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1.
The oxygen reduction reaction (orr) was studied on composite electrodes GC/PPy/PPy(NixCo3−xO4)/PPy with x=0.3 and 1, in 2.5×10−3 M KOH+0.8 M KCl at room temperature. The orr takes place on the oxide particles with formation of hydrogen peroxide (H2O2), which diffuses through the polymer layers to reach the bulk of electrolyte solution. The amount of H2O2 produced, determined indirectly by iodine spectrometry, depended strongly on the oxide stoichiometry. The effects of the orr and of the generation of H2O2 on the conductivity of PPy and on the behaviour of the embedded oxide particles are discussed.  相似文献   

2.
Multilayered composite electrodes on glassy carbon, GC, having the structure GC/PPy/PPy(Ox)/PPy, with PPy the polypyrrole and Ox a mixed valence oxide of transition metals, exhibit high reactivity and stability towards the oxygen reduction reaction (orr), when the orr proceeds electrocatalytically on the oxide particles dispersed throughout the inner layer, PPy(Ox). However the nature and concentration of the doping anions, A, of PPy have a profound effect on the resulting orr currents, due to their effects on the conductivity and morphology of the PPy layers. The paper shows and discusses these effects in the case of the composite electrode with Ox = Cu1.4Mn1.6O4 and A = Cl, ClO4, NO3, PF6 and SO42−, in acid solution (pH 2.2). Optimal conditions were encountered with Cl.  相似文献   

3.
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   

4.
In order to get homogeneous layered oxide Li[Ni1/3Mn1/3Co1/3]O2 as a lithium insertion positive electrode material, we applied the metal acetates decomposition method. The oxide compounds were calcined at various temperatures, which results in greater difference in morphological (shape, particle size and specific surface area) and the electrochemical (first charge profile, reversible capacity and rate capability) differences. The Li[Ni1/3Mn1/3Co1/3]O2 powders were characterized by means of X-ray diffraction (XRD), charge/discharge cycling, cyclic voltammetry and SEM. XRD experiment revealed that the layered Li[Ni1/3Mn1/3Co1/3]O2 material can be best synthesized at temperature of 800 °C. In that synthesized temperature, the sample showed high discharge capacity of 190 mAh g−1 as well as stable cycling performance at a current density of 0.2 mA cm−2 in the voltage range 2.3-4.6 V. The reversible capacity after 100 cycles is more than 190 mAh g−1 at room temperature.  相似文献   

5.
In the process of Li+ intercalation-deintercalation, electron removal is accompanied simultaneously. Oxygen was found to compensate electron removal both in theoretical calculations and practical experiments. Chlorine addition to LiNi0.7Co0.3O2 was expected to exchange electrons in that Cl was easier to lose electrons than O2−. LiNi0.7Co0.3O2−xClx was identified as a pure hexagonal lattice of α-NaFeO2 type by X-ray diffraction. X-ray photoelectron spectroscopy was used to analyze the influence of chlorine substitution on the oxidation state of transition-metal ions. Charge-discharge experiments and cyclic voltammetry confirmed that chlorine addition was an effective way to improve reversible capacity and structural stability in cycles.  相似文献   

6.
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   

7.
Uniform and spherical Li(Ni1/3Co1/3Mn1/3)O(2−δ)Fδ powders were synthesized via NH3 and F coordination hydroxide co-precipitation. The effect of F coordination agent on the morphology, structure and electrochemical properties of the Li(Ni1/3Co1/3Mn1/3)O(2−δ)Fδ were studied. The morphology, size, and distribution of (Ni1/3Co1/3Mn1/3)(OH)(2−δ)Fδ particle diameter were improved in a shorter reaction time through the addition of F. The study suggested that the added F improves the layered characteristics of the lattice and the cyclic performance of Li(Ni1/3Co1/3Mn1/3)O2 in the voltage range of 2.8-4.6 V. The initial capacity of the Li(Ni1/3Co1/3Mn1/3)O1.96F0.04 was 178 mAh g−1, the maximum capacity was 186 mAh g−1 and the capacity after 50 cycles was 179 mAh g−1 in the voltage range of 2.8-4.6 V.  相似文献   

8.
LiCo2/3Ni1/6Mn1/6O2 layered oxide was synthesized by the combustion method that led to a crystalline phase with good homogeneity and low particles size. The structural properties of the prepared positive electrode material were investigated by performing XRD Rietveld refinement. Practically no Li/Ni mixing was detected evidencing that the studied compound adopts almost an ideal α-NaFeO2 type structure. The Li||LiCo2/3Ni1/6Mn1/6O2 cell showed a discharge capacity of 199 mAh g−1 when cycled in the 2.7–4.6 V potential range while the best cycling performances were recorded when the upper cut off is fixed at 4.5 V. Structural changes in LixCo2/3Ni1/6Mn1/6O2 with lithium electrochemical de-intercalation were studied using X-ray diffraction. This study clearly shows the existence of a solid solution domain in the 0.1 < x < 1.0 composition range while for x = 0.1, a new phase appears explaining the decrease of the electrochemical performance when the cell is cycled at high upper cut off voltage.  相似文献   

