To address the performance limitations of conventional LiPF6-carbonate electrolytes under extreme temperatures and high-rate charging,lithium difluoro(oxalato)borate(LiDFOB)is introduced into the LiPF6-carbonate elect...To address the performance limitations of conventional LiPF6-carbonate electrolytes under extreme temperatures and high-rate charging,lithium difluoro(oxalato)borate(LiDFOB)is introduced into the LiPF6-carbonate electrolyte to form a dual-salt system.The optimization mechanism enhancing the fast-charging capability of LiNi_(0.52)Co_(0.2)Mn_(0.28)O_(2)(NCM523)cathode is systematically explored.Molecular dynamics simulations and electrochemical characterization demonstrate the reconstruction of Li+solvation structures,expanding the voltage window and reducting Li^(+)desolvation barriers.In addition,the incorporation of LiDFOB induces the generation of a LiF/Li_(x)BO_(y)F_(z)-enriched cathode-electrolyte interphase,which effectively suppresses the dissolution of transition metals.In situ impedance measurements reveal the accelerated interfacial charge transfer kinetics.As expected,the NCM523 cathode achieves an 82%state-of-charge(SOC)in 12 min at 5 C(25°C)with 87%capacity retention after 100 cycles,and exhibits a 65%higher discharge capacity at 1 C than the baseline at−20°C.The 1 Ah pouch cells based on LiNi_(0.52)Co_(0.2)Mn_(0.28)O_(2)cathodes,graphite anodes,and 0.5 wt%LiDFOB-modified electrolyte demonstrate fast-charging capabilities:charging 97%of the pouch cell capacity within 30 min(2 C)and 80%within 15 min(4 C)at 25°C.This study offers a practical electrolyte design strategy that enhances the fast-charging performance of lithium-ion batteries(LIBs)over a wide temperature range(from−20 to 25°C).展开更多
Lanthanide ions(Ln^(3+))doping provides a potential strategy to control over the luminescent properties of lead-free halide double perovskite nanocrystals(DP NCs).However,due to the low energy transfer efficiency betw...Lanthanide ions(Ln^(3+))doping provides a potential strategy to control over the luminescent properties of lead-free halide double perovskite nanocrystals(DP NCs).However,due to the low energy transfer efficiency between self-trapped exciton(STE)and Ln^(3+)ions,the characteristic emissions of Ln^(3+)ions are not prominent.Furthermore,the energy transfer mechanism between STE and Ln^(3+)ions is also elusive and requires in-depth study.We chose trace Bi^(3+)-doped Cs_(2)Ag_(0.6)Na_(0.4)InCl_(6-x)Br_(x) as a representative DP matrix to demonstrate that by tuning the bromide concentration,the Ln^(3+)emission can be greatly enhanced.Such enhanced STE and Ln^(3+)ions energy transfer originates from the high covalency of Ln-Br bond,which contributes to improve ment of the characteristic emission of Ln^(3+)ions.Furthermo re,optical spectroscopy reveals that the energy transfer mechanism from DP to Eu^(3+)ions is different from all the other doped Ln^(3+)ions.The energy transfer from DP to Eu^(3+)ions is mostly through Eu-Br charge transfer while the other Ln^(3+)ions are excited by energy transfer from STE.The distinct energy transfer mechanism has resulted from the energy separation between the excited energy level of Ln^(3+)ions and the bottom of conduction band of DP.With increasing the energy separation,the energy transfer from STE to Ln^(3+)ions is less efficient because of the generation of a larger number of phonons and finally becomes impossible for Eu^(3+)ions.Our results provide new insight into tuning the energy transfer of Ln^(3+)-doped DP NCs.展开更多
Promising aqueous zinc metal batteries(AZMBs)continue to face significant challenges regarding zinc anode reversibility due to detrimental reactions including hydrogen evolution and corrosion.Herein,the d-band center ...Promising aqueous zinc metal batteries(AZMBs)continue to face significant challenges regarding zinc anode reversibility due to detrimental reactions including hydrogen evolution and corrosion.Herein,the d-band center is used as an“intuitive descriptor”to compare the hydrogen evolution activity of zinc-based transition bimetallic oxides(ZTBOs)of fourth-period transition metal elements,and the advantages of ZnTi_(3)O_(7)(ZTO)functional protective layer in inhibiting hydrogen evolution and extending the lifespan of the zinc anode are selectively identified.展开更多
Developing efficient electrocatalysts for oxygen evolution reaction(OER)is imperative to enhance the overall efficiency of electrolysis systems and rechargeable metal-air batteries operating in aqueous solutions.High-...Developing efficient electrocatalysts for oxygen evolution reaction(OER)is imperative to enhance the overall efficiency of electrolysis systems and rechargeable metal-air batteries operating in aqueous solutions.High-entropy materials,featured with their distinctive multi-component properties,have found extensive application as catalysts in electrochemical energy storage and conversion devices.However,synthesizing nanostructured high-entropy compounds under mild conditions poses a significant challenge due to the difficulty in overcoming the immiscibility of multiple metallic constituents.In this context,the current study focuses on the synthesis of an array of nano-sized high entropy sulfides tailored for OER via a facile precursor pyrolysis method at low temperature.The representative compound,Fe Co Ni Cu Mn Sx,demonstrates remarkable OER performance,achieving a current density of 10 m A/cm^(2) at an overpotential of merely 220 m V and excellent stability with constant electrolysis at 100 m A/cm^(2) for over 400 h.The in-situ formed metal(oxy)hydroxide has been confirmed as the real active sites and its exceptional performance can be primarily attributed to the synergistic effects arising from its multiple components.Furthermore,the synthetic methodology presented here is versatile and can be extended to the preparation of high entropy phosphides,which also present favorable OER performance.This research not only introduces promising non-noble electrocatalysts for OER but also offers a facile approach to expand the family of nano high-entropy materials,contributing significantly to the field of electrochemical energy conversion.展开更多
