Capacitance performance enhancement of TiO2 doped with Ni and graphite

Nano-amorphous TiO2 was prepared by a sol-gel method. The results of X-ray diffraction (XRD) and scanning electron microscopy (SEM) show that the composite electrode material (TiO2-NiO-C) is made of powder with a grain size of 36.2 nm. Doping of nickel and graphite can increase the electrical conductivity and the specific surface area of nano-amorphous TiO2. The electrochemical properties of TiO2-NiO-C,such as self-discharge, leakage current, and cycle life, were studied using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and charge-discharge test. With a charge-discharge current density of 500 mA/g, the specific capacity of the TiO2-NiO-C composite material reaches 12.88 mAh/g. Also, the expense of capacity is only 3.88% after 500 cycles. The electrochemical capacitor with the electrode material of TiO2-NiO-C shows excellent capacity and cycling performance.     

Electrochemical hydrogen absorbing properties of graphite/AB5 alloy composite electrode

Graphite is an inexpensive carbon material, but its hydrogen absorbing performance has attracted little attention. In this paper, in order to lower the cost of nickel metal-hydride (Ni-MH) battery, graphite is used as a hydrogen absorbing material in its negative electrode. The results of charge-discharge tests show that the graphite electrode has poor electrochemical hydrogen absorbing performance. The capacity of the graphite/AB₅ alloy (90 wt%) composite electrode is close to AB₅ alloy (298 mAh/g), but it has higher charge-discharge polarization and difficulty in activation. When graphite is modified with metal nickel powder by a simple ball milling process, the capacity of the composite electrode reaches to 315 mAh/g and its activation is accelerated. The results of electrochemical impedance spectroscopy (EIS) tests show that hydrogen diffusion in the modified composite electrode is more rapid than in AB₅ alloy, thereby resulting in lower charge-discharge polarization and better discharge performance at large currents.     

Preparation,characterization and electrochemical properties of mesoporous LiFe<Subscript>0.99</Subscript>Mo<Subscript>0.01</Subscript>PO<Subscript>4</Subscript>/C

A mesoporous LiFe_0.99Mo_0.01PO₄/C composite was synthesized by the sol-gel method using (NH₄)₂MoO₄ as a doping starting material. The formation of conductive carbon, metal doping and mesopores was achieved simultaneously in the prepared material. The characterizations of crystal structures and microstructures were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), extended X-ray-absorption fine-structure (EXAFS) and X-ray-absorption near-structure spectroscopy (XANES), while the surface area was determined using N₂ adsorption techniques. Cyclic voltammetry (CV) and charge-discharge cycling performance were used to characterize its electrochemical properties. The sample possessed uniformly distributed mesopores with an average pore size of 4 nm, and the specific surface area was about 69.368 m²/g. The results show that the reversible capacity of mesoporous LiFe_0.99Mo_0.01PO₄/C is about 160 mAh/g at 0.1C, 135 mAh/g at 1C and 90 mAh/g at 5C, respectively. The capacity fading is neglectable.     

Electrochemical performance of C-La<Superscript>3+</Superscript> codoped LiFePO<Subscript>4</Subscript> synthesized by microwave heating

La³⁺ was selected to elevate the lattice electronic conductivity of LiFePO₄, and LiFePO₄/(C+La³⁺) cathode powders were synthesized by microwave heating using a domestic microwave oven for 35 min. The microstructures and morphologies of the synthesized materials were investigated by XRD and SEM. The electrochemical performances were evaluated by galvanostatic charge-discharge. The electrochemical performance of LiFePO₄ with different La³⁺ contents was studied. Results indicated that the initial specific discharge capacity of LiFePO₄/(C+La³⁺) composites with 2% La³⁺ (116.3 mAh/g) was better than that of LiFePO₄/C (105.4 mAh/g). The addition of La³⁺ further improved the electrochemical properties. So the codoping is an effective method to improve the electrochemical performance.     

Employment of encapsulated Si with mesoporous TiO2 layer as anode material for lithium secondary batteries

Silicon composite of nano-capsule type is newly applied as an active anode material for lithium ion batteries. TiO₂-encapsulated silicon powders were synthesized by a sol-gel reaction with titanium ethoxide. Silicon nanoparticles were successfully embedded into porous titanium oxide capsules that played as a buffer layer against drastic volume changes of silicon during the charge-discharge cycling, consequently leading to the retardation of the capacity fading of intrinsic silicon materials. The electrochemical and structural properties of silicon nanocomposites with different surface areas of encapsulating TiO₂ layer were characterized by X-ray diffraction(XRD), nitrogen gas adsorption analysis by the Brunauer-Emmett-Teller(BET) equation, transmission electron microscopy(TEM), and galvanostatic charge-discharge experiments.     

