Thermodynamic equilibrium theory-guided design and synthesis of Mg-doped LiFe_(0.4)Mn_(0.6)PO_(4)/C cathode for lithium-ion batteries

Mn-rich LiFe_(1-x)Mn_(x)PO_(4)(x>0.5),which combines the high operation voltage of LiMnPO_(4)with excellent rate performa nce of LiFePO4,is hindered by its sluggish kinetic properties.Herein,thermodynamic equilibrium analysis of Mn^(2+)-Fe^(2+)-Mg^(2+)-C_(2)O_(4)^(2-)-H_(2)O system is used to guide the design and preparation of insitu Mg-doped(Fe_(0.4)Mn_(0.6))_(1-x)Mg_(x)C_(2)O_(4)intermediate,which is then employed as an innovative precursor to synthesize high-performance Mg-doped LiFe_(0.4)Mn_(0.6)PO_(4).It indicates that the metal ions with a high precipitation efficiency and the stoichiometric precursors with uniform element distribution can be achieved under the optimized thermodynamic conditions.Meanwhile,accelerated Li+diffusivity and reduced charge transfer resistance originating from Mg doping are verified by various kinetic characterizations.Benefiting from the contributions of inherited homogeneous element distribution,small particle size,uniform carbon layer coating,enhanced Li+migration ability and structural stability induced by Mg doping,the Li(Fe_(0.4)Mn_(0.6))_(0.97)Mg_(0.03)PO_(4)/C exhibits splendid electrochemical performance.

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%).

S-doped mesoporous graphene modified separator for high performance lithium-sulfur batteries

Due to their low cost,environmental friendliness and high energy density,the lithium-sulfur batteries(LSB)have been regarded as a promising alternative for the next generation of rechargeable battery systems.However,the practical application of LSB is seriously hampered by its short cycle life and high self-charge owing to the apparent shuttle effect of soluble lithium polysulfides.Using MgSO_(4)@MgO composite as both template and dopant,template-guided S-doped mesoporous graphene(SMG)is prepared via the fluidized-bed chemical vapor deposition method.As the polypropylene(PP)modifier,SMG with high specific surface area,abundant mesoporous structures and moderate S doping content offers a wealth of physical and chemical adsorptive sites and reduced interfacial contact resistance,thereby restraining the serious shuttle effects of lithium polysulfides.Consequently,the LSB configured with mesoporous graphene(MG)as S host material and SMG as a separator modifier exhibits an enhanced electrochemical performance with a high average capacity of 955.64 mA h g^(-1) at 1C and a small capacity decay rate of 0.109%per cycle.Additionally,the density functional theory(DFT)calculation models have been rationally constructed and demonstrated that the doped S atoms in SMG possess higher binding energy to lithium polysulfides than that in MG,indicating that the SMG/PP separator can effectively capture soluble lithium polysulfides via chemical binding forces.This work would provide valuable insight into developing a versatile carbon-based separator modifier for LSB.

Co-doped BaFe_(2)As_(2) Josephson junction fabricated with a focused helium ion beam

Josephson junction plays a key role not only in studying the basic physics of unconventional iron-based superconductors but also in realizing practical application of thin-film based devices,therefore the preparation of high-quality iron pnictide Josephson junctions is of great importance.In this work,we have successfully fabricated Josephson junctions from Co-doped BaFe_(2)As_(2)thin films using a direct junction fabrication technique which utilizes high energy focused helium ion beam(FHIB).The electrical transport properties were investigated for junctions fabricated with various He^(+)irradiation doses.The junctions show sharp superconducting transition around 24 K with a narrow transition width of 2.5 K,and a dose correlated foot-structure resistance which corresponds to the effective tuning of junction properties by He^(+)irradiation.Significant J_c suppression by more than two orders of magnitude can be achieved by increasing the He^(+)irradiation dose,which is advantageous for the realization of low noise ion pnictide thin film devices.Clear Shapiro steps are observed under 10 GHz microwave irradiation.The above results demonstrate the successful fabrication of high quality and controllable Co-doped BaFe_(2)As_(2)Josephson junction with high reproducibility using the FHIB technique,laying the foundation for future investigating the mechanism of iron-based superconductors,and also the further implementation in various superconducting electronic devices.

Enhanced conductivity and weakened magnetism in Pb-doped Sr_(2)IrO_(4)

Group IV element Pb has been selected as the dopant to dope at the Sr site of Sr_(2)IrO_(4). It is exciting to find that the single-phase crystal structure could be maintained with a high Pb doping level of up to x=0.3 in Sr_(2-x)Pb_(x)IrO_(4). The mapping data obtained from energy-dispersive x-ray spectroscopy analyses give solid evidence that the Pb ions are uniformly distributed in the Sr_(2)IrO_(4) matrix. The incorporation of Pb leads to a moderate depression of the canted antiferromagnetic ordering state. The electrical conductivity could be greatly enhanced when the Pb doping content is higher than x=0.2.The present results give a fresh material base to explore new physics in doped Sr_(2)IrO_(4) systems.

