Electrochemical and structural characteristics of metal oxide-coated lithium manganese oxide (spinel type): Part I. In the range of 2.5–4.2 V

The electrochemical and structural characteristics of the metal oxide-coated spinel were investigated in the range of 2.5–4.2 V. Metal oxide coating on commercial spinel powder (LiMn_2−xM_xO₄, M=Zr, Nikki, Japan) was carried out using the sol–gel method. Al₂O₃/(PtO_x or CuO_x)-coated spinel exhibited improved cyclability compared to bare spinel. Impedance analysis results indicated that electrochemical resistance value was not consistent with cycle performance. The improved cycle performance of metal oxide-coated spinel may be due to formation of a new Li₂Mn₄O₉, Li₂MnO₃ phase, which is expected to have stability to phase transition (Jahn–Teller distortion).     

Porous nickel MCFC cathode coated by potentiostatically deposited cobalt oxide: II. Structural and morphological behavior in molten carbonate

Cobalt oxide was deposited on porous nickel by an electrodeposition technique as precursor of a novel MCFC cathode. The behavior of this cathode in molten (Li_0.52Na_0.48)₂CO₃ eutectics at 650 °C under an atmosphere of CO₂:air (30:70) was studied before and after 50 h of exposure by different techniques. Before the exposure, the deposit of cobalt corresponded to a Co₃O₄ thin layer of. This crystalline structure was identified by XRD and Raman spectroscopy. After its exposure in the eutectic melt a loss of cobalt was observed by XRD, Raman spectroscopy, XPS, EDS and ICP-AES. The change in the Co₃O₄ structure into lithium–cobalt–nickel oxide (LiCo_1−yNi_yO₂) was observed by Raman spectroscopy. The SEM micrographs for Co₃O₄-coated porous nickel showed different angular shapes with respect to porous Ni. The nickel solubility for the coated porous nickel, measured by ICP-AES, decreased with respect to uncoated nickel. The Co₃O₄-coated porous nickel cathode showed, after its immersion in the molten carbonate melt, a similar porosity but a higher pore size. LiCo_1−yNi_yO₂-coated NiO offers interesting features which combine the properties of nickel, lithium and cobalt in molten carbonate. This could be a promising novel MCFC cathode material.     

Electrochemical supercapacitor behavior of nanoparticulate rutile-type Ru1−xVxO2

Rutile-type Ru_1−xV_xO₂ nanoparticles possessing high surface area were prepared by a polymerizable-complex method and its electrochemical supercapacitor behavior was studied. X-ray diffractometry, energy-dispersive X-ray analysis, and N₂ adsorption/desorption measurements were used to characterize the structure of the products. The electrochemical supercapacitor behavior of thick and thin films was studied by cyclic voltammetry in various acidic, neutral, and alkaline electrolytes. Ru_1−xV_xO₂ exhibited extremely enhanced supercapacitive properties compared to pure RuO₂. The highest surface redox activity was achieved with an acidic electrolyte. Ru_1−xV_xO₂ showed negligible surface redox activity in neutral electrolytes.     

Al2O3/SiOxNy/SiNx叠层钝化膜对PERC太阳电池性能及LID效应的研究

由于等离子体增强化学的气相沉积（PECVD）法制备的SiO_xN_y薄膜中含有大量H原子,因而具有优异的表面钝化性能。通过在PERC太阳电池的Al₂O₃/SiN_x背钝化叠层中间插入一层SiO_xN_y薄膜,形成Al₂O₃/SiO_xN_y/SiN_x结构,可避免SiN_x所带的固定正电荷对Al₂O₃负电荷场钝化效应的负面影响。试验结果表明,硅片少子寿命从原来的130 μs提高至162 μs,电池转换效率增加0.09%。同时,基于Al₂O₃/SiO_xN_y/SiN_x背钝化的PERC太阳电池的LID也得到了改善,由对照组的1.83%下降到实验组的1.09%。     

Preparation and electrochemical characteristics of LiNi1/3Mn1/3Co1/3O2 coated with metal oxides coating

LiNi_1/3Mn_1/3Co_1/3O₂ prepared by a spray drying method exhibited poor cyclic performance when it was operated at rates of 0.5C and 2C in 3–4.6 V. A metal oxide (ZrO₂, TiO₂, and Al₂O₃) coating (3 wt%) could effectively improve its cyclic performance at both 0.5C and 2C. Electrochemical impedance spectroscopy (EIS) studies suggested that both the surface resistance and the charge transfer resistance of the bare LiNi_1/3Mn_1/3Co_1/3O₂ significantly increase after 100 cycles, whose origin is mainly related to the change in both the particle surface and electrode morphologies. The presence of a thin metal oxide layer could remarkably suppress the increase in the total resistance (sum of the surface resistance and the charge transfer resistance), which was attributed to the improvement in good cyclic performances.     

