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1.
A sol-gel method with ethylene diamine tetraacetic acid and citric acid as co-chelates is employed for the synthesis of P2-type Na2/3Mn1/2Fe1/4Co1/4O2 as cathode material for sodium-ion batteries. Among the various calcination temperatures, the Na2/3Mn1/2Fe1/4Co1/4O2 with a pure P2-type phase calcined at 900 °C demonstrates the best cycle capacity, with a first discharge capacity of 157 mA h g?1 and a capacity retention of 91 mA h g?1 after 100 cycles. For comparison, the classic P2-type Na2/3Mn1/2Fe1/2O2 cathode prepared under the same conditions shows a comparable first discharge capacity of 150 mA h g?1 but poorer cycling stability, with a capacity retention of only 42 mA h g?1 after 100 cycles. Based on X-ray photoelectron spectroscopy, the introduction of cobalt together with sol-gel synthesis solves the severe capacity decay problem of P2-type Na2/3Mn1/2Fe1/2O2 by reducing the content of Mn and slowing down the loss of Mn on the surface of the Na2/3Mn1/2Fe1/4Co1/4O2, as well as by improving the activity of Fe3+ and the stability of Fe4+ in the electrode. This research is the first to demonstrate the origin of the excellent cycle stability of Na2/3Mn1/2Fe1/4Co1/4O2, which may provide a new strategy for the development of electrode materials for use in sodium-ion batteries.  相似文献   

2.
《Ceramics International》2016,42(13):14587-14594
A facile chemical deposition method has been adopted to prepare cerium fluoride (CeF3) surface modified LiNi1/3Co1/3Mn1/3O2 as cathode material for lithium-ion batteries. Structure analyses reveal that the surface of LiNi1/3Co1/3Mn1/3O2 particles is uniformly coated by CeF3. Electrochemical tests indicate that the optimal CeF3 content is 1 wt%. The 1 wt% CeF3-coated LiNi1/3Co1/3Mn1/3O2 can deliver a discharge capacity of 107.1 mA h g−1 even at 5 C rate, while the pristine does only 57.3 mA h g−1. Compared to the pristine, the 1 wt% CeF3-coated LiNi1/3Co1/3Mn1/3O2 exhibits the greatly enhanced capacity and cycling stability in the voltage range of 3.0–4.5 V, which suggests that the CeF3 coating has the positive effect on the high-voltage application of LiNi1/3Co1/3Mn1/3O2. According to the analyses from electrochemical impedance spectra, enhanced electrochemical performance is mainly because the stable CeF3 coating layer can prevent the HF-containing electrolyte from continuously attacking the LiNi1/3Co1/3Mn1/3O2 cathode and retard the passivating layer growth on the cathode.  相似文献   

3.
Economy and efficiency are two important indexes of lithium-ion batteries (LIBs) materials. In this work, nitrogen doped hollow porous coaxial carbon fiber/Co3O4 composite (N-PHCCF/Co3O4) is fabricated using the fibers of waste bamboo leaves as the template and carbon resource by soaking and thermal treatment, respectively. The N-PHCCF/Co3O4 exhibits an outstanding electrochemical performance as anode material for lithium ion batteries, due to the nitrogen doping, coaxial configuration and porous structure. Specifically, it delivers a high discharge reversible specific capacity of 887 mA h g?1 after 100 cycles at the current density of 100 mA g?1. Furthermore a high capability of 415 mA h g?1 even at 1 A g?1 is exhibited. Most impressively, the whole process is facile and scalable,exhibiting recycling of resource and turning waste into treasure in an eco-friendly way.  相似文献   

