Sol-gel synthesis of nanometer silicon/silicon suboxide/carbon anode material

A stacked Si/SiO_(x)/C composite anode material with carbon-coated structure was prepared by sol-gel method combined with carbothermal reduction using organic silicon.The results of X-ray diffractometry, scanning electron microscopy, and elemental analysis show that the Si/SiO_(x)/C material is a secondary particle with a porous micronanostructure, and the presence of nanometer silicon does not affect the carbothermal reduction and carbon coating.Electrochemical test results indicate that the specific capacity and first coulombic efficiency of SiO_(x)/C composite with nanometer silicon can be increased to 1 946.05 mAh/g and 76.49%,respectively.The reversible specific capacity of Si/SiO_(x)/C material blended with graphite is 749.69 mAh/g after 100 cycles at a current density of 0.1 C,and the capacity retention rate is up to 89.03%.Therefore, the composite has excellent electrochemical cycle stability.

Doping effects on the electro-degradation of phenol on doped titanium suboxide anodes

Titanium suboxide is an excellent electrode material for many oxidization reactions.In this article,the electrodes of pure Ti_4O_7,doped Ti_4O_7and the mixed-crystal of Ti_4O_7and Ti_5O_9were prepared to evaluate their activities and doping effects in the electro-degradation of phenol.It was revealed by the HPLC analysis results that the degradation intermediates and routes were significantly affected by the doping element.On the pure Ti_4O_7anode,a series of classic intermediates were obtained from benzoquinone and hydroquinone to various carboxylic acids.These intermediates were degraded gradually to the final organic intermediate of oxalate in all experiments.At last,oxalate was oxidized to CO_2and H_2O.Distinctively,the Y-doped Ti_4O_7 anode directly broke phenol toα-ketoglutaric acid without the intermediates of benzoquinone and hydroquinone.The strong oxidization ability of the Y-doped Ti_4O_7 anode might be responsible for the highest COD removal ratio.In contrast,the Ga-doped Ti_4O_7 anode showed the worst degradation activity in this article.Three intermediates of benzoquinone,hydroquinone and maleic acid were found during the degradation.Benefiting from the weak ability,oxalate was efficiently accumulated with a very high yield of 74.6%.The results demonstrated promising applications from electrochemical preparation to wastewater degradation by adjusting the doping reagent of Ti_4O_7 electrodes.

Image lithography in telluride suboxide thin film through controlling “virtual” bandgap

In this work, TeO_(0.7)thin films were prepared by the reactive magnetron-controlling sputtering method. Complex gray-scale patterns were successfully fabricated on TeO_(0.7)thin films through the laser direct writing method.The structural origin of TeO_(0.7)thin film was investigated for gray-scale pattern formation. It is found that multiple gray-scale levels are dependent on the "virtual" bandgap energy of TeO_(0.7)thin films. The bandgap energy changes lead to refractive index and reflectivity difference. Thus, gray-scale tones can be formed. By accurately controlling laser energy, various "virtual" bandgaps can be generated in TeO_(0.7)thin films, and colorful gray-scale levels can be formed. Experimental results indicate that TeO_(0.7)thin film can be used as micro/nano image writing material.

Mg-doped,carbon-coated,and prelithiated SiO_(x) as anode materials with improved initial Coulombic efficiency for lithium-ion batteries

Silicon suboxide(SiO_(x),x≈1)is promising in serving as an anode material for lithium-ion batteries with high capacity,but it has a low initial Coulombic efficiency(ICE)due to the irreversible formation of lithium silicates during the first cycle.In this work,we modify SiO_(x) by solid-phase Mg doping reaction using low-cost Mg powder as a reducing agent.We show that Mg reduces SiO_(2) in SiO_(x) to Si and forms MgSiO_(3) or Mg_(2)SiO_(4).The MgSiO_(3) or Mg_(2)SiO_(4) are mainly distributed on the surface of SiO_(x),which suppresses the irreversible lithium-ion loss and enhances the ICE of SiO_(x).However,the formation of MgSiO_(3) or Mg_(2)SiO_(4) also sacrifices the capacity of SiO_(x).Therefore,by controlling the reaction process between Mg and SiO_(x),we can tune the phase composition,proportion,and morphology of the Mg-doped SiO_(x) and manipulate the performance.We obtain samples with a capacity of 1226 mAh g^(–1) and an ICE of 84.12%,which show significant improvement over carbon-coated SiO_(x) without Mg doping.By the synergistical modification of both Mg doping and prelithiation,the capacity of SiO_(x) is further increased to 1477 mAh g^(–1) with a minimal compromise in the ICE(83.77%).