The effects of the particle size and active materials on the discharge properties of the Li/Fe(X)S<Subscript>2</Subscript> electrode

Although Li/S batteries produce an efficient initial discharge capacity, they have poor cycle characteristics due to the loss of the active material that occurs in these batteries. Therefore, the material of the metal sulfide series has recently been studied as a substitute. In the present study, the possibility of fine FeS₂ and Fe(x)S₂ compound powders (x=Ni, Co, Mo) are examined using a mechanical alloying method, and the discharge capacity is measured. The mean particle size of the FeS₂ compound powders was measured to be 600 nm at a milling time of 40 h. This data was attained through the utilization of the SEM morphologies. The initial discharge capacity of a Li/FeS₂ battery was 430 mAh/g-FeS₂ if into a fine powder for 20 h milled, and 890 mA/g-FeS₂ if into a fine powder for 30 h milled. Moreover, it was found that if there is an addition of Ni or Co into the compound, it would increase the discharge properties. Fe(x)S₂ composite powders were synthesized in order to improve the cycle life of the battery. From the charge-discharge test results, the initial discharge capacity of the Fe(Ni)S₂ electrode was 845 mAh/g. The initial discharge capacity of the Fe(Co)S₂ electrode was 500 mAh/g, but it showed a better cycle performance than the discharge capacity of electrodes with either additions of Ni or Mo.     

B参杂对NiO/Ni(OH)2电极材料电容性能的影响

通过化学镀再电化学氧化的方法在铜片表面制备出带有微米微坑和微米微球的均一NiO/Ni(OH)₂和B参杂的NiO/Ni(OH)₂(B)两种电极材料,采用扫描电镜(SEM/EDX)、X射线衍射(XRD)、X射线光电子能谱(XPS)和电化学技术对所制备的两种电极材料进行表征和电化学性能测试。SEM、XRD和XPS的测试结果表明, 所制备的两种电极材料由Ni、NiO和Ni(OH)₂组成,并且NiO/Ni(OH)₂(B)中B的参杂量可达14.6wt%。循环伏安测量和恒电流充放电试验表明,两种电极材料均具有较高的电化学活性和可逆性;在1 A/g的充放电电流密度下, 两种NiO/Ni(OH)₂和NiO/Ni(OH)₂(B)电极材料经历10000次充放电循环后分别给出了1380 和1930F/g的比电容, 显示出较高的比电容特性和良好的电化学稳定性;电化学阻抗谱表明NiO/Ni(OH)₂(B)电极材料较NiO/Ni(OH)₂电化学反应电阻降低了约2个数量级;Ragone曲线揭示了所制备的两种电极材料具有较高的功率密度和较低的能量密度。B的参杂使得NiO/Ni(OH)₂(B)电极材料表面氧化物含量增大并且形成微米微球形貌,增大了电极表面积以及与电解液的接触和润湿作用,降低了电极材料表面能带带隙能,从而导致较小的电化学反应电阻和电导率的提高是其显示优异赝电容性能的主要原因。     

Photoresponse and donor concentration of plasma-sprayed TiO<Subscript>2</Subscript> and TiO<Subscript>2</Subscript>-ZnO electrodes

The photoelectrochemical characteristics of plasma-sprayed porous TiO₂, TiO₂-5%ZnO, and TiO₂-10%ZnO electrodes in 0.1 N NaOH solution were studied through a three-electrode cell system. The microstructure, morphology, and composition of the electrodes were analyzed using an electron probe surface roughness analyzer (ERA-8800FE), scanning electron microscopy, and x-ray diffraction. The results indicate that the sprayed electrodes have a porous microstructure, which is affected by the plasma spray parameters and composition of the powders. The TiO₂-ZnO electrodes consist of anatase TiO₂, rutile TiO₂, and Zn₂Ti₃O₈ phase. The photoresponse characteristics of the plasma-sprayed electrodes are comparable to those of single-crystal TiO₂, but the breakdown voltage is close to 0.5 V (versus that of a saturated calomel electrode). The short-circuit photocurrent density (J _SC) increases with a decrease of donor concentration, which was calculated according to the Gartner-Butler model. For the lowest donor concentration of a TiO₂-5%ZnO electrode sprayed under an arc current of 600 A, the short-circuit J _SC is approximately 0.4 mA/cm² higher than that of the TiO₂ electrodes under 30 mW/cm² xenon light irradiation. The J _SC increases linearly with light intensity. The original version of this paper was published as part of the DVS Proceedings: “Thermal Spray Solutions: Advances in Technology and Application,” International Thermal Spray Conference, Osaka, Japan, 10–12 May 2004, CD-Rom, DVS-Verlag GmbH, Düsseldorf, Germany.     

