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1.
Sn-doped Li-rich layered oxides of Li1.2Mn0.54-x Ni0.13Co0.13Sn x O2 have been synthesized via a sol-gel method, and their microstructure and electrochemical performance have been studied. The addition of Sn4+ ions has no distinct influence on the crystal structure of the materials. After doped with an appropriate amount of Sn4+, the electrochemical performance of Li1.2Mn0.54-x Ni0.13Co0.13Sn x O2 cathode materials is significantly enhanced. The optimal electrochemical performance is obtained at x = 0.01. The Li1.2Mn0.53Ni0.13Co0.13Sn0.01O2 electrode delivers a high initial discharge capacity of 268.9 mAh g?1 with an initial coulombic efficiency of 76.5% and a reversible capacity of 199.8 mAh g?1 at 0.1 C with capacity retention of 75.2% after 100 cycles. In addition, the Li1.2Mn0.53Ni0.13Co0.13Sn0.01O2 electrode exhibits the superior rate capability with discharge capacities of 239.8, 198.6, 164.4, 133.4, and 88.8 mAh g?1 at 0.2, 0.5, 1, 2, and 5 C, respectively, which are much higher than those of Li1.2Mn0.54Ni0.13Co0.13O2 (196.2, 153.5, 117.5, 92.7, and 43.8 mAh g?1 at 0.2, 0.5, 1, 2, and 5 C, respectively). The substitution of Sn4+ for Mn4+ enlarges the Li+ diffusion channels due to its larger ionic radius compared to Mn4+ and enhances the structural stability of Li-rich oxides, leading to the improved electrochemical performance in the Sn-doped Li1.2Mn0.54Ni0.13Co0.13O2 cathode materials.  相似文献   

2.
Carbon surface-modified Li-excess layered oxide solid solution Li[Li0.2Mn0.54Ni0.13Co0.13]O2 cathode is fabricated through a liquid phase route using polyvinylpyrrolidone as carbon source. X-ray diffraction and X-ray photoelectron spectroscopy indicate that the crystal structure and the chemical states of elements for Li[Li0.2Mn0.54Ni0.13Co0.13]O2 are kept after carbon surface treatment. The high-resolution transmission electron microscopy demonstrated the existence of very little carbon on the surface and the clear boundary after carbon treatment. The carbon surface-modified sample delivers a discharge capacity of 293.2 mAh?g?1 at C/10 rate (suppose 1 C rate?=?250 mA?g?1) and 191.6 mAh?g?1 at 1 C rate between 2.0 and 4.8 V; the capacity retention rate is ~86 % after 70 cycles at 1 C rate. Superior electrochemical properties can be contributed to the carbon surface modification in these aspects including minimizing nanoparticle aggregation and cell polarization, increasing the electronic conductivity, suppressing the elimination of oxide ion vacancies, as well as suppressing the formation of the thick solid electrolyte interfacial layer. Moreover, the annealing process of carbon surface modification might be able to consume Li2CO3 impurity partly and cause the recrystallization of the surface disordered layer.  相似文献   

3.
Li- and Mn-rich layered Li1.2Ni0.13Co0.13Mn0.54O2 cathode material was synthesized using sonochemical method followed by annealing at 700, 800, and 900 °C for 10 h. The material was characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopy (TEM), Raman spectroscopy, and electrochemical techniques. Its performance as a cathode material for Li-ion batteries was examined. With the sample annealed at 900 °C, an initial specific capacity of 240 mAh g?1 was obtained, which decreased to 215 mAh g?1 after 80 cycles, thus retaining about 90 % of its initial capacity. In contrast, samples annealed at lower temperatures exhibited lower capacity retention upon cycling. Thus, the final annealing temperature was found to have a significant effect on the electrochemical stability of this material in terms of capacity, average voltage, and rate capability. The advantage of this synthesis, which includes a sonochemical stage, compared with a conventional co-precipitation synthesis, was also confirmed.  相似文献   

