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1.
LiNi0.6CoxMn0.4−xO2 (x = 0.05, 0.10, 0.15, 0.2) cathode materials are prepared, and their structural and electrochemical properties are investigated using X-ray diffraction (XRD), scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), differential scanning calorimetric (DSC) and charge–discharge test. The results show that well-ordering layered LiNi0.6CoxMn0.4−xO2 (x = 0.05, 0.10, 0.15, 0.2) cathode materials are successfully prepared in air at 850 °C. The increase of the Co content in LiNi0.6Mn0.4−xCoxO2 leads to the acceleration of the grain growth, the increase of the initial discharge capacity and the deterioration of the cycling performance of LiNi0.6Mn0.4−xCoxO2. It also leads to the enhancement of the ratio Ni3+/Ni2+ in LiNi0.6CoxMn0.4−xO2, which is approved by the XPS analysis, resulting in the increase of the phase transition during cycling. This is speculated to be main reason for the deteriotion of the cycling performance. All synthesized LiNi0.6CoxMn0.4−xO2 samples charged at 4.3 V show exothermic peaks with an onset temperature of larger than 255 °C, and give out less than 400 J g−1 of total heat flow associated with the peaks in DSC analysis profile, exhibiting better thermal stability. LiNi0.6Co0.05Mn0.35O2 with low Co content and good thermal stability presents a capacity of 156.6 mAh g−1 and 98.5% of initial capacity retention after 50 cycles, showing to be a promising cathode materials for Li-ion batteries.  相似文献   

2.
We investigated the effect of CO2 on layered Li1+zNi1−xyCoxMyO2 (M = Al, Mn) cathode materials for lithium ion batteries which were prepared by solid-state reactions. Li1+zNi(1−x)/2CoxMn(1−x)/2O2 (Ni/Mn mole ratio = 1) singularly exhibited high storage stability. On the other hand, Li1+zNi0.80Co0.15Al0.05O2 samples were very unstable due to CO2 absorption. XPS and XRD measurements showed the reduction of Ni3+ to Ni2+ and the formation of Li2CO3 for Li1+zNi0.80Co0.15Al0.05O2 samples after CO2 exposure. SEM images also indicated that the surfaces of CO2-treated samples were covered with passivation films, which may contain Li2CO3. The relationship between CO2-exposure time and CO32− content suggests that there are two steps in the carbonation reactions; the first step occurs with the excess Li components, Li2O for example, and the second with LiNi0.80Co0.15Al0.05O2 itself. It is well consistent with the fact that the discharge capacity was not decreased and the capacity retention was improved until the excess lithium is consumed and then fast deterioration occurred.  相似文献   

3.
Cathode materials prepared by a co-precipitation are 0.3Li2MnO3·0.7LiMn1−xNiyCo0.1O2 (0.2 ≤ x ≤ 0.4) cathode materials with a layered-spinel structure. In the voltage range of 2.0-4.6 V, the cathodes show more than one redox reaction peak during its cyclic voltammogram. The Li/0.3Li2MnO3·0.7LiMn1−xNiyCo0.1O2 (x = 0.3, y = 0.2) cell shows the initial discharge capacity of about 200 mAh g−1. However, when x = 0.2 and y = 0.1, the cell exhibits a rapid decrease in discharge capacity and poor cycle life.  相似文献   

4.
Structural, electrical and electrochemical properties of Mn-substituted phospho-olivines LiFe1−yMnyPO4 were investigated and compared to those of LiFePO4. Rietvield refined XRD patterns taken in the course of delithiation process showed apparent difference between phase compositions of these cathode materials upon lithium extraction. Contrary to the LiFePO4 and LiMnPO4 compositions for which a two-phase mechanism of electrochemical lithium extraction/insertion is observed, in case of Mn-substituted LiFe1−yMnyPO4 samples a single-phase mechanism of deintercalation was observed in the studied range of lithium concentration. Electrochemical characterization of the cathode materials were performed in Li/Li+/LixFe1−yMnyPO4-type cells for y = 0.0, 0.25, 0.55, 0.75 and 1.0 compositions. Voltammery studies showed low reversibility of the lithium extraction process in the high-voltage “manganese” range, while in the “iron” range the reversibility of lithium extraction is high. Impedance measurements of the LiFe1−yMnyPO4 cathode materials, which enabled separation of the ionic and electronic components of their entire electrical conductivity, showed distinct influence of Mn content on the electronic part of conductivity. EIS measurements performed at different states of cell charge revealed that the charge-transfer impedance in LixFe1−yMnyPO4 is much lower than that of LixFePO4.  相似文献   

