, the specific capacity was about 80 mAh g-1, which can satisfy for transportation applications if having a more flat discharge flat.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
Samples with the nominal stoichiometry Li1.05Cr0.1Mn1.9O4-zFz(z=0,0.05,0.1,0.15,and 0.2) were synthesized via the solid-state reaction method and characterized by X-ray powder diffraction(XRD),scanning electron mi...Samples with the nominal stoichiometry Li1.05Cr0.1Mn1.9O4-zFz(z=0,0.05,0.1,0.15,and 0.2) were synthesized via the solid-state reaction method and characterized by X-ray powder diffraction(XRD),scanning electron microscopy(SEM),galvanostatic charge/discharge, and slow rate cyclic voltammetry(SSCV) techniques.The results show that the pure spinel phase indexed to Fd3m can be obtained when z=0, 0.05,and 0.1.The substitution of F for O with z≤0.1 contributes to the increase of initial capacity compared with Li1.05Cr0.1Mn1.9O4 spinels. However,when the F-dopant content is designed to be 0.15 and 0.2,the Li1.05Cr0.1Mn1.9O4-zFZ samples deliver relatively low capacity and poor cycling properties at 55℃.展开更多
Y-doped LiVPO4F cathode materials were prepared by a carbothermal reduction(CTR) process. The properties of the Y-doped LiVPOaF samples were investigated by X-ray diffraction (XRD) and electrochemical measurements...Y-doped LiVPO4F cathode materials were prepared by a carbothermal reduction(CTR) process. The properties of the Y-doped LiVPOaF samples were investigated by X-ray diffraction (XRD) and electrochemical measurements. XRD studies show that the Y-doped LiVPOaF samples have the same triclinic structure as the undoped LiVPO4F. The Li extraction/insertion performances of Y-doped LiVPO4F samples were investigated through charge/discharge, cyclic voltammogram (CV) , and electrochemical impedance spectra(EIS). The optimal doping content of Y is x=0.04 in LiYxV1-xPO4F system. The Y-doped LiVPO4F samples show a better cyclic ability. The electrode reaction reversibility is enhanced, and the charge transfer resistance is decreased through the Y-doping. The improved electrochemical performances of the Y-doped LiVF'OaF cathode materials are atlributed to the addidon of Y^3+ ion by stabilizing the Iriclinic structure.展开更多
To improve the electrical conductivity of LiFePO4 cathode materials, the ZnO modified LiFePO4/C cathode materials are synthesized by a two-step process including solid state synthesis method and precipitation method. ...To improve the electrical conductivity of LiFePO4 cathode materials, the ZnO modified LiFePO4/C cathode materials are synthesized by a two-step process including solid state synthesis method and precipitation method. The structures and compositions of ZnO modified LiFePO4/C cathode materials are characterized and analyzed by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and energy dispersive spectroscopy, which indicates that the existence of ZnOhas little or no effect on the crystal structure, particles size and morphology of LiFePO4. The electrochemical performances are also characterized and analyzed with charge-discharge test, cyclic voltammetry and electrochemical impedance spectroscopy. The results show that the existence of ZnO improves the specific capability and lithium ion diffusion rate of LiFePO4 cathode materials and reduces the charge transfer resistance of cell, and the one with 3 wt% ZnO exhibits the best electrochemical performance.展开更多
Cathode materials,nickel doped Cr_(8)O_(21),were synthesized by a solid-state method.The effects of Ni doping on the electrochemical performances of Cr_(8)O_(21) were investigated.The experimental results show that th...Cathode materials,nickel doped Cr_(8)O_(21),were synthesized by a solid-state method.The effects of Ni doping on the electrochemical performances of Cr_(8)O_(21) were investigated.The experimental results show that the discharge capacities of the samples depend on the nickel contents,which increases firstly and then decreases with increasing Ni contents.Optimized Ni_(0.5)Cr_(7.5)O_(21)delivers a first capacity up to 392.6 m Ah·g^(-1)at 0.1C.In addition,Ni doped sample also demonstrates enhanced cycling stability and rate capability compared with that of the bare Cr_(8)O_(21).At 1 C,an initial discharge capacity of 348.7 m Ah·g^(-1)was achieved for Ni_(0.5)Cr_(7.5)O_(21),much higher than 271.4 m Ah·g^(-1)of the un-doped sample,with an increase of more than 28%.Electrochemical impedance spectroscopy results confirm that Ni doping reduces the growth of interface resistance and charge transfer resistance,which is conducive to the electrochemical kinetic behaviors during charge-discharge.展开更多