4.
《Ceramics International》2016,42(4):5397-5402
Lithium (Li)-rich layered oxides are considered promising cathode materials for Li-ion batteries because of their favorable properties. Here, we report our recent finding in the novel oxide, aluminum fluoride (AlF3)-modified Li1.2Mn0.54Ni0.13Co0.13O2 (LMNCAF), which was synthesized via a facile, cost-effective and readily scalable solid-state reaction. LMNCAF possess an F and Al co-doped core structure with a LiF nano-coating on its surface which leads to considerably enhancement in the electrochemical performance of the oxide. The initial discharge capacity (at 0.05 C) increased from 212 mA h g−1 for Li1.2Mn0.54Ni0.13Co0.13O2 to 291 mA h g−1 for LMNCAF. A much higher discharge capacity of 211 mA h g−1 was obtained for LMNCAF after 99 charge/discharge cycles at 0.2 C compared with that of Li1.2Mn0.54Ni0.13Co0.13O2 (160 mA h g−1). Our preliminary results suggest that AlF3 modification is an effective strategy to tailor the physicochemical and electrochemical properties of Li-rich layered oxides.  相似文献   

5.
《Ceramics International》2017,43(4):3866-3872
Key issues including poor rate capability and limited cycle life span should be addressed for the extended application of LiNi0.5Co0.2Mn0.3O2 cathode. The suppressed Li+/Ni2+ site exchange, enlarged LiO2 inter-slab space and reduced impedance, which could facilitate the structure stability, were achieved by controlled Niobium (Nb) doping and contributed to enhanced performance even at elevated temperature (55 °C). The detailed role of the doped Nb was investigated thoroughly and systematically with the help of XRD, SEM, XPS and related electrochemical tests. The full and accurate results demonstrate that the Li(Ni0.5Co0.2Mn0.3)0.99Nb0.01O2 sample with appropriate Nb doping amount possess high capacity retention of 93.77% after 100 cycles at 1.0 C and improved rate performance with 125.5 mA h g−1 at 5.0 C, which are much better than that of the LiNi0.5Co0.2Mn0.3O2. Moreover, at high temperature of 55 °C, Nb doping shows more remarkable effect on stabilizing the structure and 88.63% of the initial reversible capacity could be retained, which is ~20% higher than the LiNi0.5Co0.2Mn0.3O2. This study intensively determines that controlled Nb doping could be effectively maintain the structure stability of advanced LiNi0.5Co0.2Mn0.3O2 cathode and promote the development of high energy density lithium ion batteries.  相似文献   

6.
Optimization of electrodes for charge storage with appropriate processing conditions places significant challenges in the developments for high performance charge storage devices. In this article, metal cobaltite spinels of formula MCo2O4 (where M = Mn, Zn, Fe, Ni and Co) are synthesized by oxalate decomposition method followed by calcination at three typical temperatures, viz. 350, 550, and 750 °C and examined their performance variation when used as anodes in lithium ion batteries. Phase and structure of the materials are studied by powder x-ray diffraction (XRD) technique. Single phase MnCo2O4,ZnCo2O4 and Co3O4 are obtained for all different temperatures 350 °C, 550 °C and 750 °C; whereas FeCo2O4 and NiCo2O4 contained their constituent binary phases even after repeated calcination. Morphologies of the materials are studied via scanning electron microscopy (SEM): needle-shaped particles of MnCo2O4 and ZnCo2O4, submicron sized particles of FeCo2O4 and agglomerated submicron particle of NiCo2O4 are observed. Galvanostatic cycling has been conducted in the voltage range 0.005–3.0 V vs. Li at a current density of 60 mA g?1 up to 50 cycles to study their Li storage capabilities. Highest observed charge capacities are: MnCo2O4 – 365 mA h g?1 (750 °C); ZnCo2O4 – 516 mA h g?1 (550 °C); FeCo2O4 – 480 mA h g?1 (550 °C); NiCo2O4 – 384 mA h g?1 (750 °C); and Co3O4 – 675 mA h g?1 (350 °C). The Co3O4 showed the highest reversible capacity of 675 mA h g?1; the NiO present in NiCo2O4 acts as a buffer layer that results in improved cycling stability; the ZnCo2O4 with long needle-like shows good cycling stability.  相似文献   

