Mechanism of high-concentration electrolyte inhibiting the destructive effect of Mn(Ⅱ)on the performance of lithium-ion batteries

By optimizing electrolyte formulation to inhibit the deposition of transition metal ions(TMIs) on the surface of the graphite anode is an effective way to improve the electrochemical performance of lithium-ion batteries.At present,it is generally believed the formation of an effective interfacial film on the surface of the anode electrode is the leading factor in reducing the dissolution of TMIs and prevent TMIs from being embedded in the electrode.It ignores the influence of the solvation structures in the electrolyte system with different composition,and is not conducive to the design of the electrolyte formulation from the perspective of changing the concentration and the preferred solvent to inhibit the degradation of battery performance caused by TMIs deposition.In this work,by analyzing the special solvation structures of the high-concentra tion electrolyte,we study the main reason why high-concentration electrolyte inhibits the destructive effect of Mn(Ⅱ) on the electrochemical performance of LIBs.By combining the potentialresolved in-situ electrochemical impedance spectroscopy technology(PRIs-EIS) and density functional theory(DFT) calculation,we find that Mn(Ⅱ) mainly exists in the form of contact ions pairs(CIPs) and aggregates(AGGs) in high-concentration electrolyte.These solvation structures can reduce the destructive effect of Mn(Ⅱ) on battery performance from two aspects:on the one hand,it can rise the lowest unoccupied orbital(LUMO) value of the solvation structures of Mn(Ⅱ),thereby reducing the chance of its reduction;on the other hand,the decrease of Mn2+ions reduction can reduce the deposition of metallic manganese in the solid electrolyte interphase(SEI),thereby avoiding the continuous growth of the SEI.This study can be provided inspiration for the design of electrolytes to inhibit the destructive effect of TMls on LIBs.

Regulating solid electrolyte interphases on phosphorus/carbon anodes via localized high-concentration electrolytes for potassium-ion batteries

The resourceful and inexpensive red phosphorus has emerged as a promising anode material of potassium-ion batteries(PIBs) for its large theoretical capacities and low redox potentials in the multielectron alloying/dealloying reactions,yet chronically suffering from the huge volume expansion/shrinkage with a sluggish reaction kinetics and an unsatisfactory interfacial stability against volatile electrolytes.Herein,we systematically developed a series of localized high-concentration electrolytes(LHCE) through diluting high-concentration ether electrolytes with a non-solvating fluorinated ether to regulate the formation/evolution of solid electrolyte interphases(SEI) on phosphorus/carbon(P/C) anodes for PIBs.Benefitting from the improved mechanical strength and structural stability of a robust/uniform SEI thin layer derived from a composition-optimized LHCE featured with a unique solvation structure and a superior K+migration capability,the P/C anode with noticeable pseudocapacitive behaviors could achieve a large reversible capacity of 760 mA h g^(-1)at 100 mA g^(-1),a remarkable capacity retention rate of 92.6% over 200 cycles at 800 mA g^(-1),and an exceptional rate capability of 334 mA h g^(-1)at8000 mA g^(-1).Critically,a suppressed reduction of ether solvents with a preferential decomposition of potassium salts in anion-derived interfacial reactions on P/C anode for LHCE could enable a rational construction of an outer organic-rich and inner inorganic-dominant SEI thin film with remarkable mechanical strength/flexibility to buffer huge volume variations and abundant K+diffusion channels to accelerate reaction kinetics.Additionally,the highly reversible/durable full PIBs coupling P/C anodes with annealed organic cathodes further verified an excellent practical applicability of LHCE.This encouraging work on electrolytes regulating SEI formation/evolution would advance the development of P/C anodes for high-performance PIBs.

Structural optimization and performance trade-off strategies for semi-crystalline sulfonated poly(arylene ether ketone) membranes in high-concentration direct methanol fuel cells

Direct methanol fuel cells(DMFCs) have attracted extensive attention as promising next-generation energy conversion devices. However, commercialized proton exchange membranes(PEMs) hardly fulfill the demand of methanol tolerance for DMFCs employing high-concentration methanol solutions.Herein, we report a series of semi-crystalline poly(arylene ether ketone) PEMs with ultra-densely sulfonic-acid-functionalized pendants linked by flexible alkyl chains, namely, SL-SPEK-x(where x represents the molar ratio of the novel monomer containing multiple phenyl side chain to the bisfluoride monomers). The delicate structural design rendered SL-SPEK-x membranes with high crystallinity and well-defined nanoscale phase separation between hydrophilic and hydrophobic phases. The reinforcement from poly(ether ketone) crystals enabled membranes with inhibited dimensional variation and methanol penetration. Furthermore, microphase separation significantly enhanced proton conductivity. The SL-SPEK-12.5 membrane achieved the optimum trade-off between proton conductivity(0.182 S cm^(-1), 80 ℃), water swelling(13.6%, 80 ℃), and methanol permeability(1.6 × 10^(-7)cm~2 s^(-1)). The DMFC assembled by the SL-SPEK-12.5 membrane operated smoothly with a 10 M methanol solution, outputting a maximum power density of 158.3 mW cm^(-2), nearly twice that of Nafion 117(94.2 mW cm^(-2)). Overall, the novel structural optimization strategy provides the possibility of PEMs surviving in high-concentration methanol solutions, thus facilitating the miniaturization and portability of DMFC devices.

