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1.
Electrochemical and thermal properties of Co3(PO4)2- and AlPO4-coated LiNi0.8Co0.2O2 cathode materials were compared. AlPO4-coated LiNi0.8Co0.2O2 cathodes exhibited an original specific capacity of 170.8 mAh g−1 and had a capacity retention (89.1% of its initial capacity) between 4.35 and 3.0 V after 60 cycles at 150 mA g−1. Co3(PO4)2-coated LiNi0.8Co0.2O2 cathodes exhibited an original specific capacity of 177.6 mAh g−1 and excellent capacity retention (91.8% of its initial capacity), which was attributed to a lithium-reactive Co3(PO4)2 coating. The Co3(PO4)2 coating material could react with LiOH and Li2CO3 impurities during annealing to form an olivine LixCoPO4 phase on the bulk surface, which minimized any side reactions with electrolytes and the dissolution of Ni4+ ions compared to the AlPO4-coated cathode. Differential scanning calorimetry results showed Co3(PO4)2-coated LiNi0.8Co0.2O2 cathode material had a much improved onset temperature of the oxygen evolution of about 218 °C, and a much lower amount of exothermic-heat release compared to the AlPO4-coated sample.  相似文献   

2.
N Sharma 《Electrochimica acta》2004,49(7):1035-1043
The electrochemical performance of mixed oxides, Ca2Fe2O5 and Ca2Co2O5 for use in Li-ion batteries was studied with Li as the counter electrode. The compounds were prepared and characterized by X-ray diffraction and SEM. Ca2Fe2O5 showed a reversible capacity of 226 mAh/g at the 14th cycle and retained 183 mAh/g at the end of 50 cycles at 60 mA/g in the voltage window 0.005-2.5 V. A reversible capacity in the range, 365-380 mAh/g, which is stable up to 50 charge-discharge cycles is exhibited by Ca2Co2O5 in the voltage window, 0.005-3.0 V and at 60 mA/g. This corresponds to recycleable moles of Li of 3.9±0.1 (theoretical: 4.0). Significant improvement in the cycling performance and attainable reversible capacity were noted for Ca2Co2O5 on cycling to an upper cut-off voltage of 3.0 V as compared to 2.5 V. Coulombic efficiency for both compounds is >98%. Electrochemical impedance spectroscopy (EIS) data clearly indicate the reversible formation/decomposition of polymeric surface film on the electrode surface of Ca2Co2O5 in the voltage window, 0.005-3.0 V. Cyclic voltammetry results compliment the galvanostatic cycling data.  相似文献   

3.
Layered metastable lithium manganese oxides, Li2/3[Ni1/3−xMn2/3−yMx+y]O2 (x = y = 1/36 for M = Al, Co, and Fe and x = 2/36, y = 0 for M = Mg) were prepared by the ion exchange of Li for Na in P2-Na2/3[Ni1/3−xMn2/3−yMx+y]O2 precursors. The Al and Co doping produced the T#2 structure with the space group Cmca. On the other hand, the Fe and Mg doped samples had the O6 structure with space group R-3m. Electron diffraction revealed the 1:2 type ordering within the Ni1/3−xMn2/3−yMx+yO2 slab. It was found that the stacking sequence and electrochemical performance of the Li cells containing T#2-Li2/3[Ni1/3Mn2/3]O2 were affected by the doping with small amounts of Al, Co, Fe, and Mg. The discharge capacity of the Al doped sample was around 200 mAh g−1 in the voltage range between 2.0 and 4.7 V at the current density of 14.4 mA g−1 along with a good capacity retention. Moreover, for the Al and Co doped and undoped oxides, the irreversible phase transition of the T#2 into the O2 structure was observed during the initial lithium deintercalation.  相似文献   

4.
Cathode active materials with a composition of LiNi0.9Co0.1O2 were synthesized by a solid-state reaction method at 850 °C using Li2CO3, NiO or NiCO3, and CoCO3 or Co3O4, as the sources of Li, Ni, and Co, respectively. Electrochemical properties, structure, and microstructure of the synthesized LiNi0.9Co0.1O2 samples were analyzed. The curves of voltage vs. x in LixNi0.9Co0.1O2 for the first charge–discharge and the intercalated and deintercalated Li quantity Δx were studied. The destruction of unstable 3b sites and phase transitions were discussed from the first and second charge–discharge curves of voltage vs. x in LixNi0.9Co0.1O2. The LiNi0.9Co0.1O2 sample synthesized from Li2CO3, NiO, and Co3O4 had the largest first discharge capacity (151 mA h/g), with a discharge capacity deterioration rate of −0.8 mA h/g/cycle (that is, a discharge capacity increasing 0.8 mA h/g per cycle).  相似文献   