Phosphorus-based anode is a promising anode for sodium-ion batteries(SIBs)due to its high specific capacity,however,suffers from poor electronic conductivity and unfavorable electrochemical reversibility.Incorporating...Phosphorus-based anode is a promising anode for sodium-ion batteries(SIBs)due to its high specific capacity,however,suffers from poor electronic conductivity and unfavorable electrochemical reversibility.Incorporating metals such as copper(Cu)into phosphorus has been demonstrated to not only improve the electronic conductivity but also accommodate the volume change during cycling,yet the underline sodiation mechanism is not clear.Herein,take a copper phosphide and reduced graphene oxide(CuP_(2)/C)composite as an example,which delivers a high reversible capacity of>900 mAh/g.Interestingly,it is revealed that the native oxidation PO_(x)components of the CuP_(2)/C composite show higher electrochemical reversibility than the bulk Cu P_(2),based on a quantitative analysis of high-resolution solid-state^(31)P NMR,ex-situ XPS and synchrotron X-ray diffraction characterization techniques.The sodiation products Na_(3)PO_(4) and Na_(4)P_(2)O_(7) derived from PO_(x) could react with Na-P alloys and regenerate to PO_(x) during charge process,which probably accounts for the high reversible capacity of the Cu P_(2)/C anode.The findings also illustrate that the phosphorus transforms into nanocrystalline Na_(3)P and Na_(x)P alloys,which laterally shows crystallization-amorphization evolution process during cycling.展开更多
Effects of La, N, and P doping on the structural, electronic and optical properties of TiO_2 synthesized from TiCl_4 hydrolysis via a microwave-hydrothermal process were investigated by X-ray diffraction, transmission...Effects of La, N, and P doping on the structural, electronic and optical properties of TiO_2 synthesized from TiCl_4 hydrolysis via a microwave-hydrothermal process were investigated by X-ray diffraction, transmission electron microscopy, N_2 adsorption-desorption isotherm, X-ray photoelectron spectroscopy, electron paramagnetic resonance, UV-vis absorbance spectroscopy, photoelectrochemical measurements, and photoluminescence spectroscopy. The results showed that the presence of La in the tri-doped TiO_2 played a predominant role in inhibiting the recombination of the photogenerated electrons and holes. The existence of the substitutional N, interstitial N, and oxygen vacancies in TiO_2 lattices led to the band gap narrowing. It was P-doping rather than La or N doping that played a key role in inhibiting both anatase-to-rutile phase transformation and crystal growth, in stabilizing the mesoporous textural properties, and in increasing the content of surface bridging hydroxyl. Moreover, the tri-doping significantly enhanced the surface Ti^（4＋）-O^（2-）-Ti^（4＋）-O^（-·） species. All above-mentioned factors cooperated to result in the enhanced photoactivity of the tri-doped TiO_2. As a result, it exhibited the highest photoactivity towards the degradation of 4-chlorophenol（4-CP） under visible-light irradiation among all samples, which was much superior to commercial P25 TiO_2.展开更多
Highly active electrocatalysts based on Layered Double Hydroxides(LDH)towards oxygen evolution reactions(OER)are required for the applications of renewable energy-conversion technology.The improvement of conductivity ...Highly active electrocatalysts based on Layered Double Hydroxides(LDH)towards oxygen evolution reactions(OER)are required for the applications of renewable energy-conversion technology.The improvement of conductivity and electron-transporting capability for LDH materials remains an enormous challenge yet.Here,we synthesized carbon nanotube supported quaternary FeCoNiW-LDH ultrathin nanosheets with 1 nm thickness via one-pot hydrothermal methods,which exhibit enhanced OER activity due to the synergistic effect of modified CNTs and doped W^6+onto LDH nanosheets catalysts.The loaded carbon nanotubes can directly result in the improved conductivity.In addition,W^6+doping in LDH can modify the electronic structure and further enhance the conductivity of electrocatalysts.FeCoNiW-LDH/CNT exhibits a small overpotential(258 mV)at a current density of 10 mA·cm^–2 and low Tafel slope(41 mV decade^–1)towards OER in alkaline solutions,outperforming the noble metal RuO2 catalysts.展开更多
Single-band red upconversion luminescence(UCL) is vital to in vivo bioimaging as well as "see and treat" biomedicines. Herein, starting with the previously reported β-NaErF4:Tm UCNPs, we examined the effect...Single-band red upconversion luminescence(UCL) is vital to in vivo bioimaging as well as "see and treat" biomedicines. Herein, starting with the previously reported β-NaErF4:Tm UCNPs, we examined the effects of both Yb^(3+) doping and inert shell coating on the red-to-green(R/G) ratio for Er3+ based UCL. The doping of Yb^(3+) into the β-NaErF4:Tm3+ core not only enhances the whole UCL intensity, but also raises the R/G ratio by 1.25 times. In addition, the coating of an inert NaYF4 shell, which is usually adopted for the enhancement of UCL intensity, further boosts the R/G value up to as high as 77.92. This work may benefit the potential bioimaging application of single-band red UCL.展开更多
High entropy alloys(HEAs)have been the star materials in electrocatalysis research in recent years.One of their key features is the greatly increased multiplicity of active sites compared to conventional catalytic mat...High entropy alloys(HEAs)have been the star materials in electrocatalysis research in recent years.One of their key features is the greatly increased multiplicity of active sites compared to conventional catalytic materials.This increased multiplicity stimulates a cocktail effect and a scaling-relation breaking effect,and results in improved activity.However,the multiplicity of active sites in HEAs also poses new problems for mechanistic studies.One apparent problem is the inapplicability to HEA catalysts of the currently most popular mechanistic study method,which uses the electrocatalytic theoretical framework(ETF)based on the computational hydrogen electrode(CHE).The ETF uses a single adsorption energy to represent the catalyst,i.e.,a catalyst is represented by a'point'in the volcanic relationship.It naturally does not involve the multiplicity of active sites of a catalyst,and hence loses brevity in expressing the cocktail effect and scaling-relation breaking effect in HEA catalysis.This paper attempts to solve this inapplicability.Based on the fact that the adsorption energy distribution of HEAs is close to a normal distribution,the mean and variance of the adsorption energy distribution are introduced as descriptors of the ETF,replacing the original single adsorption energy.A quantitative relationship between the variance and the cocktail and scaling-relation braking effects is established.We believe the method described in this work will make the ETF more effective in mechanistic studies of HEA electrocatalysis.展开更多
