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 equilibri...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.展开更多
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–diffusio...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.展开更多
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 abili...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.展开更多
To demonstrate flexible and tandem device applications,a low-temperature Cu_(2)ZnSnSe_(4)(CZTSe)deposition process,combined with efficient alkali doping,was developed.First,high-quality CZTSe films were grown at 480℃...To demonstrate flexible and tandem device applications,a low-temperature Cu_(2)ZnSnSe_(4)(CZTSe)deposition process,combined with efficient alkali doping,was developed.First,high-quality CZTSe films were grown at 480℃by a single co-evaporation,which is applicable to polyimide(PI)substrate.Because of the alkali-free substrate,Na and K alkali doping were systematically studied and optimized to precisely control the alkali distribution in CZTSe.The bulk defect density was significantly reduced by suppression of deep acceptor states after the(NaF+KF)PDTs.Through the low-temperature deposition with(NaF+KF)PDTs,the CZTSe device on glass yields the best efficiency of 8.1%with an improved Voc deficit of 646 mV.The developed deposition technologies have been applied to PI.For the first time,we report the highest efficiency of 6.92%for flexible CZTSe solar cells on PI.Additionally,CZTSe devices were utilized as bottom cells to fabricate four-terminal CZTSe/perovskite tandem cells because of a low bandgap of CZTSe(~1.0 eV)so that the tandem cell yielded an efficiency of 20%.The obtained results show that CZTSe solar cells prepared by a low-temperature process with in-situ alkali doping can be utilized for flexible thin-film solar cells as well as tandem device applications.展开更多
In this paper we present a novel report on the upconversion luminescence performance of NaY0.92Yb0.05Er0.03F4 enhanced by Zr^4+ codoping. The luminescence intensity of the tridoped hexagonal NaYF_4 synthesized by a h...In this paper we present a novel report on the upconversion luminescence performance of NaY0.92Yb0.05Er0.03F4 enhanced by Zr^4+ codoping. The luminescence intensity of the tridoped hexagonal NaYF_4 synthesized by a hydrothermal method increased to the maximum, about seven times of the non-Zr^4+ sample when the Zr^4+ codoping concentration rose to 6 mol%, while the luminescence lifetime was also prolonged by Zr^4+ codoping. To explore the relationships between the microstructure and upconversion properties, X-ray powder diffraction, field emission scanning electron microscope, electron energy-dispersive spectroscopy and upconversion emission spectroscopy were employed. From these characterizations, we found that the codoping of Zr^4+ could modulate the crystal microstructure of NaYF_4 for higher upconversion luminescence intensity and longer lifetime. This study may be helpful for the design and synthesis of high-performance upconversion materials.展开更多
Li3V2-2/3xMnx(PO4)3(0≤x≤0.12) powders were synthesized by sol-gel method. The effect of Mn2+-doping on the structure and electrochemical performances of Li3V2(PO4)3/C was characterized by XRD, SEM, XPS, galva...Li3V2-2/3xMnx(PO4)3(0≤x≤0.12) powders were synthesized by sol-gel method. The effect of Mn2+-doping on the structure and electrochemical performances of Li3V2(PO4)3/C was characterized by XRD, SEM, XPS, galvanostatic charge /discharge and electrochemical impedance spectroscopy(EIS). The XRD study shows that a small amount of Mn2+-doped does not alter the structure of Li3V2(PO4)3/C materials, and all Mn2+-doped samples are of pure single phase with a monoclinic structure (space group P21/n). The XPS analysis indicates that valences state of V and Mn are +3 and +2 in Li3V1.94Mn0.09(PO4)3/C, respectively, and the citric acid in raw materials was decomposed into carbon during calcination, and residual carbon exists in Li3V1.94Mn0.09(PO4)/C. The results of electrochemical measurements show that Mn2+-doping can improve the cyclic stability and rate performance of these cathode materials. The