A review on the critical challenges and progress of SiO_(x)-based anodes for lithium-ion batteries

With the advantages of abundant resources,high specific capacity,and relatively stable cycling performance,silicon suboxides(SiO_(x) ,x<2)have been recently suggested as promising anodes for next-generation lithium-ion batteries(LIBs).SiO_(x) exhibits superior storage capability because of the presence of silicon and smaller volume change upon charge/discharge than Si owing to the buffering effect of the initial lithiation products of inert lithium oxide and lithium silicates,enabling a stable cycle life of electrodes.However,significant improvements such as overcoming issues related to volume changes in cycling and initial irreversible capacity loss and enhancing the ionic and electronic charge transport in poorly conducting SiO_(x) electrodes,are still needed to achieve the satisfactory performance required for commercial applications.This review summarizes recent progress on the cycling performance and initial coulombic efficiency of SiO_(x) .Advances in the design of particle morphology and composite composition,prelithiation and prereduction methods,and usage of electrolyte additives and optimized electrode binders are discussed.Perspectives on the promising research directions that might lead to further improvement of the electrochemical properties of SiO_(x) -based anodes are noted.This paper can serve as a basis for the research and development of high-energy-density LIBs.

Sandwich-like structure C/SiO_(x)@graphene anode material with high electrochemical performance for lithium ion batteries

Silicon suboxide(SiO_(x),0<x<2)is recognized as one of the next-generation anode materials for high-energy-density lithium ion batteries(LIBs)due to its high theoretical specific capacity and abundant resource.However,the severe mechanical instability arising from large volume variation upon charge/discharge cycles frustrates its electrochemical performance.Here we propose a well-designed sandwich-like structure with sandwiched SiO_(x) nanoparticles between graphene sheets and amorphous carbon-coating layer so as to improve the structural stability of SiO_(x) anode materials during cycling.Graphene sheets and carbon layer together construct a three-dimensional conductive network around SiO_(x) particles,which not only improves the electrode reactions kinetics,but also homogenizes local current density and thus volume variation on SiO_(x) surface.Moreover,Si-O-C bonds between SiO_(x) and graphene endow the strong particle adhesion on graphene sheets,which prevents SiO_(x) peeling from graphene sheets.Owing to the synergetic effects of the structural advantages,the C/SiO_(x)@graphene material exhib-its an excellent cyclic performance such as 890 mAh/g at 0.1 C rate and 73.7%capacity retention after 100 cycles.In addition,it also delivers superior rate capability with a capacity recovery of 886 mAh/g(93.7%recovery rate)after 35 cycles of ascending steps at current range of 0.1-5 C and finally back to 0.1 C.This study provides a novel strategy to improve the structural stability of high-capacity anode materials for lithium/sodium ion batteries.

Invalidation manner and mechanism of new type NbO electrolytic capacitor anode

Niobium suboxide powder was pressed and sintered in vacuum into NbO electrolytic capacitor sintered anode..High voltage and constant current formation experiment was performed on NbO electrolytic capacitor anode,during which electrolyte was 0.01 % Ha PO4 solution, temperature was 90 C and current was 50 mA per gram sample. Through the relationship between anode voltage and time and scanning electron microscopy(SEM) images of invalidated anode and normal forming anode, invalidation manner and mechanism of NbO electrolytic capacitor anode were discussed. The results show that, the main invalidation manner of NbO electrolytic capacitor anode is not short circuit but open circuit, which is different to that of traditional Ta electrolytic capacitor anode. The reason of invalidation is that anode oxide film whose thickness increases gradually penetrates the "connection neck" among anode powder particles, which leads to the open circuit invalidation of anode. Compared with Ta electrolytic capacitor,NbO electrolytic capacitor has better security.

Tradeoffbetween Narrowing Optical Band Gap and Enhancing Electrical Conductivity of the Metal Nanoparticles-Modified Titanium Oxide Films

The n-type semiconducting titanium oxide thin films are well-known as electron transporting interlayer in photovoltaic cells. The favorable characteristics of interlayers in photovoltaics are high optical transmittance （T%）, wide band gap energy （Eg） and high electrical conductivity （σ）. Modifying titanium oxide films with metal nanoparticles would increase electrical conductivity but reduce optical band gap energy. We developed the sol-gel derived titanium suboxide （TiOx） films modified with silver （Ag） or gold （Au） or copper （Cu） nanoparticles （NPs）. This study explores a tradeoff between narrowing optical band gap and enhancing electrical conductivity of nanostructured TiOx films by controlling the Au- or Ag- or Cu-NPs loading concentrations （mol%） in titania. The Au- and Cu-NPs loading concentration of 4 mol% should meet a tradeoff which yields the higher T%, wider Eg and higher compared to those of pure TiOx films. In addition, since the pure Cu is not thermodynamically stable in ambience as compared to Au and Ag, the stability of as-obtained colloidal CuNPs is also examined. A careful examination of the time evolution of surface plasmon resonance （SPR） bands of CuNPs indicates that their stability is only up to 4 h.