The intergranular microcracking in polycrystalline Ni-rich cathode particle is led by anisotropic volume change and stress corrosion along grain boundary,accelerating battery performance decay.Herein,we have suggested...The intergranular microcracking in polycrystalline Ni-rich cathode particle is led by anisotropic volume change and stress corrosion along grain boundary,accelerating battery performance decay.Herein,we have suggested a simple but advanced solid-state method that ensures both uniform transition metal distribution and single-crystalline morphology for Ni-rich cathode synthesis without sophisticated coprecipitation.Pelletization-assisted mechanical densification(PAMD)process on solid-state precursor mixture enables the dynamic mass transfer through the increased solid-solid contact area which facilitates the grain growth during sintering process,readily forming micro-sized single-crystalline particle.Furthermore,the improved chemical reactivity by a combination of capillary effect and vacancyassisted diffusion provides homogeneous element distribution within each primary particle.As a result,single-crystalline Ni-rich cathode with PAMD process has eliminated a potential evolution of intergranular cracking,thus achieving superior energy retention capability of 85%over 150 cycles compared to polycrystalline Ni-rich particle even after high-pressure calendering process(corresponding to electrode density of~3.6 g cm^(-3))and high cut-off voltage cycling.This work provides a concrete perspective on developing facile synthetic route of micron-sized single-crystalline Ni-rich cathode materials for high energy density lithium-ion batteries(LIBs).展开更多
Ni-rich cathode materials show great potential of applying in high-energy lithium ion batteries,but their inferior cycling stability hinders this process.Study on the electrode/electrolyte interfacial reaction is indi...Ni-rich cathode materials show great potential of applying in high-energy lithium ion batteries,but their inferior cycling stability hinders this process.Study on the electrode/electrolyte interfacial reaction is indispensable to understand the capacity failure mechanism of Ni-rich cathode materials and further address this issue.This work demonstrates the domain size effects on interfacial side reactions firstly,and further analyzes the inherent mechanism of side reaction induced capacity decay through comparing the interfacial behaviors before and after MgO coating.It has been determined that LiF deposition caused thicker SEI films may not increase the surface film resistance,while HF erosion induced surface phase transition will increase the charge transfer resistance,and the later plays the dominant factor to declined capacity of Ni-rich cathode materials.This work suggests strategies to suppress the capacity decay of layered cathode materials and provides a guidance for the domain size control to match the various applications under different current rates.展开更多
All-solid-state batteries potentially exhibit high specific energy and high safety,which is one of the development directions for nextgeneration lithium-ion batteries.The compatibility of all-solid composite electrode...All-solid-state batteries potentially exhibit high specific energy and high safety,which is one of the development directions for nextgeneration lithium-ion batteries.The compatibility of all-solid composite electrodes with high-nickel layered cathodes and inorganic solid electrolytes is one of the important problems to be solved.In addition,the interface and mechanical problems of high-nickel layered cathodes and inorganic solid electrolyte composite electrodes have not been thoroughly addressed.In this paper,the possible interface and mechanical problems in the preparation of high-nickel layered cathodes and inorganic solid electrolytes and their interface reaction during charge–discharge and cycling are reviewed.The mechanical contact problems from phenomena to internal causes are also analyzed.Uniform contact between the high-nickel cathode and solid electrolyte in space and the ionic conductivity of the solid electrolyte are the prerequisites for the good performance of a high-nickel layered cathode.The interface reaction and contact loss between the high-nickel layered cathode and solid electrolyte in the composite electrode directly affect the passage of ions and electrons into the active material.The buffer layer constructed on the high-nickel cathode surface can prevent direct contact between the active material and electrolyte and slow down their interface reaction.An appropriate protective layer can also slow down the interface contact loss by reducing the volume change of the high-nickel layered cathode during charge and discharge.Finally,the following recommendations are put forward to realize the development vision of high-nickel layered cathodes:(1)develop electrochemical systems for high-nickel layered cathodes and inorganic solid electrolytes;(2)elucidate the basic science of interface and electrode processes between high-nickel layered cathodes and inorganic solid electrolytes,clarify the mechanisms of the interfacial chemical and electrochemical reactions between the two materials,and address the intrinsic safety issues;(3)strengthen the development of research and engineering technologies and their preparation methods for composite electrodes with high-nickel layered cathodes and solid electrolytes and promote the industrialization of all-solid-state batteries.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