Selective removal of CO from hydrogen-rich stream over CuO/CexSn1−xO2–Al2O3 catalysts

The solid solutions of Ce_xSn_1−xO₂ incorporated with alumina to form Ce_xSn_1−xO₂–Al₂O₃ mixed oxides, by the suspension/co-precipitation method, were used to prepare CuO/Ce_xSn_1−xO₂–Al₂O₃ catalysts for the selective oxidation of CO in excess hydrogen. Incorporating Al₂O₃ increased the dispersion of Ce_xSn_1−xO₂, but did not change their main structures and did not weaken their redox properties. Doping Sn⁴⁺ into CeO₂ increased the mobility of lattice oxygen and enhanced the activity of the 7%CuO/Ce_xSn_1−xO₂–Al₂O₃ catalyst in the selective oxidation of CO. The selective oxidation of CO was weakened as the doped fraction of Sn⁴⁺ exceeded 0.5. Incorporating appropriate amounts of Sn⁴⁺ and Al₂O₃ could obtain good candidates 7%CuO/Ce_xSn_1−xO₂–Al₂O₃(20%), 1–x=0.1–0.5, for a preferential oxidation (PROX) unit in a polymer electrolyte membrane fuel cell system for removing CO. Its activity was comparable with, and its selectivity was much larger than, that of the noble catalyst 5%Pt/Al₂O₃.     

Ag/Al2O3(Li2O)/g-C3N4光催化乙醇制取环氧乙烷

本文制备了一系列Ag/Al₂O₃(Li₂O)/g-C₃N₄复合催化剂,考察了其可见光催化乙醇制取环氧乙烷的性能。Li₂O可调变Al₂O₃表面的酸性,从而降低了主要副产物乙醛的选择性。Ag/Al₂O₃(Li₂O) 在g-C₃N₄上的负载量对产物环氧乙烷的选择性有较大影响,当Ag/Al₂O₃(Li₂O) 负载量为5wt%时,乙醇具有较高的转换率,且环氧乙烷的选择性高达100%。     

Electrochemical performance of thermally-grown SiO2 as diffusion barrier layer for integrated lithium-ion batteries

Direct integration of lithium-ion battery (LIB) with electronic devices on the same Si substrate can significantly miniaturize autonomous micro systems. For achieving direct integration, a barrier layer is essential to be inserted between LIB and the substrate for blocking Li⁺ diffusion. In this paper, the feasibility of thermal SiO₂ film as the barrier layer is investigated by electrochemical characterization and X-ray photoelectron spectroscopy (XPS). Due to the negligible side reactions of thermal SiO₂ with electrolyte, the solid electrolyte interphase (SEI) layer formed on the surface of the barrier layer is thin and the SEI content mainly consists of hydrocarbon together with slight polyethylene oxide (PEO), Li_xPO_yF_z, and Li₂CO₃. Although 8-nm thermal SiO₂ effectively prevents the substrate from alloying with Li⁺, the whole film changes to Li silicate after electrochemical cycling due to the irreversible chemical reactions of SiO₂ with electrolyte. This degrades the performance of the barrier layer against the electrolyte penetration, thus leading to the existence of Li⁺ (in the form of F-Si-Li) and solvent decompositions (with the products of hydrocarbon and PEO) near the barrier layer/substrate interface. Moreover, it is found that the reaction kinetics of thermal SiO₂ with electrolyte decrease significantly with increasing the SiO₂ thickness and no reactions are found in the bulk of the 30-nm SiO₂ film. Therefore, thermal SiO₂ with an appropriate thickness is a promising barrier layer for direct integration.     