Methods for transforming rare earth(RE)sulfate into chloride mainly include extraction process with organophosphonic mono-acids or aliphatic acids and precipitation process with ammonium bicarbonate(NH4 HCO3).In this ...Methods for transforming rare earth(RE)sulfate into chloride mainly include extraction process with organophosphonic mono-acids or aliphatic acids and precipitation process with ammonium bicarbonate(NH4 HCO3).In this paper,alkylphenoxy carboxylic acids(HAs)ofp-dodecylphenoxy acetic acid(HA-Ⅰ),pdodecylphenoxypropanoic acid(HA-Ⅱ)and p-dodecylphenoxybutyric acid(HA-Ⅲ),which were liquid at room temperature were synthesized and characterized.The precipitation mechanisms of RE elements with the HAs were investigated and the HA/RE molar ratios of the solid complexes were determined as3:1 by equi-molar series method which accord with the principle of charge balance.Applicability of HAs for the transformation of RE sulfate from concentrated sulfuric acid roasted RE concentrate into chloride via precipitation method was discussed.100%HA-Ⅱwas selected as the liquid organic precipitant without dilution of volatile solvent soracceleration of phase separation by phase-modifiers.The RE sulfate solution can be precipitated by HA-Ⅱafter neutralization with liquid NaOH and stripped with concentrated HCl at room temperature.High concentration of RE chloride of 218.1 g/L with low residue of sulfate radical of 0.536 g/L was obtained.The residual organic precipitant in the raffinate solution was tested to be lower than 8 mg/L at 25℃and the chemical oxygen demand(COD)in wastewater was less than 50 mg/L.展开更多
The gradient mechanical properties, variation of stress with strain and surface cracking behavior of expanded austenite developed on 316L austenitic stainless steel were investigated by nanoindentation tests, X-ray re...The gradient mechanical properties, variation of stress with strain and surface cracking behavior of expanded austenite developed on 316L austenitic stainless steel were investigated by nanoindentation tests, X-ray residual stress analysis and scanning electron microscope observation in four-point bending tests. The results show that the plastic properties of the carburizing layer including true initial yield strengths and strain hardening exponents increase significantly from substrate to surface, while the true elastic modulus just improves slightly. Due to the onset of plastic flow, the residual stresses are almost equivalent to the true initial yield strengths from surface to the depth of ～10 lm. The results of four-point bending tests show that surface stress increases linearly with the increase in strain until the strain reaches～1.0%, after that the plastic yield happens. The expanded austenite surface layer is brittle, and the cracks will be created at the strain of ～1.4%.The cracking stress is about～2.4 GPa.展开更多
Hydrogen peroxide(H_(2)O_(2))is one of the most important chemicals,which are commonly used in the paper and pulp industry,water purification and environmental protection[1-3].Most of the commercial available H_(2)O_(...Hydrogen peroxide(H_(2)O_(2))is one of the most important chemicals,which are commonly used in the paper and pulp industry,water purification and environmental protection[1-3].Most of the commercial available H_(2)O_(2) is produced by the anthraquinone oxidation process,which is environment unfriendly.展开更多
Ion-absorbed rare earth ores radioactive residues(IREORR)are a class of waste residue from the production of rare earth elements(REEs).Because of its radioactive dose,IREORR are usually stored in waste warehouses.IREO...Ion-absorbed rare earth ores radioactive residues(IREORR)are a class of waste residue from the production of rare earth elements(REEs).Because of its radioactive dose,IREORR are usually stored in waste warehouses.IREORR are difficult to be disposed of.However,it contains relatively high concentrations of REEs,which can be considered as a valuable secondary resource.In this paper,a novel process is developed for the separation of thorium(Th)and recovery of REEs from IREORR hydrochloric acid leachate with primary amine N1923 and Cyanex?572,respectively.The effects of sulfate concentration,extractant concentration and pH on N1923 extraction in hydrochloric acid solution were investigated in detail.The results show that the extraction capacity of N1923 can be improved by adding sulfate to the solution and increasing the concentration of N1923.Acidity has little effect on the extraction of Th when pH is higher than 1.As for the stripping,REEs are more easily stripped from loaded organic phase than Th,and nitric acid is a better stripping agent than hydrochloric acid.Combined with the extraction of Cyanex■572 for REEs,a fractional extraction experiment for separating Th and enriching of REEs was performed.The yield of Th is higher than 99.9%and the concentration of REEs is enriched to 183.84 g/L.展开更多
Sodium-based dual-ion batteries(SDIBs) have gained tremendous attention due to their virtues of high operating voltage and low cost, yet it remains a tough challenge for the development of ideal anode material of SDIB...Sodium-based dual-ion batteries(SDIBs) have gained tremendous attention due to their virtues of high operating voltage and low cost, yet it remains a tough challenge for the development of ideal anode material of SDIBs featuring with high kinetics and long durability. Herein, we report the design and fabrication of N-doped carbon film-modified niobium sulfur–selenium(NbSSe/NC) nanosheets architecture, which holds favorable merits for Na^(+) storage of enlarged interlayer space, improved electrical conductivity, as well as enhanced reaction reversibility, endowing it with high capacity, high-rate capability and high cycling stability. The combined electrochemical studies with density functional theory calculation reveal that the enriched defects in such nanosheets architecture can benefit for facilitating charge transfer and Na+ adsorption to speed the electrochemical kinetics. The NbSSe/NC composites are studied as the anode of a full SDIBs by pairing the expanded graphite as cathode, which shows an impressively cyclic durability with negligible capacity attenuation over 1000 cycles at 0.5 A g^(-1), as well as an outstanding energy density of 230.6 Wh kg^(-1) based on the total mass of anode and cathode.展开更多