A spherical-like Ni_(0.6)Co_(0.2)Mn_(0.2)(OH)_2 precursor was tuned homogeneously to synthesize LiNi_(0.6)Co_(0.2)Mn_(0.2)O_2 as a cathode material for lithium-ion batteries.The effects of calcination temperature on t...A spherical-like Ni_(0.6)Co_(0.2)Mn_(0.2)(OH)_2 precursor was tuned homogeneously to synthesize LiNi_(0.6)Co_(0.2)Mn_(0.2)O_2 as a cathode material for lithium-ion batteries.The effects of calcination temperature on the crystal structure,morphology,and the electrochemical performance of the as-prepared LiNi_(0.6)Co_(0.2)Mn_(0.2)O_2 were investigated in detail.The as-prepared material was characterized by X-ray diffraction,scanning electron microscopy,laser particle size analysis,charge–discharge tests,and cyclic voltammetry measurements.The results show that the spherical-like LiNi_(0.6)Co_(0.2)Mn_(0.2)O_2 material obtained by calcination at 900°C displayed the most significant layered structure among samples calcined at various temperatures,with a particle size of approximately 10 μm.It delivered an initial discharge capacity of 189.2 m Ah×g^(-1) at 0.2C with a capacity retention of 94.0% after 100 cycles between 2.7 and 4.3 V.The as-prepared cathode material also exhibited good rate performance,with a discharge capacity of 119.6 m Ah×g^(-1) at 5C.Furthermore,within the cut-off voltage ranges from 2.7 to 4.3,4.4,and 4.5 V,the initial discharge capacities of the calcined samples were 170.7,180.9,and 192.8 m Ah×g^(-1),respectively,at a rate of 1C.The corresponding retentions were 86.8%,80.3%,and 74.4% after 200 cycles,respectively.展开更多
Lithium element has attracted remarkable attraction for energy storage devices, over the past 30 years. Lithium is a light element and exhibits the low atomic number 3, just after hydrogen and helium in the periodic t...Lithium element has attracted remarkable attraction for energy storage devices, over the past 30 years. Lithium is a light element and exhibits the low atomic number 3, just after hydrogen and helium in the periodic table. The lithium atom has a strong tendency to release one electron and constitute a positive charge, as Li<sup> </sup>. Initially, lithium metal was employed as a negative electrode, which released electrons. However, it was observed that its structure changed after the repetition of charge-discharge cycles. To remedy this, the cathode mainly consisted of layer metal oxide and olive, e.g., cobalt oxide, LiFePO<sub>4</sub>, etc., along with some contents of lithium, while the anode was assembled by graphite and silicon, etc. Moreover, the electrolyte was prepared using the lithium salt in a suitable solvent to attain a greater concentration of lithium ions. Owing to the lithium ions’ role, the battery’s name was mentioned as a lithium-ion battery. Herein, the presented work describes the working and operational mechanism of the lithium-ion battery. Further, the lithium-ion batteries’ general view and future prospects have also been elaborated.展开更多
For constructing next-generation lithium-ion batteries with advanced performances,pursuit of highcapacity Li-rich cathodes has caused considerable attention.So far,the low discharge specific capacity and serious capac...For constructing next-generation lithium-ion batteries with advanced performances,pursuit of highcapacity Li-rich cathodes has caused considerable attention.So far,the low discharge specific capacity and serious capacity fading are strangling the development of Fe-based Li-rich materials.To activate the extra-capacity of Fe-based Li-rich cathode materials,a facile molten salt method is exploited using an alkaline mixture of LiOH–LiNO3–Li2O2 in this work.The prepared Li1.09(Fe0.2Ni0.3Mn0.5)0.91O2 material yields high discharge specific capacity and good cycling stability.The discharge specific capacity shows an upward tendency at 0.1 C.After 60 cycles,a high reversible specific capacity of ~250 m Ah g-1is delivered.The redox of Fe3+/Fe4+and Mn3+/Mn4+are gradually activated during cycling.Notably,the redox reaction of Fe2+/Fe3+can be observed reversibly below 2 V,which is quite different from the material prepared by a traditional co-precipitation method.The stable morphology of fine nanoparticles(100–300 nm)is considered benefiting for the distinctive electrochemical performances of Li1.09(Fe0.2Ni0.3Mn0.5)0.91O2.This study demonstrates that molten salt method is an inexpensive and effective approach to activate the extra capacity of Fe-based Li-rich cathode material for high-performance lithium-ion batteries.展开更多