4.
运用共沉淀和元素化学沉积相结合的方法,制备出了具有Ag/C 包覆层的层状富锂固溶体材料Li[Li0.2Mn0.54Ni0.13Co0.13]O2. 通过X 射线衍射(XRD)、场发射扫描电子显微镜(SEM)、透射电子显微镜(TEM)、恒流充放电、循环伏安(CV),电化学阻抗谱(EIS)和X 射线能量散射谱(EDS)方法,研究了Ag/C 包覆层对Li[Li0.2Mn0.54Ni0.13Co0.13]O2电化学性能的影响. 结果表明,Ag/C 包覆层的厚度约为25 nm,Ag/C 包覆在保持了固溶体材料α-NaFeO2 六方层状晶体结构的前提下,显著地改善了Li[Li0.2Mn0.54Ni0.13Co0.13]O2 的电化学性能. 在2.0-4.8 V(vs Li/Li+)的电压范围内,首次放电(0.05C)容量由242.6 mAh·g-1提高到272.4 mAh·g-1,库仑效率由67.6%升高到77.4%;在0.2C倍率下,30 次循环后,Ag/C 包覆的电极材料容量为222.6 mAh·g-1,比未包覆电极材料的容量高出14.45%;包覆后的电极材料在1C下的容量仍为0.05C下的81.3%. 循环伏安及电化学交流阻抗谱研究表明,Ag/C包覆层抑制了材料在充放电过程中氧的损失,有效降低了Li[Li0.2Mn0.54Ni0.13Co0.13]O2颗粒的界面膜电阻与电化学反应电阻.  相似文献   

5.
以共沉淀法制备的[Mn0.54Ni0.13Co0.13]1.25CO3为前驱体,配锂焙烧获得了富锂锰基固溶体Li[Li0.2Mn0.54Ni0.13Co0.13]O2,然后分别用柠檬酸、柠檬酸三铵对该材料进行表面预处理。结果表明经柠檬酸(铵)处理后,Li[Li0.2Mn0.54Ni0.13Co0.13]O2中分别有16.37wt%和13.14wt%的锂被化学脱出。充放电测试结果表明,表面处理后的样品首次效率有了较大的提高(由63.5%分别提高到了80.2%和80.7%),0.2C循环40次容量保持率分别由91.43%提高到97.42%和92.72%,1C容量由处理前的149.5 mAh.g-1提高到179.5mAh.g-1和181.5 mAh.g-1,表明处理后材料的循环性能和倍率性能都得到了改善。这主要是由于柠檬酸(铵)处理,预先脱出了Li2MnO3组分中的部分Li2O,并在材料表面生成了类尖晶石结构的材料。  相似文献   

6.
为了改善富锂锰基正极材料Li1.2Mn0.54Ni0.13Co0.13O2 的循环性能,采用燃烧法合成了正极材料Li1.2Mn0.54-xNi0.13Co0.13ZrxO2(x=0.00,0.01,0.02,0.03,0.06). 通过X射线衍射(XRD)和扫描电镜(SEM)对其结构与形貌进行了表征,利用恒电流充放电测试,循环伏安(CV)及电化学交流阻抗谱(EIS)技术对其电化学性能进行测试. 结果表明,Li1.2Mn0.54-xNi0.13Co0.13ZrxO2(x=0.00,0.01,0.02,0.03,0.06)正极材料均具有α-NaFeO2型层状结构;在室温,2.0-4.8 V电压范围,以0.1C和1.0C(充放电电流以1.0C=180 mA·g-1计算)倍率充放电进行测试,样品Li1.2Mn0.52Ni0.13Co0.13Zr0.02O2的首次放电比容量分别为280.3 和206.4 mAh·g-1. 其中,在1.0C倍率下,100次循环后容量保持率由原来的73.2%提高到88.9%;以5.0C倍率充放电进行测试,经50次循环后,掺杂正极材料的放电比容量为76.5 mAh·g-1,而未掺杂材料仅有15.0 mAh·g-1. 在50、25 和-10 ℃,2.0C倍率条件下,掺杂正极材料的电化学性能均得到有效改善,其中,在- 10℃ 经过50 次循环后正极材料Li1.2Mn0.52Ni0.13Co0.13Zr0.02O2比未掺杂的正极材料相比,其放电比容量提高了61.1%.  相似文献   