Li3V1.94Mn0.09(PO4)3/C cathode material shows the best cyclic stability and rate performance. For example, at the discharge current density of 40 mA/g, after 100 cycles, the discharge capacity of Li3V1.94Mn0.09(PO4)3/C declines from initial 158.8 mA·h/g to 120.5 mA·h/g with a capacity retention of 75.9%; however, that of the Mn-undoed sample declines from 164.2 mA·h/g to 72.6 mA·h/g with a capacity retention of 44.2%. When the discharge current is increased up to 1C, the intial discharge capacity of Li3V1.94Mn0.09(PO4)3/C still reaches 146.4 mA·h/g, and the discharge capacity maintains at 107.5 mA·h/g after 100 cycles. The EIS measurement indicates that Mn2+-doping with a appropriate amount of Mn2+ decreases the charge transfer resistance, which is favorable for the insertion/extraction of Li+.展开更多
Aluminum doped zinc oxide (AZO), as an electrically conductive material, was applied to coating on the surface of olivine-type LiFePO4 synthesized by solid-state method. The charge-discharge test results show that t...Aluminum doped zinc oxide (AZO), as an electrically conductive material, was applied to coating on the surface of olivine-type LiFePO4 synthesized by solid-state method. The charge-discharge test results show that the rate performance and low-temperature performance of LiFePO4 are greatly improved by the surface treatment. Even at 20C rate, the discharge specific capacity of 100.9 mA.h/g was obtained by the AZO-coated LiFePO4 at room temperature. At -20 ℃, the discharge specific capacity at 0.2C for un-coated LiFePO4 and the coated one are 50.3 mA.h/g and 119.4 mA.h/g, respectively. It should be attributed to the electrically conductive AZO-coating which increases the electronic conductivity of LiFePO4. Furthermore, the surface-coating increases the tap-density of LiFePO4. The results indicate that the AZO-coated LiFePO4 is a good candidate of cathode material for applying in lithium power batteries.展开更多
To enhance the photocatalytic activity of B-BiVO4,Ni-doped B?BiVO4photocatalyst(Ni-B-BiVO4)was synthesized through sol-gel and impregnation method.The photocatalysts were characterized by XPS,XRD,SEM,EDS,BET and UV-Vi...To enhance the photocatalytic activity of B-BiVO4,Ni-doped B?BiVO4photocatalyst(Ni-B-BiVO4)was synthesized through sol-gel and impregnation method.The photocatalysts were characterized by XPS,XRD,SEM,EDS,BET and UV-Vis DRS techniques.The results showed that single or double doping did not change the crystalline structure and morphology,but the particle size decreased with Ni doping.The band gap energy absorption edge of Ni-B-BiVO4shifted to a longer wavelength compared with undoped,B or Ni single doped BiVO4.More V4+and surface hydroxyl oxygen were observed in BiVO4after Ni-B co-doping.When the optimal mass fraction of Ni is0.30%,the degradation rate of MO in50min is95%for0.3Ni-B-BiVO4sample which also can effectively degrade methyl blue(MB),acid orange(AOII)II and rhodamine B(RhB).The enhanced photocatalytic activity is attributed to the synergistic effects of B and Ni doping.展开更多
Fe-doped BiVO4with hierarchical flower-like structure was prepared via a hydrothermal method using sodium dodecylbenzene sulfonate(SDBS)as structure directing agent.X-ray diffraction(XRD),scanning electron microscope(...Fe-doped BiVO4with hierarchical flower-like structure was prepared via a hydrothermal method using sodium dodecylbenzene sulfonate(SDBS)as structure directing agent.X-ray diffraction(XRD),scanning electron microscope(SEM),transmissionelectron microscope(TEM),high resolution transmission electron microscope(HRTEM),X-ray photoelectron spectroscopy(XPS)and UV-Vis were applied for characterization of the as-prepared samples.The formation mechanism of flower-like structure wasproposed based on the evolution of morphology as a function of hydrothermal time.Fe-doped into substitutional sites of BiVO4effectively improved the migration and separation of photogenerated carrier and enhanced the utilization of visible light.Flower-likeFe-doped BiVO4showed much higher visible-light-driven photocatalytic efficiency for degradation of methyl blue compared withthe pristine BiVO4.And the sample with a Fe/Bi mole ratio of2.5%showed the highest photocatalytic efficiency.展开更多