微波原位制备作为锂离子电池电极材料的石墨烯/TiO2 纳米复合物

通过改造的家用微波炉,实现了原位高效制备石墨烯/TiO₂纳米复合物。结果表明：微波辅助法能够在商用锐钛矿型TiO₂纳米颗粒表面均匀制备石墨烯纳米片,通过SiO₂/Si的剧烈电晕放电,其制备时间仅需数分钟（最短3 min）。石墨烯纳米片的尺寸大约为50 nm且缺陷很少。TiO₂晶体结构仍为锐钛矿型,主要归功于极短的制备周期和较低的反应温度（600~700 ℃）。石墨烯具有优异的电导率,可以提升锂离子扩散速率、提高电子传输速率并降低接触电阻。在1 C（170 mA·g^-1）条件下石墨烯/TiO₂纳米复合物的电池放电比容量提高了2倍。与商业化锐钛矿型TiO₂纳米颗粒相比,在1 C到5 C的不同充放电倍率下,石墨烯/TiO₂纳米复合物的比容量差距显著扩大。     

Preparation of anatase TiO<Subscript>2</Subscript> with assistance of surfactant OP-10 and its electrochemical properties as an anode material for lithium ion batteries

With the assistance of nonionic surfactant (OP-10) and surface-selective surfactant (CH₃COOH), anatase TiO₂ was prepared as an anode material for lithium ion batteries. The morphology, the crystal structure, and the electrochemical properties of the prepared anatase TiO₂ were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), electrochemical impedance spectroscopy (EIS), and galvanostatic charge and discharge test. The result shows that the prepared anatase TiO₂ has high discharge capacity and good cyclic stability. The maximum discharge capacity is 313 mAh·g⁻¹, and there is no significant capacity decay from the second cycle.     

Synthesis of LiFePO<Subscript>4</Subscript>/C as cathode material by a novel optimized hydrothermal method

Olivine LiFePO 4 , as a cathode material for lithium ion batteries, was prepared by a novel optimized hydrothermal method; afterwards, the product mixed with glucose was two-step (350℃ and 700℃) calcinated under high-purity N 2 atmosphere to obtain the LiFePO 4 /C composite. The study on the hydrothermal preparation method, which focused on the influences of molar ratios, initial pH value, reaction temperature, and duration, was made to promote the resultant performances and to investigate the relations between the performances and the reaction conditions. The resultant samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and electrochemical tests, which include charge-discharge, electrochemical impedance spectroscopy, and cyclic voltammetry. The result shows that the optimal hydrothermal condition is to set the Li:Fe:P molar ratio at 3:1:1 and the reaction temperature at 180℃ for 5 h duration with an initial pH value of 7. The optimized sample, with an average particle size of 100 to 300 nm and a discharge capacity of 118.2 mAh·g-1 at 0.1C, exhibits a stable and narrow-gapped charge-discharge platform and small capacity losses after cycles.     

Surface modification of LiNi<Subscript>1/3</Subscript>Co<Subscript>1/3</Subscript>Mn<Subscript>1/3</Subscript>O<Subscript>2</Subscript> with Cr<Subscript>2</Subscript>O<Subscript>3</Subscript> for lithium ion batteries

Cr 2 O 3-coated LiNi 1/3 Co 1/3 Mn 1/3 O 2 cathode materials were synthesized by a novel method. The structure and electrochemical properties of prepared cathode materials were measured using X-ray diffraction (XRD), scanning electron microscopy (SEM), charge-discharge tests, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). The measured results indicate that surface coating with 1.0 wt% Cr 2 O 3 does not affect the LiNi 1/3 Co 1/3 Mn 1/3 O 2 crystal structure (α-NaFeO 2 ) of the cathode material compared to the pristine material, the surfaces of LiNi 1/3 Co 1/3 Mn 1/3 O 2 samples are covered with Cr 2 O 3 well, and the LiNi 1/3 Co 1/3 Mn 1/3 O 2 material coated with Cr 2 O 3 has better electrochemical performance under a high cutoff voltage of 4.5 V. Moreover, at room temperature, the initial discharging capacity of LiNi 1/3 Co 1/3 Mn 1/3 O 2 material coated with 1.0 wt.% Cr 2 O 3 at 0.5C reaches 169 mAh·g 1 and the capacity retention is 83.1% after 30 cycles, while that of the bare LiNi 1/3 Co 1/3 Mn 1/3 O 2 is only 160.8 mAh·g 1 and 72.5%. Finally, the coated samples are found to display the improved electrochemical performance, which is mainly attributed to the suppression of the charge-transfer resistance at the interface between the cathode and the electrolyte.     