7.
The Li-rich Li1.3[Ni0.35Mn0.65]O2+x microspheres are firstly prepared and subsequently transferred into the Al2O3-coated Li-rich Li1.3[Ni0.35Mn0.65]O2+x microspheres by a simple deposition method. The as-prepared samples are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and charge/discharge tests. The results reveal that the Al2O3-coated Li-rich Li1.3[Ni0.35Mn0.65]O2+x sample has a typical α-NaFeO2 layered structure with the existence of Li2MnO3-type integrated component, and the Al2O3 layer is uniformly coated on the surface of the spherical Li-rich Li1.3[Ni0.35Mn0.65]O2+x particles with a thickness of about 4 nm. Importantly, the Al2O3-coated Li-rich sample exhibits obviously improved electrochemical performance compared with the pristine one, especially the 2 wt.% Al2O3-coated sample shows the best electrochemical properties, which delivers an initial discharge capacity of 228 mAh g?1 at a rate of 0.1 C in the voltage of 2.0–4.6 V, and the first coulombic efficiency is up to 90 %. Furthermore, the 2 wt.% Al2O3-coated sample represents excellent cycling stability with capacity retention of 90.9 % at 0.33 C after 100 cycles, much higher than that of the pristine one (62.2 %). Particularly, herein, the typical inferior rate capability of Li-rich layered cathode is apparently improved, and the 2 wt.% Al2O3-coated sample also shows a high rate capability, which can deliver a capacity of 101 mAh g?1 even at 10 C. Besides, the thin Al2O3 layer can reduce the charge transfer resistance and stabilize the surface structure of active material during cycling, which is responsible for the improvement of electrochemical performance of the Li-rich Li1.3[Ni0.35Mn0.65]O2+x .  相似文献   

8.
Spherical Li[Ni0.5Mn0.3Co0.2]O2 was prepared by both the continuous hydroxide co-precipitation method and continuous carbonate co-precipitation method under different calcined temperatures. The physical properties and electrochemical behaviors of Li[Ni0.5Mn0.3Co0.2]O2 prepared by two methods were characterized by X-ray diffraction, scanning electron microscope, and electrochemical measurements. It has been found that different preparation methods will result in the differences in the morphology (shape, particle size, and tap density), structure stability, and the electrochemical characteristics (shape of initial charge/discharge curve, cycle stability, and rate capability) of the final product Li[Ni0.5Mn0.3Co0.2]O2. The physical and electrochemical properties of the spherical Li[Ni0.5Mn0.3Co0.2]O2 prepared by continuous hydroxide co-precipitation is apparently superior to the one prepared by continuous carbonate co-precipitation method. The optimal sample prepared by continuous hydroxide co-precipitation at 820 °C exhibits a hexagonally ordered layer structure, high special discharge capacity, good capacity retention, and excellent rate capability. It delivers high initial discharge capacity of 175.2 mAh g?1 at 0.2 C rate between 3.0 and 4.3 V, and the capacity retention of 98.8 % can be maintained after 50 cycles. While the voltage range is broadened up to 2.5 and 4.6 V vs. Li+/Li, the special discharge capacities at 0.2 C, 0.5 C, 1 C, 2 C, 5 C, and 10 C rates are as high as 214.3, 205.0, 198.3, 183.3, 160.1 and 135.2 mAh g?1, respectively.  相似文献   

