Aqueous Zn-ion batteries(AZIBs)are recognized as a promising energy storage system with intrinsic safety and low cost,but its applications still rely on the design of high-capacity and stable-cycling cathode materials...Aqueous Zn-ion batteries(AZIBs)are recognized as a promising energy storage system with intrinsic safety and low cost,but its applications still rely on the design of high-capacity and stable-cycling cathode materials.In this work,we present an intercalation mechanism-based cathode materials for AZIB,i.e.the vanadium oxide with pre-intercalated manganese ions and lattice water(noted as MVOH).The synergistic effect between Mn^(2+)and lattice H_(2)O not only expands the interlayer spacing,but also significantly enhances the structural stability.Systematic in-situ and ex-situ characterizations clarify the Zn^(2+)/H^(+)co–(de)intercalation mechanism of MVOH in aqueous electrolyte.The demonstrated remarkable structure stability,excellent kinetic behaviors and ion-storage mechanism together enable the MVOH to demonstrate satisfactory specific capacity of 450 mA h g^(−1)at 0.2 A g^(−1),excellent rate performance of 288.8 mA h g^(−1)at 10 A g^(−1)and long cycle life over 20,000 cycles at 5 A g^(−1).This work provides a practical cathode material,and contributes to the understanding of the ion-intercalation mechanism and structural evolution of the vanadium-based cathode for AZIBs.展开更多
The in-situ oxidation of manganese sulfate solution with H2O_(2),sodium hypochlorite,potassium permanganate and oxygen as oxidants was investigated by means of SEM,EDS,XRD,BET and infrared analysis,and the effects of ...The in-situ oxidation of manganese sulfate solution with H2O_(2),sodium hypochlorite,potassium permanganate and oxygen as oxidants was investigated by means of SEM,EDS,XRD,BET and infrared analysis,and the effects of different oxidants on the morphology,phase composition,surface properties and specific surface area of manganese oxides were investigated.The experimental results show that the diameter of manganese oxide particles prepared with H_(2)O_(2)is the smallest,about 50 nm,and the specific surface area is the largest,63.8764 m^(2)/g.It has the advantages of abundant surface hydroxyl groups,no introduction of other impurities and large adsorption potential.It is most suitable to be used as an oxidant for oxidizing manganese sulfate solution to prepare manganese oxide by in-situ oxidation.Nano manganese oxide prepard by H_(2)O_(2)in-situ oxidation method is used as adsorbent to adsorb cobalt and nickel impurities in manganese sulfate.When the reaction pH is 6,the reaction time is 30min and the amount of adsorbent is 1.0 g,the adsorption rates of cobalt and nickel impurities in 100ml manganese sulfate solution are 97.59%and 97.67%,respectively.The residual amounts of cobalt and nickel meet the industrial process standard of first-class products(Co,Ni w/%≤0.005)of high-purity manganese sulfate(Hg/t4823-2015)for batteries.The study plays a guiding role in the preparation and regulation of manganese oxide,and provides a new method with high efficiency,purity and adsorbent availability for the preparation of high-purity manganese sulfate solution.展开更多
Iron-rich electrolytic manganese residue(IREMR)is an industrial waste produced during the processing of electrolytic metal manganese,and it contains certain amounts of Fe and Mn resources and other heavy metals.In thi...Iron-rich electrolytic manganese residue(IREMR)is an industrial waste produced during the processing of electrolytic metal manganese,and it contains certain amounts of Fe and Mn resources and other heavy metals.In this study,the slurry electrolysis technique was used to recover high-purity Fe powder from IREMR.The effects of IREMR and H2SO4 mass ratio,current density,reaction temper-ature,and electrolytic time on the leaching and current efficiencies of Fe were studied.According to the results,high-purity Fe powder can be recovered from the cathode plate,and the slurry electrolyte can be recycled.The leaching efficiency,current efficiency,and purity of Fe reached 92.58%,80.65%,and 98.72wt%,respectively,at a 1:2.5 mass ratio of H2SO4 and IREMR,reaction temperature of 60℃,electric current density of 30 mA/cm^(2),and reaction time of 8 h.In addition,vibrating sample magnetometer(VSM)analysis showed that the coercivity of electrolytic iron powder was 54.5 A/m,which reached the advanced magnetic grade of electrical pure-iron powder(DT4A coercivity standard).The slurry electrolytic method provides fundamental support for the industrial application of Fe resource recovery in IRMER.展开更多
