Structural Engineering of Anode Materials for Low-Temperature Lithium-Ion Batteries:Mechanisms,Strategies,and Prospects

The severe degradation of electrochemical performance for lithium-ion batteries(LIBs)at low temperatures poses a significant challenge to their practical applications.Consequently,extensive efforts have been contributed to explore novel anode materials with high electronic conductivity and rapid Li^(+)diffusion kinetics for achieving favorable low-temperature performance of LIBs.Herein,we try to review the recent reports on the synthesis and characterizations of low-temperature anode materials.First,we summarize the underlying mechanisms responsible for the performance degradation of anode materials at subzero temperatures.Second,detailed discussions concerning the key pathways(boosting electronic conductivity,enhancing Li^(+)diffusion kinetics,and inhibiting lithium dendrite)for improving the low-temperature performance of anode materials are presented.Third,several commonly used low-temperature anode materials are briefly introduced.Fourth,recent progress in the engineering of these low-temperature anode materials is summarized in terms of structural design,morphology control,surface&interface modifications,and multiphase materials.Finally,the challenges that remain to be solved in the field of low-temperature anode materials are discussed.This review was organized to offer valuable insights and guidance for next-generation LIBs with excellent low-temperature electrochemical performance.

Valence electronic engineering of superhydrophilic Dy-evoked Ni-MOF outperforming RuO_(2) for highly efficient electrocatalytic oxygen evolution

Tackling the problem of poor conductivity and catalytic stability of pristine metal-organic frameworks(MOFs) is crucial to improve their oxygen evolution reaction(OER) performance.Herein,we introduce a novel strategy of dysprosium(Dy) doping,using the unique 4f orbitals of this rare earth element to enhance electrocatalytic activity of MOFs.Our method involves constructing Dy-doped Ni-MOF(Dy@Ni-MOF) nanoneedles on carbon cloth via a Dy-induced valence electronic perturbation approach.Experiments and density functional theory(DFT) calculations reveal that Dy doping can effectively modify the electronic structure of the Ni active centers and foster a strong electronic interaction between Ni and Dy.The resulting benefits include a reduced work function and a closer proximity of the d-band center to the Fermi level,which is conducive to improving electrical conductivity and promoting the adsorption of oxygen-containing intermediates.Furthermore,the Dy@Ni-MOF achieves superhydrophilicity,ensuring effective electrolyte contact and thus accelerating reaction kinetics,Ex-situ and in-situ analysis results manifest Dy_(2)O_(3)/NiOOH as the actual active species.Therefore,Dy@Ni-MOF shows impressive OER performance,significantly surpassing Ni-MOF.Besides,the overall water splitting device with Dy@NiMOF as an anode delivers a low cell voltage of 1.51 V at 10 mA cm^(-2) and demonstrates long-term stability for 100 h,positioning it as a promising substitute for precious metal catalysts.

A novel process for the recovery of iron,titanium,and vanadium from vanadium-bearing titanomagnetite:sodium modification–direct reduction coupled process

A sodium modification–direct reduction coupled process was proposed for the simultaneous extraction of V and Fe from vanadium- bearing titanomagnetite. The sodium oxidation of vanadium oxides to water-soluble sodium vanadate and the transformation of iron oxides to metallic iron were accomplished in a single-step high-temperature process. The increase in roasting temperature favors the reduction of iron oxides but disfavors the oxidation of vanadium oxides. The recoveries of vanadium, iron, and titanium reached 84.52%, 89.37%, and 95.59%, respectively. Moreover, the acid decomposition efficiency of titanium slag reached 96.45%. Compared with traditional processes, the novel process provides several advantages, including a shorter flow, a lower energy consumption, and a higher utilization efficiency of vanadium-bearing titanomagnetite resources. © 2017, University of Science and Technology Beijing and Springer-Verlag Berlin Heidelberg.

Recovery of valuable metals from a low-grade nickel ore using an ammonium sulfate roasting-leaching process

Metal leaching from a low-grade nickel ore was investigated using an ammonium sulfate roasting-water leaching process. The nickel ore was mixed with ammonium sulfate, followed by roasting and finally leaching with water. During the process the effects of the amotmt of ammonium sulfate, roasting temperature, and roasting time on the leaching recovery of metal elements were analyzed. The optimum technological parameters were determined as follows： ammonium sulfate/ore ratio, 0.8 g/g; roasting temperature, 400℃; and roasting time, 2 h. Under the optimum condition the leaching recoveries ofNi, Cu, Fe, and Mg were 83.48%, 76.24%, 56.43%, and 62.15%, respectively. Furthermore, the dissolution kinetics of Ni and Mg from the nickel ore was studied. The apparent activation energies for the leaching reaction of Ni and Mg were 18.782 and 10.038 kJ.mo1-1, which were consistent with the values of diffusion control reactions. Therefore, the results demonstrated that the leaching recoveries of Ni and Mg were controlled by diffusion.