LiFePO4 cathode material was synthesized by a solid-state reaction using doping several elements (Nb5 + ,Zr4 + ). The starting materials were mixed with a high-efficient sander and treated thermally under flowing N2. ...LiFePO4 cathode material was synthesized by a solid-state reaction using doping several elements (Nb5 + ,Zr4 + ). The starting materials were mixed with a high-efficient sander and treated thermally under flowing N2. The samples were characterized by X-ray diffraction (XRD), field-emission gun electron microscopy (FEG), and their electrochemical performance was investigated in the term of cycling behavior. Room temperature discharge capacity about 140.6 mA·h·g-1 was obtained at C/5 rate.展开更多
It is of great significance to develop clean and new energy sources with high-efficient energy storage technologies,due to the excessive use of fossil energy that has caused severe environmental damage.There is great ...It is of great significance to develop clean and new energy sources with high-efficient energy storage technologies,due to the excessive use of fossil energy that has caused severe environmental damage.There is great interest in exploring advanced rechargeable lithium batteries with desirable energy and power capabilities for applications in portable electronics,smart grids,and electric vehicles.In practice,high-capacity and low-cost electrode materials play an important role in sustaining the progresses in lithium-ion batteries.This review aims at giving an account of recent advances on the emerging high-capacity electrode materials and summarizing key barriers and corresponding strategies for the practical viability of these electrode materials.Effective approaches to enhance energy density of lithium-ion batteries are to increase the capacity of electrode materials and the output operation voltage.On account of major bottlenecks of the power lithium-ion battery,authors come up with the concept of integrated battery systems,which will be a promising future for high-energy lithium-ion batteries to improve energy density and alleviate anxiety of electric vehicles.展开更多
We study the crystal structure of a triplite-structured (Li0.5Fe0.5)SO4F with full Li+/Fe2+ mixing. This promising polyanion cathode material for lithium-ion batteries operates at 3.9 V versus Li+/Li with a theor...We study the crystal structure of a triplite-structured (Li0.5Fe0.5)SO4F with full Li+/Fe2+ mixing. This promising polyanion cathode material for lithium-ion batteries operates at 3.9 V versus Li+/Li with a theoretical capacity of 151 mAh/g. Its unique cation mixing structure does not block the Li+ diffusion and results in a small lattice volume change during the charge/discharge process. The calculations show that it has a three-dimensional network for Li-ion migration with an activation energy ranging from 0.53 eV to 0.68 eV, which is comparable with that in LiFePO4 with only one-dimensional channels. This work suggests that further exploring cathode materials with full cation mixing for Li-ion batteries will be valuable.展开更多
基金supported by the National Natural Science Foundation of China(No.51274075)the National Environmental Technology Special Project(No.201009028)Guangdong Province-department University-industry Collaboration Project(Grant No.2012B091100315)
文摘With the rapid development of consumer electronics and electric vehicles(EV), a large number of spent lithium-ion batteries(LIBs) have been generated worldwide. Thus, effective recycling technologies to recapture a significant amount of valuable metals contained in spent LIBs are highly desirable to prevent the environmental pollution and resource depletion. In this work, a novel recycling technology to regenerate a LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 cathode material from spent LIBs with different cathode chemistries has been developed. By dismantling, crushing,leaching and impurity removing, the LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2(selected as an example of LiNi_xCo_yMn_(1-x-y)O_2) powder can be directly prepared from the purified leaching solution via co-precipitation followed by solid-state synthesis. For comparison purposes, a fresh-synthesized sample with the same composition has also been prepared using the commercial raw materials via the same method. X-ray diffraction(XRD), scanning electron microscopy(SEM) and electrochemical measurements have been carried out to characterize these samples. The electrochemical test result suggests that the re-synthesized sample delivers cycle performance and low rate capability which are comparable to those of the freshsynthesized sample. This novel recycling technique can be of great value to the regeneration of a pure and marketable LiNi_xCo_yMn_(1-x-y)O_2 cathode material with low secondary pollution.