A screen-printed Ce0.8Sm0.2O1.9 film solid oxide fuel cell with a Ba0.5Sr0.5Co0.8Fe0.2O3−δ cathode

Screen-printing technology was developed to fabricate Ce_0.8Sm_0.2O_1.9 (SDC) electrolyte films onto porous NiO–SDC green anode substrates. After sintering at 1400 °C for 4 h, a gas-tight SDC film with a thickness of 12 μm was obtained. A novel cathode material of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ was subsequently applied onto the sintered SDC electrolyte film also by screen-printing and sintered at 970 °C for 3 h to get a single cell. A fuel cell of Ni–SDC/SDC (12 μm)/Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ provides the maximum power densities of 1280, 1080, 670, 370, 180 and 73 mW cm⁻² at 650, 600, 555, 505, 455 and 405 °C, respectively, using hydrogen as fuel and stationary air as oxidant. When dry methane was used as fuel, the maximum power densities are 876, 568, 346 and 114 mW cm⁻² at 650, 600, 555 and 505 °C, respectively. The present fuel cell shows excellent performance at lowered temperatures.     

The effect of multivalent cation dopants on lithium manganese spinel cathodes

The cycling stability of 4 V Li_xMn₂O₄ electrodes in lithium, flooded electrolyte glass cells has been improved by the addition of multivalent cation dopants (Mg²⁺, Zn²⁺ and Al³⁺). Optimal dopant levels to achieve maximum capacity and the greatest stability with repeated cycling have been determined. The effect of doping the oxygen-rich spinel Li₂Mn₄O₉, was also determined and shown to make no significant improvement in the life cycle stability in the 3 V region.     

LiMn2O4 electrode prepared by gold–titanium codeposition with improved cyclability

An LiMn₂O₄ electrode was prepared based on mixed-metals (gold–titanium) codeposition method. By this method, titanium oxide is also incorporated into the electroactive film formed on substrate electrode. Formation of titanium oxide on the spinel surface avoids dissolution of Mn from the spinel at elevated temperatures. TiO₂can act as a bridge between the spinel particles to reduce the interparticle resistance and as a good material for the Li intercalation/deintercalation. Thus, electrochemical performance of the LiMn₂O₄ spinel can be improved by the surface modification with TiO₂. This action improves cyclability for lithium battery performance and reduces capacity fades of LiMn₂O₄ at elevated temperatures.     

Enhancing the elevated temperature performance of Li/LiMn2O4 cells by reducing LiMn2O4 surface area

Lithium-rich spinels were obtained with the same structure but different surface area by two different synthesis routes, namely the “once-annealed” and the “twice-annealed” methods. The elevated temperature performance of Li/Li_1+xMn₂O₄ cell is significantly improved using a spinel cathode with a small surface area: the cell at 50°C lost 5% of the initial capacity over the first 100 cycles based on a spinel cathode with the small surface area of 1.2 m²/g compared to 8% based on a large one of 6.2 m²/g. Also the mechanism responsible for the reaction of LiMn₂O₄ with LiOH to form lithium-rich spinel has been investigated.     

Conditions to prepare PPy/Al2O3/Al used as a solid-state capacitor from aqueous malic solutions

The electrosynthesis of polypyrrole (PPy) has been achieved on aluminium in aqueous medium of malic acid by means of cyclic voltammetry, potentiostatic and galvanostatic techniques. Scanning electron microscopy (SEM) and X-ray microanalysis by dispersion energy spectroscopy (EDS) applying on surfaces show that the PPy coating is developed from the metal surface through the cracks of the initial Al₂O₃ layer. Moreover, the results reveal that the homogeneity of the film achieved increases with the time of electropolymerization.

A mechanism involving the participation of the supporting electrolyte and the pyrrole (Py) in distinct active sites was proposed based on the linear sweep voltammetry. It is observed for all the applied electrochemical techniques that the pyrrole concentration has to be higher than 0.1 M to allow the polypyrrole electrodeposition in acid medium.

Scanning electron microscopy, secondary electrons (SE) and backscattering electrons (BE), shows that the PPy coating obtained in galvanostatic and potentiostatic modes starts with small islands at weak applied potentials or current densities. The corrosion results in 3% NaCl medium show that the PPy coating decreases the corrosion behaviour of the aluminium. The bilayer Al₂O₃/PPy shows a capacitor with future applications.     