Simultaneous extraction of gold and zinc from refractory carbonaceous gold ore by chlorination roasting process

A novel process based on chlorination roasting was proposed to simultaneously recover gold and zinc from refractory carbonaceous gold ore by using NaCl as chlorination agent.The effects of roasting temperature,roasting time and NaCl content on the volatilization rates of gold and zinc were investigated.The reaction mechanism and the phase transition process were also analyzed by means of SEM,EDS and XRD.The results demonstrated that under the optimal conditions of NaCl content of 10%,roasting temperature of 800℃,roasting time of 4 h and gas flow rate of 1 L/min,the rates of gold and zinc were 92%and 92.56%,respectively.During low-temperature chlorination roasting stage,a certain content of sulfur was beneficial to the chlorination reactions of gold and zinc;and during high-temperature chlorination roasting stage,the crystal structure of vanadium-bearing mica was destroyed,and the vanadium-containing oxides were beneficial to the chlorinating volatilization of gold and zinc.Eventually,the chlorinated volatiles of gold and zinc could be recovered by alkaline solution.

Effect of Plasma Spheroidization Process on the Microstructure and Crystallographic Phases of Silica, Alumina and Nickel Particles

During the plasma spheroidization process powders undergo different changes in their microstructures and crystal phases. In this paper, simple calculation of heat transfer between the plasma and a suspended particle was performed based on three hypotheses for the purpose of guiding experiments. Experimental investigation of the crystal phases and microstructural changes during the plasma processing was made using silica, alumina and nickel powders as starting materials. It has been revealed from the experimental results that these materials undergo different changes in crystal phases and microstructures, and these changes are essentially determined by the structures, properties and aggregate states of the starting materials.

Whole-Process Pollution Control for Cost-Effective and Cleaner Chemical Production A Case Study of the Tungsten Industry in China

In this research,a methodology named whole-process pollution control(WPPC)is demonstrated that improves the effectiveness of process optimization.This methodology considers waste/emission treatment as a step of the whole production process with respect to the minimization of cost and environmental impact for the whole process.The following procedures are introduced in a WPPC process optimization:①a material and energy flow investigation and optimization based on a systematic understanding of the distribution and physiochemical properties of potential pollutants;②a process optimization to increase the utilization efficiency of different elements and minimize pollutant emissions;and③an evaluation to reveal the effectiveness of the optimization strategies.The production of ammonium paratungstate was chosen for the case study.Two factors of the different optimization schemes-namely the cost-effectiveness factor and the environmental impact indicator-were evaluated and compared.This research demonstrates that by considering the nature of potential pollutants,technological innovations,economic viability,environmental impacts,and regulation requirements,WPPC can efficiently optimize a metal production process.

Utilization of gold-bearing and iron-rich pyrite cinder via a chlorination–volatilization process

The chlorination-volatilization process has been adopted to make full use of gold-bearing and iron-rich pyrite cinder. However, problems of low recovery rate, pulverization of pellets, and ring formation have been encountered during the industrialization of this process. The effects of various parameters on the volatilization rates of valuable metals and on the compressive strength of roasted pellets were investigated in this paper. The parameters include the CaCl_2 dosage, heating temperature, and holding time. The results show that heating temperature is the most important parameter for the recovery of target metals. More CaCl_2 was needed for the recovery of zinc than for the recovery of gold, silver, and lead. CaCl_2 started to react with sulfides/SO_2/SiO_2 at temperatures below the melting point of CaCl_2 to generate Cl_2/HCl. Gaseous CaCl_2 was formed at higher temperatures and could react with any of the components. The compressive strength of roasted CaCl_2-bearing pellets first decreased slowly with increasing temperature at temperatures lower than 873 K, which could result in the pulverization of pellets during heating. Their compressive strength increased dramatically with increasing temperature at temperatures greater than 1273 K. Certain quantities of CaCl_2 and Fe(Ⅱ) could improve the compressive strength of the roasted pellets; however, the addition of excessive CaCl_2 decreased the compressive strength of pellets.