基金Project supported by the National Natural Science Foundation of China (20273047)
文摘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.
文摘Al-doped LiVPO4F cathode materials LiAlxV1-xPO4F were prepared by two-step reactions based on a car-bothermal reduction (CTR) process. The properties of the Al-doped LiVPO4F were investigated by X-ray diffraction (XRD),scanning electron microscopy (SEM),and electrochemical measurements. XRD studies show that the Al-doped LiVPO4F has the same triclinic structure (space group p-↑1 ) as the undoped LiVPO4F. The SEM images exhibit that the particle size of Al-doped LiVPO4F is smaller than that of the undoped LiVPO4F and that the smallest particle size is only about 1 μm. The Al-doped LiVPO4F was evaluated as a cathode material for secondary lithium batteries,and exhibited an improved reversibility and cycleability,which may be attributed to the addition of Al^3+ ion by stabilizing the triclinic structure.
文摘LiFePO4/Carbon composite cathode material was prepared using starch as carbon source by spray-pelleting and subsequent pyrolysis in N2. The samples were characterized by XRD, SEM, Raman, and their electrochemical performance was investigated in terms of cycling behavior. There has a special micro-morphology via the process, which is favorable to electrochemical properties. The discharge capacity of the LiFePO4.C composite was 170 mAh g-1, equal to the theoretical specific capacity at 0.1 C rate. At 4 C current density, the specific capacity was about 80 mAh g-1, which can satisfy for transportation applications if having a more flat discharge flat.
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.
基金supported by the National Natural Science Foundation of China(No.50702007)Beijing Municipal Natural Science Foundation(No.2083029)
文摘Samples with the nominal stoichiometry Li1.05Cr0.1Mn1.9O4-zFz(z=0,0.05,0.1,0.15,and 0.2) were synthesized via the solid-state reaction method and characterized by X-ray powder diffraction(XRD),scanning electron microscopy(SEM),galvanostatic charge/discharge, and slow rate cyclic voltammetry(SSCV) techniques.The results show that the pure spinel phase indexed to Fd3m can be obtained when z=0, 0.05,and 0.1.The substitution of F for O with z≤0.1 contributes to the increase of initial capacity compared with Li1.05Cr0.1Mn1.9O4 spinels. However,when the F-dopant content is designed to be 0.15 and 0.2,the Li1.05Cr0.1Mn1.9O4-zFZ samples deliver relatively low capacity and poor cycling properties at 55℃.
基金Funded by the Sponsor Teams for Innovation in the Construction of Talent Highlands in Guangxi Institutions of Higher Learning(GuiJiaoRen [2007]71)Guangxi Natural Science Foundation(No.0832259)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 High-lands in Guangxi Institutions of Higher Learning(GuiJiaoRen [2007]71)
文摘Y-doped LiVPO4F cathode materials were prepared by a carbothermal reduction(CTR) process. The properties of the Y-doped LiVPOaF samples were investigated by X-ray diffraction (XRD) and electrochemical measurements. XRD studies show that the Y-doped LiVPOaF samples have the same triclinic structure as the undoped LiVPO4F. The Li extraction/insertion performances of Y-doped LiVPO4F samples were investigated through charge/discharge, cyclic voltammogram (CV) , and electrochemical impedance spectra(EIS). The optimal doping content of Y is x=0.04 in LiYxV1-xPO4F system. The Y-doped LiVPO4F samples show a better cyclic ability. The electrode reaction reversibility is enhanced, and the charge transfer resistance is decreased through the Y-doping. The improved electrochemical performances of the Y-doped LiVF'OaF cathode materials are atlributed to the addidon of Y^3+ ion by stabilizing the Iriclinic structure.