5.
The influence of titanium doping level in Ba0.6Sr0.4Co1−yTiyO3−δ (BSCT) oxides on their phase structure, electrical conductivity, thermal expansion coefficient (TEC), and single-cell performance with BSCT cathodes has been investigated. The incorporation of Ti can lead to the phase transition of Ba0.6Sr0.4CoO3−δ from hexagonal to cubic structure. The solid solution limitation of Ti in Ba0.6Sr0.4Co1−yTiyO3−δ is 0.15–0.3 under 1100 °C. BSCT shows a small polaron conduction behavior and the electrical conductivity increases steadily in the testing temperature range (300–900 °C), leading to a relatively high conductivity at high temperatures. The electrical conductivity decreases with increasing Ti content. The addition of Ti deteriorates the cathode performance of BSCT slightly but decreases the TEC significantly. The TEC of BSCT is about 14 × 10−6 K−1, which results in a good physical compatibility of BSCT with Gd0.2Ce0.8O2−δ (GDC) electrolyte. BSCT also shows excellent thermal cyclic stability of electrical conductivity and good chemical stability with GDC. These properties make BSCT a promising cathode candidate for intermediate temperature solid oxide fuel cells (IT-SOFCs).  相似文献   

6.
Sub-micro spinel LiNi0.5−xMn1.5+xO4 (x < 0.1) cathode materials powder was successfully synthesized by the ultrasonic-assisted co-precipitation (UACP) method. The structure and electrochemical performance of this as-prepared powder were characterized by powder XRD, SEM, XPS, CV and the galvanostatic charge–discharge test in detail. XRD shows that there is a small LiyNi1−yO impurity peak placed close to the (4 0 0) line of the spinel LiNi0.5−xMn1.5+xO4, and the powders are well crystallized. XPS exhibits that the Mn oxidation state is between +3 and +4, and Ni oxidation state is +2 in LiNi0.5−xMn1.5+xO4. SEM shows that the prepared powders (UACP) have the uniform and narrow size distribution which is less than 200 nm. Galvanostatic charge–discharge test indicates that the initial discharge capacities for the LiNi0.5−xMn1.5+xO4 (UACP) at C/3, 1C and 2C, are 130.2, 119.0 and 110.0 mAh g−1, respectively. After 100 cycles, their capacity retentions are 99.8%, 88.2%, and 73.5%, respectively. LiNi0.5−xMn1.5+xO4 (UACP) at C/3 discharge rate exhibits superior capacity retention upon cycling, and it also shows well high current discharge performance. CV curve implies that LiNi0.5−xMn1.5+xO4 (x < 0.1) spinel synthesized by ultrasonic-assisted co-precipitation method has both reversibility and cycle capability because of the ultrasonic-catalysis.  相似文献   

7.
In this work structural and transport properties of layered Li1+x(Mn1/3Co1/3Ni1/3)1−xO2 oxides (x = 0; 0.03; 0.06) prepared by a “soft chemistry” method are presented. The excessive lithium was found to significantly improve transport properties of the materials, a corresponding linear decrease of the unit cell parameters was observed. The electrical conductivity of Li1.03(Mn1/3Co1/3Ni1/3)0.97O2 composition was high enough to use this material in a form of a pellet, without any additives, in lithium batteries and characterize structural and transport properties of deintercalated Li1.03−y(Mn1/3Co1/3Ni1/3)0.97O2 compounds. For deintercalated samples a linear increase of the lattice parameter c together with a linear decrease of the parameter a with the increasing deintercalation degree occurred, but only up to 0.4-0.5 mol of extracted lithium. Further deintercalation showed a reversal of the trend. Electrical conductivity measurements performed of Li1.03−y(Mn1/3Co1/3Ni1/3)0.97O2 samples (y = 0.1; 0.3; 0.5; 0.6) showed an ongoing improvement, almost two orders of magnitude, in relation to the starting composition. Additionally, OCV measurements, discharge characteristics and lithium diffusion coefficient measurements were performed for Li/Li+/Li1.03−y(Mn1/3Co1/3Ni1/3)0.97O2 cells.  相似文献   

8.
A network of CoxNiyAlz layered triple hydroxides (LTHs) nanosheets was prepared by the potentiostatic deposition process at −1.0 V (vs. Ag/AgCl) onto stainless steel electrodes. X-ray diffraction patterns show that the CoxNiyAlzLTHs belong to the hexagonal system with layered structure. Cyclic voltammetry and charge discharge measurements in the potential range of −0.1 to 0.5 V and 0.0–0.4 V, respectively, vs. Ag/AgCl in 1 M KOH electrolyte indicate that CoxNiyAlzLTHs have excellent supercapacitive characteristics. The maximum specific capacitance of ∼1263 F g−1 was obtained for Co0.59Ni0.21Al0.20LTH. The impedance studies indicated highly conducting nature of the CoxNiyAlzLTHs.  相似文献   