9.
Pure LiFePO4 and LiNi x Fe1?x PO4/C (x?=?0.00–0.20) nanocomposite cathode materials have been synthesized by cheap and convenient sol–gel-assisted carbothermal reduction method. X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy, and inductively coupled plasma have been used to study the phase, morphology, and chemical composition of un-doped and Ni-doped materials. XRD patterns display the slight shrinkage in crystal lattice of LiFePO4 after Ni2+ doping. The SEM images have revealed that Ni-doped particles are not agglomerated and the particle sizes are practically homogeneously distributed. The particle size is found between 50 and 100 nm for LiNi0.20Fe0.80PO4/C sample. The discharge capacity at 0.2 C rate has increased up to 155 mAh g?1 for the LiNi0.05Fe0.95PO4/C sample and good capacity retention of 99.1 % over 100 cycles, while that of the unsubstituted LiFePO4/C and pure LiFePO4 has showed only 122 and 89 mAh g?1, respectively. Doping with Ni has a noticeable effect on improving its electrical conductivity. However, serious electrochemical declension will occur when its doping density is beyond 0.05 mol LiNi0.20Fe0.80PO4/C electrode shows only 118 mAh g?1, which is less than un-doped LiFePO4/C sample at 0.2 C. The cycling voltammogram demonstrates that Ni-doped LiNi0.05Fe0.95PO4/C electrode has more stable lattice structure, enhanced conductivity, and diffusion coefficient of Li+ ions, in which Ni2+ is regarded to act as a column in crystal lattice structure to prevent the collapse during cycling process.  相似文献   

10.
The parameters of synthesis by the spray method of cathode materials Li1.2Ni0.13Co0.13Mn0.54O2 and Li1.25Ni0.12Co0.12Mn0.51O2, differing in lithium content were studied. The phase and granulometric composition, the morphology of the powder particles obtained, as well as an influence of temperature, total metal concentration, and pH of the solution on the properties of powders of cathode materials were studied. The discharge capacities of the obtained materials reached 260 mAh g?1 in the range of 2.5?4.8 V.  相似文献   

11.
The cathode-active materials, layered Li[Ni0.6Co0.2Mn0.2]O2, were synthesized by two different routes: spray-drying and solid-state methods. The influence of synthesis routes on the crystal structure, morphology, and electrochemical performance of the samples were characterized by X-ray diffraction, scanning electron microscope, and charge/discharge test. As a result, both samples showed a typical hexagonal structure with a single phase. However, the difference in synthesis route resulted in the difference in morphology and electrochemical performance, such as reversible capacity and the rate capability. The initial discharge capacity of sample synthesized by spray-drying method at room temperature and 50 °C were 173.1 and 181.2 mAh g?1, respectively, which were higher than those of 166.8 and 177.5 mAh g?1 for sample synthesized by solid-state method. The cycling performance was also evaluated. Sample synthesized by spray-drying method exhibits a higher discharge capacity and better cycling performance than those prepared by solid-state method, even at elevated temperature.  相似文献   

12.
Lithium-rich manganese oxide (Li2MnO3) is prepared by reverse microemulsion method employing Pluronic acid (P123) as a soft template and studied as a positive electrode material. The as-prepared sample possesses good crystalline structure with a broadly distributed mesoporosity but low surface area. As expected, cyclic voltammetry and charge–discharge data indicate poor electrochemical activity. However, the sample gains surface area with narrowly distributed mesoporosity and also electrochemical activity after treating in 4 M H2SO4. A discharge capacity of about 160 mAh g?1 is obtained. When the acid-treated sample is heated at 300 °C, the resulting porous sample with a large surface area and dual porosity provides a discharge capacity of 240 mAh g?1. The rate capability study suggests that the sample provides about 150 mAh g?1 at a specific discharge current of 1.25 A g?1. Although the cycling stability is poor, the high rate capability is attributed to porous nature of the material.  相似文献   