The effect of steam-treatment to HZSM-5 zeolite and Mo/HZSM-5 with a steaming time range of 0.5-1 h on the catalytic performance of methane dehydro-aromatization （MDA） over Mo/HZSM-5 catalyst prepared with impregnat...The effect of steam-treatment to HZSM-5 zeolite and Mo/HZSM-5 with a steaming time range of 0.5-1 h on the catalytic performance of methane dehydro-aromatization （MDA） over Mo/HZSM-5 catalyst prepared with impregnation has been studied in detail in combination with the characterization of 1H MAS NMR technique. Both the deactivation rate constant （kd） and the Brtnsted acid sites per unit cell were calculated to quantitatively evaluate the stability of Mo/HZSM-5 catalysts treated with steam at 813 K before and after impregnation of molybdenum species, and the corresponding variation of their Brtnsted acid sites. The results reveal that a V-shape relationship between kd and the number of B 1 acid sites per unit cell is presented on Mo/HZSM-5 catalyst under the tested steam-treatment and reaction conditions.展开更多
The applications of bionic methodology developed by the Laboratory of Design and Material Selection as basis in the creation of junction elements were demonstrated. These elements favor the application of Ecodesign in...The applications of bionic methodology developed by the Laboratory of Design and Material Selection as basis in the creation of junction elements were demonstrated. These elements favor the application of Ecodesign in reference to the effectiveness of product dismount aiming the reduction of ambient impact in all its phases of use. The creation, the development and the confection of new junction elements were described, and case studies of new products developed specifically with this purpose were presented.展开更多
Leaching method is usually used to extract rare earth(RE)elements from ion adsorbed RE ores.In the leaching process,some impurities such as aluminum(Al)enter the leaching solution.The separation of Al from RE by carbo...Leaching method is usually used to extract rare earth(RE)elements from ion adsorbed RE ores.In the leaching process,some impurities such as aluminum(Al)enter the leaching solution.The separation of Al from RE by carboxylic acid extractant 4-octyloxybenzoic acid(POOA)was studied in this article.By changing the pH value,temperature,solvent,saponification degree and other parameters,the extraction and separation performance of POOA in chloride system was systematically studied.Through specific extraction experiments and slope analysis,it can be seen that the stoichiometric ratio of POOA to Al is 3:1during the extraction process.The separation factor of Al^(3+)and Pr^(3+)can reach about 160.00.Compared with easily emulsified naphthenic acid,POOA achieves better phase separation.The above results show that saponified POOA(S-POOA)has a good separation effect on Al and RE.Under the condition of low concentration stripping acid of 0.60 mol/L HCl,the developed extraction system can be almost completely stripped,and the stripping rate reaches 97.52%.The regenerated POOA can be directly used for the recycling extraction.展开更多
Carbon materials are crucially important for the realization of potassium-ion batteries.However,the potassium storage mechanisms in various carbon materials are incompletely understood.Herein,solid-state ^(13)C nuclea...Carbon materials are crucially important for the realization of potassium-ion batteries.However,the potassium storage mechanisms in various carbon materials are incompletely understood.Herein,solid-state ^(13)C nuclear magnetic resonance(NMR) spectroscopy coupled with Raman and X-ray diffraction(XRD) techniques are employed to study the reaction mechanism in a soft carbon quantitatively.It is revealed that the insertion of potassium ions into the soft carbon firstly induces a transformation of the disordered region to short-range ordered stacking,involving both the pristine local unorganized and organized carbon layers.Subsequently,potassium ions intercalate into the rearranged carbon structure,finally producing the nano-sized KC_(8).Moreover,a remarkable c apacity of 322 mAh·g^(-1) with a low mid potassiation voltage of <0.3 V is present for the prepared soft carbon,which is on account of the underlying potassium storage sites,including the disordered stacking carbon as a main component of the soft carbon.These results suggest that regulating the disordered stacking region in the turbostratic structure of soft carbon is a critical issue for further improving the potassium storage performance.展开更多
Hybrid materials are attracting intensive attention for their applications in electronics, photoelectronics, LEDs, field-effect transistors, etc. Engineering new hybrid materials and further exploiting their new funct...Hybrid materials are attracting intensive attention for their applications in electronics, photoelectronics, LEDs, field-effect transistors, etc. Engineering new hybrid materials and further exploiting their new functions will be significant for future science and technique development. In this work, alternatively stacked self-assembled CoAl LDH/MoS2 nanohybrid has been successfully synthesized by an exfoliation-flocculation method from positively charged CoAl LDH nanosheets（CoAl-NS） with negatively charged MoS2 nanosheets（MoS2-NS）. The CoAl LDH/MoS2 hybrid material exhibits an enhanced catalytic performance for oxygen evolution reaction（OER） compared with original constituents of CoAl LDH nanosheets and MoS2 nanosheets. The enhanced OER catalytic performance of CoAl LDH/MoS2 is demonstrated to be due to the improved electron transfer, more exposed catalytic active sites, and accelerated oxygen evolution reaction kinetics.展开更多
Organic–inorganic halide perovskite solar cells(PSCs)have delivered power conversion efficiency(PCE)on par with that of crystalline silicon solar cells,due to the considerable effort on the optimization of perovskite...Organic–inorganic halide perovskite solar cells(PSCs)have delivered power conversion efficiency(PCE)on par with that of crystalline silicon solar cells,due to the considerable effort on the optimization of perovskite materials and devices[1].The three-dimensional(3D)perovskite-based PSCs with the standard n–i–p architecture gave a certified PCE of25.5%[2].However,the poor device stability under operating conditions remains an obstacle to commercialization.The 3D hybrid perovskite materials are susceptible to oxygen,UV light,humidity,heat,and electric fields[3].To improve device stability,two main strategies are applied:(1)improving the intrinsic stability[4];(2)providing sufficient protection.展开更多
基金financially supported by the National Natural Science Foundation of China (Grant No. 52372191)the National Natural Science Foundation of China (Grant No. 22271106)+2 种基金the National Science Foundation of China (Grant Nos. 52073286 (C.-Z.L.), 22275185 (C.-Z.L.))the Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(2021ZZ115 (C.-Z.L.)the XMIREM Autonomously Deployment Project (2023GG01 (C.-Z.L.))