Element doping is a simple and effective method to improve photocatalytic activity of g-C3N4. However, the doping model and mechanism of metal elements are still uncharacterized. In this study, we found that Fe(Ⅲ) ca...Element doping is a simple and effective method to improve photocatalytic activity of g-C3N4. However, the doping model and mechanism of metal elements are still uncharacterized. In this study, we found that Fe(Ⅲ) can be doped into g-C3N4 through the coordination between amidogen and Fe(Ⅲ). After activity tests, it was found that this coordination doping of Fe(Ⅲ) could enhance the Rh B oxidation and Cr(Ⅵ) reduction activities of g-C3N4 in interesting ways, but it is not helpful for the NO-removal performance of g-C3N4. Characterization and calculation results show that the coordination of Fe(Ⅲ) can not only improve the transfer of photogenerated electrons, but it also can passivate the carbon site of triazine rings, which is the active site of NO-removal. This study revealed some doping mechanisms and effect mechanisms of elemental metal in photocatalysis.展开更多
Photocatalytic hydrogen production based on semiconductor photocatalysts has been considered as one of the most promising strategies to resolve the global energy shortage.Graphitic carbon nitride(g‐C3N4)has been a st...Photocatalytic hydrogen production based on semiconductor photocatalysts has been considered as one of the most promising strategies to resolve the global energy shortage.Graphitic carbon nitride(g‐C3N4)has been a star visible‐light photocatalyst in this field due to its various advantages.However,pristine g‐C3N4usually exhibits limited activity.Herein,to enhance the performance of g‐C3N4,alkali metal ion(Li+,Na+,or K+)‐doped g‐C3N4are prepared via facile high‐temperature treatment.The prepared samples are characterized and analyzed using the technique of XRD,ICP‐AES,SEM,UV‐vis DRS,BET,XPS,PL,TRPL,photoelectrochemical measurements,photocatalytic tests,etc.The resultant doped photocatalysts show enhanced visible‐light photocatalytic activities for hydrogen production,benefiting from the increased specific surface areas(which provide more active sites),decreased band gaps for extended visible‐light absorption,and improved electronic structures for efficient charge transfer.In particular,because of the optimal tuning of both microstructure and electronic structure,the Na‐doped g‐C3N4shows the most effective utilization of photogenerated electrons during the water reduction process.As a result,the highest photocatalytic performance is achieved over the Na‐doped g‐C3N4photocatalyst(18.7?mol/h),3.7times that of pristine g‐C3N4(5.0?mol/h).This work gives a systematic study for the understanding of doping effect of alkali metals in semiconductor photocatalysis.展开更多
The exploration of active and long-lived oxygen reduction reaction(ORR)catalysts for the commercialization of zinc-air batteries are of immense significance but challenging.Herein,the sulfur doped FeWO_(4)embedded in ...The exploration of active and long-lived oxygen reduction reaction(ORR)catalysts for the commercialization of zinc-air batteries are of immense significance but challenging.Herein,the sulfur doped FeWO_(4)embedded in the multi-dimensional nitrogen-doped carbon structure(S-FeWO_(4)/NC)was successfully synthesized.The doped S atoms optimized the charge distribution in FeWO_(4)and enhanced the intrinsic activity.At the same time,S doping accelerated the formation of reaction intermediates during the adsorption reduction of O_(2)on the surface of S-FeWO_(4)/NC.Accordingly,the S-FeWO_(4)/NC catalyst showed more positive half-wave potential(0.85 V)and better stability than that of the FeWO_(4)/NC catalyst.Furthermore,the S-FeWO_(4)/NC-based zinc-air battery exhibited considerable power density of 150.3m W cm^(-2),high specific capacity of 912.7 m A h g^(-1),and prominent cycle stability up to 220 h.This work provides an assistance to the development of cheap and efficient tungsten-based oxygen reduction catalysts and the promotion of its application in the zinc-air battery.展开更多