Regulating the dopant clustering in LiZnAs-based diluted magnetic semiconductor

Tuning of the magnetic interaction plays the vital role in reducing the clustering of magnetic dopant in diluted magnetic semiconductors(DMS).Due to the not well understood magnetic mechanism and the interplay between different magnetic mechanisms,no efficient and universal tuning strategy is proposed at present.Here,the magnetic interactions and formation energies of isovalent-doped(Mn) and aliovalent(Cr)-doped LiZnAs are studied based on density functional theory(DFT).It is found that the dopant–dopant distance-dependent magnetic interaction is highly sensitive to the carrier concentration and carrier type and can only be explained by the interplay between two magnetic mechanisms,i.e.,superexchange and Zener’s p–d exchange model.Thus,the magnetic behavior and clustering of magnetic dopant can be tuned by the interplay between two magnetic mechanisms.The insensitivity of the tuning effect to U parameter suggests that our strategy could be universal to other DMS.

Advanced Nonflammable Localized High-Concentration Electrolyte For High Energy Density Lithium Battery

The key to realize long-life high energy density lithium batteries is to exploit functional electrolytes capable of stabilizing both high voltage cathode and lithium anode.The emergence of localized high-concentration electrolytes(LHCEs)shows great promise for ameliorating the above-mentioned interfacial issues.In this work,a lithium difluoro(oxalate)borate(LiDFOB)based nonflammable dual-anion LHCE is designed and prepared.Dissolving in the mixture of trimethyl phosphate(TMP)/1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropylether(D_(2)),the continuously consumption of LiDFOB is suppressed by simply introducing lithium nitrate(LiNO_(3)).Meantime,as most of the TMP molecular are coordinated with Li^(+),the electrolyte does not show incompatibility issue between neither metal lithium nor graphite anode.Therefore,it demonstrates excellent capability in stabilizing the interface of Ni-rich cathode and regulating lithium deposition morphology.The Li||LiNi_(0.87)Co_(0.08)Mn_(0.05)O_(2)(NCM87)batteries exhibit high capacity retention of more than 90%after 200 cycles even under the high cutoff voltage of 4.5 V,1 C rate.This study offers a prospective method to develop safe electrolytes suitable for high voltage applications,thus providing higher energy densities.

New SOI power device with multi-region high-concentration fixed interface charge and the model of breakdown voltage

A new SOI power device with multi-region high-concentration fixed charge（MHFC） is reported. The MHFC is formed through implanting Cs or I ion into the buried oxide layer（BOX）, by which the high-concentration dynamic electrons and holes are induced at the top and bottom interfaces of BOX. The inversion holes can enhance the vertical electric field and raise the breakdown voltage since the drain bias is mainly generated from the BOX. A model of breakdown voltage is developed, from which the optimal spacing has also been obtained. The numerical results indicate that the breakdown voltage of device proposed is increased by 287% in comparison to that of conventional LDMOS.

Heteroatom dopant strategy triggered high-potential plateau to non-graphitized carbon with highly disordered microstructure for high-performance sodium ion storage

Non-graphitized carbon(NGC)has been extensively utilized as carbonaceous anode in sodium-ion batteries(SIBs).However,more optimization to achieve competitive capacity and stability is still challenging for SIBs.In the study,the dopant strategy is utilized to construct nitrogen/sulfur-doped non-graphitized carbon(N-NGC or S-NGC)shell decorated on three-dimensional graphene foam(GF)as a self-support electrode.The highly disordered microstructures of heteroatom doped carbons are produced by applying a low-temperature pyrolysis treatment to precursors containing nitrogen and sulfur.The DFT calculations of Na-ion adsorption energies at diverse heteroatom sites show marginal-S,pyrrolic N and pyridinic N with more intensive Na-ion adsorption ability than middle-S,C=O and pristine carbon.The N-NGC with dominant small graphitic regions delivers adsorption ability to Na-ion,while the S-NGC with significant single carbon lattice stripes demonstrates redox reaction with Na-ion.Evidently,in comparison with only adsorption-driven slope regions at high potential for N-NGC,the redox reaction-generated potentialplateau enables non-graphitized S-NGC superior discharge/charge capacity and cycle-stability in the slope region.This work could provide deep insight into the rational design of non-graphitized carbon with rich microstructure and composition.

