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1.
The carbon-coated Li[Ni1/3Co1/3Mn1/3]O2 was synthesized from the porous Li[Ni1/3Co1/3Mn1/3]O2 precursor using citric acid as the carbon source. The electrochemical results showed that both cycling performance and rate capability were improved by the carbon-coating of the Li[Ni1/3Co1/3Mn1/3]O2 materials. It is proposed that the enhanced electrochemical properties by the carbon-coating are attributed to the increased electronic conductivity because the carbon distributed among the surfaces of spherical Li[Ni1/3Co1/3Mn1/3]O2 powders favored the transference of electron and reduced cell polarization.  相似文献   

2.
Layered LiNi0.4Co0.2Mn0.4O2, Li[Li0.182Ni0.182Co0.091Mn0.545]O2, Li[Li1/3Mn2/3]O2 powder materials were prepared by rheological phase method. XRD characterization shows that these samples all have analogous structure to LiCoO2. Li[Li0.182Ni0.182Co0.091Mn0.545]O2 can be considered to be the solid solution of LiNi0.4Co0.2Mn0.4O2 and Li[Li1/3Mn2/3]O2. Detailed information from XRD, ex situ XPS measurement and electrochemical analysis of these three materials reveals the origin of the irreversible plateau (4.5 V) of Li[Li0.182Ni0.182Co0.091Mn0.545]O2 electrode. The irreversible oxidation reaction occurred in the first charging above 4.5 V is ascribed to the contribution of Li[Li1/3Mn2/3]O2 component, which maybe extract Li+ from the transition layer in Li[Li1/3Mn2/3]O2 or Li[Li0.182Ni0.182Co0.091Mn0.545]O2 through oxygen release. This step also activates Mn4+ of Li[Li1/3Mn2/3]O2 or Li[Li0.182Ni0.182Co0.091Mn0.545]O2, it can be reversibly reduced/oxidized between Mn4+ and Mn3+ in the subsequent cycles.  相似文献   

3.
Layered transition metal oxide LiNi x Co y MnzO2 cathode materials with different Li amount were successfully synthesized via co-precipitation method. Monodispersed Li[Ni0.5Co0.2Mn0.3]O2 and Li-rich Li1.1[Ni0.5Co0.2Mn0.3]O2 spherical agglomeration consisted of secondary particles, which is favorable for the higher tap-density of materials, can be easily obtained. The pouch-typed cells with obtained materials were assembled to investigate electrochemical performance at level of full-cell. The results show that the assembled pouch-typed full-cells with Li-rich sample present higher capacity, better rate capability and cycle life.  相似文献   

4.
To improve the electrochemical properties of Li[Ni1/3Co1/3Mn1/3]O2 at high charge end voltage (4.6 V), a series of the mixed transition metal compounds, Li(Ni1/3Co1/3 − x Mn1/3M x )O2 (M = Mg, Cr, Al; x = 0.05), were synthesized via hydroxide coprecipitation method. The effects of doping Mg, Cr, and Al on the structure and the electrochemical performances of Li[Ni1/3Co1/3Mn1/3]O2 were compared by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), galvanostatic charge–discharge tests, and electrochemical impedance spectroscopy. The XRD results show that all the samples keep layered structures with R3m space group as the Li[Ni1/3Co1/3Mn1/3]O2. SEM images show that all the compounds have spherical shapes and the Cr-doped sample has the largest particle size. Furthermore, galvanostatic charge–discharge tests confirm that the Cr-doped electrode shows improved cycling performance than the undoped material. The capacity retention of Li(Ni1/3Co1/3 − 0.05Mn1/3Cr0.05)O2 is 97% during 50 cycles at 2.8∼4.6 V. The improved cycling performance at high voltage can be attributed to the larger particle size and the prevention of charge transfer resistance (R ct) increase during cycling.  相似文献   

5.
A series of the mixed transition metal compounds, Li[(Ni1/3Co1/3Mn1/3)1–x-y Al x B y ]O2-z F z (x = 0, 0.02, y = 0, 0.02, z = 0, 0.02), were synthesized via coprecipitation followed by a high-temperature heat-treatment. XRD patterns revealed that this material has a typical α-NaFeO2 type layered structure with R3- m space group. Rietveld refinement explained that cation mixing within the Li(Ni1/3Co1/3Mn1/3)O2 could be absolutely diminished by Al-doping. Al, B and F doped compounds showed both improved physical and electrochemical properties, high tap-density, and delivered a reversible capacity of 190 mAh/g with excellent capacity retention even when the electrodes were cycled between 3.0 and 4.7 V.  相似文献   