5.
Non-spherical Li(Ni1/3Co1/3Mn1/3)O2 powders have been synthesized using a two-step drying method with 5% excess LiOH at 800 °C for 20 h. The tap-density of the powder obtained is 2.95 g cm−3. This value is remarkably higher than that of the Li(Ni1/3Co1/3Mn1/3)O2 powders obtained by other methods, which range from 1.50 g cm−3 to 2.40 g cm−3. The precursor and Li(Ni1/3Co1/3Mn1/3)O2 are characterized by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and scanning electron microscope (SEM). XPS studies show that the predominant oxidation states of Ni, Co and Mn in the precursor are 2+, 3+ and 4+, respectively. XRD results show that the Li(Ni1/3Co1/3Mn1/3)O2 material obtained by the two-step drying method has a well-layered structure with a small amount of cation mixing. SEM confirms that the Li(Ni1/3Co1/3Mn1/3)O2 particles obtained by this method are uniform. The initial discharge capacity of 167 mAh g−1 is obtained between 3 V and 4.3 V at a current of 0.2 C rate. The capacity of 159 mAh g−1 is retained at the end of 30 charge-discharge cycle with a capacity retention of 95%.  相似文献   

6.
A series of ZnxMg1 − xGa2O4:Co2+ spinels (x = 0, 0.25, 0.5, 0.75, and 1.0) was successfully produced through low-temperature burning method by using Mg(NO3)2·4H2O, Zn(NO3)2·6H2O, Ga(NO3)3·6H2O, CO(NH2)2, NH4NO3, and Co(NO3)2·6H2O as raw materials. The product was characterized by X-ray diffraction, transmission electron microscopy, and photoluminescence spectroscopy. The product was not merely a simple mixture of MgGa2O4 and ZnGa2O4; rather, it formed a solid solution. The lattice constant of ZnxMg1 − xGa2O4:Co2+ (0 ≤ x ≤ 1.0) crystals has a good linear relationship with the doping density, x. The synthesized products have high crystallinities with neat arrays. Based on an analysis of the form and position of the emission spectrum, the strong emission peak around the visible region (670 nm) can be attributed to the energy level transition [4T1(4P) → 4A2(4F)] of Co2+ in the tetrahedron. The weak emission peak in the near-infrared region can be attributed to the energy level transition [4T1(4P) → 4T2(4F)] of Co2+ in the tetrahedron.  相似文献   

7.
The stability of one material, Ti/CuxCo3−xO4, as anode and also cathode was investigated for electrolysis of alkaline aqueous solution. The electrodes were prepared by thermal decomposition method with x varied from 0 to 1.5. The accelerated life test illustrated that the electrodes with x = 0.3 nominally showed the best performance, with a total service life of 1080 h recorded in 1 M NaOH solution under alternating current direction at 1 A cm−2 and 35 °C. The effects of copper content in electrode coating were examined in terms of electrode stability, surface morphology, coating resistivity and coating compositions. The presence of Cu in the spinel structure of Co3O4 could significantly enhance the electrochemical and physicochemical properties. The trends of crystallographic properties and surface morphology have been analyzed systemically before, during and after the electrodes were employed in alkaline electrolysis. The oxygen evolution would lead to the consumption of the coating material and the progressive cracking of the coating. Along with hydrogen evolution, cobalt oxide could be reduced to metal Co and Co(OH)2 with particle sizes changed to smaller values in crystal and/or amorphous form at the cathode. The formation of Co is the key process for this electrode to serve as both anode and cathode. It is also the main reason leading to the eventual failure of the electrodes.  相似文献   

8.
In this work, treatment of an azo dye solution containing C.I. Basic Red 46 (BR46) by photoelectro-Fenton (PEF) combined with photocatalytic process was studied. Carbon nanotube-polytetrafluoroethylene (CNT-PTFE) electrode was used as cathode. The investigated photocatalyst was TiO2 nanoparticles (Degussa P25) having 80% anatase and 20% rutile, specific surface area (BET) 50 m2/g, and particle size 21 nm immobilized on glass plates. A comparison of electro-Fenton (EF), UV/TiO2, PEF and PEF/TiO2 processes for decolorization of BR46 solution was performed. Results showed that color removal follows the decreasing order: PEF/TiO2 > PEF > EF > UV/TiO2. The influence of the basic operational parameters such as initial pH of the solution, initial dye concentration, the size of anode, applied current, kind of ultraviolet (UV) light and initial Fe3+ concentration on the degradation efficiency of BR46 was studied. The mineralization of the dye was investigated by total organic carbon (TOC) measurements that showed 98.8% mineralization of 20 mg/l dye at 6 h using PEF/TiO2 process. An artificial neural network (ANN) model was developed to predict the decolorization of BR46 solution. The findings indicated that artificial neural network provided reasonable predictive performance (R2 = 0.986).  相似文献   