碳类粒子对固体推进剂束流发散角度影响的实验研究

以石墨烯和碳粉两种碳类粒子作为掺杂剂定向改性固体推进剂,借助高速摄影技术和自搭建的束流发散角度测量系统,对比并分析不同掺杂比例和工作条件对改性推进剂束流发散角度的影响,确定了掺杂粒子的最优掺杂比例和工作条件。结果表明,石墨烯和碳粉的最优掺杂比例均为7%,且石墨烯的束流发散角度更小,生成稳定等离子体流的响应时间更短。同时,石墨烯更适配于小激光能量供给下的工作条件,而碳粉更适配于大激光能量供给下的工作条件。

利用掺杂层研究磁化靶中的能斯特效应

双层磁化套筒靶在内层采用高原子序数(Z)材料,减少了因能斯特效应导致的磁通损失并降低点火要求,为磁化靶聚变提供了一种备选方案。然而,添加高Z材料也可能增加由于物质混合而产生的辐射损失。通过在金属套筒中使用带有塑料掺杂的锗作为高Z替代物,初步分析了磁场能斯特输运和物质混合对磁化套筒惯性聚变的影响。与单层套筒相比,双层套筒靶展示出温度和磁通的显著增加,从而使聚变产额提高了154%。将碳氢掺杂剂添加到最内层的锗中,模拟了物质混合对聚变产额的影响。研究结果表明,锗与CH混合,保持较低的混合比例,能够显著提高聚变产额。

钙钛矿太阳能电池中无掺杂聚合物空穴传输材料研究进展

基于传统空穴传输材料(HTM)的钙钛矿太阳能电池(PSC)已经实现了超过25%的能量转换效率,然而这些HTM通常需要添加吸湿性掺杂剂来实现高迁移率和可加工性,从而降低了器件稳定性。为解决该问题,无掺杂HTM受到广泛关注。总结了近年来用于高效PSC的无掺杂聚合物HTM的结构和性能,并分析了其中的构效关系,提出了高效无掺杂聚合物HTM的结构设计原理,并展望了未来的发展趋势。

铝掺杂氧化锌纳米粉末制备及其对PET的抗静电改性

采用化学共沉淀法制备了不同含量的Al单元掺杂氧化锌(AZO)纳米粉体,并将自制的纳米AZO粉末用于聚对苯二甲酸乙二酯(PET)制备,以提高PET的抗静电性能。利用X射线行射、扫描电子显微镜、热重分析、表面电阻测试仪等测试手段,探究了Al单元掺杂对AZO粉体结构、形貌及电性能的影响。在PET制备过程中加入AZO,探究AZO对PET抗静电性能的影响。结果表明:所制备的AZO纳米粉体为结晶度良好的六方纤锌矿结构。Al掺杂浓度影响AZO粉体形貌、晶体结构及电性能。随着Al掺杂浓度的增加,粉体的结晶质量降低,电性能先变好后变差,粉体尺寸变大,出现团聚、结块现象。适度的Al掺杂可使AZO电阻率达到最低,改善AZO的导电性能。在Al掺杂浓度为2%时,AZO纳米粉体的电性能最佳,电阻率为5.3×10^(4)Ω/m^(2)。使用制备的AZO纳米粉末作为导电填料能有效改善PET的抗静电性能,降低PET/AZO复合材料的表面电阻率,使材料由绝缘体转变为静电耗散体,抗静电性能增强。AZO填充量在0.005%时复合材料的表面电阻率最低,为1.16×10^(10)Ω/m^(2)。

Mg/Fe site-specific dual-doping to boost the performance of cobalt-free nickle-rich layered oxide cathode for high-energy lithium-ion batteries