基金Supported by the Applied Basic Research Project of Sichuan Province(2011JY0101)the Key Fund Project of Sichuan Education Department(13ZA0111)+2 种基金the Natural Science Fund Project of Sichuan Education Department(11ZB239)the Science and Technology Research Project of Mianyang(12G031-1)the Key Project of Mianyang Normal University(2012A11)
文摘To improve the electrical conductivity of LiFePO4 cathode materials, the ZnO modified LiFePO4/C cathode materials are synthesized by a two-step process including solid state synthesis method and precipitation method. The structures and compositions of ZnO modified LiFePO4/C cathode materials are characterized and analyzed by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and energy dispersive spectroscopy, which indicates that the existence of ZnOhas little or no effect on the crystal structure, particles size and morphology of LiFePO4. The electrochemical performances are also characterized and analyzed with charge-discharge test, cyclic voltammetry and electrochemical impedance spectroscopy. The results show that the existence of ZnO improves the specific capability and lithium ion diffusion rate of LiFePO4 cathode materials and reduces the charge transfer resistance of cell, and the one with 3 wt% ZnO exhibits the best electrochemical performance.
基金National Natural Science Foundation of China(No.51790490)。
文摘Cathode materials,nickel doped Cr_(8)O_(21),were synthesized by a solid-state method.The effects of Ni doping on the electrochemical performances of Cr_(8)O_(21) were investigated.The experimental results show that the discharge capacities of the samples depend on the nickel contents,which increases firstly and then decreases with increasing Ni contents.Optimized Ni_(0.5)Cr_(7.5)O_(21)delivers a first capacity up to 392.6 m Ah·g^(-1)at 0.1C.In addition,Ni doped sample also demonstrates enhanced cycling stability and rate capability compared with that of the bare Cr_(8)O_(21).At 1 C,an initial discharge capacity of 348.7 m Ah·g^(-1)was achieved for Ni_(0.5)Cr_(7.5)O_(21),much higher than 271.4 m Ah·g^(-1)of the un-doped sample,with an increase of more than 28%.Electrochemical impedance spectroscopy results confirm that Ni doping reduces the growth of interface resistance and charge transfer resistance,which is conducive to the electrochemical kinetic behaviors during charge-discharge.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korea government(MEST)(2021R1A2C1095408)supported by Basic Science Research Program through the National Research Foundation of Korea(NRF)funded by the Ministry of Education(2022R1A6A1A03051158)。
文摘The intergranular microcracking in polycrystalline Ni-rich cathode particle is led by anisotropic volume change and stress corrosion along grain boundary,accelerating battery performance decay.Herein,we have suggested a simple but advanced solid-state method that ensures both uniform transition metal distribution and single-crystalline morphology for Ni-rich cathode synthesis without sophisticated coprecipitation.Pelletization-assisted mechanical densification(PAMD)process on solid-state precursor mixture enables the dynamic mass transfer through the increased solid-solid contact area which facilitates the grain growth during sintering process,readily forming micro-sized single-crystalline particle.Furthermore,the improved chemical reactivity by a combination of capillary effect and vacancyassisted diffusion provides homogeneous element distribution within each primary particle.As a result,single-crystalline Ni-rich cathode with PAMD process has eliminated a potential evolution of intergranular cracking,thus achieving superior energy retention capability of 85%over 150 cycles compared to polycrystalline Ni-rich particle even after high-pressure calendering process(corresponding to electrode density of~3.6 g cm^(-3))and high cut-off voltage cycling.This work provides a concrete perspective on developing facile synthetic route of micron-sized single-crystalline Ni-rich cathode materials for high energy density lithium-ion batteries(LIBs).
基金supported by the National Key R&D Program of China(2016YFB0100301)the National Natural Science Foundation of China(21875022,51802020,U1664255)+2 种基金the Science and Technology Innovation Foundation of Beijing Institute of Technology Chongqing Innovation Center(2020CX5100006)the Young Elite Scientists Sponsorship Program by CAST(2018QNRC001)the support from the Beijing Institute of Technology Research Fund Program for Young Scholars。
文摘Ni-rich cathode materials show great potential of applying in high-energy lithium ion batteries,but their inferior cycling stability hinders this process.Study on the electrode/electrolyte interfacial reaction is indispensable to understand the capacity failure mechanism of Ni-rich cathode materials and further address this issue.This work demonstrates the domain size effects on interfacial side reactions firstly,and further analyzes the inherent mechanism of side reaction induced capacity decay through comparing the interfacial behaviors before and after MgO coating.It has been determined that LiF deposition caused thicker SEI films may not increase the surface film resistance,while HF erosion induced surface phase transition will increase the charge transfer resistance,and the later plays the dominant factor to declined capacity of Ni-rich cathode materials.This work suggests strategies to suppress the capacity decay of layered cathode materials and provides a guidance for the domain size control to match the various applications under different current rates.