三维泡沫状结构生物质碳/MoS2复合材料的电化学储锂性能

以废弃油茶籽粕作为碳源,将MoS2负载于生物质碳上,再涂覆聚多巴胺盐酸盐构建复合型生物质碳/MoS2电极材料.研究不同MoS2含量复合电极材料的电化学储锂性能.SEM观察结果表明,该复合材料具有以MoS2作为夹层的三维泡沫状结构.XRD和HRTEM测试结果表明MoS2的层间距增大.XPS分析结果显示,活性材料中已形成M...     

Mechanism for the degradation of MmNi<Subscript>3.9</Subscript>Co<Subscript>0.6</Subscript>Mn<Subscript>0.3</Subscript>Al<Subscript>0.2</Subscript> electrode and effects of additives on electrode degradation for Ni-MH secondary batteries

Electrode degradation can affect the lifetime and safety of Ni-MH secondary batteries. This study examined the factors responsible for the degradation of metal hydride (MH) electrodes. The charge-discharge characteristics and cycle life of an MmNi_3.9Co_0.6Mn_0.3Al_0.2 (Mm: misch metal) type MH electrode were examined in a cell with a KOH electrolyte. After the charge-discharge cycles, the surface morphology of the electrodes was analyzed to monitor the extent of degradation. Electrochemical impedance spectroscopy provided information on the conductivity of the electrode. X-ray photon spectroscopy (XPS) was used to quantify the degradation of the electrode in terms of its composition. The MH electrodes degraded with cycling. This phenomenon was more prominent at higher C-rates and temperatures. The electrode degradation was attributed to the loss of active material from the current collector by the repeated absorption and desorption of hydrogen and the formation of an Al₂O₃ oxide layer on the electrode surface with cycling. In addition, the effects of the addition of Co nano and Y₂O₃ powder on the degradation of the MmNi_3.9Co_0.6Mn_0.3Al_0.2 electrode were examined. The addition of the Y₂O₃ and Co nano powder significantly improved the performance of the MH electrode by increasing the cycle life and initial activation rate.     

Effects of defects generated in ALD TiO<Subscript>2</Subscript> films on electrical properties and interfacial reaction in TiO<Subscript>2</Subscript>/SiO<Subscript>2</Subscript>/Si system upon annealing in vacuum

Thin TiO₂ layers grown at 130°C on SiO₂-coated Si substrates by atomic layer deposition (ALD) using TTIP and H₂O as precursors were annealed, and the effects of the annealing temperature on the resulting electrical properties of TiO₂ and the interface properties between a Pt electrode and TiO₂ were examined using transmission line model (TLM) structures. The as-deposited TiO₂ thin film had an amorphous structure with OH groups and a high resistivity of 6×10³Ω-cm. Vacuum annealing at 700 °C transformed the amorphous film into an anatase structure and reduced its resistivity to 0.04Ω-cm. In addition, the vacuum-annealing of the TiO₂/SiO₂ structure at 700°C produced free silicon at the TiO₂-SiO₂ interface as a result of the reaction between the Ti interstitials and SiO₂. The SiO₂ formed on the TiO₂ surface caused a Schottky contact, which was characterized by the TLM method. The use of the TLM method enabled the accurate measurement of the resistivity of the vacuum-annealed TiO₂ films and the characterization of the Schottky contacts of the metal electrode to the TiO₂.     

Preparation of spherical spinel LiCr<Subscript>0.04</Subscript>Mn<Subscript>1.96</Subscript>O<Subscript>4</Subscript> cathode materials based on the slurry spray drying method

Regular spherical chromium doped spinel lithium manganese oxides (LiCr_0.04Mn_1.96O₄) with an average particle size of about 20 μm were prepared by the slurry spray drying process. The materials were compared with non-spherical LiCr_0.04Mn_1.96O₄ materials prepared by the common drying process, and all materials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), laser particle analyzer and Brunauer-Emmett-Teller (BET) specific surface area test. Electrochemical performances of these cathode materials were studied by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and Li/LiCr_0.04Mn_1.96O₄ battery test. The results show that the spherical active material is single spinel structure, compact, and with narrow particle size distribution and low BET specific surface area. Compared with the non-spherical material, the spherical material prepared by the spray drying process shows a lower electrochemical impedance, a fewer electrochemical polarization and a better charge/discharge rate capability and capacity retention at elevated temperatures.     