Rational structure design to realize high-performance SiOx@C anode material for lithium ion batteries

Silicon suboxide(SiOx)is considered to be one of the most promising materials for next-generation anode due to its high energy density.For its preparation,the wet-chemistry method is a cost-effective and readily scalable route,while the so-derived SiOx usually shows lower capacity compared with that prepared by high temperature-vacuum evaporation route.Herein,we present an elaborate particle structure design to realize the wet-chemistry preparation of a high-performance SiOx/C nanocomposite.Dandelion-like highly porous SiOx particle coated with conformal carbon layer is designed and prepared.The highly-porous SiOx skeleton provides plenty specific surface for intimate contact with carbon layer to allow a deep reduction of SiOx to a low O/Si ratio at relatively low temperature(700℃),enabling a high specific capacity.The abundant mesoscale voids effectively accommodate the volume variation of SiOx skeleton,ensuring the high structural stability of SiOx@C during lithiation/delithiation process.Meanwhile,the three-dimensional(3D)conformal carbon layer provides a fast electron/ion transportation,allowing an enhanced electrodereaction kinetics.Owing to the optimized O/Si ratio and well-engineered structure,the prepared SiOx@C electrode delivers an ultra-high capacity(1,115.8 mAh·g^-1 at 0.1 A·g^-1 after 200 cycles)and ultra-long lifespan(635 mAh·g^-1 at 2 A·g^-l after 1,000 cycles).To the best of our knowledge,the achieved combination of ultra-high specific capacity and ultra-long cycling life is unprecedented.

Efficient fluidization intensification process to fabricate in-situ dispersed(SiO+G)/CNTs composites for high-performance lithium-ion battery anode applications

An efficient fluidization process intensification method was proposed to prepare carbon nanotube(CNT)-enhanced high-performance SiO anodes for lithium-ion batteries.The introduction of graphite particles decreased bonding among SiO particles,inhibiting agglomerate growth and enhancing fluidization.The(SiO+G)/CNTs composites were synthesized by fluidized bed chemical vapor deposition with the CNTs grown in-situ,which ensured uniform dispersion and superior anchoring of the CNTs.The in-situ-grown CNTs and stacked graphite ensured excellent structural stability and conductivity.The synthesized(SiO+G)/CNTs delivered a stable reversible capacity of 466 mAh g^(−1) after 125 cycles and a capacity of∼200 mAh g^(−1) at 2 A g^(−1).The charging results indicated that the 3D network structure comprising CNTs and graphite not only effectively buffered the electrode expansion but also greatly improved mechanical flexibility.

Sub-stoichiometric functionally graded titania fibres for water-splitting applications

The photo-electro-chemical （PEC） splitting of water requires semiconductor materials with a minimum energy gap of 1.23 eV along with conduction and valence bands overlapping the oxidation of H20 and reduction of H＋ respectively. This work overcomes the limitations of stoichiometric titania by manufacturing fine scale fibres that exhibit a compositional gradient of oxygen vacancies across the fibre length. In such a fibre configuration the fibre end that is chemically reduced to a relatively small extent performs as the photoanode and the oxygen vacan- cies enhance the absorption of light. The fibre end that is reduced the most consists of Magn61i phases and exhibits metallic electrical conductivity that enhances the electron-hole separation. The structure and composition of the functionally graded fibres, which were manufactured through extrusion, pressureless sintering and carbo-thermal reduction, are studied using XRD and electron microscopy. Electrochemical impedance spectroscopy measure- ments were performed in a three-electrode electrochemical system and showed that the oxygen vacancies in the functionally graded fibres affect the fiat band potential and have increased carrier density. The efficiency of the system was evaluated with PEC measurements that shows higher efficiency for the functionally graded fibres com- pared to homogeneous TiO2 or Magn61i phase fibres. The functionally graded and fine scale fibres have the potential to be used as an array of active fibres for water splitting applications.