9.
A crystalline LiNi0.65Co0.25Mn0.10O2 electrode material was synthesized by the combustion method at 900 °C for 1 h. Rietveld refinement shows less than 3% of Li/Ni disorder in the structure. Lithium extraction involves only the Ni2+/Ni4+ redox couple while Co3+ and Mn4+ remain electrochemically inactive. No structural transition was detected during cycling in the whole composition range 0 < x < 1.0. Furthermore, the hexagonal cell volume changes by only 3% when all lithium was removed indicating a good mechanical stability of the studied compound. LiNi0.65Co0.25Mn0.10O2 has a discharge capacity of 150 mAh/g in the voltage range 2.5-4.5 V, but the best electrochemical performance was obtained with an upper cut-off potential of 4.3 V. Magnetic measurements reveal competing antiferromagnetic and ferromagnetic interactions - varying in strength as a function of lithium content - yielding a low temperature magnetically frustrated state. The evolution of the magnetic properties with lithium content confirms the preferential oxidation of Ni ions compared to Co3+ and Mn4+ during the delithiation process.  相似文献   

10.
Columbite MgNb2O6 (MN) and ZnNb2O6 (ZN) ceramics produced by the reaction-sintering process were investigated. Secondary phases Mg0.652Nb0.598O2.25 and Mg0.66Nb11.33O29 were found in MgNb2O6 pellets. After 1250 °C sintering for 2 h, a density 4.85 g/cm3 (97.1% of the theoretical value) was obtained in MgNb2O6 pellets. In ZnNb2O6 pellets, no secondary phase formed. The maximum density 5.55 g/cm3 (98.7% of the theoretical value) occurs at 1200 and 1180 °C sintering for 2 and 4 h, respectively.  相似文献   

11.
Ultrafine powders of LiCoO2, nonstoichiometric LiNiO2 and LiNi0.9Co0.1O2 were prepared under mild hydrothermal conditions. The influence of the molar ratio of Li/Co, Li/Ni and Li/(Ni + Co) was studied. The final products were investigated by XRD, TEM and EDS. To synthesize a stoichiometric LiNiO2 under mild hydrothermal conditions was found to be a big challenge. Transmission electron microscopies (TEM) revealed the formation of well-crystallized LiCoO2 and LiNi0.9Co0.1O2 with average size of 100 nm and 10 nm, respectively.  相似文献   

12.
Yang Liu 《Electrochimica acta》2008,53(8):3296-3304
Co3O4/RuO2·xH2O composites with various Ru content (molar content of Ru = 5%, 10%, 20%, 50%) were synthesized by one-step co-precipitation method. The precursors were prepared via adjusting pH of the mixed aqueous solutions of Co(NO3)2·6H2O and RuCl3·0.5H2O by using Pluronic123 as a soft template. For the composite with molar ratio of Co:Ru = 1:1 annealed at 200 °C, Brunauer-Emmet-Teller (BET) results indicated that the composite showed mesoporous structure, and the specific surface area of the composite was as high as 107 m2 g−1. The electrochemical performances of these composites were measured in 1 M KOH electrolyte. Compared with the composite prepared without template, the composite with P123 exhibited a higher specific capacitance. When the molar content of Ru was rising, the specific capacitance of the composites increased significantly. It was also observed that the crystalline structures as well as the electrochemical activities were strongly dependent on the annealing temperature. A capacitance of 642 F/g was obtained for the composite (Co:Ru = 1:1) annealed at 150 °C. Meanwhile, the composites also exhibited good cycle stability. Besides, the morphologies and textural characteristic of the samples were also investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM).  相似文献   

13.
Layered LiNi0.6Co0.2Mn0.2O2 materials were synthesized at different sintering temperatures using spray-drying precursor with molar ratio of Li/Me = 1.04 (Me = transition metals). The influences of sintering temperature on crystal structure, morphology and electrochemical performance of LiNi0.6Co0.2Mn0.2O2 materials have been characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and charge-discharge test. As a result, material synthesized at 850 °C has excellent electrochemical performance, delivering an initial discharge capacity of 173.1 mAh g− 1 between 2.8 and 4.3 V at a current density of 16 mA g− 1 and exhibiting good cycling performance.  相似文献   