9.
A series of cathode materials with molecular notation of xLi[Li1/3Mn2/3]O2·(1 − x)Li[Ni1/3Mn1/3Co1/3]O2 (0 ≤ x ≤ 0.9) were synthesized by combination of co-precipitation and solid state calcination method. The prepared materials were characterized by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) techniques, and their electrochemical performances were investigated. The results showed that sample 0.6Li[Li1/3Mn2/3]O2·0.4Li[Ni1/3Mn1/3Co1/3]O2 (x = 0.6) delivers the highest capacity and shows good capacity-retention, which delivers a capacity ∼250 mAh g−1 between 2.0 and 4.8 V at 18 mA g−1.  相似文献   

10.
Li1+x(Ni1/3Mn1/3Co1/3)1−xO2 layered materials were synthesized by the co-precipitation method with different Li/M molar ratios (M = Ni + Mn + Co). Elemental titration evaluated by inductively coupled plasma spectrometry (ICP), structural properties studied by X-ray diffraction (XRD), Rietveld analysis of XRD data, scanning electron microscopy (SEM) and magnetic measurements carried out by superconducting quantum interference devices (SQUID) showed the well-defined α-NaFeO2 structure with cationic distribution close to the nominal formula. The Li/Ni cation mixing on the 3b Wyckoff site of the interlayer space was consistent with the structural model [Li1−yNiy]3b[Lix+yNi(1−x)/3−yMn(1−x)/3Co(1−x)/3]3aO2 (x = 0.02, 0.04) and was very small. Both Rietveld refinements and magnetic measurements revealed a concentration of Ni2+-3b ions lower than 2%; moreover, for the optimized sample synthesized at Li/M = 1.10, only 1.43% of nickel ions were located into the Li sublattice. Electrochemical properties were investigated by galvanostatic charge-discharge cycling. Data obtained with Li1+x(Ni1/3Mn1/3Co1/3)1−xO2 reflected the high degree of sample optimization. An initial discharge capacity of 150 mAh g−1 was delivered at 1 C-rate in the cut-off voltage of 3.0-4.3 V. More than 95% of its initial capacity was retained after 30 cycles at 1 C-rate. Finally, it is demonstrated that a cation mixing below 2% is considered as the threshold for which the electrochemical performance does not change for Li1+x(Ni1/3Mn1/3Co1/3)1−xO2.  相似文献   

11.
Sr2Fe1−xCoxNbO6 (0.1 ≤ x ≤ 0.9) (SFCN) oxides with perovskite structure have been developed as the cathode materials for intermediate-temperature solid oxide fuel cells (IT-SOFCs). These materials are synthesized via solid-state reaction and characterized by XRD, SEM, electrical conductivity, AC impedance spectroscopy and DC polarization measurements. The reactivity tests show that the Sr2Fe1−xCoxNbO6 electrodes are chemically compatible with the Zr0.85Y0.15O1.925 (YSZ) and Ce1.9Gd0.1O1.95 (CGO) electrolytes at 1200 °C, and the electrode forms a good contact with the electrolyte after sintering at 1200 °C for 12 h. The total electrical conductivity that has a considerable effect on the electrode properties is determined in a temperature range from 200 °C to 800 °C. The highest conductivity of 5.7 S cm−1 is found for Sr2Fe0.1Co0.9NbO6 at 800 °C in air. The electrochemical performances of these cathode materials are studied using impedance spectroscopy at various temperatures and oxygen partial pressures. Two different kinds of reaction rate-limiting steps exist on the Sr2Fe0.1Co0.9NbO6 electrode, depending on the temperature. The Sr2Fe0.1Co0.9NbO6 electrode on CGO electrolyte exhibits a polarization resistance of 0.74 Ω cm2 at 750 °C in air, which indicates that the Sr2Fe0.1Co0.9NbO6 electrode is a promising cathode material for IT-SOFCs.  相似文献   