Extraction of valuable metals from Ti-bearing blast furnace slag using ammonium sulfate pressurized pyrolysis−acid leaching processes

A novel method of extracting valuable metals from Ti-bearing blast furnace slag(TBBF slag)via pressure pyrolysis of recyclable ammonium sulfate(AS)−acid leaching process was proposed.The results show that when pressurized roasting at an AS-to-slag mass ratio 3:1 and 370℃for 90 min,the extraction rates of titanium,aluminum and magnesium reached 94.5%,91.9%and 97.4%,respectively.The acid leaching solution was subjected to re-crystallization in a boiling state to obtain a titanium product having a TiO2 content of 94.1%.The above crystallization mother liquor was adjusted to pH=6 and pH≥12.2,respectively,and then qualified Al2O3 and MgO products were obtained.The analysis through XRD and SEM−EDS proves that the main phases in roasted samples were NH4AlSO4,CaSO4 and TiOSO4.The thermodynamic analysis presents that the main minerals of perovskite,spinel and diopside in raw ore could spontaneously react with the intermediate produced by AS under optimal conditions.

Apparent Kinetics for Electrosynthesis Process of Chromic Acid

A new green technique for producing chromic acid via an electrosynthesis method was studied.The kinetic experiments were carried out on the direct electrosynthesis reaction of chromic acid from sodium dichromate in a self-made electrosynthesis reactor with a multiple-unit metal oxides combination anode,a stainless steel cathode,and a reinforcing combination Nafion 324 cation exchange membrane.The apparent kinetic data were experimentally measured at different reaction time under different reaction conditions by relating many essential cell processes and their interaction,as well as their synergistic effect to the whole electrochemical synthesis process.The results show that the electrosynthesis reaction process follows a quasi-first-order reaction kinetic characteristic.The apparent kinetic model of the electrosynthesis reaction was established,and kinetic parameters were calculated.

Optimal Design of Water Utilization Network with Energy Integration in Process Industries

Effective utilization of water and energy is the key factor of sustainable development in process industries, and also an important science and technology problem to be solved in systems engineering. In this paper,two new methods of optimal design of water utilization network with energy integration in process industries are presented, that is, stepwise and simultaneous optimization methods. They are suitable for both single contaminant and multi-contaminant systems, and the integration of energy can be carried out in the whole process system, not only limited in water network, so that energy can be utilized effectively. The two methods are illustrated by case study.

Effects of the continuous cooling process conditions on the crystallization and liberation characteristics of anosovite in Ti-bearing titanomagnetite smelting slag

This study involved the investigation of the effects of the continuous cooling process conditions on the crystallization and liberation characteristics of anosovite in Ti-bearing titanomagnetite smelting slag. The samples were heated until melting and then the temperature was held at 1650℃ for nearly 0.5 h;subsequently, the samples were cooled at different cooling rates to different temperatures and water-quenched after being held for different times at these temperatures. Last, the obtained crystallized samples were used to analyze the crystallization and liberation characteristics. It was found that, during the continuous cooling process, anosovite particles were found to initially precipitate in the slag at a relatively high crystallization temperature, showing the characteristics of euhedral crystal. The precipitation and growth of anosovite grain is strong and the morphology of anosovite was basically not affected by the continuous cooling conditions. From the morphology perspective, the formed anosovite is an excellent Ti-rich phase to be selective separated. The formation of spinel and diopside is negative for the liberation and selective separation of the anosovite phase. The crystallization diagrams of TiO2-MgO-CaO-SiO2-Al2O3-FeO slag undergoing different continuous cooling processes were constructed to help to determine the optimal continuous cooling–quenching condition for selective separation of anosovite. Moreover, the addition of B2O3 can enlarge the range of the optimal continuous cooling–quenching conditions for selective separation of anosovite.