14.
A high-performance LiNi0.8Co0.2O2 cathode was successfully fabricated by a sol-gel coating of CeO2 to the surface of the LiNi0.8Co0.2O2 powder and subsequent heat treatment at 700 °C for 5 h. The surface-modified and pristine LiNi0.8Co0.2O2 powders were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), slow rate cyclic voltammogram (CV), and differential scanning calorimetry (DSC). Unlike pristine LiNi0.8Co0.2O2, the CeO2-coated LiNi0.8Co0.2O2 cathode exhibits no decrease in its original specific capacity of 182 mAh/g (versus lithium metal) and excellent capacity retention (95% of its initial capacity) between 4.5 and 2.8 V after 55 cycles. The results indicate that the surface treatment should be an effective way to improve the comprehensive properties of the cathode materials for lithium ion batteries.  相似文献   

15.
LiNi1/3Co1/3Mn1/3O2 and LiCoO2 cathode materials were synthesized by using a supercritical water (SCW) method with a metal salt solution in a batch reactor. Stoichiometric LiNi1/3Co1/3Mn1/3O2 was successfully synthesized in a 10-min reaction without calcination, while overlithiated LiCoO2 (Li1.15CoO2) was synthesized using the batch SCW method. The physical properties and electrochemical performances of LiNi1/3Co1/3Mn1/3O2 were compared to those of Li1.15CoO2 by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), and charge/discharge cycling tests. The XRD pattern of LiNi1/3Co1/3Mn1/3O2 was found to be similar to that of Li1.15CoO2, showing clear splitting of the (0 0 6)/(1 0 2) and (1 0 8)/(1 1 0) peak pairs as particular characteristics of the layered structure. In addition, both cathode powders showed good crystallinity and phase purity, even though a short reaction time without calcination was applied to the SCW method. The initial specific discharge capacities of the Li1.15CoO2 and LiNi1/3Co1/3Mn1/3O2 powders at a current density of 0.24 mA/cm2 in 2.5-4.5 V were 149 and 180 mAh/g, and their irreversible capacity loss was 20 and 17 mAh/g, respectively. The discharge capacities of the Li1.15CoO2 and LiNi1/3Co1/3Mn1/3O2 powders decreased with cycling and remained at 108 and 154 mAh/g after 30 cycles, which are 79% and 89% of the initial capacities. Compared to the overlithiated LiCoO2 cathode powders, the LiNi1/3Co1/3Mn1/3O2 cathode powders synthesized by SCW method had better electrochemical performances.  相似文献   

16.
Sen Zhang 《Electrochimica acta》2007,52(25):7337-7342
Li[Ni1/3Co1/3Mn1/3]O2 cathode material for lithium ion batteries was prepared by mixing metal hydroxide, (Ni1/3Co1/3Mn1/3)(OH)2, with 6% excess LiOH followed by calcinations. The (Ni1/3Co1/3Mn1/3)(OH)2 with secondary particle of about 12 μm was prepared by hydroxide co-precipitation. The tap density of the obtained Li[Ni1/3Co1/3Mn1/3]O2 powder was 2.56 ± 0.21 g cm−3. The powder was characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), particle size distribution (PSD) and galvanostatic charge-discharge cycling. The XRD pattern of Li[Ni1/3Co1/3Mn1/3]O2 revealed a well ordered hexagonal layered structure with low cation mixing. Secondary particles with size of 13-14 μm and primary particles with size of about 1 μm can be identified from the SEM observations. In the voltage range of 2.8-4.3 V, the initial discharge capacity of the Li[Ni1/3Co1/3Mn1/3]O2 electrode was 166.6 mAh g−1, and 96.5% of the initial capacity was retained after 50 charge-discharge cycling.  相似文献   

17.
S. Zhang  C. Deng  B.L. Fu  L. Ma 《Powder Technology》2010,198(3):373-400
A carbonate co-precipitation method was employed to prepare spherical Li[Ni1/3Co1/3Mn1/3]O2 cathode material. The precursor, [Ni1/3Co1/3Mn1/3]CO3, was prepared using ammonia as chelating agent under CO2 atmosphere. The spherical Li[Ni1/3Co1/3Mn1/3]O2 was prepared by mixing the precalcined [Ni1/3Co1/3Mn1/3]CO3 with LiOH followed by high temperature calcination. The preparation conditions such as ammonia concentration, co-precipitation temperature, calcination temperature and Li/[Ni1/3Co1/3Mn1/3] ratio were varied to optimize the physical and electrochemical properties of the prepared Li[Ni1/3Co1/3Mn1/3]O2. The structural, morphological, and electrochemical properties of the prepared LiNi1/3Co1/3Mn1/3O2 were characterized by XRD, SEM, and galvanostatic charge-discharge cycling. The optimized material has a spherical particle shape and a well ordered layered structure, and it also has an initial discharge capacity of 162.7 mAh g− 1 in a voltage range of 2.8-4.3 V and a capacity retention of 94.8% after a hundred cycles. The optimized ammonia concentration, co-precipitation temperature, calcination temperature, and Li/[Ni1/3Co1/3Mn1/3] ratio are 0.3 mol L− 1, 60 °C, 850 °C, and 1.10, respectively.  相似文献   