Multifunctional non-precious catalysts for hydrogen/oxygen evolution reaction(HER/OER) and oxygen reduction reaction(ORR) constitute the bottleneck in the applications in electrochemical overall water splitting(OWS) a...Multifunctional non-precious catalysts for hydrogen/oxygen evolution reaction(HER/OER) and oxygen reduction reaction(ORR) constitute the bottleneck in the applications in electrochemical overall water splitting(OWS) and Zn-air batteries. Herein, a trifunctional electrocatalyst of urchin-like Al,P-codoped Co3O4 microspheres supported on Ni foam(denoted as AP-CONPs/NF) was fabricated via a hydrothermal process and subsequent low-temperature annealing and phosphorization, exhibiting enhanced OER, HER and ORR activities compared with single-doped and undoped samples. Their surface self-organized microstructure and excellent "superaerophobic" feature make a high bubble repellency, which boost diffusion of reactants and electrolyte-electrode intimate contact. The codoping of Al and P elements into Co3O4 betters right the balance among surface chemical state, the increased oxygen vacancies and the promoted charge transfer. Encouraged by these synergistic advantages, the AP-CONPs/NF was further employed as excellent bifunctional electrodes for the OWS(low cell voltage of 1.57 V at 10 mA cm-2) and as air cathode for rechargeable Zn-air batteries(high power density of 89.1 mW cm-2), which demonstrates a great feasibility for practical applications.展开更多
Non-stoichiometric compound fluoride-doped LiFePO4/C cathode materials were synthesized via solid-state reaction using MgF2 and AlF3 as dopant. The fluoride-doped LiFePO4/C samples were characterized by X-ray diffract...Non-stoichiometric compound fluoride-doped LiFePO4/C cathode materials were synthesized via solid-state reaction using MgF2 and AlF3 as dopant. The fluoride-doped LiFePO4/C samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and electrochemical testing. The results show that the materials are well crystallized and fluoride doping cannot change the space structure of LiFePO4. Slight amounts of Fe2O3 with no fluoride impurity were detected. Charge-discharge curves show that fluoride-doped samples have higher capacity at low rates compared with undoped LiFePO4/C. AlF3-doped samples have highest capacity at high discharge current. Both doped samples have larger polarization voltage than undoped samples. All samples exhibit good cycle stability.展开更多
Pristine LiNi0.5Mn1.5O4and Na-doped Li0.95Na0.05Ni0.5Mn1.5O4cathode materials were synthesized by a simple solid-statemethod.The effects of Na+doping on the crystalline structure and electrochemical performance of LiN...Pristine LiNi0.5Mn1.5O4and Na-doped Li0.95Na0.05Ni0.5Mn1.5O4cathode materials were synthesized by a simple solid-statemethod.The effects of Na+doping on the crystalline structure and electrochemical performance of LiNi0.5Mn1.5O4cathode materialwere systematically investigated.The samples were characterized by XRD,SEM,FT-IR,CV,EIS and galvanostatic charge/dischargetests.It is found that both pristine and Na-doped samples exhibit secondary agglomerates composed of well-defined octahedralprimary particle,but Na+doping decreases the primary particle size to certain extent.Na+doping can effectively inhibit the formationof LixNi1-xO impurity phase,enhance the Ni/Mn disordering degree,decrease the charge-transfer resistance and accelerate the lithiumion diffusion,which are conductive to the rate capability.However,the doped Na+ions tend to occupy8a Li sites,which forces equalamounts of Li+ions to occupy16d octahedral sites,making the spinel framework less stable,therefore the cycling stability is notimproved obviously after Na+doping.展开更多
基金financially supported by the National Natural Science Foundation of China(No.51904250)the China Postdoctoral Science Foundation(No.2021M692254)+2 种基金the Sichuan Science and Technology Program(No.2022YFG0098)the Fundamental Research Funds for the Central Universities(Nos.2021CDSN-02,2022SCU12002,2022CDZG-17,2022CDSN-08,2022CDZG-9)the Hohhot Science and Technology Program(No.2023-Jie Bang Gua Shuai-Gao-3)。
文摘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.