Extraction behaviours of titanium and other impurities in the decomposition process of ilmenite by highly concentrated KOH solution

To effectively utilize ilmenite and recycle KOH solution, the extraction behaviours of titanium and other associated impurities in the decomposition process of ilmenite by highly concentrated KOH solution were studied. Experiments on the extraction behaviours of tita- nium as well as other associated impurities of ilmenite such as iron, silicon, calcium, and aluminium were carried out. The effects of various parameters, including reaction temperature, KOH concentration, reaction time, alkali-to-ore mass ratio, and particle size on the extraction rate of titanium and other impurities were examined. When the finely ground ore （58-75 ~tm） reacted with KOH solution （80wt%） in an al- kali-to-ore mass ratio of 7：1 at 260~C for 60 min, almost complete extraction of titanium was achieved, while the extraction rate of aluminium was 78% and that of other impurities was less than 22%. Moreover, high purity （98.2wt%） TiO2 with the anatase structure could be gained in the purification process.

Process design and economic analysis of methacrylic acid extraction for three organic solvents

In this work,a techno-economic study for the solvent based extraction of methacrylic acid from an aqueous solution is presented.The involved phase equilibrium calculations in process design are verified by measured experimental data.First,experiments are conducted with different solvent candidates to measure LLE(liquid–liquid equilibrium)data and to establish the effects of extraction temperature and dosage of solvent.Next,the binary interaction parameters for the UNIQUAC model to be used for equilibrium calculations are fine-tuned with measured data.Then,a process for the solvent based extraction of methacrylic acid recovery is designed and verified through simulation with the regressed UNIQUAC model parameters.The optimal configuration of the process flowsheet is determined by minimizing the total annualized cost.Among the three solvent candidates considered-cyclohexane,hexane and toluene-the highest efficiency and the lowest total annualized cost is found with toluene as the solvent.

The potential of ionic liquids in biopharmaceutical engineering

Biopharmaceuticals,such as proteins,peptides,nucleic acids and vaccines,bring about great hopes for the prevention and treatment of various diseases,but the industrialization of these products still faces challenges such as structural instability,inefficient bioactivity and low bioavailability.Ionic liquids(ILs),the marvelous solvent media with inimitable and tunable properties,may provide alternative solutions to overcome the above problems of biopharmaceutical industry.Progress has gradually been made through studies by combination of ILs with biomacromolecules.The applications involved the stabilization,protection,and delivery of biopharmaceuticals.Recent trends are being forwarded to using ILs in vaccines and nucleic acid drugs.However,challenges remain on the toxicity and safety issues.Besides,the cost of adding ILs to the benefits of biopharmaceuticals need to be considered.

On the database-based strategy of candidate extractant generation for de-phenol process in coking wastewater treatment

A database-based strategy of candidate generation was proposed for molecular design of new de-phenol extractants following the idea of finding new applications of existing commercial compounds. The strategy has the advantage that the environmental, safety and health risks of candidate compounds are known and controllable. In this work, the Existing Commercial Compounds(ECC) database and special combined search strategy were developed as the base for the proposed CAMD method following such idea, and molecules for phenol extraction used in coking wastewater treatment were selected from the ECC database. The candidate solvents cover the following categories: ketones, esters, ethers, alcohols, anhydrides and benzene compounds, which are consistent with the de-phenol extractants commonly used in the industry or experiment. The compounds with higher partition coefficient and selectivity than widely used methyl isobutyl ketone(MIBK) are mainly ketones. 26 obtained molecules show higher partition coefficient and selectivity than MIBK, which are suggested to be further investigated by experiment. Furthermore, analysis of these potential molecules may present the effective functional groups as the initial group set to generate new molecular structures of de-phenol extractants. The results show that the proposed method enables us to efficiently generate chemicals with benefits of less time, less economical cost, and known environmental impact as well.

Reductive leaching of low-grade manganese ore with pre-processed cornstalk

Cornstalk is usually directly used as a reductant in reduetive leaching manganese. However, low utilization of cornstalk makes low manganese dissolution ratio, In the research, pretreatment for cornstalk was proposed to improve manganese dissolution ratio. Cornstalk was preprocessed by a heated sulfuric acid solution （1.2 M of sulfuric acid concentration） for 10 min at 80℃. Thereafter, both the pretreated solution and the residue were used as a reductant for manganese leaching. This method not only exhibited superior activity for hydrolyzing cornstalk but also enhanced manganese dissolution. These effects were attributed to an increase in the amount of reductive sugars resulting from lignin hydrolysis. Through acid pretreatment for cornstalk, the manganese dissolution ratio was improved from 50.14% to 83.46%. The present work demonstrates for the first time the effective acid pretreatment of cornstalk to provide a cost-effective reductant for manganese leaching.