Layer-type LiNi0.9Mn0.1O2is promising to be the primary cathode material for lithium-ion batteries(LIBs)due to its excellent electrochemical performance.Unfortunately,the cathode with high nickel content suffers from severely detrimental structural transformation that causes rapid capacity attenuation.Herein,site-specific dual-doping with Fe and Mg ions is proposed to enhance the structural stability of LiNi0.9Mn0.1O2.The Fe3+dopants are inserted into transition metal sites(3b)and can favorably provide additional redox potential to compensate for charge and enhance the reversibility of anionic redox.The Mg ions are doped into the Li sites(3a)and serve as O_(2)^(-)-Mg^(2+)-O_(2)^(-)pillar to reinforce the electrostatic cohesion between the two adjacent transition-metal layers,which further suppress the cracking and the generation of harmful phase transitions,ultimately improving the cyclability.The theoretical calculations,including Bader charge and crystal orbital Hamilton populations(COHP)analyses,confirm that the doped Fe and Mg can form stable bonds with oxygen and the electrostatic repulsion of O_(2)^(-)-O_(2)^(-)can be effectively suppressed,which effectively mitigates oxygen anion loss at the high delithiation state.This dual-site doping strategy offers new avenues for understanding and regulating the crystalline oxygen redox and demonstrates significant potential for designing high-performance cobalt-free nickel-rich cathodes.

Three-dimensional crystal defect imaging by STEM depth sectioning

One of the major innovations awaiting in electron microscopy is full three-dimensional imaging at atomic resolution.Despite the success of aberration correction to deep sub-angstrom lateral resolution,spatial resolution in depth is still far from atomic resolution.In scanning transmission electron microscopy(STEM),this poor depth resolution is due to the limitation of the illumination angle.To overcome this physical limitation,it is essential to implement a next-generation aberration corrector in STEM that can significantly improve the depth resolution.This review discusses the capability of depth sectioning for three-dimensional imaging combined with large-angle illumination STEM.Furthermore,the statistical analysis approach remarkably improves the depth resolution,making it possible to achieve three-dimensional atomic resolution imaging at oxide surfaces.We will also discuss the future prospects of three-dimensional imaging at atomic resolution by STEM depth sectioning.

Effects of Different Grinding Methods on the Quality of Soybean Bean Milk

[Objectives] This study was conducted to improve the nutritional value of soybean milk, enrich the variety and taste of soybean milk, and find healthy food that is more conducive to people s nutritional needs. [Methods] Whole soybean milk was prepared by grinding with a grinding wheel at a low concentration (low-concentration grinding) and a stainless steel mill at a high concentration (high-concentration grinding). The sensory, physical and chemical characteristics and anti-nutritional factors of whole soybean milk produced by different grinding methods were studied. [Results] Compared with low-concentration grinding, the protein content in soybean milk prepared by high-concentration grinding increased by 24%, and the dietary fiber content increased by 74.7%. Before and after high-pressure homogenization, the particle size D(4, 3) of soybean milk prepared by low-concentration grinding was 212.1 and 93.59 μm, respectively, and the particle size D(4, 3) of soybean milk prepared by high-concentration grinding was 134.0 and 64.64 μm, respectively. The trypsin inhibitor activity and phytic acid content of soybean milk prepared by high-concentration grinding were significantly lower than those of soybean milk prepared by low-concentration grinding. [Conclusions] This study improves the diet structure of the broad masses of people, strengthens people s physique, and provides a new idea for the implementation and development of China s "Soybean Action Programme".

Effect of Sb dopant amount on the structure and electrocatalytic capability of Ti/Sb-SnO_2 electrodes in the oxidation of 4-chlorophenol

Ti/Sb-SnO2 anodes were prepared by thermal decomposition to examine the influence of the amount of Sb dopant on the structure and electrocatalytic capability of the electrodes in the oxidation of 4-chlorophenol. The physicochemical properties of the Sb-SnO2 coating were markedly influenced by different amounts of Sb dopant. The electrodes, which contained 5% Sb dopant in the coating, presented a much more homogenous surface and much smaller mud-cracks, compared with Ti/Sb-SnO2 electrodes containing 10% or 15% Sb dopant, which exibited larger mud cracks and pores on the surface. However, the main microstructure remained unchanged with the addition of the Sb dopant. No new crystal phase was observed by X-ray diffraction （XRD）. The electrochemical oxidation of 4-chlorophenol on the Ti/SnO2 electrode with 5% Sb dopant was inclined to electrochemical combustion; while for those containing more Sb dopant, intermediate species were accumulated. The electrodes with 5% Sb dopant showed the highest efficiency in the bulk electrolysis of 4-chlorophenol at a current density of 20 mA/cm^2 for 180 min; and the removal rates of 4-chlorophenol and COD were 51.0% and 48.9%, respectively.