文摘All-solid-state batteries potentially exhibit high specific energy and high safety,which is one of the development directions for nextgeneration lithium-ion batteries.The compatibility of all-solid composite electrodes with high-nickel layered cathodes and inorganic solid electrolytes is one of the important problems to be solved.In addition,the interface and mechanical problems of high-nickel layered cathodes and inorganic solid electrolyte composite electrodes have not been thoroughly addressed.In this paper,the possible interface and mechanical problems in the preparation of high-nickel layered cathodes and inorganic solid electrolytes and their interface reaction during charge–discharge and cycling are reviewed.The mechanical contact problems from phenomena to internal causes are also analyzed.Uniform contact between the high-nickel cathode and solid electrolyte in space and the ionic conductivity of the solid electrolyte are the prerequisites for the good performance of a high-nickel layered cathode.The interface reaction and contact loss between the high-nickel layered cathode and solid electrolyte in the composite electrode directly affect the passage of ions and electrons into the active material.The buffer layer constructed on the high-nickel cathode surface can prevent direct contact between the active material and electrolyte and slow down their interface reaction.An appropriate protective layer can also slow down the interface contact loss by reducing the volume change of the high-nickel layered cathode during charge and discharge.Finally,the following recommendations are put forward to realize the development vision of high-nickel layered cathodes:(1)develop electrochemical systems for high-nickel layered cathodes and inorganic solid electrolytes;(2)elucidate the basic science of interface and electrode processes between high-nickel layered cathodes and inorganic solid electrolytes,clarify the mechanisms of the interfacial chemical and electrochemical reactions between the two materials,and address the intrinsic safety issues;(3)strengthen the development of research and engineering technologies and their preparation methods for composite electrodes with high-nickel layered cathodes and solid electrolytes and promote the industrialization of all-solid-state batteries.
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financially supported by NSAF(No.U1530155)Ministry of Science and Technology(MOST)of China,US–China Collaboration on Cutting-edge Technology Development of Electric Vehicle,the Nation Key Basic Research Program of China(No.2015CB251100)Beijing Key Laboratory of Environmental Science and Engineering(No.20131039031)
文摘A spherical-like Ni_(0.6)Co_(0.2)Mn_(0.2)(OH)_2 precursor was tuned homogeneously to synthesize LiNi_(0.6)Co_(0.2)Mn_(0.2)O_2 as a cathode material for lithium-ion batteries.The effects of calcination temperature on the crystal structure,morphology,and the electrochemical performance of the as-prepared LiNi_(0.6)Co_(0.2)Mn_(0.2)O_2 were investigated in detail.The as-prepared material was characterized by X-ray diffraction,scanning electron microscopy,laser particle size analysis,charge–discharge tests,and cyclic voltammetry measurements.The results show that the spherical-like LiNi_(0.6)Co_(0.2)Mn_(0.2)O_2 material obtained by calcination at 900°C displayed the most significant layered structure among samples calcined at various temperatures,with a particle size of approximately 10 μm.It delivered an initial discharge capacity of 189.2 m Ah×g^(-1) at 0.2C with a capacity retention of 94.0% after 100 cycles between 2.7 and 4.3 V.The as-prepared cathode material also exhibited good rate performance,with a discharge capacity of 119.6 m Ah×g^(-1) at 5C.Furthermore,within the cut-off voltage ranges from 2.7 to 4.3,4.4,and 4.5 V,the initial discharge capacities of the calcined samples were 170.7,180.9,and 192.8 m Ah×g^(-1),respectively,at a rate of 1C.The corresponding retentions were 86.8%,80.3%,and 74.4% after 200 cycles,respectively.
文摘Lithium element has attracted remarkable attraction for energy storage devices, over the past 30 years. Lithium is a light element and exhibits the low atomic number 3, just after hydrogen and helium in the periodic table. The lithium atom has a strong tendency to release one electron and constitute a positive charge, as Li<sup> </sup>. Initially, lithium metal was employed as a negative electrode, which released electrons. However, it was observed that its structure changed after the repetition of charge-discharge cycles. To remedy this, the cathode mainly consisted of layer metal oxide and olive, e.g., cobalt oxide, LiFePO<sub>4</sub>, etc., along with some contents of lithium, while the anode was assembled by graphite and silicon, etc. Moreover, the electrolyte was prepared using the lithium salt in a suitable solvent to attain a greater concentration of lithium ions. Owing to the lithium ions’ role, the battery’s name was mentioned as a lithium-ion battery. Herein, the presented work describes the working and operational mechanism of the lithium-ion battery. Further, the lithium-ion batteries’ general view and future prospects have also been elaborated.