Performance and capacity fading reason of LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript>/graphite batteries after storing at high temperature

Spinel LiMn₂O₄ was synthesized by a solid-state method. A 204468-size battery was fabricated and stored at 55°C. The structure and morphology of the LiMn₂O₄ cathode were analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM) technique. Energy dispersive spectroscopy (EDS) was used to analyze the surface component of the carbon anode. The discharge capacities of LiMn₂O₄ stored for 0, 24, 48, and 96 h are 106, 98, 96, and 92 mAh·g⁻¹, respectively. The cyclic performance is improved after storage. The capacity retentions of LiMn₂O₄ stored for 0, 24, 48, and 96 h are 83.8%, 85.8%, 86.9%, and 88.6% after 180 cycles. The intensity of all the LiMn₂O₄ diffraction peaks is weakened. Mn is detected from the carbon electrode when the battery is stored for 96 h. Cyclic voltammograms and electrochemical impedance spectroscopy (EIS) were used to examine the surface state of the electrode after storage. The results show that the resistance and polarization of LiMn₂O₄/electrolyte is increased after storage, which is responsible for the fading of capacity.     

Synthetically Controlled,Carbon-Coated Co<Subscript>2</Subscript>SnO<Subscript>4</Subscript>/SnO<Subscript>2</Subscript> Composite Anode for Lithium-ion Batteries

The inherent drawbacks of Co₂SnO₄ in demonstrating the closer-to-theoretical capacity value behavior and the inadmissible volume-expansion-related capacity fade behavior have been surpassed by choosing a tailor-made material composition of Co₂SnO₄/SnO₂, prepared at two different temperatures such as 400°C and 600°C to obtain residual carbon-containing and carbon-free compositions, respectively. Among the products, carbon-coated Co₂SnO₄/SnO₂ composite exhibits better electrochemical performance compared with that of the carbon-free product mainly because of the beneficial effect of carbon in accommodating the volume-expansion-related issues arising from the alloying/de-alloying mechanism. A combination of conversion reaction and alloying/de-alloying mechanism is found to play a vital role in exhibiting closer-to-theoretical capacity values. In other words, an appreciable specific capacity value of 834 mAh g^?1 has been exhibited by Co₂SnO₄/SnO₂ anode containing carbon coating, thus, demonstrating the possibility to improve the electrochemical performance of the title anode through carbon coating, which is realized as a result of the addition of carefully manipulated synthesis conditions.     

Chemical state and ultra-fine structure analysis of biocompatible TiO<Subscript>2</Subscript> nanotube-type oxide film formed on titanium substrate

TiO₂ nanotube-type oxide film on Ti substrate has been fabricated using an electrochemical method, and the chemical bonding state, ultra-fine structures, and surface characteristics of the TiO₂ nanotube layer have been investigated. The formation and growth of a self-organized nanotube layer can be achieved directly by anodization in NH₄-containing electrolytes. The diameter, length, and wall thickness of the nanotube are significantly affected by anodizing conditions such as applied voltage, current density, and anodizing time. The length limiting factor of nanotube growth was found to be the diffusion of ionic species in the electrolyte. XRD investigations revealed that annealed nanotubes have anatase and rutile structure, and some Ti-peaks from the Ti substrate were observed. From the compositional analysis of TiO₂ nanotubes layer using Energy Dispersive Spectroscopy (EDS), Ti, O, and P elements were obtained in the wall nanotube layer. For incorporated P-containing in the TiO₂ nanotube layer, various chemical states were presented, which were revealed mostly in the forms of H₂PO₄, HPO₄ ^2-, and PO₄ ^3-.     

Synthesis and electrochemical performances of LiCoO<Subscript>2</Subscript> recycled from the incisors bound of Li-ion batteries

A new LiCoO₂ recovery technology for Li-ion batteries was studied in this paper. LiCoO₂ was peeled from the Al foil with dimethyl acetamide (DMAC), and then polyvinylidene fluoride (PVDF) and carbon powders in the active material were eliminated by high temperature calcining. Subsequently, Li₂CO₃, LiOH·H₂O and LiAc·2H₂O were added into the recycled powders to adjust the Li/Co molar ratio to 1.00. The new LiCoO₂ was obtained by calcining the mixture at 850°C for 12 h in air. The structure and morphology of the recycled powders and resulting samples were studied by XRD and SEM techniques, respectively. The layered structure of LiCoO₂ synthesized by adding Li₂CO₃ is the best, and it is found to have the best characteristics as a cathode material in terms of charge-discharge capacity and cycling performance. The first discharge capacity is 160 mAh·g⁻¹ between 3.0–4.3 V. The discharge capacity after cycling for 50 times is still 145.2 mAh·g⁻¹.