6.
Layered Li[Li0.16Ni0.21Mn0.63]O2 and Li[Li0.2Ni0.2Mn0.6]O2 compounds were successfully synthesized by radiated polymer gel (RPG) method. The effect of deficient Li on the structure and electrochemical performance was investigated by means of X-ray diffraction, X-ray absorption near-edge spectroscopy and electrochemical cell cycling. The reduced Ni valence in Li[Li0.16Ni0.21Mn0.63]O2 leads to a higher capacity owing to faster Li+ chemical diffusivity relative to the baseline composition Li[Li0.2Ni0.2Mn0.6]O2. Cyclic voltammograms (CV) and a simultaneous direct current (DC) resistance measurement were also performed on Li/Li[Li0.16Ni0.21Mn0.63]O2 and Li/Li[Li0.2Ni0.2Mn0.6]O2 cells. Li[Li0.16Ni0.21Mn0.63]O2 shows better electrochemical performance with a reversible capacity of 158 mA hg−1 at 1C rate at 20 °C.  相似文献   

7.
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   

8.
The effect of the lithium boron oxide glass coating on the electrochemical performance of LiNi1/3Co1/3Mn1/3O2 has been investigated via solution method. The morphology, structure, and electrochemical properties of the bare and coated LiNi1/3Co1/3Mn1/3O2 are characterized by scanning electron microscopy, X-ray diffraction, electrochemical impedance spectroscopy, and charge–discharge tests. The results showed that the lattice structure of LiNi1/3Co1/3Mn1/3O2 is not changed after coating. The coating sample shows good high-rate discharge performance (148 mAh g−1 at 5.0 C rate) and cycling stability even at high temperature (with the capacities retention about 99% and 87% at room and elevated temperature after 50 cycles). The Li+ diffusion coefficient is also largely improved, while the charge transfer resistance, side reactions within cell, and the erosion of Hydrofluoric Acid all reduced. Consequently, the good electrochemical performances are obtained.  相似文献   

9.
Cathode materials Li[CoxMn1−x]O2 for lithium secondary batteries have been prepared by a new route—precursor method of layered double hydroxides (LDHs). In situ high-temperature X-ray diffraction (HT-XRD) and thermogravimetric analysis coupled with mass spectrometry (TG-MS) were used to monitor the structural transformation during the reaction of CoMn LDHs and LiOH·H2O: firstly the layered structure of LDHs transformed to an intermediate phase with spinel structure; then the distortion of the structure occurred with the intercalation of Li+ into the lattice, resulting in the formation of layered Li[CoxMn1−x]O2 with α-NaFeO2 structure. Extended X-ray absorption fine structure (EXAFS) data showed that the Co-O bonding length and the coordination number of Co were close to those of Mn in Li[CoxMn1−x]O2, which indicates that the local environments of the transitional metals are rather similar. X-ray photoelectron spectroscopy (XPS) was used to measure the oxidation state of Co and Mn. The influences of Co/Mn ratio on both the structure and electrochemical property of Li[CoxMn1−x]O2 have been investigated by XRD and electrochemical tests. It has been found that the products synthesized by the precursor method demonstrated a rather stable cycling behavior, with a reversible capacity of 122.5 mAh g−1 for the layered material Li[Co0.80Mn0.20]O2.  相似文献   

10.
Layered LiNi1/3Co1/3Mn1/3O2 nanoparticles were prepared by modified Pechini method and used as cathode materials for Li-ion batteries. The pyrolytic behaviors of the foamed precursors were analyzed by use of simultaneous thermogravimetric and differential thermal analysis (TG-DTA). Structure, morphology and electrochemical performance characterization of the samples were investigated by X-ray diffraction (XRD), field emission scanning electron macroscopy(SEM), Brunauer-Emmett-Teller (BET) specific surface area and charge–discharge tests. The results showed that the samples prepared by modified Pechini method caclined at 900 °C for 10 h were indexed to pure LiNi1/3Co1/3Mn1/3O2 with well hexagonal structure. The particle size was in a range of 100–300 nm. The specific surface area was larger than that of the as-obtained sample by Pechini method. Initial discharge capacity of 163.8 mAh/g in the range 2.8–4.4 V (vs. Li/Li+) and at 0.1C for LiNi1/3Co1/3Mn1/3O2 prepared by modified Pechini method was obtained, higher than that of the sample prepared by Pechini method (143.5 mAh/g). Moreover, the comparison of electrochemical results at different current rates indicated that the sample prepared by modified Pechini method exhibited improved rate capability.  相似文献   