Hole-Doped Nonvolatile and Electrically Controllable Magnetism in van der Waals Ferroelectric Heterostructures

Electrical control of magnetism in van der Waals semiconductors is a promising step towards development of two-dimensional spintronic devices with ultralow power consumption for processing and storing information.Here, we propose a design for two-dimensional van der Waals heterostructures(vdWHs) that can host ferroelectricity and ferromagnetism simultaneously under hole doping. By contacting an In Se monolayer and forming an InSe/In_(2)Se_(3) vd WH, the switchable built-in electric field from the reversible out-of-plane polarization enables robust control of the band alignment. Furthermore, switching between the two ferroelectric states(P_↑ and P_↓)of hole-doped In_(2)Se_(3) with an external electric field can interchange the ON and OFF states of the nonvolatile magnetism. More interestingly, doping concentration and strain can effectively tune the magnetic moment and polarization energy. Therefore, this provides a platform for realizing multiferroics in ferroelectric heterostructures,showing great potential for use in nonvolatile memories and ferroelectric field-effect transistors.

A Simple Urea Approach to N-Dopedα-Mo_(2)C with Enhanced Superconductivity

Chemical doping is a critical factor in the development of new superconductors or optimizing the superconducting transition temperature(T_(c))of the parent superconducting materials.Here,a new simple urea approach is developed to synthesize the N-dopedα-Mo_(2)C.Benefiting from the simple urea method,a broad superconducting dome is found in the Mo_(2)C_(1−x)N_(x)(0≤x≤0.49)compositions.X-ray diffraction results show that the structure of𝛼α-Mo_(2)C remains unchanged and there is a variation of lattice parameters with nitrogen doping.Resistivity,magnetic susceptibility,and heat capacity measurement results confirm that T_(c)was strongly increased from 2.68K(x=0)to 7.05K(x=0.49).First-principles calculations and our analysis indicate that increasing nitrogen doping leads to a rise in the density of states at the Fermi level and doping-induced phonon softening,which enhances electron–phonon coupling.This results in an increase in𝑇T_(c)and a sharp rise in the upper critical field.Our findings provide a promising strategy for fabricating transition metal carbonitrides and provide a material platform for further study of the superconductivity of transition metal carbides.

Neutral and metallic vs.charged and semiconducting surface layer in acceptor doped CeO_(2)

The monomolecular surface layer of acceptor doped CeO_(2) may become neutral and metallic or charged and semiconducting.This is revealed in the theoretical analysis of the oxygen pressure dependence of the surface defects concentration in acceptor doped ceria with two different dopant types and operated under different oxygen pressures.Recently published experimental data for highly reduced Sm0.2Ce0.8O1.9-x(SDC)containing a fixed valence dopant Sm3+are very different from those published for Pr0.1Ce0.9O_(2)-x(PCO) with the variable valence dopant Pr4+/Pr3+being reduced under milder conditions.The theoretical analysis of these experimental results fits very well the experimental results of SDC and PCO.It leads to the following predictions:the highly reduced surface of SDC is metallic and neutral,the metallic surface electron density of state is gs=0.9×10^(38)J-1·m^(-2)(1.4×1015eV^(-1)·cm^(-2)),the electron effective mass is meff,s=3.3me,and the phase diagram of the reduced surface has theα(fcc)structure as in the bulk.In PCO a double layer is predicted to be formed between the surface and the bulk with the surface being negatively charged and semiconducting.The surface of PCO maintains high Pr^(3+) defect concentration as well as relative high oxygen vacancy concentration at oxygen pressures higher than in the bulk.The reasons for the difference between a metallic and semiconducting surface layer of acceptor doped CeO_(2) are reviewed,as well as the key theoretical considerations applied in coping with this problem.For that we make use of the experimental data and theoretical analysis available for acceptor doped ceria.