基金Project supported by the Natural Science Foundation of Gansu Province(Grant No.22JR5RA404).
文摘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.
基金Funded by National Key Research and Development Program of China (No.2021YFA1600203)。
文摘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.
基金financially supported by the Korea Institute of Energy Research(KIER)(grant no.C3-2401,2402,2403)the National Research Foundation(grant no.2022M3J1A1063019)funded by the Ministry of Science and ICT
文摘To demonstrate flexible and tandem device applications,a low-temperature Cu_(2)ZnSnSe_(4)(CZTSe)deposition process,combined with efficient alkali doping,was developed.First,high-quality CZTSe films were grown at 480℃by a single co-evaporation,which is applicable to polyimide(PI)substrate.Because of the alkali-free substrate,Na and K alkali doping were systematically studied and optimized to precisely control the alkali distribution in CZTSe.The bulk defect density was significantly reduced by suppression of deep acceptor states after the(NaF+KF)PDTs.Through the low-temperature deposition with(NaF+KF)PDTs,the CZTSe device on glass yields the best efficiency of 8.1%with an improved Voc deficit of 646 mV.The developed deposition technologies have been applied to PI.For the first time,we report the highest efficiency of 6.92%for flexible CZTSe solar cells on PI.Additionally,CZTSe devices were utilized as bottom cells to fabricate four-terminal CZTSe/perovskite tandem cells because of a low bandgap of CZTSe(~1.0 eV)so that the tandem cell yielded an efficiency of 20%.The obtained results show that CZTSe solar cells prepared by a low-temperature process with in-situ alkali doping can be utilized for flexible thin-film solar cells as well as tandem device applications.
基金supported by the National Natural Science Foundation of China(No.51102047,51472050)State Key Laboratory of Photocatalysis on Energy and Environment Open Project
文摘In this paper we present a novel report on the upconversion luminescence performance of NaY0.92Yb0.05Er0.03F4 enhanced by Zr^4+ codoping. The luminescence intensity of the tridoped hexagonal NaYF_4 synthesized by a hydrothermal method increased to the maximum, about seven times of the non-Zr^4+ sample when the Zr^4+ codoping concentration rose to 6 mol%, while the luminescence lifetime was also prolonged by Zr^4+ codoping. To explore the relationships between the microstructure and upconversion properties, X-ray powder diffraction, field emission scanning electron microscope, electron energy-dispersive spectroscopy and upconversion emission spectroscopy were employed. From these characterizations, we found that the codoping of Zr^4+ could modulate the crystal microstructure of NaYF_4 for higher upconversion luminescence intensity and longer lifetime. This study may be helpful for the design and synthesis of high-performance upconversion materials.