文摘To address the performance limitations of conventional LiPF6-carbonate electrolytes under extreme temperatures and high-rate charging,lithium difluoro(oxalato)borate(LiDFOB)is introduced into the LiPF6-carbonate electrolyte to form a dual-salt system.The optimization mechanism enhancing the fast-charging capability of LiNi_(0.52)Co_(0.2)Mn_(0.28)O_(2)(NCM523)cathode is systematically explored.Molecular dynamics simulations and electrochemical characterization demonstrate the reconstruction of Li+solvation structures,expanding the voltage window and reducting Li^(+)desolvation barriers.In addition,the incorporation of LiDFOB induces the generation of a LiF/Li_(x)BO_(y)F_(z)-enriched cathode-electrolyte interphase,which effectively suppresses the dissolution of transition metals.In situ impedance measurements reveal the accelerated interfacial charge transfer kinetics.As expected,the NCM523 cathode achieves an 82%state-of-charge(SOC)in 12 min at 5 C(25°C)with 87%capacity retention after 100 cycles,and exhibits a 65%higher discharge capacity at 1 C than the baseline at−20°C.The 1 Ah pouch cells based on LiNi_(0.52)Co_(0.2)Mn_(0.28)O_(2)cathodes,graphite anodes,and 0.5 wt%LiDFOB-modified electrolyte demonstrate fast-charging capabilities:charging 97%of the pouch cell capacity within 30 min(2 C)and 80%within 15 min(4 C)at 25°C.This study offers a practical electrolyte design strategy that enhances the fast-charging performance of lithium-ion batteries(LIBs)over a wide temperature range(from−20 to 25°C).
基金Project supported by the Research Project of Mindu Innovation Laboratory(2021ZZ114)Natural Science Foundation of Xiamen(3502Z20227255)+1 种基金Major Research Project of Xiamen(3502Z20191015)the Science and Technology Major Project of Fujian Province(2021HZ021013)。
文摘Lanthanide ions(Ln^(3+))doping provides a potential strategy to control over the luminescent properties of lead-free halide double perovskite nanocrystals(DP NCs).However,due to the low energy transfer efficiency between self-trapped exciton(STE)and Ln^(3+)ions,the characteristic emissions of Ln^(3+)ions are not prominent.Furthermore,the energy transfer mechanism between STE and Ln^(3+)ions is also elusive and requires in-depth study.We chose trace Bi^(3+)-doped Cs_(2)Ag_(0.6)Na_(0.4)InCl_(6-x)Br_(x) as a representative DP matrix to demonstrate that by tuning the bromide concentration,the Ln^(3+)emission can be greatly enhanced.Such enhanced STE and Ln^(3+)ions energy transfer originates from the high covalency of Ln-Br bond,which contributes to improve ment of the characteristic emission of Ln^(3+)ions.Furthermo re,optical spectroscopy reveals that the energy transfer mechanism from DP to Eu^(3+)ions is different from all the other doped Ln^(3+)ions.The energy transfer from DP to Eu^(3+)ions is mostly through Eu-Br charge transfer while the other Ln^(3+)ions are excited by energy transfer from STE.The distinct energy transfer mechanism has resulted from the energy separation between the excited energy level of Ln^(3+)ions and the bottom of conduction band of DP.With increasing the energy separation,the energy transfer from STE to Ln^(3+)ions is less efficient because of the generation of a larger number of phonons and finally becomes impossible for Eu^(3+)ions.Our results provide new insight into tuning the energy transfer of Ln^(3+)-doped DP NCs.
基金support from National Natural Science Foundation of China(52272198 and 22109163)。
文摘Promising aqueous zinc metal batteries(AZMBs)continue to face significant challenges regarding zinc anode reversibility due to detrimental reactions including hydrogen evolution and corrosion.Herein,the d-band center is used as an“intuitive descriptor”to compare the hydrogen evolution activity of zinc-based transition bimetallic oxides(ZTBOs)of fourth-period transition metal elements,and the advantages of ZnTi_(3)O_(7)(ZTO)functional protective layer in inhibiting hydrogen evolution and extending the lifespan of the zinc anode are selectively identified.
基金financially supported by the National Natural Science Foundation of China(Nos.22209183,22225902,U22A20436)the Advanced Talents of Jiangsu University,China(No.23JDG027)。
文摘Developing efficient electrocatalysts for oxygen evolution reaction(OER)is imperative to enhance the overall efficiency of electrolysis systems and rechargeable metal-air batteries operating in aqueous solutions.High-entropy materials,featured with their distinctive multi-component properties,have found extensive application as catalysts in electrochemical energy storage and conversion devices.However,synthesizing nanostructured high-entropy compounds under mild conditions poses a significant challenge due to the difficulty in overcoming the immiscibility of multiple metallic constituents.In this context,the current study focuses on the synthesis of an array of nano-sized high entropy sulfides tailored for OER via a facile precursor pyrolysis method at low temperature.The representative compound,Fe Co Ni Cu Mn Sx,demonstrates remarkable OER performance,achieving a current density of 10 m A/cm^(2) at an overpotential of merely 220 m V and excellent stability with constant electrolysis at 100 m A/cm^(2) for over 400 h.The in-situ formed metal(oxy)hydroxide has been confirmed as the real active sites and its exceptional performance can be primarily attributed to the synergistic effects arising from its multiple components.Furthermore,the synthetic methodology presented here is versatile and can be extended to the preparation of high entropy phosphides,which also present favorable OER performance.This research not only introduces promising non-noble electrocatalysts for OER but also offers a facile approach to expand the family of nano high-entropy materials,contributing significantly to the field of electrochemical energy conversion.