Reactive template-derived interfacial engineering of CoP/CoO heterostructured porous nanotubes towards superior electrocatalytic hydrogen evolution

The development of economical,efficient,and robust electrocatalysts toward the hydrogen evolution reaction(HER)is highly imperative for the rapid advancement of renewable H2 energy-associated technologies.Extensive utilization of the heterointerface effect can endow the catalysts with remarkably boosted electrocatalytic performance due to the modified electronic state of active sites.Herein,we demonstrate deliberate crafting of CoP/CoO heterojunction porous nanotubes(abbreviated as CoP/CoO PNTs hereafter)using a self-sacrificial template-engaged strategy.Precise control over the Kirkendall diffusion process of the presynthesized cobalt–aspartic acid complex nanowires is indispensable for the formation of CoP/CoO heterostructures.The topochemical transformation strategy of the reactive templates enables uniform and maximized construction of CoP/CoO heterojunctions throughout all the porous nanotubes.The establishment of CoP/CoO heterojunctions could considerably modify the electronic configuration of the active sites and also improve the electric conductivity,which endows the resultant CoP/CoO PNTs with enhanced intrinsic activity.Simultaneously,the hollow and porous nanotube architectures allow sufficient accessibility of exterior/interior surfaces and molecular permeability,drastically promoting the reaction kinetics.Consequently,when used as HER electrocatalysts,the well-designed CoP/CoO PNTs show Pt-like activity,with an overpotential of only 61 mV at 10mA cm^(−2) and excellent stability in 1.0M KOH medium,exceeding those of the vast majority of the previously reported nonprecious candidates.Density functional theory calculations further substantiate that the construction of CoP/CoO heterojunctions enables optimization of the Gibbs free energies for water adsorption and H adsorption,resulting in boosted HER intrinsic activity.The present study may provide in-depth insights into the fundamental mechanisms of heterojunction-induced electronic regulation,which may pave the way for the rational design of advanced Earth-abundant electrocatalysts in the future.

Simulation and design of a heat-integrated double-effect reactive distillation process for propylene glycol methyl ether production

A double-effect reactive distillation(DERD)process was proposed for the production of propylene glycol methyl ether from propylene oxide and methanol to overcome the shortcoming of low selectivity and high-energy consumption in the tubular plug-flow reactor.A single-column reactive distillation(RD)process was conducted under optimized operating conditions based on sensitivity analysis as a reference.The results demonstrated that the proposed DERD process is able to achieve more than 95%selectivity of the desired product.After that,a design approach of the DERD process with an objective of the minimum operating cost was proposed to achieve further energy savings in the RD process.The proposed DERD configuration can provide a large energy-savings by totally utilization of the overhead vapor steam in the high-pressure RD column.A comparison of the single-column RD process revealed that the proposed DERD process can reduce the operating cost and the total annual cost of 25.3%and 30.7%,respectively,even though the total capital cost of DERD process is larger than that of the RD process.

Interfacial engineering of transition-metal sulfides heterostructures with built-in electric-field effects for enhanced oxygen evolution reaction

Developing highly efficient,durable,and non-noble electrocatalysts for the sluggish anodic oxygen evolution reaction(OER)is the pivotal for meeting the practical demand in water splitting.However,the current transition-metal electrocatalysts still suffer from low activity and durability on account of poor interfacial reaction kinetics.In this work,a facile solid-state synthesis strategy is developed to construct transition-metal sulfides heterostructures(denoted as MS_(2)/NiS_(2),M=Mo or W)for boosting OER electrocatalysis.As a result,MoS2/NiS2 and WS2/NiS2 show lower overpotentials of 300 mV and 320 mV to achieve the current density of 10 mA·cm^(-2),and smaller Tafel slopes of 60 mV.dec^(-1) and 83 mV.dec^(-1)in 1 mol·L^(-1) KOH,respectively,in comparison with the single MoS2,WS2,NiS2,as well as even the benchmark RuO2.The experiments reveal that the designed heterostructures have strong electronic interactions and spontaneously develop a built-in electric field at the heterointerface with uneven charge distribution based on the difference of band structures,which promote interfacial charge transfer,improve absorptivity of OH-,and modulate the energy level more comparable to the OER.Thus,the designed transition-metal sulfides heterostructures exhibit a remarkably high electrocatalytic activity for OER.This study provides a simple strategy to manipulate the heterostructure interface via an energy level engineering method for OER and can be extended to fabricate other heterostructures for various energy-related applications.