9.
Synthetic optimization of Li[Ni1/3Co1/3Mn1/3]O2 via co-precipitation   总被引:1,自引:0,他引:1  
Li[Ni1/3Co1/3Mn1/3]O2 powders were synthesized from co-precipitated spherical metal hydroxide, (Ni1/3Co1/3Mn1/3)(OH)2. The preparation of metal hydroxide was significantly dependent on synthetic conditions, such as pH, amount of chelating agent, stirring speed, etc. The optimized condition resulted in (Ni1/3Co1/3Mn1/3)(OH)2, of which the particle size distribution was uniform and the particle shape was spherical, as observed by scanning electron microscopy. Calcination of the uniform metal hydroxide with LiOH at higher temperature led to a well-ordered layer-structured Li[Ni1/3Co1/3Mn1/3]O2, as confirmed by Rietveld refinement of X-ray diffraction pattern. Due to the homogeneity of the metal hydroxide, (Ni1/3Co1/3Mn1/3)(OH)2, the final product, Li[Ni1/3Co1/3Mn1/3]O2, was also significantly uniform, i.e., the average particle size was of about 10 μm in diameter and the distribution was relatively narrow. As a result, the corresponding tap-density was also high approximately 2.39 g cm−3, of which the value is comparable to that of commercialized LiCoO2. In the voltage range of 2.8-4.3, 2.8-4.4, and 2.8-4.5 V, the discharge capacities of Li[Ni1/3Co1/3Mn1/3]O2 electrode were 159, 168, and 177 mAh g−1, respectively. For elevated temperature operation (55 °C), the resulted capacity was of about 168 mAh g−1 with an excellent cyclability.  相似文献   

10.
In this research, we studied the first cycle characteristics of Li[Ni1/3Co1/3Mn1/3]O2 charged up to 4.7 V. Properties, such as valence state of the transition metals and crystallographic features, were analyzed by X-ray absorption spectroscopy and X-ray and neutron diffractions. Especially, two plateaus observed around 3.75 and 4.54 V were investigated by ex situ X-ray absorption spectroscopy. XANES studies showed that the oxidation states of transition metals in Li[Ni1/3Co1/3Mn1/3]O2 are mostly Ni2+, Co3+ and Mn4+. Based on neutron diffraction Rietveld analysis, there is about 6% of all nickel divalent (Ni2+) ions mixed with lithium ions (cation mixing). Meanwhile, it was found that the oxidation reaction of Ni2+/Ni4+ is related to the lower plateau around 3.75 V, but that of Co3+/Co4+ seems to occur entire range of x in Li1−x[Ni1/3Co1/3Mn1/3]O2. Small volume change during cycling was attributed to the opposite variation of lattice parameter “c” and “a” with charging-discharging.  相似文献   

11.
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   

12.
Spherical Li[Ni1/3Co1/3Mn1/3]O2 powders were synthesized from LiOH·H2O and coprecipitated spherical metal hydroxide, (Ni1/3Mn1/3Co1/3)(OH)2 and coated with Al(OH)3. The Al(OH)3-coated Li[Ni1/3Co1/3Mn1/3]O2 showed a capacity retention of 80% at 320 mA g−1 (2 C-rate) based on 20 mA g−1 (0.1 C-rate), while the pristine Li[Ni1/3Co1/3Mn1/3]O2 delivered only 45% at the same current density. Also, unlike pristine Li[Ni1/3Co1/3Mn1/3]O2, the Al(OH)3-coated Li[Ni1/3Co1/3Mn1/3]O2 cathode exhibits excellent rate capability and good thermal stability.  相似文献   

