Protonated and layered transition metal oxides as solid acids for dehydration of biomass-based fructose into 5-hydroxymethylfurfural

A serial of protonated and layered transition metal oxides, including layered HTaWO6, HNbMoO6 as well as HNbWO6, were synthesized by solid-state reaction and ion-exchange. The layered HTaWO6 has been systematically studied as a solid acid to realize the dehydration of fructose to 5-hydroxymethylfurfural (HMF). The transition metal oxide samples were characterized with ICP-OES, EDS, XRD, XPS, SEM, TGA, FT-IR, N-2 adsorption-desorption and NH3-TPD. The influential factors such as reaction temperature, reaction time, solvent, catalyst amount and substrate concentration were deeply investigated. The optimized fructose conversion rate of 99% with HMF yield of 67% were achieved after 30 min at 140 degrees C in dimethylsulfoxide. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.

Preparation of layered oxide Li(Co_(1/3)Ni_(1/3)Mn_(1/3))O_2 via the sol-gel process

To obtain homogenous layered oxide Li（Co1/3Ni1/3Mn1/3）O2 as a lithium insertion positive electrode material, the sol-gel process using citric acid as a chelating agent was applied. The material Li（Co1/3Ni1/3Mn1/3）O2 was synthesized at different calcination temperatures. XRD experiment indicated that the layered Li（Co1/3Ni1/3Mn1/3）O2 material could be synthesized at a lower temperature of 800℃, and the oxidation state of Co, Ni, and Mn in the cathode confirmed by XPS were ＋3, ＋2, and ＋4, respectively. SEM observations showed that the synthesized material could form homogenous particle morphology with the particle size of about 200 nm. In spite of different calcination temperatures, the charge-discharge curves of all the samples for the initial cycle were similar, and the cathode synthesized at 900℃ showed a small irreversible capacity loss of 11.24% and a high discharge capacity of 212.2 mAh·g^-1 in the voltage range of 2.9-4.6 V.

Surface engineering of P2-type cathode material targeting long-cycling and high-rate sodium-ion batteries

The widespread interest in layered P2-type Mn-based cathode materials for sodium-ion batteries(SIBs)stems from their cost-effectiveness and abundant resources.However,the inferior cycle stability and mediocre rate performance impede their further development in practical applications.Herein,we devised a wet chemical precipitation method to deposit an amorphous aluminum phosphate(AlPO_(4),denoted as AP)protective layer onto the surface of P2-type Na_(0.55)Ni_(0.1)Co_(0.7)Mn_(0.8)O_(2)(NCM@AP).The resulting NCM@5AP electrode,with a 5 wt%coating,exhibits extended cycle life(capacity retention of78.4%after 200 cycles at 100 mA g^(-1))and superior rate performance(98 mA h g^(-1)at 500 mA g^(-1))compared to pristine NCM.Moreover,our investigation provides comprehensive insights into the phase stability and active Na^(+)ion kinetics in the NCM@5AP composite electrode,shedding light on the underlying mechanisms responsible for the enhanced performance observed in the coated electrode.

Understanding voltage hysteresis and decay during anionic redox reaction in layered transition metal oxide cathodes:A critical review

The emergence of anionic redox reactions in layered transition metal oxide cathodes provides practical opportunity to boost the energy density of rechargeable batteries.However,the activation of anionic redox reaction in layered oxides has significant voltage hysteresis and decay that reduce battery performance and limit commercialization.Here,we critically review the up-todate development of anionic redox reaction in layered oxide cathodes,summarize the proposed reaction mechanism,and unveil their connection to voltage hysteresis and decay based on the state-of-the-art progress.In addition,advances associated with various modification approaches to mitigate the voltage hysteresis/decay in layered transition metal oxide cathodes are also included.Finally,we conclude with an appraisal of further research directions including rational design of high-performance layered oxide cathodes with reversible anionic redox reactions and suppressed voltage hysteresis/decay.Findings will be of immediate benefit to the development of layered oxide cathodes for high performance rechargeable batteries.