Promising alloys for intermediate-temperature solid oxide fuel cell interconnect application

The formation of a low Cr-volatility and electrically conductive oxide outer layer atop an inner chromia layer via thermal oxidation is highly desirable for preventing chromium evaporation from solid oxide fuel cell (SOFC) metallic interconnects at the SOFC operation temperatures. In this paper, a number of ferritic Fe–22Cr alloys with different levels of Mn and Ti as well as a Ni-based alloy Haynes 242 were cyclically oxidized in air at 800 °C for twenty 100-h cycles. No oxide scale spallation was observed during thermal cycling for any of these alloys. A mixed Mn₂O₃/TiO₂ surface layer and/or a (Mn, Cr)₃O₄ spinel outer layer atop a Cr₂O₃ inner layer was formed for the Fe–22Cr series alloys, while an NiO outer layer with a Cr₂O₃ inner layer was developed for Haynes 242 after cyclic oxidation. For the Fe–22Cr series alloys, the effects of Mn and Ti contents as well as alloy purity on the oxidation resistance and scale area specific resistance were evaluated. The performance of the ferritic alloys was compared with that of Haynes 242. The mismatch in thermal expansion coefficient between the different layers in the oxide scale was identified as a potential concern for these otherwise promising alloys.     

Processing options for CdTe thin film solar cells

Processing options for addressing critical issues associated with the fabrication of thin film CdTe solar cells are presented, including window and buffer layer processing, post-deposition treatment, and formation of stable low resistance contacts. The paper contains fundamental data, engineering relationships and device results. Chemical surface deposited CdS and Cd_1−xZn_xS films are employed as the n-type heteropartner window layers. Maintaining junction quality with ultra-thin window layers is facilitated by use of a high resistance oxide buffer layer, such as SnO₂, In₂O₃ or Ga₂O₃, between the heteropartner and the transparent conductive oxide. Thermal annealing of the CdTe/CdS heterostructure in the presence of CdCl₂ and O₂ shifts the chemical equilibrium on the surface of the absorber layer, which influences the bulk electrical properties. Aspects of back contacting CdTe/CdS devices, including etching, Cu application, contact annealing, back contact chemistry and secondary contacts, are discussed. Two commonly employed etches used to produce a Te-rich layer, nitric acid/phosphoric acid mixtures and Br₂/methanol are compared, including the nature and stability of the final treated CdTe surface. The diagnostic abilities of the surface sensitive VASE and GIXRD techniques are highlighted. Various methods of Cu delivery are discussed with consideration to; reaction with Te, processing simplicity, processing time and possible industrial scale-up. Some aspects of back contact stability are presented, including discussion of apparent robust back contacts, which contain a thick Te component.     

Novel device structure for Cu(In,Ga)Se2 thin film solar cells using transparent conducting oxide back and front contacts

Cu(In_1−xGa_x)Se₂ (CIGS)-based thin film solar cells fabricated using transparent conducting oxide (TCO) front and back contacts were investigated. The cell performance of substrate-type CIGS devices using TCO back contacts was almost the same as that of conventional CIGS solar cells with metallic Mo back contacts when the CIGS deposition temperatures were below 500 °C for SnO₂:F and 520 °C for ITO. CIGS thin film solar cells fabricated with ITO back contacts had an efficiency of 15.2% without anti-reflection coatings. However, the cell performance deteriorated at deposition temperatures above 520 °C. This is attributed to the increased resistivity of the TCO’s due to the removal of fluorine from SnO₂ or undesirable formation of a Ga₂O₃ thin layer at the CIGS/ITO interface. The formation of Ga₂O₃ was eliminated by inserting an intermediate layer such as Mo between ITO and CIGS. Furthermore, bifacial CIGS thin film solar cells were demonstrated as being one of the applications of semi-transparent CIGS devices. The cell performance of bifacial devices was improved by controlling the thickness of the CIGS absorber layer. Superstrate-type CIGS thin film solar cells with an efficiency of 12.8% were fabricated using a ZnO:Al front contact. Key techniques include the use of a graded band gap Cu(In,Ga)₃Se₅ phase absorber layer and a ZnO buffer layer along with the inclusion of Na₂S during CIGS deposition.     