基金financially supported by National Nature Science Foundation of China(Nos.21805278,22272175 and 22209075)the Fujian Science and Technology Planning Projects of China(Nos.2022T3067 and 2023H0045)+1 种基金the Self-deployment Project Research Programs of Haixi Institutes,Chinese Academy of Sciences(No.CXZX-2022-JQ12)the Self-deployment project of XIREM(No.2023GG02)。
文摘Phosphorus-based anode is a promising anode for sodium-ion batteries(SIBs)due to its high specific capacity,however,suffers from poor electronic conductivity and unfavorable electrochemical reversibility.Incorporating metals such as copper(Cu)into phosphorus has been demonstrated to not only improve the electronic conductivity but also accommodate the volume change during cycling,yet the underline sodiation mechanism is not clear.Herein,take a copper phosphide and reduced graphene oxide(CuP_(2)/C)composite as an example,which delivers a high reversible capacity of>900 mAh/g.Interestingly,it is revealed that the native oxidation PO_(x)components of the CuP_(2)/C composite show higher electrochemical reversibility than the bulk Cu P_(2),based on a quantitative analysis of high-resolution solid-state^(31)P NMR,ex-situ XPS and synchrotron X-ray diffraction characterization techniques.The sodiation products Na_(3)PO_(4) and Na_(4)P_(2)O_(7) derived from PO_(x) could react with Na-P alloys and regenerate to PO_(x) during charge process,which probably accounts for the high reversible capacity of the Cu P_(2)/C anode.The findings also illustrate that the phosphorus transforms into nanocrystalline Na_(3)P and Na_(x)P alloys,which laterally shows crystallization-amorphization evolution process during cycling.
基金Project supported by the Natural Science Foundation of Heilongjiang Province(E201323)the Science and Technology Research Program of Education Bureau of Heilongjiang Province(12531213)
文摘Effects of La, N, and P doping on the structural, electronic and optical properties of TiO_2 synthesized from TiCl_4 hydrolysis via a microwave-hydrothermal process were investigated by X-ray diffraction, transmission electron microscopy, N_2 adsorption-desorption isotherm, X-ray photoelectron spectroscopy, electron paramagnetic resonance, UV-vis absorbance spectroscopy, photoelectrochemical measurements, and photoluminescence spectroscopy. The results showed that the presence of La in the tri-doped TiO_2 played a predominant role in inhibiting the recombination of the photogenerated electrons and holes. The existence of the substitutional N, interstitial N, and oxygen vacancies in TiO_2 lattices led to the band gap narrowing. It was P-doping rather than La or N doping that played a key role in inhibiting both anatase-to-rutile phase transformation and crystal growth, in stabilizing the mesoporous textural properties, and in increasing the content of surface bridging hydroxyl. Moreover, the tri-doping significantly enhanced the surface Ti^（4＋）-O^（2-）-Ti^（4＋）-O^（-·） species. All above-mentioned factors cooperated to result in the enhanced photoactivity of the tri-doped TiO_2. As a result, it exhibited the highest photoactivity towards the degradation of 4-chlorophenol（4-CP） under visible-light irradiation among all samples, which was much superior to commercial P25 TiO_2.
基金National Postdoctoral Program for Innovative Talents of China(No.BX201600164)the National Natural Science Foundation of China(Nos 21701175)。
文摘Highly active electrocatalysts based on Layered Double Hydroxides(LDH)towards oxygen evolution reactions(OER)are required for the applications of renewable energy-conversion technology.The improvement of conductivity and electron-transporting capability for LDH materials remains an enormous challenge yet.Here,we synthesized carbon nanotube supported quaternary FeCoNiW-LDH ultrathin nanosheets with 1 nm thickness via one-pot hydrothermal methods,which exhibit enhanced OER activity due to the synergistic effect of modified CNTs and doped W^6+onto LDH nanosheets catalysts.The loaded carbon nanotubes can directly result in the improved conductivity.In addition,W^6+doping in LDH can modify the electronic structure and further enhance the conductivity of electrocatalysts.FeCoNiW-LDH/CNT exhibits a small overpotential(258 mV)at a current density of 10 mA·cm^–2 and low Tafel slope(41 mV decade^–1)towards OER in alkaline solutions,outperforming the noble metal RuO2 catalysts.
基金Project supported by the National Key Research and Development Program of China(2016YFB0701003)the National Natural Science Foundation of China(51872288,11674318,51472242,21673242)
文摘Single-band red upconversion luminescence(UCL) is vital to in vivo bioimaging as well as "see and treat" biomedicines. Herein, starting with the previously reported β-NaErF4:Tm UCNPs, we examined the effects of both Yb^(3+) doping and inert shell coating on the red-to-green(R/G) ratio for Er3+ based UCL. The doping of Yb^(3+) into the β-NaErF4:Tm3+ core not only enhances the whole UCL intensity, but also raises the R/G ratio by 1.25 times. In addition, the coating of an inert NaYF4 shell, which is usually adopted for the enhancement of UCL intensity, further boosts the R/G value up to as high as 77.92. This work may benefit the potential bioimaging application of single-band red UCL.
文摘High entropy alloys(HEAs)have been the star materials in electrocatalysis research in recent years.One of their key features is the greatly increased multiplicity of active sites compared to conventional catalytic materials.This increased multiplicity stimulates a cocktail effect and a scaling-relation breaking effect,and results in improved activity.However,the multiplicity of active sites in HEAs also poses new problems for mechanistic studies.One apparent problem is the inapplicability to HEA catalysts of the currently most popular mechanistic study method,which uses the electrocatalytic theoretical framework(ETF)based on the computational hydrogen electrode(CHE).The ETF uses a single adsorption energy to represent the catalyst,i.e.,a catalyst is represented by a'point'in the volcanic relationship.It naturally does not involve the multiplicity of active sites of a catalyst,and hence loses brevity in expressing the cocktail effect and scaling-relation breaking effect in HEA catalysis.This paper attempts to solve this inapplicability.Based on the fact that the adsorption energy distribution of HEAs is close to a normal distribution,the mean and variance of the adsorption energy distribution are introduced as descriptors of the ETF,replacing the original single adsorption energy.A quantitative relationship between the variance and the cocktail and scaling-relation braking effects is established.We believe the method described in this work will make the ETF more effective in mechanistic studies of HEA electrocatalysis.