18.
We reported here on the synthesis, the crystal structure and the study of the structural changes during the electrochemical cycling of layered LiNi0.1Mn0.1Co0.8O2 positive electrode material. Rietveld refinement analysis shows that this material exhibits almost an ideal α-NaFeO2 structure with practically no lithium-nickel disorder. The SQUID measurements confirm this structural result and evidenced that this material consists of Ni2+, Mn4+ and Co3+ ions.Unlike LiNiO2 and LiCoO2 conventional electrode materials, there was no structural modification upon lithium removal in the whole 0.42 ≤ x ≤1.0 studied composition range. The peaks revealed in the incremental capacity curve were attributed to the successive oxidation of Ni2+ and Co3+ while Mn4+ remains electrochemically inactive.  相似文献   

19.
Co-doped Li3V2−xCox(PO4)3/C (x = 0.00, 0.03, 0.05, 0.10, 0.13 or 0.15) compounds were prepared via a solid-state reaction. The Rietveld refinement results indicated that single-phase Li3V2−xCox(PO4)3/C (0 ≤ x ≤ 0.15) with a monoclinic structure was obtained. The X-ray photoelectron spectroscopy (XPS) analysis revealed that the cobalt is present in the +2 oxidation state in Li3V2−xCox(PO4)3. XPS studies also revealed that V4+ and V3+ ions were present in the Co2+-doped system. The initial specific capacity decreased as the Co-doping content increased, increasing monotonically with Co content for x > 0.10. Differential capacity curves of Li3V2−xCox(PO4)3/C compounds showed that the voltage peaks associated with the extraction of three Li+ ions shifted to higher voltages with an increase in Co content, and when the Co2+-doping content reached 0.15, the peak positions returned to those of the unsubstituted Li3V2(PO4)3 phase. For the Li3V1.85Co0.15(PO4)3/C compound, the initial capacity was 163.3 mAh/g (109.4% of the initial capacity of the undoped Li3V2(PO4)3) and 73.4% capacity retention was observed after 50 cycles at a 0.1 C charge/discharge rate. The doping of Co2+into V sites should be favorable for the structural stability of Li3V2−xCox(PO4)3/C compounds and so moderate the volume changes (expansion/contraction) seen during the reversible Li+ extraction/insertion, thus resulting in the improvement of cell cycling ability.  相似文献   

20.
A series of Eu2+ and Ce3+ doped/co-doped Sr3Al2O5Cl2 afterglow phosphors that presented various bright colors were successfully synthesized via high temperature solid state reaction. The structure and luminescence properties of the obtained samples were characterized by X-ray powder diffraction (XRD), photoluminescence (PL) spectra and decay curves as well as the thermoluminescence (TL) glow curves. The XRD results showed that all the phase could be indexed to the orthorhombic structure with the space group P212121. After being exposed to a 254 nm or 365 nm mercury lamp, blue/yellow-orange afterglow emissions with broad bands peaking around 620 nm/435 nm, which were ascribed to the characteristic 4f65d–4f7/5d1–4f1 transitions of Eu2+/Ce3+, could be observed in phosphors of Sr3Al2O5Cl2:Eu2+/Sr3Al2O5Cl2:Ce3+, respectively. Because of the overlap spectral range between the Sr3Al2O5Cl2:Eu2+ and Sr3Al2O5Cl2:Ce3+ phosphors, the energy transfer (ET) from Ce3+ to Eu2+ occurred. The related ET process was discussed in detail. Moreover, the incorporation of Ce3+ could significantly prolong the afterglow duration of Sr3Al2O5Cl2:Eu2+ phosphor, which was due to the increase of trap concentration. Consequently, 6 h of the afterglow duration could be observed in Sr3Al2O5Cl2:1.0%Eu2+, 0.5%Ce3+ sample, exhibiting much longer than that of Sr3Al2O5Cl2: 1.0%Eu2+ (3 h). From the afterglow decay curves and the fitting results, the optimal concentration of Ce3+ for the enhanced afterglow property was experimentally determined to be 0.5%.  相似文献   

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