基金Project (20771100) supported by the National Natural Science Foundation of China
文摘Li3V2-2/3xMnx(PO4)3(0≤x≤0.12) powders were synthesized by sol-gel method. The effect of Mn2+-doping on the structure and electrochemical performances of Li3V2(PO4)3/C was characterized by XRD, SEM, XPS, galvanostatic charge /discharge and electrochemical impedance spectroscopy(EIS). The XRD study shows that a small amount of Mn2+-doped does not alter the structure of Li3V2(PO4)3/C materials, and all Mn2+-doped samples are of pure single phase with a monoclinic structure (space group P21/n). The XPS analysis indicates that valences state of V and Mn are +3 and +2 in Li3V1.94Mn0.09(PO4)3/C, respectively, and the citric acid in raw materials was decomposed into carbon during calcination, and residual carbon exists in Li3V1.94Mn0.09(PO4)/C. The results of electrochemical measurements show that Mn2+-doping can improve the cyclic stability and rate performance of these cathode materials. The Li3V1.94Mn0.09(PO4)3/C cathode material shows the best cyclic stability and rate performance. For example, at the discharge current density of 40 mA/g, after 100 cycles, the discharge capacity of Li3V1.94Mn0.09(PO4)3/C declines from initial 158.8 mA·h/g to 120.5 mA·h/g with a capacity retention of 75.9%; however, that of the Mn-undoed sample declines from 164.2 mA·h/g to 72.6 mA·h/g with a capacity retention of 44.2%. When the discharge current is increased up to 1C, the intial discharge capacity of Li3V1.94Mn0.09(PO4)3/C still reaches 146.4 mA·h/g, and the discharge capacity maintains at 107.5 mA·h/g after 100 cycles. The EIS measurement indicates that Mn2+-doping with a appropriate amount of Mn2+ decreases the charge transfer resistance, which is favorable for the insertion/extraction of Li+.
文摘Aluminum doped zinc oxide (AZO), as an electrically conductive material, was applied to coating on the surface of olivine-type LiFePO4 synthesized by solid-state method. The charge-discharge test results show that the rate performance and low-temperature performance of LiFePO4 are greatly improved by the surface treatment. Even at 20C rate, the discharge specific capacity of 100.9 mA.h/g was obtained by the AZO-coated LiFePO4 at room temperature. At -20 ℃, the discharge specific capacity at 0.2C for un-coated LiFePO4 and the coated one are 50.3 mA.h/g and 119.4 mA.h/g, respectively. It should be attributed to the electrically conductive AZO-coating which increases the electronic conductivity of LiFePO4. Furthermore, the surface-coating increases the tap-density of LiFePO4. The results indicate that the AZO-coated LiFePO4 is a good candidate of cathode material for applying in lithium power batteries.
基金Projects (21207093,51004072) supported by the National Natural Science Foundation of China for YouthProject (LJQ2014023) supported by the Liaoning Excellent Talents in University,China+1 种基金Project (L20150178) supported by the General Scientific Research Projects Foundation of Liaoning Educational Committee,ChinaProject (N140303002) supported by the Fundamental Research Funds for the Central Universities,China
文摘To enhance the photocatalytic activity of B-BiVO4,Ni-doped B?BiVO4photocatalyst(Ni-B-BiVO4)was synthesized through sol-gel and impregnation method.The photocatalysts were characterized by XPS,XRD,SEM,EDS,BET and UV-Vis DRS techniques.The results showed that single or double doping did not change the crystalline structure and morphology,but the particle size decreased with Ni doping.The band gap energy absorption edge of Ni-B-BiVO4shifted to a longer wavelength compared with undoped,B or Ni single doped BiVO4.More V4+and surface hydroxyl oxygen were observed in BiVO4after Ni-B co-doping.When the optimal mass fraction of Ni is0.30%,the degradation rate of MO in50min is95%for0.3Ni-B-BiVO4sample which also can effectively degrade methyl blue(MB),acid orange(AOII)II and rhodamine B(RhB).The enhanced photocatalytic activity is attributed to the synergistic effects of B and Ni doping.
基金Project(51102025)supported by the National Natural Science Foundation of ChinaProject(14JJ7040)supported by Natural Science Foundation of Hunan Province,ChinaProject(2014GH561172)supported by China Torch Program
文摘Fe-doped BiVO4with hierarchical flower-like structure was prepared via a hydrothermal method using sodium dodecylbenzene sulfonate(SDBS)as structure directing agent.X-ray diffraction(XRD),scanning electron microscope(SEM),transmissionelectron microscope(TEM),high resolution transmission electron microscope(HRTEM),X-ray photoelectron spectroscopy(XPS)and UV-Vis were applied for characterization of the as-prepared samples.The formation mechanism of flower-like structure wasproposed based on the evolution of morphology as a function of hydrothermal time.Fe-doped into substitutional sites of BiVO4effectively improved the migration and separation of photogenerated carrier and enhanced the utilization of visible light.Flower-likeFe-doped BiVO4showed much higher visible-light-driven photocatalytic efficiency for degradation of methyl blue compared withthe pristine BiVO4.And the sample with a Fe/Bi mole ratio of2.5%showed the highest photocatalytic efficiency.