Effect of polymorphic phase transformations in Al2O3 film on oxidation kinetics of aluminum powders

Thermogravimetry was used to study the oxidation of aluminum powders at elevated temperatures. Aluminum powders of various particle sizes and surface morphologies were heated in oxygen up to 1500 °C at different heating rates. Partially oxidized samples were recovered from selected intermediate temperatures and the oxide phases present were analyzed by X-ray diffraction. The experimental data were related to current information on stabilities and phase changes of Al₂O₃ polymorphs. Aluminum powders were observed to oxidize in four distinct stages in the temperature range from 300 to 1500 °C. During stage I, from 300 to about 550 °C, the thickness of the natural amorphous alumina layer on the particle surface increases. The rate of this process is controlled by the outward diffusion of Al cations. At about 550 °C, when the oxide layer thickness exceeds the critical thickness of amorphous alumina of about 4 nm, the oxide transforms into γ-Al₂O₃. The specific volume of γ-Al₂O₃ is less than that of amorphous alumina; therefore, the newly formed γ-Al₂O₃ only partially covers the aluminum surface. The oxidation rate increases rapidly at the onset of stage II, but it decreases when the γ-Al₂O₃ layer becomes continuous. During stage III oxidation, the γ-Al₂O₃ layer grows and partially transforms into the structurally similar θ-Al₂O₃ polymorph. Finally, oxidation stage IV is observed after the transition to stable -Al₂O₃ results in an abrupt reduction of oxidation rate. Qualitative analysis of the rates of oxidation at the different stages enables one to understand the wide range of aluminum ignition temperatures observed for particles of different sizes.     

Effect of Co content on performance of LiAl1/3−xCoxNi1/3Mn1/3O2 compounds for lithium-ion batteries

Layered LiAl_1/3−xCo_xNi_1/3Mn_1/3O₂ (0  x  1/3) compounds were studied via the combination of computational and experimental approach. The calculated voltage curve of LiNi_1/3Al_1/3Mn_1/3O₂ compound is presented, indicating it is of great potential for a cathode material of lithium-ion batteries. Unfortunately, it was found that the LiNi_1/3Al_1/3Mn_1/3O₂ compound without impurity phase could not be synthesized via a sol–gel process. To obtain a layered compound without impurity phase, partial of Al is replaced by Co in LiNi_1/3Al_1/3Mn_1/3O₂ compound in this study. Layered LiAl_1/3−xCo_xNi_1/3Mn_1/3O₂ (0  x  1/3) compounds were synthesized via sol–gel reaction at 900 °C under a oxygen stream. Single phase of the LiAl_1/3−xCo_xNi_1/3Mn_1/3O₂ in 1/6  x  1/3 region could be prepared successfully. The discharge capacity and conductivity increased with an increase in the Co-substitution content. The enhancement of the conductivity and phase purity by the introduction of Co content shows profound influence on the performance of the LiAl_1/3−xCo_xNi_1/3Mn_1/3O₂ compounds.     

Effect of support on catalytic properties of Rh catalysts for steam reforming of 2-propanol

Catalytic performance of Rh catalyst supported on CeO₂, Al₂O₃, SiO₂, ZrO₂, MgO or TiO₂ for steam reforming of 2-propanol has been studied. The performance was greatly influenced by the type of the supports through interactions between Rh and supports. CeO₂-supported Rh catalyst resulted in the highest selectivity among the catalysts studied here. It probably has a longer catalytic life than Al₂O₃-supported catalysts actually known to be stable, because the amount of coke deposited on it was much smaller than that on the Al₂O₃-supported one. This mitigation of coke deposition has been explained by a reduction and oxidation cycle of CeO₂.     

Capacity fading with oxygen loss for manganese spinels upon cycling at elevated temperatures

The nominal LiMn₂O₄ and Li-doped spinels with different oxygen stoichiometry were prepared and investigated for capacity fading upon cycling at elevated temperatures. The discharge plateau at 3.2 V originating from oxygen defects in manganese spinels is observed to grow very quickly to nearly a maximum scale in initial 15 cycles at 60 °C. Meanwhile, the majority of capacity fading is lost. Therefore, the quick capacity fading in the initial stage is associated with the increase of oxygen deficiencies or oxygen loss upon cycling. It is proposed that the oxygen loss is originated from the decomposition of instable spinel phases that containing little Li cations on the 8a sites ([□₁]_8a[Mn_2−x]_16d[O_4−δ□_δ]_32e, etc.), which are formed upon charging to the upper voltage limit. This phenomenon is much severe for nominal LiMn₂O₄ spinels with oxygen deficiencies. After partial substitution of Mn with Li, part of the Li cations on the 8a sites will be retained upon charging to the upper voltage limit. Thereafter, the cycling performance can be improved for the stabilized spinel phases formed upon charging.