Density functional theory study of B- and Si-doped carbons and their adsorption interactions with sulfur compounds

Understanding the adsorption interactions between carbon materials and sulfur compounds has far-reaching impacts,in addition to their well-known important role in energy storage and conversion,such as lithium-ion batteries.In this paper,properties of intrinsic B or Si single-atom doped,and B-Si codoped graphene(GR)and graphdiyne(GDY)were investigated by using density functional theory-based calculations,in which the optimal doping configurations were explored for potential applications in adsorbing sulfur compounds.Results showed that both B or Si single-atom doping and B-Si codoping could substantially enhance the electron transport properties of GR and GDY,improving their surface activity.Notably,B and Si atoms displayed synergistic effects for the codoped configurations,where B-Si codoped GR/GDY exhibited much better performance in the adsorption of sulfurcontaining chemicals than single-atom doped systems.In addition,results demonstrated that,after B-Si codoping,the adsorption energy and charge transfer amounts of GDY with sulfur compounds were much larger than those of GR,indicating that B-Si codoped GDY might be a favorable material for more effectively interacting with sulfur reagents.

Cation-doped LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2) cathode with high rate performance

The nickel-rich layered cathode material LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)has high energy density,lower cost and is a promising cathode material currently under development.However,its electrochemical and structural stability is poor during cycling.Among the many modification methods,cation doping has been consistently proven to be an effective strategy for enhancing electrochemical performance.Herein,the NCM811 cathode material was modified by solid-phase reactions with Mg and Al doped.In addition,the corresponding mechanism of NCM811 cathode material-doped modification is explored by density functional theory(DFT)calculations,and we have extended this approach to other ternary cathode materials with different ratios and obtained universal laws.Combined with DFT calculations,the results show that Mg2+occupies the Li+site and reduces the degree of Li^(+)/Ni^(2+) mixture;Al^(3+) acts as a structural support during charging and discharging to prevent structural collapse.The electrochemical properties were tested by an electrochemical workstation and the LAND system,and the results showed that the capacity retention rate increased to varying degrees from 63.66%to 69.87%and 89.05%for NCM811-Mg and NCM811-Al at room temperature after 300 cycles,respectively.This study provides a theoretical basis and design strategy for commercializing cationic-doped modification of nickel-rich cathode materials.

Rational Design of Cost-Effective Metal-Doped ZrO_(2)for Oxygen Evolution Reaction

The design of cost-effective electrocatalysts is an open challenging for oxygen evolution reaction(OER)due to the“stable-oractive”dilemma.Zirconium dioxide(ZrO_(2)),a versatile and low-cost material that can be stable under OER operating conditions,exhibits inherently poor OER activity from experimental observations.Herein,we doped a series of metal elements to regulate the ZrO_(2)catalytic activity in OER via spin-polarized density functional theory calculations with van der Waals interactions.Microkinetic modeling as a function of the OER activity descriptor(G_(O*)-G_(HO*))displays that 16 metal dopants enable to enhance OER activities over a thermodynamically stable ZrO_(2)surface,among which Fe and Rh(in the form of single-atom dopant)reach the volcano peak(i.e.the optimal activity of OER under the potential of interest),indicating excellent OER performance.Free energy diagram calculations,density of states,and ab initio molecular dynamics simulations further showed that Fe and Rh are the effective dopants for ZrO_(2),leading to low OER overpotential,high conductivity,and good stability.Considering cost-effectiveness,single-atom Fe doped ZrO_(2)emerged as the most promising catalyst for OER.This finding offers a valuable perspective and reference for experimental researchers to design cost-effective catalysts for the industrial-scale OER production.

Appreciable Enhancement of Photocatalytic Performance for N-doped SrMoO_(4) via the Vapor-thermal Method

A series of nitrogen-doped SrMoO_(4) with different Sr/N mole ratio (R=0,0.05,0.10,0.15,0.20,0.40,and 0.60) were synthesized using urea as the N source via the vapor-thermal method.The photocatalytic degradation ability of all samples was evaluated using methylene blue (MB) as a target contaminant.The band gaps of N-doped samples are all higher than that of pristine ones,which is only 3.12 eV.BET specific surface area S_(BET) and pore volume are increased due to the N doping.And the greater increase of S_(BET),the faster the photodegradation speed of methylene blue on SrMoO_(4).More specifically,the degradation efficiency of MB is improved up to 87%in 100 min.

Magnetocaloric properties of Nd-doped Gd5Si4 microparticles and nanopowders

The preparation of materials with enhanced magnetocaloric properties is crucial for magnetic refrigeration. In thisstudy, Nd-doped Gd5Si4 microparticles and nanomaterials were synthesized using the reduction–diffusion method. Theimpact of Nd doping with varying compositions on the structure and entropy change properties of the materials was investigated.The Curie temperatures of both the micron- and nano-sized materials ranged from 190 K to 210 K, which were lowerthan previously reported values. Micron-sized samples doped with 1% Nd exhibited superior magnetocaloric properties,demonstrating a maximum entropy change of 4.98 J·kg^(-1)·K^(-1) at 5 T, with an entropy change exceeding 4 J·kg^(-1)·K^(-1)over a wide temperature range of approximately 70 K. Conversely, the nanomaterials had broader entropy change peaks butlower values. All samples exhibited a second-order phase transition, as confirmed by the Arrott plots.