基金supported by the Nature Science Foundations of Hebei Province (B2016210071, B2016210111)the Natural Science Foundation of Hebei Education Department (QN2016057, ZD2015082, ZC2016045)+3 种基金the National College Students’ Innovative Entrepreneurial Training Project of Chinasupported by the Chinese National 973 Program (2015CB251106)the Joint Funds of the National Natural Science Foundation of China (U1564206)Major achievements Transformation Project for Central University in Beijing
文摘For constructing next-generation lithium-ion batteries with advanced performances,pursuit of highcapacity Li-rich cathodes has caused considerable attention.So far,the low discharge specific capacity and serious capacity fading are strangling the development of Fe-based Li-rich materials.To activate the extra-capacity of Fe-based Li-rich cathode materials,a facile molten salt method is exploited using an alkaline mixture of LiOH–LiNO3–Li2O2 in this work.The prepared Li1.09(Fe0.2Ni0.3Mn0.5)0.91O2 material yields high discharge specific capacity and good cycling stability.The discharge specific capacity shows an upward tendency at 0.1 C.After 60 cycles,a high reversible specific capacity of ~250 m Ah g-1is delivered.The redox of Fe3+/Fe4+and Mn3+/Mn4+are gradually activated during cycling.Notably,the redox reaction of Fe2+/Fe3+can be observed reversibly below 2 V,which is quite different from the material prepared by a traditional co-precipitation method.The stable morphology of fine nanoparticles(100–300 nm)is considered benefiting for the distinctive electrochemical performances of Li1.09(Fe0.2Ni0.3Mn0.5)0.91O2.This study demonstrates that molten salt method is an inexpensive and effective approach to activate the extra capacity of Fe-based Li-rich cathode material for high-performance lithium-ion batteries.
文摘LiFePO4 cathode material was synthesized by a solid-state reaction using doping several elements (Nb5 + ,Zr4 + ). The starting materials were mixed with a high-efficient sander and treated thermally under flowing N2. The samples were characterized by X-ray diffraction (XRD), field-emission gun electron microscopy (FEG), and their electrochemical performance was investigated in the term of cycling behavior. Room temperature discharge capacity about 140.6 mA·h·g-1 was obtained at C/5 rate.
基金supported by National Natural Science Foundation of China(No.51902340)Chongqing Natural Science Foundation,and Chongqing Postdoctoral Science Foundation(No.2021000051).
文摘It is of great significance to develop clean and new energy sources with high-efficient energy storage technologies,due to the excessive use of fossil energy that has caused severe environmental damage.There is great interest in exploring advanced rechargeable lithium batteries with desirable energy and power capabilities for applications in portable electronics,smart grids,and electric vehicles.In practice,high-capacity and low-cost electrode materials play an important role in sustaining the progresses in lithium-ion batteries.This review aims at giving an account of recent advances on the emerging high-capacity electrode materials and summarizing key barriers and corresponding strategies for the practical viability of these electrode materials.Effective approaches to enhance energy density of lithium-ion batteries are to increase the capacity of electrode materials and the output operation voltage.On account of major bottlenecks of the power lithium-ion battery,authors come up with the concept of integrated battery systems,which will be a promising future for high-energy lithium-ion batteries to improve energy density and alleviate anxiety of electric vehicles.
基金supported by the National High Technology Research and Development Program of China (Grant No. 2009AA033101)
文摘We study the crystal structure of a triplite-structured (Li0.5Fe0.5)SO4F with full Li+/Fe2+ mixing. This promising polyanion cathode material for lithium-ion batteries operates at 3.9 V versus Li+/Li with a theoretical capacity of 151 mAh/g. Its unique cation mixing structure does not block the Li+ diffusion and results in a small lattice volume change during the charge/discharge process. The calculations show that it has a three-dimensional network for Li-ion migration with an activation energy ranging from 0.53 eV to 0.68 eV, which is comparable with that in LiFePO4 with only one-dimensional channels. This work suggests that further exploring cathode materials with full cation mixing for Li-ion batteries will be valuable.