Cocoon-shaped P3-type K0.5Mn0.7Ni0.3O2 as an advanced cathode material for potassium-ion batteries

Potassium ion batteries(PIBs)are emerging as potential next-generation energy storage systems on account of their low cost and high theoretical energy density.Nevertheless,they also face challenges of low specific capacity and suboptimal cycling stability.Herein,we synthesize a cocoon-like P3-type K_(0.5)Mn_(0.7)Ni_(0.3)O_(2)(KMNO)cathode material by a self-template method.The KMNO cocoons possess a hierarchical layered architecture composed of nanoparticle stacking,which can accelerate the transport kinetics of potassium ions,mitigate the stress caused by K^(+)intercalation and deintercalation,and improve structural stability.In addition,Ni can not only alleviate the Jahn-Teller distortion and suppress the phase transition to stabilize the structure,but also act as an electrochemically active element,providing the capacity of two electrons from Ni2+to Ni4+.Combining the advantages of structure and nickel substitution,the P3-type KMNO cocoons are used for electrochemical performance testing of PIB cathodes,delivering an excellent rate capability of 57.1 m A h g^(-1)at 500 m A g^(-1)and a remarkable cycling stability of 77.0%over 300 cycles at 100 m A g^(-1).Impressively,the KMNO cocoons//pitch-derived soft carbon assembled full battery exhibits superior electrochemical performance with a reversible capacity of 79.7 m A h g^(-1)at 50 m A g^(-1).Moreover,ex-situ XRD also further reveals a solid solution phase reaction with a volume change of only 1.46%.This work furnishes a suitable approach to fabricating highperformance layered oxide cathodes for PIBs with outstanding cycling stability and rate capability.

Progress on multiphase layered transition metal oxide cathodes of sodium ion batteries

As one of the most promising secondary batteries in large-scale energy storage,sodium ion batteries(SIBs) have attracted wide attention due to the abundant raw materials and low cost.Layered transition metal oxides are one kind of popular cathode material candidates because of its easy synthesis and large theoretical specific capacity.Yet,the most common P2 and O3 phases show distinct structural characteristics respectively.O3 phase can serve as a sodium reservoir,but it usually suffers from serious phase transition and sluggish kinetics.For the P2 phase,it allows the fast sodium ion migration in the bulk and the structure can maintain stable,but it is lack of sodium,showing a great negative effect on Coulombic efficiency in full cell.Thus,single phase structure almost cannot achieve satisfied comprehensive sodium storage performances.Under these circumstances,exploiting novel multiphase cathodes showing synergetic effect may give solution to these problems.In this review,we summarize the recent development of multiphase layered transition metal oxide cathodes of SIBs,analyze the mechanism and prospect the future potential research directions.

Insights into Ti doping for stabilizing the Na_(2/3)Fe_(1/3)Mn_(2/3)O_(2)cathode in sodium ion battery

Iron-and manganese-based layered metal oxides,as cathodes for sodium ion batteries,have received widespread attention because of the low cost and high specific capacity.However,the Jahn-teller effect of Mn^(3+)ions and the resulted unstable structure usually lead to continuously capacity decay.Herein,Titanium(Ti)has been successfully doped into Na_(2/3)Fe_(2/3)Mn_(2/3)O_(2)to suppress the Jahn-Teller distortion and improve both cycling and rate performance of sodium ion batteries.In situ high-energy synchrotron X-ray diffraction study shows that Ti-doped compound(Na_(2/3)Fe_(1/3)Mn_(0.57)Ti_(0.1)O_(2))can maintain the single P2 phase without any phase transition during the whole charging/discharging process.Various electrochemical characterizations are also applied to explore the better kinetics of sodium ions transfer in the Na_(2/3)Fe_(1/3)Mn_(0.5)7 Ti_(0.1)O_(2).This work provides a comprehensive insight into the Ti-doping effects on the performance from both structural and electro kinetic perspectives.