文摘Element doping is a simple and effective method to improve photocatalytic activity of g-C3N4. However, the doping model and mechanism of metal elements are still uncharacterized. In this study, we found that Fe(Ⅲ) can be doped into g-C3N4 through the coordination between amidogen and Fe(Ⅲ). After activity tests, it was found that this coordination doping of Fe(Ⅲ) could enhance the Rh B oxidation and Cr(Ⅵ) reduction activities of g-C3N4 in interesting ways, but it is not helpful for the NO-removal performance of g-C3N4. Characterization and calculation results show that the coordination of Fe(Ⅲ) can not only improve the transfer of photogenerated electrons, but it also can passivate the carbon site of triazine rings, which is the active site of NO-removal. This study revealed some doping mechanisms and effect mechanisms of elemental metal in photocatalysis.
基金supported by the National Natural Science Foundation of of China(51472191,21407115,21773179)the Natural Science Foundation of Hubei Province of China(2017CFA031)the Opening Project of Key Laboratory of Optoelectronic Chemical Materials and Devices,Ministry of Education(JDGD-201509)~~
文摘Photocatalytic hydrogen production based on semiconductor photocatalysts has been considered as one of the most promising strategies to resolve the global energy shortage.Graphitic carbon nitride(g‐C3N4)has been a star visible‐light photocatalyst in this field due to its various advantages.However,pristine g‐C3N4usually exhibits limited activity.Herein,to enhance the performance of g‐C3N4,alkali metal ion(Li+,Na+,or K+)‐doped g‐C3N4are prepared via facile high‐temperature treatment.The prepared samples are characterized and analyzed using the technique of XRD,ICP‐AES,SEM,UV‐vis DRS,BET,XPS,PL,TRPL,photoelectrochemical measurements,photocatalytic tests,etc.The resultant doped photocatalysts show enhanced visible‐light photocatalytic activities for hydrogen production,benefiting from the increased specific surface areas(which provide more active sites),decreased band gaps for extended visible‐light absorption,and improved electronic structures for efficient charge transfer.In particular,because of the optimal tuning of both microstructure and electronic structure,the Na‐doped g‐C3N4shows the most effective utilization of photogenerated electrons during the water reduction process.As a result,the highest photocatalytic performance is achieved over the Na‐doped g‐C3N4photocatalyst(18.7?mol/h),3.7times that of pristine g‐C3N4(5.0?mol/h).This work gives a systematic study for the understanding of doping effect of alkali metals in semiconductor photocatalysis.
基金the support of the National Natural Science Foundation of China(Nos.22178148,U21A20328)the Natural Science Foundation of Jiangsu Province(No.BK20191430)+2 种基金the Six Talent Peaks Project in Jiangsu Province(No.XNY-009)the Jiangsu Province and Education Ministry CoSponsored Synergistic Innovation Center of Modern Agricultural Equipment(No.XTCX2029)a Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions。
文摘The exploration of active and long-lived oxygen reduction reaction(ORR)catalysts for the commercialization of zinc-air batteries are of immense significance but challenging.Herein,the sulfur doped FeWO_(4)embedded in the multi-dimensional nitrogen-doped carbon structure(S-FeWO_(4)/NC)was successfully synthesized.The doped S atoms optimized the charge distribution in FeWO_(4)and enhanced the intrinsic activity.At the same time,S doping accelerated the formation of reaction intermediates during the adsorption reduction of O_(2)on the surface of S-FeWO_(4)/NC.Accordingly,the S-FeWO_(4)/NC catalyst showed more positive half-wave potential(0.85 V)and better stability than that of the FeWO_(4)/NC catalyst.Furthermore,the S-FeWO_(4)/NC-based zinc-air battery exhibited considerable power density of 150.3m W cm^(-2),high specific capacity of 912.7 m A h g^(-1),and prominent cycle stability up to 220 h.This work provides an assistance to the development of cheap and efficient tungsten-based oxygen reduction catalysts and the promotion of its application in the zinc-air battery.