Manganese cobaltite(MnCo_(2)_(4))is a promising electrode material because of its attractive redox chemistry and excellent charge storage capability.Our previous work demonstrated that the octahedrally-coordinated Mn ...Manganese cobaltite(MnCo_(2)_(4))is a promising electrode material because of its attractive redox chemistry and excellent charge storage capability.Our previous work demonstrated that the octahedrally-coordinated Mn are prone to react with the hydroxyl ions in alkaline electrolyte upon electrochemical cycling and separates on the surface of spinel to reconstruct into d-MnO_(2) nanosheets irreversibly,thus results in a change of the reaction mechanism with Kþion intercalation.However,the low capacity has greatly limited its practical application.Herein,we found that the tetrahedrally-coordinated Co_(2) þions were leached when MnCo_(2)_(4) was equilibrated in 1 mol L^(-1) HCl solution,leading to the formation of layered CoOOH on MnCo_(2)_(4) surface which is originated from the covalency competition induced selective breakage of the CoT–O bond in CoT–O–CoO and subsequent rearrangement of free Co_(6) octahedra.The as-formed CoOOH is stable upon cycling in alkaline electrolyte,exhibits conversion reaction mechanism with facile proton diffusion and is free of massive structural evolution,thus enables utilization of the bulk electrode material and realizes enhanced specific capacity as well as facilitated charge transfer and ion diffusion.In general,our work not only offers a feasible approach to deliberate modification of MnCo_(2)_(4)'s surface structure,but also provides an in-depth understanding of its charge storage mechanism,which enables rational design of the spinel oxides with promising charge storage properties.展开更多
The presence of toxic elements in manganese slag(MSG)poses a threat to the environment due to potential pollution.Utilizing CO_(2) curing on MS offers a promising approach to immobilize toxic substances within this ma...The presence of toxic elements in manganese slag(MSG)poses a threat to the environment due to potential pollution.Utilizing CO_(2) curing on MS offers a promising approach to immobilize toxic substances within this material,thereby mitigating their release into the natural surroundings.This study investigates the impact of CO_(2) cured MS on various rheological parameters,including slump flow,plastic viscosity(η),and yield shear stress(τ).Additionally,it assesses flexural and compressive strengths(f_(t) and f_(cu)),drying shrinkage rates(DSR),durability indicators(chloride ion migration coefficient(CMC),carbonization depth(CD)),and the leaching behavior of heavy metal elements.Microscopic examination via scanning electron microscopy(SEM)is employed to elucidate the underlying mechanisms.The results indicate that CO_(2) curing significantly enhances the slump flow of ultra-high performance concrete(UHPC)by up to 51.2%.Moreover,it reduces UHPC’sηandτby rates ranging from 0%to 52.7%and 0%to 40.2%,respectively.The DSR exhibits a linear increase corresponding to the mass ratio of CO_(2) cured MS.Furthermore,CO_(2) curing enhances both f_(t) and f_(cu) of UHPC by up to 28.7%and 17.6%,respectively.The electrical resistance is also improved,showing an increase of up to 53.7%.The relationship between mechanical strengths and electrical resistance follows a cubic relationship.The CO_(2) cured MS demonstrates a notable decrease in the CMC and CD by rates ranging from 0%to 52.6%and 0%to 26.1%,respectively.The reductions of leached chromium(Cr)and manganese(Mn)are up to 576.3%and 1312.7%,respectively.Overall,CO_(2) curing also enhances the compactness of UHPC,thereby demonstrating its potential to improve both mechanical and durability properties.展开更多