12.
The structural changes of the composite cathode made by mixing spinel LiMn2O4 and layered LiNi1/3Co1/3Mn1/3O2 in 1:1 wt% in both Li-half and Li-ion cells during charge/discharge are studied by in situ XRD. During the first charge up to ∼5.2 V vs. Li/Li+, the in situ XRD spectra for the composite cathode in the Li-half cell track the structural changes of each component. At the early stage of charge, the lithium extraction takes place in the LiNi1/3Co1/3Mn1/3O2 component only. When the cell voltage reaches at ∼4.0 V vs. Li/Li+, lithium extraction from the spinel LiMn2O4 component starts and becomes the major contributor for the cell capacity due to the higher rate capability of LiMn2O4. When the voltage passed 4.3 V, the major structural changes are from the LiNi1/3Co1/3Mn1/3O2 component, while the LiMn2O4 component is almost unchanged. In the Li-ion cell using a MCMB anode and a composite cathode cycled between 2.5 V and 4.2 V, the structural changes are dominated by the spinel LiMn2O4 component, with much less changes in the layered LiNi1/3Co1/3Mn1/3O2 component, comparing with the Li-half cell results. These results give us valuable information about the structural changes relating to the contributions of each individual component to the cell capacity at certain charge/discharge state, which are helpful in designing and optimizing the composite cathode using spinel- and layered-type materials for Li-ion battery research.  相似文献   

13.
SrF2-coated LiNi1/3Co1/3Mn1/3O2 cathode materials with improved cycling performance over 2.5–4.6 V were investigated. The structural and electrochemical properties of the materials were studied using X-ray diffraction (XRD), scanning electron microscope (SEM), charge–discharge tests and electrochemical impedance spectra (EIS). The results showed that the crystalline SrF2 with about 10–50 nm particle size is uniformly coated on the surface of LiNi1/3Co1/3Mn1/3O2 particles. As the coating amount increased from 0.0 to 2.0 mol%, the initial capacity and rate capability of the coated LiNi1/3Co1/3Mn1/3O2 decreased slightly owing to the increase of the charge-transfer resistance; however, the cycling stability was improved by suppressing the increase of the resistance during cycling. 4.0 mol% SrF2-coated LiNi1/3Co1/3Mn1/3O2 showed remarkable decrease of the initial capacity. 2.0 mol% coated sample exhibited the best electrochemical performance. It presented an initial discharge capacity of 165.7 mAh g−1, and a capacity retention of 86.9% after 50 cycles at 4.6 V cut-off cycling.  相似文献   

14.
Prospective positive-electrode (cathode) materials for a lithium secondary battery, viz., Li[Li0.2Ni0.2−x/2Mn0.6−x/2Crx]O2 (x = 0, 0.02, 0.04, 0.06, 0.08), were synthesized using a solid-state pyrolysis method. The structural and electrochemical properties were examined by means of X-ray diffraction, cyclic voltammetry, SEM and charge–discharge tests. The results demonstrated that the powders maintain the α-NaFeO2-type layered structure regardless of the chromium content in the range x ≤ 0.08. The Cr doping of x = 0.04 showed improved capacity and rate capability comparing to undoped Li[Li0.2Ni0.2Mn0.6]O2. ac impedance measurement showed that Cr-doped electrode has the lower impedance value during cycling. It is considered that the higher capacity and superior rate capability of Cr-doping samples would be ascribed to the reduced resistance of the electrode during cycling.  相似文献   

15.
Submicron-sized LiNi1/3Co1/3Mn1/3O2 cathode materials were synthesized using a simple self-propagating solid-state metathesis method with the help of ball milling and the following calcination. A mixture of Li(ac)·2H2O, Ni(ac)2·4H2O, Co(ac)2·4H2O, Mn(ac)2·4H2O (ac = acetate) and excess H2C2O4·2H2O was used as starting material without any solvent. XRD analyses indicate that the LiNi1/3Co1/3Mn1/3O2 materials were formed with typical hexagonal structure. The FESEM images show that the primary particle size of the LiNi1/3Co1/3Mn1/3O2 materials gradually increases from about 100 nm at 700 °C to 200–500 nm at 950 °C with increasing calcination temperature. Among the synthesized materials, the LiNi1/3Co1/3Mn1/3O2 material calcined at 900 °C exhibits excellent electrochemical performance. The steady discharge capacities of the material cycled at 1 C (160 mA g−1) rate are at about 140 mAh g−1 after 100 cycles in the voltage range 3–4.5 V (versus Li+/Li) and the capacity retention is about 87% at the 350th cycle.  相似文献   