MoO_(x) and V_(2)O_(x) as hole and electron transport layers through functionalized intercalation in normal and inverted organic optoelectronic devices

To achieve fabrication and cost competitiveness in organic optoelectronic devices that include organic solar cells(OSCs)and organic light-emitting diodes(OLEDs),it is desirable to have one type of material that can simultaneously function as both the electron and hole transport layers(ETLs and HTLs)of the organic devices in all device architectures(i.e.,normal and inverted architectures).We address this issue by proposing and demonstrating Cs-intercalated metal oxides(with various Cs mole ratios)as both the ETL and HTL of an organic optoelectronic device with normal and inverted device architectures.Our results demonstrate that the new approach works well for widely used transition metal oxides of molybdenum oxide(MoOx)and vanadium oxide(V_(2)O_(x)).Moreover,the Cs-intercalated metaloxide-based ETL and HTL can be easily formed under the conditions of a room temperature,water-free and solution-based process.These conditions favor practical applications of OSCs and OLEDs.Notably,with the analyses of the Kelvin Probe System,our approach of Cs-intercalated metal oxides with a wide mole ratio range of transition metals(Mo or V)/Cs from 1:0 to 1:0.75 can offer significant and continuous work function tuning as large as 1.31 eV for functioning as both an ETL and HTL.Consequently,our method of intercalated metal oxides can contribute to the emerging large-scale and low-cost organic optoelectronic devices.

ZnO-PCBM bilayers as electron transport layers in low-temperature processed perovskite solar cells

We investigate an electron transport bilayer fabricated at 〈110℃ to form all low-temperature processed, thermally stable, efficient perovskite solar cells with negligible hysteresis. The components of the bilayer create a symbiosis that results in improved devices compared with either of the components being used in isolation. A sol-gel derived ZnO layer facilitates improved energy level alignment and enhanced charge carrier extraction and a [6,6]-phenyl-C61-butyric acid methyl ester （PCBM） layer to reduce hysteresis and enhance perovskite thermal stability. The creation of a bilayer structure allows materials that are inherently unsuitable to be in contact with the perovskite active layer to be used in efficient devices through simple surface modification strategies.

Layered K_(0.54)Mn_(0.78)Mg_(0.22)O_(2)as a high-performance cathode material for potassium-ion batteries

Layered Mn-based oxides are one of the promising cathode materials for potassium-ion batteries(KIBs)owing to their high theoretical capacities,abundant material supply,and simple synthesis method.However,the structural deterioration resulting from the Jahn-Teller effect of Mn ions hinders their further development in KIBs.Herein,a novel Mn-based layered oxide,K_(0.54)Mn_(0.78)Mg_(0.22)O_(2),is successfully designed and fabricated as KIBs cathode for the first time.It delivers smooth charging/discharging curves with high specific capacity of 132.4 mAh·g^(‒1)at 20 mA·g^(‒1)and good high-rate cycling stability with a capacity retention of 84%over 100 cycles at 200 mA·g^(‒1).Combining in-situ X-ray diffraction(XRD)and ex-situ X-ray photoelectron spectroscopy(XPS)analysis,the storage of K-ions by K_(0.54)Mn_(0.78)Mg_(0.22)O_(2)is revealed to be a solid-solution processes with reversible slip of the crystal lattice.The studies suggest that the rational doping of inactive Mg2+can effectively suppress the Jahn-Teller effect and provide outstanding structure stability.This work deepens the understanding of the structural evolution of Mn-based layered materials doped with inactive materials during de/potassiation processes.

Empowering higher energy sodium-ion battery cathode by oxygen chemistry

Sodium(Na)ion batteries(SIBs)promise low-cost energy storage systems but are still restricted by insufficient energy density.Introducing oxygen(O)redox into the design of the Na-storage cathode is presently considered an effective avenue to generate extra capacity in solving the energy density bottleneck.The succeeding issues are how to overcome the irreversible electrochemical behavior accompanied by O release.Meanwhile,the O redox chemistry and subsequent structural evolution remain ambiguous so far.Here,we deliberate on the O redox mechanism in Na-storage transition metal oxides.Challenges associated with the reaction irreversibility and structural collapse are summarized by virtue of the advanced characterization techniques.Beyond that,strategies that potentially enhance the electrochemical properties of O redox and future research perspectives on exploring useable O redox cathode materials are outlined.