The Electrocatalytic Performance of Rare Earth Ion Doped Co_(0.2)Ni_(0.8)-MOF-74 Catalyst for Nitrogen Reduction

We took Co_(0.2)Ni_(0.8)-MOF-74 with bimetallic synergistic effect as the basic material,and selected rare earth ions Ho,Gd,and Er with ion radii close to Co and Ni as the research objects for doping.The influence of rare earth ion doping amount and doping type on the eNRR performance of the catalyst was explored.The experimental results show that the ammonia yield rate and Faraday efficiency doped with Co_(0.2)Ni_(0.8)-MOF-0.5Ho are the highest,reaching 1.28×10^(-10)mol·s^(-1)·cm^(-2)/39.8%,which is higher than the1.12×10^(-10)mol·s^(-1)·cm^(-2)/32.2%of Co_(0.2)Ni_(0.8)-MOF-74,and is about 14.3%/23.7%higher than that without doping,respectively.And the stability of Co_(0.2)Ni_(0.8)-MOF-0.5 Ho is good(after 80 hours of continuous testing,the current density did not significantly decrease).This is mainly due to doping,which gives Co_(0.2)Ni_(0.8)-MOF-74 a larger specific surface area and catalytic active sites.The catalyst doped at the same time has more metal cation centers,which increases the electron density of the metal centers and enhances the corresponding eNRR performance.

Controllable fabrication of FeCoS_(4) nanoparticles/S-doped bowl-shaped hollow carbon as efficient lithium storage anode

To address the low conductivity and easy agglomeration of transition metal sulfide nanoparticles,FeCoS_(4) nanoparticles embedded in S-doped hollow carbon(FeCoS_(4)@S-HC)composites were successfully fabricated through a combination of hydrothermal processes and sulfidation treatment.The unique bowlshaped FeCoS_(4)/S-HC composites exhibit excellent structural stability with a high specific surface area of 303.7 m^(2)·g^(-1) and a pore volume of 0.93 cm^(3)·g^(-1).When applied as anode material for lithium-ion batteries,the FeCoS_(4)@S-HC anode exhibits efficient lithium storage with high reversible specific capacity(970.2 mA·h·g^(-1) at 100 mA·g^(-1))and enhanced cycling stability(574 mA·h·g^(-1) at 0.2 A·g^(-1) after 350 cycles,a capacity retention of 84%).The excellent lithium storage is attributed to the fact that the bimetallic FeCoS_(4) nanoparticles with abundant active sites can accelerate the electrochemical reaction kinetics,and the bowl-shaped S-HC structure can provide a stable mechanical structure to suppress volume expansion.

Unveiling the pressure-driven metal–semiconductor–metal transition in the doped TiS_(2)

Conventional theories expect that materials under pressure exhibit expanded valence and conduction bands,leading to increased electrical conductivity.Here,we report the electrical properties of the doped 1T-TiS_(2) under high pressure by electrical resistance investigations,synchrotron x-ray diffraction,Raman scattering and theoretical calculations.Up to 70 GPa,an unusual metal-semiconductor-metal transition occurs.Our first-principles calculations suggest that the observed anti-Wilson transition from metal to semiconductor at 17 GPa is due to the electron localization induced by the intercalated Ti atoms.This electron localization is attributed to the strengthened coupling between the doped Ti atoms and S atoms,and the Anderson localization arising from the disordered intercalation.At pressures exceeding 30.5 GPa,the doped TiS_(2) undergoes a re-metallization transition initiated by a crystal structure phase transition.We assign the most probable space group as P2_(1)2_(1)2_(1).Our findings suggest that materials probably will eventually undergo the Wilson transition when subjected to sufficient pressure.

Lewis acid-doped transition metal dichalcogenides for ultraviolet–visible photodetectors

Ultraviolet photodetectors(UV PDs)are widely used in civilian,scientific,and military fields due to their high sensitivity and low false alarm rates.We present a temperature-dependent Lewis acid p-type doping method for transition metal dichalcogenides(TMDs),which can effectively be used to extend the optical response range.The p-type doping based on surface charge transfer involves the chemical adsorption of the Lewis acid SnCl_(4)as a light absorption layer on the surface of WS_(2),significantly enhancing its UV photodetection performance.Under 365 nm laser irradiation,WS_(2)PDs exhibit response speed of 24 ms/20 ms,responsivity of 660 mA/W,detectivity of 3.3×10^(11)Jones,and external quantum efficiency of 226%.Moreover,we successfully apply this doping method to other TMDs materials(such as MoS_(2),MoSe_(2),and WSe_(2))and fabricate WS_(2) lateral p–n heterojunction PDs.