基金Project supported by the National Key R&D Program of China(2017YFE0106900)Science and Technology Major Projects of Fujian Province(2015HZ0001-3)+2 种基金Natural Science Foundation of Fujian Province(2016J05058)Hundreds of Talents ProgramScience and Technology Service Network Initiative from Chinese Academy of Sciences
文摘Methods for transforming rare earth(RE)sulfate into chloride mainly include extraction process with organophosphonic mono-acids or aliphatic acids and precipitation process with ammonium bicarbonate(NH4 HCO3).In this paper,alkylphenoxy carboxylic acids(HAs)ofp-dodecylphenoxy acetic acid(HA-Ⅰ),pdodecylphenoxypropanoic acid(HA-Ⅱ)and p-dodecylphenoxybutyric acid(HA-Ⅲ),which were liquid at room temperature were synthesized and characterized.The precipitation mechanisms of RE elements with the HAs were investigated and the HA/RE molar ratios of the solid complexes were determined as3:1 by equi-molar series method which accord with the principle of charge balance.Applicability of HAs for the transformation of RE sulfate from concentrated sulfuric acid roasted RE concentrate into chloride via precipitation method was discussed.100%HA-Ⅱwas selected as the liquid organic precipitant without dilution of volatile solvent soracceleration of phase separation by phase-modifiers.The RE sulfate solution can be precipitated by HA-Ⅱafter neutralization with liquid NaOH and stripped with concentrated HCl at room temperature.High concentration of RE chloride of 218.1 g/L with low residue of sulfate radical of 0.536 g/L was obtained.The residual organic precipitant in the raffinate solution was tested to be lower than 8 mg/L at 25℃and the chemical oxygen demand(COD)in wastewater was less than 50 mg/L.
基金supported financially by the National Natural Science Foundation of China(Nos.51475224 and 51605164)the Natural Science Foundation of Jiangsu Higher Education Institutions of China(No.14KJA470002)
文摘The gradient mechanical properties, variation of stress with strain and surface cracking behavior of expanded austenite developed on 316L austenitic stainless steel were investigated by nanoindentation tests, X-ray residual stress analysis and scanning electron microscope observation in four-point bending tests. The results show that the plastic properties of the carburizing layer including true initial yield strengths and strain hardening exponents increase significantly from substrate to surface, while the true elastic modulus just improves slightly. Due to the onset of plastic flow, the residual stresses are almost equivalent to the true initial yield strengths from surface to the depth of ～10 lm. The results of four-point bending tests show that surface stress increases linearly with the increase in strain until the strain reaches～1.0%, after that the plastic yield happens. The expanded austenite surface layer is brittle, and the cracks will be created at the strain of ～1.4%.The cracking stress is about～2.4 GPa.
基金supported by the NSF for Distinguished Young Scholars of Fujian Province(Grant no.2017 J07004)。
文摘Hydrogen peroxide(H_(2)O_(2))is one of the most important chemicals,which are commonly used in the paper and pulp industry,water purification and environmental protection[1-3].Most of the commercial available H_(2)O_(2) is produced by the anthraquinone oxidation process,which is environment unfriendly.
基金supported by the National Key R&D Program of China(2017YFE0106900)Science and Technology Major Project of Ganzhou(2018)Fujian Program for High-Level Entrepreneurial and Innovative Talents Introduction and Science and Technology Service Network Initiative from Chinese Academy of Sciences。
文摘Ion-absorbed rare earth ores radioactive residues(IREORR)are a class of waste residue from the production of rare earth elements(REEs).Because of its radioactive dose,IREORR are usually stored in waste warehouses.IREORR are difficult to be disposed of.However,it contains relatively high concentrations of REEs,which can be considered as a valuable secondary resource.In this paper,a novel process is developed for the separation of thorium(Th)and recovery of REEs from IREORR hydrochloric acid leachate with primary amine N1923 and Cyanex?572,respectively.The effects of sulfate concentration,extractant concentration and pH on N1923 extraction in hydrochloric acid solution were investigated in detail.The results show that the extraction capacity of N1923 can be improved by adding sulfate to the solution and increasing the concentration of N1923.Acidity has little effect on the extraction of Th when pH is higher than 1.As for the stripping,REEs are more easily stripped from loaded organic phase than Th,and nitric acid is a better stripping agent than hydrochloric acid.Combined with the extraction of Cyanex■572 for REEs,a fractional extraction experiment for separating Th and enriching of REEs was performed.The yield of Th is higher than 99.9%and the concentration of REEs is enriched to 183.84 g/L.
基金financially supported by the National key Research & Development Program of China (2022YFE0115900, 2021YFA1501500)the National Natural Science Foundation of China (Nos. 22225902, U22A20436, 22209185)+3 种基金the CAS-Commonwealth Scientific and Industrial Research Organization (CSIRO) Joint Research Projects (121835KYSB20200039)the Joint Fund of the Yulin University and the Dalian National Laboratory for Clean Energy (Grant. YLUDNL Fund 2021011)Fujian Province Central Government Guides to Science and Technology Development Special Project (No. 2022L3024)Natural Science Foundation of Fujian Province, China (No. 2021J02020)。
文摘Sodium-based dual-ion batteries(SDIBs) have gained tremendous attention due to their virtues of high operating voltage and low cost, yet it remains a tough challenge for the development of ideal anode material of SDIBs featuring with high kinetics and long durability. Herein, we report the design and fabrication of N-doped carbon film-modified niobium sulfur–selenium(NbSSe/NC) nanosheets architecture, which holds favorable merits for Na^(+) storage of enlarged interlayer space, improved electrical conductivity, as well as enhanced reaction reversibility, endowing it with high capacity, high-rate capability and high cycling stability. The combined electrochemical studies with density functional theory calculation reveal that the enriched defects in such nanosheets architecture can benefit for facilitating charge transfer and Na+ adsorption to speed the electrochemical kinetics. The NbSSe/NC composites are studied as the anode of a full SDIBs by pairing the expanded graphite as cathode, which shows an impressively cyclic durability with negligible capacity attenuation over 1000 cycles at 0.5 A g^(-1), as well as an outstanding energy density of 230.6 Wh kg^(-1) based on the total mass of anode and cathode.