The conductive mechanisms of a titanium oxide memristor with dopant drift and a tunnel barrier

Nano-scale titanium oxide memristors exhibit complex conductive characteristics, which have already been proved by existing research. One possible reason for this is that more than one mechanism exists, and together they codetermine the conductive behaviors of the memristor. In this paper, we first analyze the theoretical base and conductive process of a memristor, and then propose a compatible circuit model to discuss and simulate the coexistence of the dopant drift and tunnel barrier-based mechanisms. Simulation results are given and compared with the published experimental data to prove the possibility of the coexistence. This work provides a practical model and some suggestions for studying the conductive mechanisms of memristors.

Influences of anionic and cationic dopants on the morphology and optical properties of PbS nanostructures

Selenium and zinc are used as anionic and cationic dopant elements to dope PbS nanostructures. The undoped and doped PbS nanostructures are grown using a thermal evaporation method. Scanning electron microscopy （SEM） results show similar morphologies for the undoped and doped PbS nanostructures. X-ray diffraction （XRD） patterns of three sets of the nanostructures indicate that these nanostructures each have a PbS structure with a cubic phase. Evidence of dopant incorporation is demonstrated by X-ray photoelectron spectroscopy （XPS）. Raman spectra of the synthesized samples con- firm the XRD results and indicate five Raman active modes, which relate to the PbS cubic phase for all the nanostructures. Room temperature photoluminescence （PL） and UV-Vis spectrometers are used to study optical properties of the undoped and doped PbS nanostructures. Optical characterization shows that emission and absorption peaks are in the infrared （IR） region of the electromagnetic spectrum for all PbS nanostructures. In addition, the optical studies of the doped PbS nanos- tructures reveal that the band gap of the Se-doped PbS is smaller, and the band gap of the Zn-doped PbS is bigger than the band gap of the undoped PbS nanostructures.

Experimental Study on Treatment of High-concentrated Sulfur Wastewater by Process of Depositing Natrojarosite and Its Environmental Significance

High-concentrated sulfur wastewater with sodium and COD （chemical oxygen demand） up to 26000 mg/L from a chemical plant, Jiangsu Province of China has been treated by deposition of natrojarosite in lab. The results indicated that the COD of the wastewater was decreased sharply from 26000 mg/L to 1001 mg/L, with removal rate of COD up to 96% by twice precipitations of natrojarosite and twice oxidation of H202. The treated sulfur wastewater reached the requirement of subsequent biochemical treatment to water quality. The optimal operational parameters should be controlled on pH value between 2.50 and 3.20 and 50 g FeCly6H2O solid added in per liter wastewater. The study provided an experimental basis for pretreatment of high-concentrated sulfur wastewater and proposed a new mineralogical method on treatment of other wastewaters. Depositing process of jarosite and its analogs should be able to be used to treat wastewater from mine and other industries to remove S, Fe and other toxic and harmful elements, such as As, Cr, Hg, Pb, etc. in the water.

DASP: Defect and Dopant ab-initio Simulation Package

In order to perform automated calculations of defect and dopant properties in semiconductors and insulators, we developed a software package, the Defect and Dopant ab-initio Simulation Package(DASP), which is composed of four modules for calculating:(ⅰ) elemental chemical potentials,(ⅱ) defect(dopant) formation energies and charge-state transition levels,(ⅲ) defect and carrier densities and(ⅳ) carrier dynamics properties of high-density defects. DASP uses the materials genome database for quick determination of competing secondary phases when calculating the elemental chemical potential that stabilizes compound semiconductors. DASP calls the ab-initio software to perform the total energy, structural relaxation and electronic structure calculations of the defect supercells with different charge states, based on which the defect formation energies and charge-state transition levels are calculated. Then DASP can calculate the equilibrium densities of defects and electron and hole carriers as well as the Fermi level in semiconductors under different chemical potential conditions and growth/working temperature. For high-density defects, DASP can calculate the carrier dynamics properties such as the photoluminescence(PL) spectrum and carrier capture cross sections which can interpret the deep level transient spectroscopy(DLTS). Here we will show three application examples of DASP in studying the undoped GaN, C-doped GaN and quasi-one-dimensional SbSeI.

Effect of Some Metal Ion Dopants on Electrochemical Properties of Ni(OH)_2 Film Electrode

The Ni(OH) 2 film electrodes doped respectively with alkali-earth metal aluminum, lead, partial transition metal and some rare-earth metal(altogether 17 kinds of metals) ions were prepared by cathode electrodeposition. The electrode reaction reversibility, the difficult extent of oxygen evolution, the proton diffusion coefficient, the discharge potential of middle value and the active material utilization of the Ni(OH) 2 film electrode were compared with those of the ones doped with the metal ions by means of cyclic voltammetry, potential step and constant current charge-discharge experiments. It was found that Ca 2+ , Co 2+ , Cd 2+ , Al 3+ etc. have obviously positive effect.