7.
《Ceramics International》2007,33(6):1093-1098
Spherical and fine-sized Li(Ni1/3Co1/3Mn1/3)O2 particles were prepared using spray pyrolysis. Precursor particles with mixed Mn2O3, Co3O4 and NiO compositions were prepared using spray pyrolysis from aqueous and polymeric precursor solutions. The precursor particles prepared from the aqueous solution had hollow and porous morphologies. The precursor particles prepared from the polymeric precursor solution with citric acid and ethylene glycol were spherical in shape and had filled morphologies. The spherical precursor particles with filled morphologies formed spherical, fine-sized Li(Ni1/3Co1/3Mn1/3)O2 particles with filled morphologies after post-treatment with LiOH. The mean crystallite sizes of the Li(Ni1/3Co1/3Mn1/3)O2 particles prepared from spray solutions with and without lithium at the post-treatment temperature of 800 °C were 56 and 31 nm, respectively. The initial discharge capacities of the Li(Ni1/3Co1/3Mn1/3)O2 particles prepared using spray pyrolysis from spray solutions with and without lithium were 178 and 181 mAh g−1, respectively, after a post-treatment temperature of 800 °C.  相似文献   

8.
《Ceramics International》2017,43(15):11848-11854
LiNi0.5Co0.2Mn0.3O2 (523) coated with ~ 20 nm thick Y2O3 nano-membrane is prepared via a sol-type chemical precipitation process based on electrostatic attraction between the materials. The nano-Y2O3-coated 523 cathode can deliver 160.3 mA h g−1 (87.8% of its initial discharge capacity) after 50 cycles at 1 C (180 mA g−1) between 3.0 and 4.6 V by coin cell testing, while the pristine 523 keeps only 146.2 mA h g−1 with 78.6% capacity retention left. The capacity retention rate increases from 50% to 86.7% after 150 cycles at 1 C in 3.0–4.35 V by soft package testing under 45 °C. Through this novel Y2O3 coating operation, both the charge transfer resistance and the electrode polarization of the 523 electrode have been suppressed, and its structure stability is also improved.  相似文献   

9.
Surface-interface reaction between the electrode and electrolyte plays a key role in lithium-ion storage properties, especially for high voltage cathode such as LiCoPO4 and Ni-riched cathode. Generally, surface modification is an effective method to improve the electrochemical performance of electrode materials. Herein, in order to revise the LiCoPO4 cathode with desirable properties, uniform AlF3-modified LiCoPO4 (LiCoPO4@AlF3) cathode materials in nano-sized distribution are synthesized. XRD result indicates that there is no structural transformation observed after AlF3 coating. TEM characterization and XPS analysis reveal that the surface of LiCoPO4 particle is coated by a nano-sized uniform AlF3 layer. Further, the electrochemical results indicate that AlF3 layer significantly improves the cycling and rate performances of LiCoPO4 cathode within the voltage range of 3.0–5.0 V. After a series of optimization, 4 mol% AlF3-coated LiCoPO4 material exhibits the best properties including an initial discharge capacity of 159 mA h g?1 at 0.1 C with 91% capacity retention after 50 cycles, especially a discharge capacity of 90 mA h g?1 can be obtained at 1 C rate. CV curves indicate that the polarization of cathode is reduced by AlF3 layer and EIS curves reveal that AlF3 layer relieves the increase of resistance to facilitate Li-ion transfer at the interface between electrode and electrolyte during the cycling process. The enhanced electrochemical performances are attributed to that the AlF3 layer can stabilize the interface between the cathode and electrolyte, form steady SEI film and suppress the electrolyte continuous decomposition at 5 V high voltages. This feasible strategy and novel characteristics of LiCoPO4@AlF3 could promise the prospective applications in the stat-art of special lithium-ion battery with high energy and/or power density.  相似文献   