13.
Single-crystal magnesium-doped spinel lithium manganate cathode materials are prepared by the hydrothermal method followed by the heat treatment. XRD patterns reveal that Mg2+ions have already diffused into the Li1.088Mn1.912O4 crystal structure and not affect the Fd3m space group. SEM images demonstrate that the magnesium-doped spinel lithium manganates show uniform polyhedral single crystals with 2–4 μm. Electrochemical performance demonstrates that the optimized composition of Li1.088Mg0.070Mn1.842O4 electrode exhibits the best electrochemical properties. It delivers 92.0 mAh g?1 at 8C rates and corresponds to 90.8% capacity retention (vs. 1C), far higher than those of the pristine electrode (70.4 mAh g?1 and 69.2%). In addition, the Li1.088Mg0.070Mn1.842O4 electrode also shows 95.5% capacity retention after 100 cycles at 1C, while the pristine electrode only shows 91.0% capacity retention. The excellent electrochemical performances of Li1.088Mg0.070Mn1.842O4 electrode are ascribed to the suppressed polarization, more stable crystal structure, and better kinetic characteristics.  相似文献   

14.
Natural graphite treated by mechanical activation can be directly applied to the preparation of Li3V2(PO4)3. The carbon-coated Li3V2(PO4)3 with monoclinic structure was successfully synthesized by using natural graphite as carbon source and reducing agent. The amount of activated graphite is optimized by X-ray diffraction, scanning electron microscope, transmission electron microscope, Raman spectrum, galvanostatic charge/discharge measurements, cyclic voltammetry, and electrochemical impedance spectroscopy tests. Our results show that Li3V2(PO4)3 (LVP)-10G exhibits the highest initial discharge capacity of 189 mAh g?1 at 0.1 C and 162.9 mAh g?1 at 1 C in the voltage range of 3.0–4.8 V. Therefore, natural graphite is a promising carbon source for LVP cathode material in lithium ion batteries.  相似文献   

15.
Porous structure Li[Ni1/3Co1/3Mn1/3]O2 has been synthesized via a facile carbonate co‐precipitation method using Li2CO3 as template and lithium‐source. The physical and electrochemical properties of the materials were examined by many characterizations including TGA, XRD, SEM, EDS, TEM, BET, CV, EIS and galvanostatic charge‐discharge cycling. The results indicate that the as‐synthesized materials by this novel method own a well‐ordered layered structure α‐NaFeO2 [space group: R‐3m(166)], porous morphology, and an average primary particle size of about 150 nm. The porous material exhibits larger specific surface area and delivers a high initial capacity of 169.9 mAh·g?1 at 0.1 C (1 C=180 mA·g?1) between 2.7 and 4.3 V, and 126.4, 115.7 mAh·g?1 are still respectively reached at high rate of 10 C and 20 C. After 100 charge‐discharge cycles at 1 C, the capacity retention is 93.3%, indicating the excellent cycling stability.  相似文献   

16.
Li4Ti5O12/Li2TiO3 composite nanofibers with the mean diameter of ca. 60 nm have been synthesized via facile electrospinning. When the molar ratio of Li to Ti is 4.8:5, the Li4Ti5O12/Li2TiO3 composite nanofibers exhibit initial discharge capacity of 216.07 mAh g?1 at 0.1 C, rate capability of 151 mAh g?1 after being cycled at 20 C, and cycling stability of 122.93 mAh g?1 after 1000 cycles at 20 C. Compared with pure Li4Ti5O12 nanofibers and Li2TiO3 nanofibers, Li4Ti5O12/Li2TiO3 composite nanofibers show better performance when used as anode materials for lithium ion batteries. The enhanced electrochemical performances are explained by the incorporation of appropriate Li2TiO3 which could strengthen the structure stability of the hosted materials and has fast Li+-conductor characteristics, and the nanostructure of nanofibers which could offer high specific area between the active materials and electrolyte and shorten diffusion paths for ionic transport and electronic conduction. Our new findings provide an effective synthetic way to produce high-performance Li4Ti5O12 anodes for lithium rechargeable batteries.  相似文献   

17.
Li3Ni x V2?x (PO4)3/C (x?=?0, 0.02, 0.04 and 0.06) samples have been synthesized via an improved sol–gel method. X-ray diffraction patterns indicate that the structure of the prepared samples retains monoclinic, and the single phase has not been changed with Ni doping. From the analysis of electrochemical performance, the Li3Ni0.04?V1.96(PO4)3/C sample exhibits the best electrochemical property. It delivers a discharge capacity of 112.1 mAh?g?1 with capacity retention of 95.2 % over 300 cycles at 10 C rate in the range of 3.0–4.8 V; cyclic voltammetry and electrochemical impedance spectra testing further prove that the electrochemical reversibility and lithium ion diffusion behavior of Li3V2(PO4)3 have also been effectively improved through Ni doping.  相似文献   