A homochrial manganese（Ⅱ） complex derived from chiral salen ligand （1R,2R）-（-）diaminocyclohexane-N,N-biscarboxyl-salicylidene） （1） has been synthesized through solvothermal procedure and characterized by IR,...A homochrial manganese（Ⅱ） complex derived from chiral salen ligand （1R,2R）-（-）diaminocyclohexane-N,N-biscarboxyl-salicylidene） （1） has been synthesized through solvothermal procedure and characterized by IR,elemental analysis,TGA,circular dichroism （CD）,powder and single-crystal X-ray crystallography.It crystallizes in monoclinic,space group C2 with a=32.987（7）,b=7.4662（15）,c=17.931（4）,β=97.82（3）°,V=4375.0（15） 3,Z=8,D c=1.544 g/cm 3,F（000）=2096,M r=508.36,μ=0.658 mm-1,the final GOOF=0.975,R=0.0676 and wR=0.2068 for 6357 observed reflections with I 2σ（Ⅰ）.The coordination polymer 1 possesses a 1D infinite zigzag chain architecture constructed by the dicarboxyl-functionalized metallosalen ligand （MnSalen）,and the polymeric chains are further assembled into a 2D supramolecular network structure via strong intermolecular hydrogen bonding interactions between the adjacent zigzag chains.展开更多
A new metal-organic complex Mn2（cbba）4（phen）2 （Hcbba = 2-（4＇-chlorine-benzoyl）- benzoic acid, phen = 1,10-phenanthroline） 1 has been hydrotherrnally synthesized and structurally characterized by single-crysta...A new metal-organic complex Mn2（cbba）4（phen）2 （Hcbba = 2-（4＇-chlorine-benzoyl）- benzoic acid, phen = 1,10-phenanthroline） 1 has been hydrotherrnally synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analyses and IR spectroscopy. The compound crystallizes in orthorhombic, space group Pbcn with α = 12.154（5）, b = 18.166（7）, c = 31.197（13） A, V = 6887（5） A^3, C80H48Cl4Mn2N4O12, Mr= 1508.90, Dc = 1.455 g/cm^3, μ（MoKα） = 0.591 mm^-1, F（000） = 3080, Z = 4, the final R = 0.0408 and wR = 0.0873 for 4033 observed reflections （I 〉 2σ（I））. In the crystal structure, the manganese atom is six-coordinated with four carboxylate oxygen atoms from three different cbba ligands and two nitrogen atoms from phen ligands, showing a distorted octahedral geometry. Furthermore, it exhibits a 3D supramolecular network through π-π interactions.展开更多
Two new three-dimensional coordination polymers, namely [Mn（L）（bpdc）]n（1）, [Mn（L）0.5（ndc）]n（2）（L = 1,4-bis（2-methylbenzimidazole）butane, H2 bpdc = 4,4＇-biphenyldicarboxylic acid, H2 ndc = 2,6-naphthale...Two new three-dimensional coordination polymers, namely [Mn（L）（bpdc）]n（1）, [Mn（L）0.5（ndc）]n（2）（L = 1,4-bis（2-methylbenzimidazole）butane, H2 bpdc = 4,4＇-biphenyldicarboxylic acid, H2 ndc = 2,6-naphthalenedicarboxylic acid） have been successfully synthesized under hydrothermal conditions. Two complexes were characterized by physico-chemical, spectroscopic methods and single-crystal X-ray diffraction. Complex 1 shows a 3D → 3D 5-fold interpenetrated network with a 4-connected uninodal dia topology. Complex 2 possesses a 3D → 3D 3-fold interpenetrating architecture with a binodal（4,5）-connected xah topology. The fluorescence and thermal properties of the title complexes were discussed.展开更多
基金supported by the grants from the Chinese Academy of Sciences(124GJHZ2023031MI)the National Natural Science Foundation of China(52173274)+1 种基金the National Key R&D Project from the Ministry of Science and Technology(2021YFA1201603)the Fundamental Research Funds for the Central Universities.
文摘Aqueous Zn-ion batteries(AZIBs)are recognized as a promising energy storage system with intrinsic safety and low cost,but its applications still rely on the design of high-capacity and stable-cycling cathode materials.In this work,we present an intercalation mechanism-based cathode materials for AZIB,i.e.the vanadium oxide with pre-intercalated manganese ions and lattice water(noted as MVOH).The synergistic effect between Mn^(2+)and lattice H_(2)O not only expands the interlayer spacing,but also significantly enhances the structural stability.Systematic in-situ and ex-situ characterizations clarify the Zn^(2+)/H^(+)co–(de)intercalation mechanism of MVOH in aqueous electrolyte.The demonstrated remarkable structure stability,excellent kinetic behaviors and ion-storage mechanism together enable the MVOH to demonstrate satisfactory specific capacity of 450 mA h g^(−1)at 0.2 A g^(−1),excellent rate performance of 288.8 mA h g^(−1)at 10 A g^(−1)and long cycle life over 20,000 cycles at 5 A g^(−1).This work provides a practical cathode material,and contributes to the understanding of the ion-intercalation mechanism and structural evolution of the vanadium-based cathode for AZIBs.