10.
This paper presents the optimal atmosphere annealing conditions for Mn1.2Co1.5Ni0.3Oδ ceramic thin films fabricated by the RF magnetron sputtering method. The microstructure and oxygen distribution, together with electrical properties, are combined and applied for determining thermal stability. All of the Mn1.2Co1.5Ni0.3Oδ films, which are annealed at various oxygen atmosphere from 1 × 10?3 to 1 × 105 Pa, exhibit a negative temperature coefficient characteristic and show a poly-crystalline spinel structure. The film which annealed at 10 Pa with the most uniform and most dense surface morphology has the minimum resistivity compared to the others. It is characterized by the highest Mn3+ and Mn4+ pair content, which gives the highest carrier concentration of ceramic films. Combined with the aging test at 125 °C for 500 h, the films annealed at 10 Pa have the minimum resistance drift (ΔR/R0 = 2.35%), which is mainly affected by the oxygen vacancy concentration. This demonstrates that the film thermistors annealed in a hypoxia state will never be stable. This is because there will be several oxidation reactions leading to a continuous generation of cationic vacancies during high temperature aging. The present results will open a way to design desired stable negative temperature coefficient thermistors by adjusting the annealing oxygen atmosphere of films.  相似文献   

11.
LiNi1?yCoyO2 (y=0.1, 0.3, and 0.5) were synthesized by a solid-state reaction method at 800 °C and 850 °C using Li2CO3, NiO, and Co3O4 as the starting materials. The electrochemical properties of the synthesized LiNi1?yCoyO2 were then investigated. For samples with the same composition, the particles synthesized at 850 °C were larger than those synthesized at 800 °C. The particles of all the samples synthesized at 850 °C were larger than those synthesized at 800 °C. LiNi0.5Co0.5O2 synthesized at 850 °C had the largest first discharge capacity (159 mA h/g), followed in order by LiNi0.7Co0.3O2 synthesized at 800 °C (158 mA h/g) and LiNi0.9Co0.1O2 synthesized at 850 °C (151 mA h/g). LiNi0.9Co0.1O2 synthesized at 850 °C had the best cycling performance with discharge capacities of 151 mA h/g at n=1 and 156 mA h/g at n=5.  相似文献   

12.
LiNi1/3Co1/3Mn1/3O2 cathode materials have been coated with Al2O3 nano-particles using sol-gel processing to improve its electrochemical properties. The X-ray diffraction (XRD) pattern of the as-prepared Al2O3 nano-particles was indexed to the cubic structure of the γ-Al2O3 phase and had an average size of ∼4 nm. The XRD showed that the structure of LiNi1/3Co1/3Mn1/3O2 was not affected by the Al2O3 coating. However, the Al2O3 coatings on LiNi1/3Co1/3Mn1/3O2 improved the cyclic life performance and rate capability without decreasing its initial discharge capacity. These electrochemical properties were also compared with those of LiAlO2-coated LiNi1/3Co1/3Mn1/3O2 cathode material. The electrochemical impedance spectroscopy (EIS) was studied to understand the enhanced electrochemical properties of the Al2O3-coated LiNi1/3Co1/3Mn1/3O2 compared to uncoated LiNi1/3Co1/3Mn1/3O2.  相似文献   

13.
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   

14.
《Ceramics International》2016,42(4):4899-4910
The Li-rich layered cathode material Li1.165Mn0.501Ni0.167Co0.167O2 with porous structure has been successfully synthesized through a facile co-precipitation approach followed with a high-temperature calcination treatment, adopting polymer microsphere (PSA) as a template and conductive agent. The PSA-assisted Li1.165Mn0.501Ni0.167Co0.167O2 composite exhibits remarkably improved cycling stability and rate capability compared with the bare composite. It delivers a high initial discharge capacity of 267.0 mA h g−1 at 0.1 C (1 C=250 mA g−1) between 2.0 V and 4.65 V. A discharge capacity of 214.9 mA h g −1 is still obtained after 100 cycles. Furthermore, the diffusion coefficients of Li+ investigated by the cyclic voltammetry technique are approximately 10−15–10−14 cm2 s−1. Such outstanding performance is mainly ascribed to: on one hand, the carbon residue of PSA after being calcined at high temperature contributes to enhance the electronic conductivity of the electrode and alleviates the volume changes during the Li+-insertion/extraction, leading to an improved rate capability; on the other hand, the unique porous structure and small particle size are conductive to increase the exposed electrochemical active surface, shorten Li+ diffusion distance and thus enhance the lithium storage capacity.  相似文献   