18.
Although LiFePO4 (LFP) is considered to be a potential cathode material for the lithium-ion batteries, its rate performance is significantly restricted by sluggish kinetics of electrons and lithium ions. Several attempts have been made so far to improve the performance of LiFePO4 by reducing the grain size, doping with aliovalent atoms, and coating conductive materials such as carbon or RuO2. We report here synthesis of LFP nanoplates by solvothermal method, tailoring the thickness as well as carbon coverage at surfaces to explore their influence on the storage performance. Due to the fact that Li+ ion diffuses along the b-axis, solvothermal method was aimed to control the thickness of nanoplates across the b-axis. We synthesized several nanoplates with various plate thicknesses along b-axis; among those, nanoplates of LFP with ~30-nm-thick b-axis having thin (2–5 nm) and uniform layer of carbon coating exhibits high storage capacity as well as high rate performances. Thus, a favorable morphology for LiFePO4 has been achieved via solvothermal method for fast insertion/extraction of Li+ as compared to spherical nanoparticles of carbon-coated LFP. Galvanostatic cycling shows a capacity of 164?±?5 mAh g?1 at 0.1 C rate, 100?±?5 mAh g?1 at 10 C rate, and 46?±?5 mAh g?1 at 30 C rate, with excellent capacity retention of up to 50 cycles. Further attempts have been made to synthesize LiMnPO4 (LMP) as well as Li(Fe1???x Mn x )PO4/C (x?=?0.5) nanoplates using solvothermal method. Although LiMnPO4 does not exhibit high storage behavior comparable with that of LiFePO4, the mixed systems have shown an impressive storage performance.  相似文献   

19.
The electrochemical properties of LaY2Ni9 alloy used as an anode in nickel-metal hydride batteries were investigated at ambient and at different temperatures. Several techniques, such as the galvanostatic charging and discharging, the constant potential discharge, and the potentiodynamic polarization, were applied to characterize these electrochemical properties. The discharge capacity of the LaY2Ni9 alloy increases to reach 258 mAh g?1 after 5 cycles and decreases to 140 mAh g?1 after 100 cycles then stabilizes around this same value indicating good cycling held. The hydrogen diffusion coefficient D H in the bulky alloy is estimated to be (1.02?±?0.11)?×?10?11 cm2 s?1 correlated with the good stability of electrochemical capacity after 100 cycles. The evolution of the ratio \( \frac{D_{\mathrm{H}}}{a^2} \) and the corrosion current density and potential are correlated with the evolution of the electrochemical capacity during the activation and for a long cycling. The enthalpy, the entropy, and the apparent activation energy of the LaY2Ni9 hydride formation are evaluated. The calculated results show that the enthalpy change, the entropy change, and the activation energy are (?42.64?±?1.08), (56.85?±?2.11), and (14.84?±?0.35)?kJ mol?1, respectively.  相似文献   

20.
通过共沉淀法制备锂离子电池富锂锰基正极材料Li1.2Mn0.534Ni0.133Co0.133O2,并对其进行AlF3包覆。实验结果表明,通过AlF3包覆,材料的电化学性能得到明显提高。在0.2C下,包覆前材料的首次放电比容量为253 mAh.g-1,首次充放电效率仅为88.8%。经过AlF3包覆,材料的首次放电比容量提高到294 mAh.g-1,首次充放电效率高达96.4%。同样,在1.0C下循环50次,未包覆材料的放电比容量由225 mAh.g-1降到185 mAh.g-1,容量保持率仅为82.2%。经过AlF3包覆,材料的放电比容量由230mAh.g-1仅降为222 mAh.g-1,容量保持率高达96.5%。  相似文献   

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