Investigation and optimization of high-valent Ta-doped SrFeO_(3-δ)as air electrode for intermediate-temperature solid oxide fuel cells

To explore highly active and thermomechanical stable air electrodes for intermediate-temperature solid oxide fuel cells(ITSOFCs),10mol%Ta5+doped in the B site of strontium ferrite perovskite oxide(SrTa_(0.1)Fe_(0.9)O_(3-δ),STF)is investigated and optimized.The effects of Ta^(5+)doping on structure,transition metal reduction,oxygen nonstoichiometry,thermal expansion,and electrical performance are evaluated systematically.Via 10mol%Ta^(5+)doping,the thermal expansion coefficient(TEC)decreased from 34.1×10^(-6)(SrFeO_(3-δ))to 14.6×10^(-6) K^(-1)(STF),which is near the TEC of electrolyte(13.3×10^(-6) K^(-1) for Sm_(0.2)Ce_(0.8)O_(1.9),SDC),indicates excellent thermomechanical compatibility.At 550-750℃,STF shows superior oxygen vacancy concentrations(0.262 to 0.331),which is critical in the oxygen-reduction reaction(ORR).Oxygen temperature-programmed desorption(O_(2)-TPD)indicated the thermal reduction onset temperature of iron ion is around 420℃,which matched well with the inflection points on the thermos-gravimetric analysis and electrical conductivity curves.At 600℃,the STF electrode shows area-specific resistance(ASR)of 0.152Ω·cm^(2) and peak power density(PPD)of 749 mW·cm^(-2).ORR activity of STF was further improved by introducing 30wt%Sm_(0.2)Ce_(0.8)O_(1.9)(SDC)powder,STF+SDC composite cathode achieving outstanding ASR value of 0.115Ω·cm2 at 600℃,even comparable with benchmark cobalt-containing cathode,Ba_(0.5)Sr_(0.5)Co_(0.8)Fe_(0.2)O_(3-δ)(BSCF).Distribution of relaxation time(DRT)analysis revealed that the oxygen surface exchange and bulk diffusion were improved by forming a composite cathode.At 650℃,STF+SDC composite cathode achieving an outstanding PPD of 1117 mW·cm^(-2).The excellent results suggest that STF and STF+SDC are promising air electrodes for IT-SOFCs.

Structure and electrical properties of polysilicon films doped with ammonium tetraborate tetrahydrate

Here,p-type polysilicon films are fabricated by ex-situ doping method with ammonium tetraborate tetrahydrate(ATT)as the boron source,named ATT-pPoly.The effects of ATT on the properties of polysilicon films are comprehensively analyzed.The Raman spectra reveal that the ATT-pPoly film is composed of grain boundary and crystalline regions.The preferred orientation is the(111)direction.The grain size increases from 16−23 nm to 21−47 nm,by~70%on average.Comparing with other reported films,Hall measurements reveal that the ATT-pPoly film has a higher carrier concentration(>10^(20)cm^(−3))and higher carrier mobility(>30 cm2/(V·s)).The superior properties of the ATT-pPoly film are attributed to the heavy doping and improved grain size.Heavy doping property is proved by the mean sheet resistance(Rsheet,m)and distribution profile.The R_(sheet,m)decreases by more than 30%,and it can be further decreased by 90%if the annealing temperature or duration is increased.The boron concentration of ATT-pPoly film annealed at 950℃ for 45 min is~3×10^(20)cm^(−3),and the distribution is nearly the same,except near the surface.Besides,the standard deviation coefficient(σ)of Rsheet,m is less than 5.0%,which verifies the excellent uniformity of ATT-pPoly film.

Improving the operational stability of perovskite solar cells with cesium-doped graphene oxide interlayer

Perovskite solar cells(PSCs)have made great advances in terms of power conversion efficiency(PCE),yet their subpar stability continues to hinder their commercialization.The interface between the perovskite layer and the charge-carrier transporting layers plays a crucial role in undermining the stability of PSCs.In this work,we propose a strategy to stabilize high-performance PSCs with PCE over 23%by introducing a cesium-doped graphene oxide(GO-Cs)as an interlayer between the perovskite and hole-transporting material.The GO-Cs treated PSCs exhibit excellent operational stability with a projected T80(the time where the device PCE reduces to 80%of its initial value)of 2143 h of operation at the maximum powering point under one sun illumination.