13.
The Co0.33Ni0.33Mn0.33Fe2O4/graphene nanocomposite for electromagnetic wave absorption was successfully synthesized from metal chlorides solutions and graphite powder by a simple and rapid microwave-assisted polyol method via anchoring the Co0.33Ni0.33Mn0.33Fe2O4 nanoparticles on the layered graphene sheets. The Fe3+, Co2+, Ni2+ and Mn2+ ions in the solutions were attracted by graphene oxide obtained from graphite and converted to the precursors Fe(OH)3, Co(OH)2, Ni(OH)2, and Mn(OH)2 under slightly alkaline conditions. After the transformations of the precursors to Co-Ni-Mn ferrites and conversion of graphene oxide to graphene under microwave irradiation at 170?°C in just 25?min, the Co0.33Ni0.33Mn0.33Fe2O4/graphene nanocomposite was prepared. The composition and structure of the nanocomposite were characterized by X-ray diffraction (XRD), inductive coupled plasma emission spectroscopy (ICP), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy (RS), transmission electron microscopy (TEM), etc. It was found that with the filling ratio of only 20?wt% and the thickness of 2.3?mm, the nanocomposite showed an ultra-wide effective absorption bandwidth (less than ?10?dB) of 8.48?GHz (from 9.52 to 18.00?GHz) with the minimum reflection loss of ??24.29?dB. Compared to pure graphene sheets, Co0.33Ni0.33Mn0.33Fe2O4 nanoparticles and the counterparts reported in literature, the nanocomposite exhibited much better electromagnetic wave absorption, mainly attributed to strong wave attenuation, as a result of synergistic effects of dielectric loss, conductive loss and magnetic loss, and to good impedance matching. In view of its thin thickness, light weight and outstanding electromagnetic wave absorption property, the nanocomposite could be used as a very promising electromagnetic wave absorber.  相似文献   

14.
Composite G/PPy/PPy(La1−xSrxMnO3)/PPy electrodes made of the perovskite La1−xSrxMnO3 embedded into a polypyrrole (PPy) layer, sandwiched between two pure PPy films, electrodeposited on a graphite support were investigated for electrocatalysis of the oxygen reduction reaction (ORR). PPy and PPy(La1−xSrxMnO3) (0≤ x ≤0.4) successive layers have been obtained on polished and pretreated graphite electrodes following sequential electrodeposition technique. The electrolytes used in the electrodeposition process were Ar saturated 0.1 mol dm−3 pyrrole (Py) plus 0.05 mol dm−3 K2SO4 with and without containing a suspension of 8.33 g L−1 oxide powder. Films were characterized by XRD, SEM, linear sweep voltammetry, cyclic voltammetry (CV) and electrochemical impedance (EI) spectroscopy. Electrochemical investigations were carried out at pH 12 in a 0.5 mol dm−3 K2SO4 plus 5 mmol dm−3 KOH, under both oxygenated and deoxygenated conditions. Results indicate that the porosity of the PPy matrix is considerably enhanced in presence of oxide particles. Sr substitution is found to have little influence on the electrocatalytic activity of the composite electrode towards the ORR. However, the rate of oxygen reduction decreases with decreasing pH of the electrolyte from pH 12 to pH 6. It is noteworthy that in contrast to a non-composite electrode of the same oxide in film form, the composite electrode exhibits much better electrocatalytic activity for the ORR.  相似文献   

15.
Cobalt oxide (Co3O4) nanotubes have been successfully synthesized by chemically depositing cobalt hydroxide in anodic aluminum oxide (AAO) templates and thermally annealing at 500 °C. The synthesized nanotubes have been characterized by scanning electron microscope (SEM), transmission electron microscope (TEM) and X-ray diffraction (XRD). The electrochemical capacitance behavior of the Co3O4 nanotubes electrode was investigated by cyclic voltammetry, galvanostatic charge-discharge studies and electrochemical impedance spectroscopy in 6 mol L−1 KOH solution. The electrochemical data demonstrate that the Co3O4 nanotubes display good capacitive behavior with a specific capacitance of 574 F g−1 at a current density of 0.1 A g−1 and a good specific capacitance retention of ca. 95% after 1000 continuous charge-discharge cycles, indicating that the Co3O4 nanotubes can be promising electroactive materials for supercapacitor.  相似文献   

16.
Layered Li1+x(Ni0.3Co0.4Mn0.3)O2−δ (x = 0, 0.03 and 0.06) materials were synthesized through the different calcination times using the spray-dried precursor with the molar ratio of Li/Me = 1.25 (Me = transition metals). The physical and electrochemical properties of the lithium excess and the stoichiometric materials were examined using XRD, AAS, BET and galvanostatic electrochemical method. As results, the lithium excess Li1.06(Ni0.3Co0.4Mn0.3)O2−δ could show better electrochemical properties, such as discharge capacity, capacity retention and C rate ability, than those of the stoichiometric Li1.00(Ni0.3Co0.4Mn0.3)O2−δ. In this paper, the effect of excess lithium on the electrochemical properties of Li1+x(Ni0.3Co0.4Mn0.3)O2−δ materials will be discussed based on the experimental results of ex situ X-ray diffraction, transmission electron microscopy (TEM) and galvanostatic intermittent titration technique (GITT)  相似文献   