11.
The reactions of the oxalate complexes [M3Q7(C2O4)3]2− (M = Mo or W; Q = S or Se) with MnII, CoII, NiII, and CuII aqua and ethylenediamine complexes in aqueous and aqueous ethanolic solutions were studied. The previously unknown heterometallic complexes [Mo3Se7(C2O4)3Ni(H2O)5]·3.5H2O (1) and K3{[Cu(en)2H2O]([Mo3S7(ox)3]2Br)}·5.5H2O (2) were synthesized. In these complexes, the oxalate clusters serve as monodentate ligands. The K(H2en)2[W3S7(C2O4)3]2Br·4H2O salt (3) was isolated from solutions containing CoII, NiII, or CuII aqua complexes and ethylenediamine. The reaction of [Mo3Se7(C2O4)3]2− with HBr produced the bromide complex [Mo3Se7Br6]2−, which was isolated as (Bu4N)2[Mo3Se7Br6] (4). Complexes 1–3 were characterized by X-ray diffraction, IR spectra, and elemental analysis. The formation of 4 was detected by electrospray mass spectrometry. Dedicated to Academician G. A. Abakumov on the occasion of his 70th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1645–1649, September, 2007.  相似文献   

12.
As a promising Li-ion battery cathode active material, lithium-rich manganese-based layer-structured oxides suffer from inferior cycle performance and poor rate capability. Herein, Nb-doped Li1.2Mn0.54Ni0.13Co0.13O2 is prepared by a sol-gel method, and the effects of Nb doping on its electrochemical performance are investigated. It is concluded that the Nb-doped Li1.2Mn0.54Ni0.13Co0.13O2, has a good layered structure along c-axis independent on the amount of Nb dopant and little cationic mixing. Nb doping for Li1.2Mn0.54Ni0.13Co0.13O2 has no obvious influence on its morphology. It is found that Nb doping can enhance the electrochemical activity of Li1.2Mn0.54Ni0.13Co0.13O2, such as improved rate performance and cycle performance under high rate conditions. Li1.2Mn0.54Ni0.13Co0.13O2 doped with 0.015 Nb shows the best cycle performance under the high rate with the capacity maintenance of 95.4% after 100 cycles under 5 C rate, which is higher than that of the undoped one by 10.5%.
Graphical abstract Rate performance of Li1.2Mn0.54-xCo0.13Ni0.13Nb x O2 materials
  相似文献   

13.
采用碳酸钠和碳酸氢铵作为沉淀剂和络合剂,在水溶液中共沉淀Mn2+、Ni2+和Co2+以获得混合过渡金属元素的碳酸盐沉淀前驱体Mn0.675Ni0.1625Co0.1625CO3。并进一步合成高容量锂离子电池正极材料Li[Li0.2Co0.13Ni0.13Mn0.54]O2。考察了3种不同加料方式对共沉淀前驱体的结构、形貌和元素比例的影响,以及对最终产物的结构、形貌和电化学性能的影响。  相似文献   

14.
Nano-structured spinel Li2Mn4O9 powder was prepared via a combustion method with hydrated lithium acetate (LiAc·2H2O), manganese acetate (MnAc2·4H2O), and oxalic acid (C2H2O4·2H2O) as raw materials, followed by calcination of the precursor at 300 °C. The sample was characterized by X-ray diffraction, scanning electron microscope, and energy-dispersive X-ray spectroscopy techniques. Electrochemical performance of the nano-Li2Mn4O9 material was studied using cyclic voltammetry, ac impedance, and galvanostatic charge/discharge methods in 2 mol L−1 LiNO3 aqueous electrolyte. The results indicated that the nano-Li2Mn4O9 material exhibited excellent electrochemical performance in terms of specific capacity, cycle life, and charge/discharge stability, as evidenced by the charge/discharge results. For example, specific capacitance of the single Li2Mn4O9 electrode reached 407 F g−1 at the scan rates of 5 mV s−1. The capacitor, which is composed of activated carbon negative electrode and Li2Mn4O9 positive electrode, also exhibits an excellent cycling performance in potential range of 0–1.6 V and keeps over 98% of the maximum capacitance even after 4,000 cycles.  相似文献   