基金supported by Foundation for University Key Teacher by the Education of Heilongjiang Province(No.1152G018)
文摘The effect of steam-treatment to HZSM-5 zeolite and Mo/HZSM-5 with a steaming time range of 0.5-1 h on the catalytic performance of methane dehydro-aromatization （MDA） over Mo/HZSM-5 catalyst prepared with impregnation has been studied in detail in combination with the characterization of 1H MAS NMR technique. Both the deactivation rate constant （kd） and the Brtnsted acid sites per unit cell were calculated to quantitatively evaluate the stability of Mo/HZSM-5 catalysts treated with steam at 813 K before and after impregnation of molybdenum species, and the corresponding variation of their Brtnsted acid sites. The results reveal that a V-shape relationship between kd and the number of B 1 acid sites per unit cell is presented on Mo/HZSM-5 catalyst under the tested steam-treatment and reaction conditions.
文摘The applications of bionic methodology developed by the Laboratory of Design and Material Selection as basis in the creation of junction elements were demonstrated. These elements favor the application of Ecodesign in reference to the effectiveness of product dismount aiming the reduction of ambient impact in all its phases of use. The creation, the development and the confection of new junction elements were described, and case studies of new products developed specifically with this purpose were presented.
基金Project supported by the National Key R&D Program of China(2017YFE0106900)Fujian Program for High-Level Entrepreneurial and Innovative Talents Introduction+1 种基金Key R&D Program of Jiangxi Province(S2020ZPYFG0029)Key Program of the Chinese Academy of Sciences(ZDRW-CN-2021-3-1)。
文摘Leaching method is usually used to extract rare earth(RE)elements from ion adsorbed RE ores.In the leaching process,some impurities such as aluminum(Al)enter the leaching solution.The separation of Al from RE by carboxylic acid extractant 4-octyloxybenzoic acid(POOA)was studied in this article.By changing the pH value,temperature,solvent,saponification degree and other parameters,the extraction and separation performance of POOA in chloride system was systematically studied.Through specific extraction experiments and slope analysis,it can be seen that the stoichiometric ratio of POOA to Al is 3:1during the extraction process.The separation factor of Al^(3+)and Pr^(3+)can reach about 160.00.Compared with easily emulsified naphthenic acid,POOA achieves better phase separation.The above results show that saponified POOA(S-POOA)has a good separation effect on Al and RE.Under the condition of low concentration stripping acid of 0.60 mol/L HCl,the developed extraction system can be almost completely stripped,and the stripping rate reaches 97.52%.The regenerated POOA can be directly used for the recycling extraction.
基金financially supported by the National Nature Science Foundation of China (Nos.21905314, 21825202,21733012,92045302 and 21603231)Newton Advanced Fellowships (No.NAF/R2/180603)+1 种基金"Scientist Studio Funding" from Tianmu Lake Institute of Advanced Energy Storage Technologies Co.,Ltdthe Science and Technology Service Network Initiative from Chinese Academy of Science (No.STS 2020T3022)。
文摘Carbon materials are crucially important for the realization of potassium-ion batteries.However,the potassium storage mechanisms in various carbon materials are incompletely understood.Herein,solid-state ^(13)C nuclear magnetic resonance(NMR) spectroscopy coupled with Raman and X-ray diffraction(XRD) techniques are employed to study the reaction mechanism in a soft carbon quantitatively.It is revealed that the insertion of potassium ions into the soft carbon firstly induces a transformation of the disordered region to short-range ordered stacking,involving both the pristine local unorganized and organized carbon layers.Subsequently,potassium ions intercalate into the rearranged carbon structure,finally producing the nano-sized KC_(8).Moreover,a remarkable c apacity of 322 mAh·g^(-1) with a low mid potassiation voltage of <0.3 V is present for the prepared soft carbon,which is on account of the underlying potassium storage sites,including the disordered stacking carbon as a main component of the soft carbon.These results suggest that regulating the disordered stacking region in the turbostratic structure of soft carbon is a critical issue for further improving the potassium storage performance.
基金financially supported by NNSFC(No.21025104,21271171,and 91022018)
文摘Hybrid materials are attracting intensive attention for their applications in electronics, photoelectronics, LEDs, field-effect transistors, etc. Engineering new hybrid materials and further exploiting their new functions will be significant for future science and technique development. In this work, alternatively stacked self-assembled CoAl LDH/MoS2 nanohybrid has been successfully synthesized by an exfoliation-flocculation method from positively charged CoAl LDH nanosheets（CoAl-NS） with negatively charged MoS2 nanosheets（MoS2-NS）. The CoAl LDH/MoS2 hybrid material exhibits an enhanced catalytic performance for oxygen evolution reaction（OER） compared with original constituents of CoAl LDH nanosheets and MoS2 nanosheets. The enhanced OER catalytic performance of CoAl LDH/MoS2 is demonstrated to be due to the improved electron transfer, more exposed catalytic active sites, and accelerated oxygen evolution reaction kinetics.
基金financial support from the National Natural Science Foundation of China(21975260)the NSFC-CNR Exchange Program(22011530391)+1 种基金the National Key Research and Development Program of China(2017YFA0206600)the National Natural Science Foundation of China(51773045,21772030,51922032,and21961160720)for financial support。
文摘Organic–inorganic halide perovskite solar cells(PSCs)have delivered power conversion efficiency(PCE)on par with that of crystalline silicon solar cells,due to the considerable effort on the optimization of perovskite materials and devices[1].The three-dimensional(3D)perovskite-based PSCs with the standard n–i–p architecture gave a certified PCE of25.5%[2].However,the poor device stability under operating conditions remains an obstacle to commercialization.The 3D hybrid perovskite materials are susceptible to oxygen,UV light,humidity,heat,and electric fields[3].To improve device stability,two main strategies are applied:(1)improving the intrinsic stability[4];(2)providing sufficient protection.