基金the National Natural Science Foundation of China(21421001,21573115,21875118)the Natural Science Foundation of Tianjin(17JCYBJC17100,19JCZDJC37700)。
文摘Multifunctional non-precious catalysts for hydrogen/oxygen evolution reaction(HER/OER) and oxygen reduction reaction(ORR) constitute the bottleneck in the applications in electrochemical overall water splitting(OWS) and Zn-air batteries. Herein, a trifunctional electrocatalyst of urchin-like Al,P-codoped Co3O4 microspheres supported on Ni foam(denoted as AP-CONPs/NF) was fabricated via a hydrothermal process and subsequent low-temperature annealing and phosphorization, exhibiting enhanced OER, HER and ORR activities compared with single-doped and undoped samples. Their surface self-organized microstructure and excellent "superaerophobic" feature make a high bubble repellency, which boost diffusion of reactants and electrolyte-electrode intimate contact. The codoping of Al and P elements into Co3O4 betters right the balance among surface chemical state, the increased oxygen vacancies and the promoted charge transfer. Encouraged by these synergistic advantages, the AP-CONPs/NF was further employed as excellent bifunctional electrodes for the OWS(low cell voltage of 1.57 V at 10 mA cm-2) and as air cathode for rechargeable Zn-air batteries(high power density of 89.1 mW cm-2), which demonstrates a great feasibility for practical applications.
基金financially supported by the National High-Technology"863"Program of China(No.2008AA11A103)
文摘Non-stoichiometric compound fluoride-doped LiFePO4/C cathode materials were synthesized via solid-state reaction using MgF2 and AlF3 as dopant. The fluoride-doped LiFePO4/C samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and electrochemical testing. The results show that the materials are well crystallized and fluoride doping cannot change the space structure of LiFePO4. Slight amounts of Fe2O3 with no fluoride impurity were detected. Charge-discharge curves show that fluoride-doped samples have higher capacity at low rates compared with undoped LiFePO4/C. AlF3-doped samples have highest capacity at high discharge current. Both doped samples have larger polarization voltage than undoped samples. All samples exhibit good cycle stability.
基金Project(E2015202356)supported by the Natural Science Foundation of Hebei Province,ChinaProject(2013009)supported by the Technology Innovation Foundation for Outstanding Youth of Hebei University,China
文摘Pristine LiNi0.5Mn1.5O4and Na-doped Li0.95Na0.05Ni0.5Mn1.5O4cathode materials were synthesized by a simple solid-statemethod.The effects of Na+doping on the crystalline structure and electrochemical performance of LiNi0.5Mn1.5O4cathode materialwere systematically investigated.The samples were characterized by XRD,SEM,FT-IR,CV,EIS and galvanostatic charge/dischargetests.It is found that both pristine and Na-doped samples exhibit secondary agglomerates composed of well-defined octahedralprimary particle,but Na+doping decreases the primary particle size to certain extent.Na+doping can effectively inhibit the formationof LixNi1-xO impurity phase,enhance the Ni/Mn disordering degree,decrease the charge-transfer resistance and accelerate the lithiumion diffusion,which are conductive to the rate capability.However,the doped Na+ions tend to occupy8a Li sites,which forces equalamounts of Li+ions to occupy16d octahedral sites,making the spinel framework less stable,therefore the cycling stability is notimproved obviously after Na+doping.