16.
K2NiF4-type structure oxides La2Cu1−xCoxO4 (x = 0.1, 0.2, 0.3) are synthesized and evaluated as cathode materials for intermediate temperature solid oxide fuel cells (IT-SOFCs). The materials are characterized by XRD, SEM and electrochemical impedance spectrum (EIS), respectively. The results show that no reaction occurs between La2Cu1−xCoxO4 electrode and Ce0.9Gd0.1O1.95 (CGO) electrolyte at 1000 °C. The electrode forms good contact with the electrolyte after sintering at 800 °C for 4 h in air. The electrode properties of La2Cu1−xCoxO4 are studied under various temperatures and oxygen partial pressures. The optimum composition of La2Cu0.8Co0.2O4 results in 0.51 Ω cm2 polarization resistance (Rp) at 700 °C in air. The rate limiting step for oxygen reduction reaction (ORR) is the charge transfer process. La2Cu0.8Co0.2O4 cathode exhibits the lowest overpotential of about 50 mV at a current density of 48 mA cm−2 at 700 °C in air.  相似文献   

17.
Amorphous LiCo1/3Mn1/3Ni1/3O2 thin films were deposited on the NASICON-type Li-ion conducting glass ceramics, Li1+x+yAlxTi2−xSiyP3−yO12 (LATSP), by radio frequency (RF) magnetron sputtering below 130 °C. The amorphous films were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The Li/PEO18-Li(CF3SO2)2N/LATSP/LiCo1/3Mn1/3Ni1/3O2/Au all-solid-state cells were fabricated to investigate the electrochemical performance of the amorphous films. It was found that the low-temperature deposited amorphous cathode film shows a high discharge voltage and a high discharge capacity of around 130 mAh g−1.  相似文献   

18.
A kind of cathode material of Pr1−xSrx FeO3 (x = 0–0.5) for intermediate temperature solid oxide fuel cells (IT-SOFCs) was prepared by the coprecipitation method. Crystal structure, thermal expansion, electrical conductivity and electrochemical performance of the Pr1−xSrxFeO3 perovskite oxide cathodes were studied by different methods. The results revealed that Prl−xSrxFeO3 exhibited similar orthorhombic structure from x = 0.1 to 0.3 and took cubic structure when x = 0.4–0.5. The unit cell volume decreased and the thermal expansion coefficient (TEC) of the materials increased as the strontium content increased. When 0 < x ≤ 0.3, the samples exhibited good thermal expansion compatibility with YSZ electrolyte. The electrical conductivity increased with the increasing of doped strontium content. When x = 0.3–0.5, the electrical conductivities were higher than 100 S cm−1. The conductivity of Pr0.8Sr0.2FeO3 was 78 S cm−1 at 800 °C. Compared with the La0.8Sr0.2MnO3 cathode, Pr0.8Sr0.2FeO3 showed higher polarization current density and lower polarization resistance (0.2038 Ω cm2). The value of I0 for Pr0.8Sr0.2FeO3 at 800 °C is 123.6 mA cm−2. It is higher than that of La0.8Sr0.2MnO3. Therefore, Pr1−xSrxFeO3 can be considered as a candidate cathode material for IT-SOFCs.  相似文献   

19.
A dense membrane of Ce0.9Gd0.1O1.95 on a porous cathode based on a mixed conducting La0.6Sr0.4Co0.2Fe0.8O3−δ was fabricated via a slurry coating/co-firing process. With the purpose of matching of shrinkage between the support cathode and the supported membrane, nano-Ce0.9Gd0.1O1.95 powder with specific surface area of 30 m2 g−1 was synthesized by a newly devised coprecipitation to make the low-temperature sinterable electrolyte, whereas 39 m2 g−1 nano-Ce0.9Gd0.1O1.95 prepared from citrate method was added to the cathode to favor the shrinkage for the La0.6Sr0.4Co0.2Fe0.8O3−δ. Bi-layers consisting of <20 μm dense ceria film on 2 mm thick porous cathode were successfully fabricated at 1200 °C. This was followed by co-firing with NiO–Ce0.9Gd0.1O1.95 at 1100 °C to form a thin, porous, and well-adherent anode. The laboratory-sized cathode-supported cell was shown to operate below 600 °C, and the maximum power density obtained was 35 mW cm−2 at 550 °C, 60 mW cm−2 at 600 °C.  相似文献   

20.
Direct borohydride fuel cells (DBFCs), with a series of perovskite-type oxides La1−xSrxCoO3 (x = 0.1-0.5) as the cathode catalysts and a hydrogen storage alloy as the anode catalyst, are studied in this paper. The structures of the perovskite-type catalysts are mainly La1−xSrxCoO3 (x = 0.1-0.5) oxides phases. However, with the increase of strontium content, the intensities of the X-ray diffraction peaks of the impure phases La2Sr2O5 and SrLaCoO4 are gradually enhanced. Without using any precious metals or expensive ion exchange membranes, a maximum current density of 275 mA cm−2 and a power density of 109 mW cm−2 are obtained with the Sr content of x = 0.2 at 60 °C for this novel type of fuel cell.  相似文献   

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