17.
Uniform hexagonal-shaped cobalt oxide (Co3O4) nanodisks were prepared in large scale via facile aqueous solution based hydrothermal process at 110 °C. The detailed structural characterizations confirmed that the synthesized products are hexagonal cobalt oxide nanodisks, possessing very well-crystalline cubic spinel structure. A coin cell of type −2032 was assembled using the synthesized Co3O4 nanodisks and its charge–discharge profile was analyzed between the voltages 0.01 and to 2.5 V vs. Li/Li+ reference electrode. The electrochemical cell composed of Li/Co3O4 delivered an initial lithium insertion capacity of 2039 mAh/g. Although the cell exhibited high irreversible capacity during the first four cycles, the columbic efficiency has been improved upon cycling.  相似文献   

18.
LiNi0.33−xMn0.33Co0.33YxO2 materials are synthesized by Y3+ substitute of Ni2+ to improve the cycling performance and rate capability. The influence of the Y3+ doping on the structure and electrochemical properties are investigated by means of X-ray diffraction (XRD), scanning electron microscope (SEM), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), X-ray photoelectron spectroscopy (XPS) and galvanostatic charge/discharge tests. LiNi0.33Mn0.33Co0.33O2 exhibits the capacity retentions of 89.9 and 87.8% at 2.0 and 4.0 C after 40 cycles, respectively. After doping, the capacity retentions of LiNi0.305Mn0.33Co0.33Y0.025O2 are increased to 97.2 and 95.9% at 2.0 and 4.0 C, respectively. The discharge capacity of LiNi0.305Mn0.33Co0.33Y0.025O2 at 5.0 C remains 75.7% of the discharge capacity at 0.2 C, while that of LiNi0.33Mn0.33Co0.33O2 is only 47.5%. EIS measurement indicates that LiNi0.305Mn0.33Co0.33Y0.025O2 electrode has the lower impedance value during cycling. It is considered that the higher capacity retention and superior rate capability of Y-doped samples can be ascribed to the reduced surface film resistance and charge transfer resistance of the electrode during cycling.  相似文献   

19.
In this study, we have successfully coated the CeO2 nanoparticles (CeONPs) layer onto the surface of the Ni-rich layered LiNi0.7Co0.2Mn0.1O2 cathode materials by a wet chemical method, which can effectively improve the structural stability of electrode. The X-ray powder diffraction (XRD), transmission electron microscope (TEM), scanning electron microscope (SEM), and X-ray photoelectron spectroscopy (XPS) are used to determine the structure, morphology, elemental composition and electronic state of pristine and surface modified LiNi0.7Co0.2Mn0.1O2. The electrochemical testing indicates that the 0.3?mol% CeO2-coated LiNi0.7Co0.2Mn0.1O2 demonstrates excellent cycling capability and rate performance, the discharge specific capacity is 161.7?mA?h?g?1 with the capacity retention of 86.42% after 100 cycles at a current rate of 0.5?C, compared to 135.7?mA?h?g?1 and 70.64% for bare LiNi0.7Co0.2Mn0.1O2, respectively. Even at 5?C, the discharge specific capacity is still up to 137.1?mA?h?g?1 with the capacity retention of 69.0%, while the NCM only delivers 95.5?mA?h?g?1 with the capacity retention of 46.6%. The outstanding electrochemical performance is assigned to the excellent oxidation capacity of CeO2 which can oxidize Ni2+ to Ni3+ and Mn3+ to Mn4+ with the result that suppress the occurrence of Li+/Ni2+ mixing and phase transmission. Furthermore, CeO2 coating layer can protect the structure to avoid the occurrence of side reaction. The CeO2-coated composite with enhanced structural stability, cycling capability and rate performance is a promising cathode material candidate for lithium-ion battery.  相似文献   

20.
A Li[Ni0.4Co0.3Mn0.3]O2 cathode was modified by applying a La2/3−XLi3XTiO3 (LLT) coating. Transmission electron microscope (TEM) images reveal that the coating layer consists of nanoparticles. The coated cathode demonstrated an enhanced rate capability, discharge capacity, and cyclic performance than the uncoated cathode. However, the influence of the coating upon these electrochemical properties is highly dependent upon the composition of the LLT coating layer. Coating layers having high La and low Li contents, such as La0.67TiO3, effectively improved the rate capability of the cathode. However, coating layers with a low La and high Li content greatly enhanced the discharge capacity of the cathode under high cut-off voltage (4.8 V) conditions. Overall, the thermal stability of the Li[Ni0.4Co0.3Mn0.3]O2 electrode was improved by the LLT coating. Storage tests confirmed that the La2/3−XLi3XTiO3 coating dramatically suppressed the dissolution of transition metals into the electrolyte.  相似文献   

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