15.
Li[Ni1/3Co1/3Mn1/3]O2 (NCM 111) is a promising alternative to LiCoO2, as it is less expensive, more structurally stable, and has better safety characteristics. However, its capacity of 155 mAh g?1 is quite low, and cycling at potentials above 4.5 V leads to rapid capacity deterioration. Here, we report a successful synthesis of lithium-rich layered oxides (LLOs) with a core of LiMO2 (R-3m, M?=?Ni, Co) and a shell of Li2MnO3 (C2/m) (the molar ratio of Ni, Co to Mn is the same as that in NCM 111). The core–shell structure of these LLOs was confirmed by XRD, TEM, and XPS. The Rietveld refinement data showed that these LLOs possess less Li+/Ni2+ cation disorder and stronger M*–O (M*?=?Mn, Co, Ni) bonds than NCM 111. The core–shell material Li1.15Na0.5(Ni1/3Co1/3)core(Mn1/3)shellO2 can be cycled to a high upper cutoff potential of 4.7 V, delivers a high discharge capacity of 218 mAh g?1 at 20 mA g?1, and retains 90 % of its discharge capacity at 100 mA g?1 after 90 cycles; thus, the use of this material in lithium ion batteries could substantially increase their energy density.
Graphical Abstract Average voltage vs. number of cycles for the core–shell and pristine materials at 20 mA g?1 for 10 cycles followed by 90 cycles at 100 mA g?1
  相似文献   

16.
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   

17.
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   

18.
In this paper, ZnO was applied to modify the surface of LiNi1/3Co1/3Mn1/3O2 cathode material by a simple method. Powder X-ray diffraction (XRD) results show that both of the pristine material and the modified material were well crystallized and closely similar to each other. The crystal parameters of pristine material increased by modified measure. Scan electron microscope (SEM) pictures exhibit that the quasispherical pristine material was modified to the squareness one. Transmission electron microscope (TEM) image clearly elucidates that ZnO (several nanometers to 20 nm) was successful coated on surface of LiNi1/3Co1/3Mn1/3O2. X-ray photo-electron spectrometry (XPS) is used to characterize the composite of the coating layer on the surface of modified material. Electrochemical performance results present that the ZnO coating layer decrease the initial capacities of LiNi1/3Co1/3Mn1/3O2 by increasing the surface layer resistances. However, the cycling performance of LiNi1/3Co1/3Mn1/3O2 was effectively improved by the ZnO coating layer.  相似文献   

19.
LiNi1/3Co1/3Mn1/3O2 cathode materials for the application of lithium ion batteries were synthesized by carbonate co-precipitation routine using different ammonium salt as a complexant. The structures and morphologies of the precursor [Ni1/3Co1/3Mn1/3]CO3 and LiNi1/3Co1/3Mn1/3O2 were investigated through X-ray diffraction, scanning electron microscope, and transmission electron microscopy. The electrochemical properties of LiNi1/3Co1/3Mn1/3O2 were examined using charge/discharge cycling and cyclic voltammogram tests. The results revealed that the microscopic structures, particle size distribution, and the morphology properties of the precursor and electrochemical performance of LiNi1/3Co1/3Mn1/3O2 were primarily dependent on the complexant. Among all as-prepared LiNi1/3Co1/3Mn1/3O2 cathode materials, the sample prepared from Na2CO3–NH4HCO3 routine using NH4HCO3 as the complexant showed the smallest irreversible capacity of 19.5 mAh g−1 and highest discharge capacity of 178.4 mAh g−1 at the first cycle as well as stable cycling performance (98.7% of the initial capacity was retained after 50 cycles) at 0.1 C (20 mA g−1) in the voltage range of 2.5–4.4 V vs. Li+/Li. Moreover, it delivered high discharge capacity of over 135 mAh g−1 at 5 C (1,000 mA g−1).  相似文献   

20.
采用喷雾干燥法合成了富锂层状氧化物正极材料0.6Li[Li1/3Mn2/3]O2·0.4LiNi5/12Mn5/12Co1/6O2(简称LNMCO),并使用Zr (CH3COO)4进行ZrO2的包覆改性。TEM测试结果显示纳米级的ZrO2颗粒附着在LNMCO的表面。包覆质量分数为1.5%的ZrO2包覆样品的首圈库伦效率和放电比容量有着显著提升,在室温下其首圈库伦效率和放电比容量(电流密度:20 mA·g-1,电压:2.0~4.8 V)分别为87.2%,279.3 mAh·g-1,而原样则为75.1%,224.1 mAh·g-1,循环100圈之后,1.5% ZrO2包覆样品的放电比容量为248.3 mAh·g-1,容量保持率为88.9%,高于原样的195.9 mAh·g-1和87.4%。  相似文献   

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