15.
《Ceramics International》2017,43(10):7668-7673
LiNi1/3Co1/3Mn1/3O2 cathode coated with a thin layer of graphene (~8 nm) is successfully synthesized by self-assembly and pyrolysis of polyelectrolyte layers on the surface of NMC particles. The graphene coated NMCs still possess a layered structure with good crystallinity and demonstrate a superior electrochemical performance (e.g., rate capability and cycling stability). The best graphene coated NMC cathode is prepared at a calcination temperature of 800 °C, exhibiting a capacity retention of ~90% vs. 78% for pristine NMC @ cycle 100 and 1 C rate. The improvement in cycling performance is further enlarged after 500 cycles (74% vs. 51%). This can be attributed to the dual functions of graphene coating in enhancing electronic conductivity and protecting NMC surface from the contact with electrolyte during the electrochemical reaction.  相似文献   

16.
《Ceramics International》2017,43(13):9960-9967
P2-type layered Na2/3Ni1/4Mn3/4O2 has been synthesized by a solid-state method and its electrochemical behavior has been investigated as a potential cathode material in aqueous hybrid sodium/lithium ion electrolyte by adopting activated carbon as the counter electrode. The results indicate that the Na+/Li+ ratio in aqueous electrolyte has a strong influence on the capacity and cyclic stability of the Na2/3Ni1/4Mn3/4O2 electrode. Increase on the Li+ content leads to a shift of the redox potential towards a high value, which is favorable for the improvement of the working voltage of the layered material as cathode. It is found that the coexistence of Na+ and Li+ in aqueous electrolyte can improve the cyclic stability for the Na2/3Ni1/4Mn3/4O2 electrode. A reversible capacity of 54 mAh g−1 was obtained with a high cyclability as the Na+/Li+ ratio was 2:2. Furthermore, an aqueous hybrid ion cell was assembled with the as-proposed Na2/3Ni1/4Mn3/4O2 as cathode and NaTi2(PO4)3/graphite synthesized in this work as anode in 1 M Na2SO4/Li2SO4 (mole ratio as 2:2) mixed electrolyte. The cell shows an average discharge voltage at 1.2 V, delivering an energy density of 36 Wh kg−1 at a power density of 16 W kg−1 based on the total mass of the active materials.  相似文献   

17.
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   

18.
Nanocomposite of graphene/α-Fe2O3 (G/α-Fe2O3) nanospindles was synthesized by a simple hydrothermal assembly method followed by thermal treatment. The α-Fe2O3 nanospindles were evenly enwrapped by the graphene nanosheets. When evaluated as an anode for Li-ion batteries (LIBs), the G/α-Fe2O3 nanocomposite showed enhanced cycling performance and rate capability compared to pure α-Fe2O3. G/α-Fe2O3 retained a reversible capacity of 607 mAh g?1 after 100 cycles at 100 mA g?1-, which is far higher than that (160 mAh g?1) of α-Fe2O3. The superior electrochemical performance of G/α-Fe2O3 can be attributed to the protection effect of graphene nanosheets to accommodate the volume change of α-Fe2O3 during lithiation/delithiation.  相似文献   

19.
A novel liquid-phase synthesis strategy is demonstrated for the preparation of the Nb-containing ceramic oxide SrCo0.9Nb0.1O3-δ (SCN). In comparison with the traditional solid-state reaction (SSR) method, the liquid-phase synthesis route offers a couple of advantages, including a lower phase formation temperature and a smaller particle size of the SCN materials that are beneficial for applications as proton-conducting fuel cell cathode. With BaCe0.4Zr0.4Y0.2O3-δ (BCZY442) as the electrolyte and the SCN synthesized in this work as the cathode, a proton-conducting solid oxide fuel cell (SOFC) shows a peak power density of 348 mW cm?2 at 700 °C, significantly higher than that of a SOFC fabricated with SCN cathode prepared using the SSR method, which can only deliver 204 mW cm?2 at the same temperature. Additionally, this new synthesis strategy allows impregnation of Sr2+, Co3+and Nb5+ on the solid backbone in aqueous solution, further improving cell performance to reach a peak power density of 488 mW cm?2 at 700 °C.  相似文献   

20.
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   

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