基金Funded by the National Natural Science Foundation of China(No.51864012)the Key Projects Supported by Science and Technology in Guizhou Province(No.[2002]KEY020)+2 种基金the Major Special Projects in Guizhou Province(No.[2022]003)the Guizhou Provincial Science Cooperation Program(Nos.[2016]5302,[2017]5788,[2018]5781,[2019]1411,and[2019]2841)the Major Special Projects in Tongren City,Guizhou Province(No.[2021]13)。
文摘The in-situ oxidation of manganese sulfate solution with H2O_(2),sodium hypochlorite,potassium permanganate and oxygen as oxidants was investigated by means of SEM,EDS,XRD,BET and infrared analysis,and the effects of different oxidants on the morphology,phase composition,surface properties and specific surface area of manganese oxides were investigated.The experimental results show that the diameter of manganese oxide particles prepared with H_(2)O_(2)is the smallest,about 50 nm,and the specific surface area is the largest,63.8764 m^(2)/g.It has the advantages of abundant surface hydroxyl groups,no introduction of other impurities and large adsorption potential.It is most suitable to be used as an oxidant for oxidizing manganese sulfate solution to prepare manganese oxide by in-situ oxidation.Nano manganese oxide prepard by H_(2)O_(2)in-situ oxidation method is used as adsorbent to adsorb cobalt and nickel impurities in manganese sulfate.When the reaction pH is 6,the reaction time is 30min and the amount of adsorbent is 1.0 g,the adsorption rates of cobalt and nickel impurities in 100ml manganese sulfate solution are 97.59%and 97.67%,respectively.The residual amounts of cobalt and nickel meet the industrial process standard of first-class products(Co,Ni w/%≤0.005)of high-purity manganese sulfate(Hg/t4823-2015)for batteries.The study plays a guiding role in the preparation and regulation of manganese oxide,and provides a new method with high efficiency,purity and adsorbent availability for the preparation of high-purity manganese sulfate solution.
基金supported by the Key Research and Development Program of Guangxi Province,China (No.AB23075174)the National Natural Science Foundation of China (No.52174386)the Science and Technology Plan Project of Sichuan Province,China (No.2022YFS0459).
文摘Iron-rich electrolytic manganese residue(IREMR)is an industrial waste produced during the processing of electrolytic metal manganese,and it contains certain amounts of Fe and Mn resources and other heavy metals.In this study,the slurry electrolysis technique was used to recover high-purity Fe powder from IREMR.The effects of IREMR and H2SO4 mass ratio,current density,reaction temper-ature,and electrolytic time on the leaching and current efficiencies of Fe were studied.According to the results,high-purity Fe powder can be recovered from the cathode plate,and the slurry electrolyte can be recycled.The leaching efficiency,current efficiency,and purity of Fe reached 92.58%,80.65%,and 98.72wt%,respectively,at a 1:2.5 mass ratio of H2SO4 and IREMR,reaction temperature of 60℃,electric current density of 30 mA/cm^(2),and reaction time of 8 h.In addition,vibrating sample magnetometer(VSM)analysis showed that the coercivity of electrolytic iron powder was 54.5 A/m,which reached the advanced magnetic grade of electrical pure-iron powder(DT4A coercivity standard).The slurry electrolytic method provides fundamental support for the industrial application of Fe resource recovery in IRMER.
基金supported by the National Key Research and Development Program of China(2022YFE0206300)the National Natural Science Foundation of China(22209047,U21A2081,22075074)+2 种基金Natural Science Foundation of Hunan Province(2020JJ5035)Hunan Provincial Department of Education Outstanding Youth Project(23B0037)Macao Science and Technology Development Fund(Macao SAR,FDCT-0096/2020/A2).
文摘Manganese cobaltite(MnCo_(2)_(4))is a promising electrode material because of its attractive redox chemistry and excellent charge storage capability.Our previous work demonstrated that the octahedrally-coordinated Mn are prone to react with the hydroxyl ions in alkaline electrolyte upon electrochemical cycling and separates on the surface of spinel to reconstruct into d-MnO_(2) nanosheets irreversibly,thus results in a change of the reaction mechanism with Kþion intercalation.However,the low capacity has greatly limited its practical application.Herein,we found that the tetrahedrally-coordinated Co_(2) þions were leached when MnCo_(2)_(4) was equilibrated in 1 mol L^(-1) HCl solution,leading to the formation of layered CoOOH on MnCo_(2)_(4) surface which is originated from the covalency competition induced selective breakage of the CoT–O bond in CoT–O–CoO and subsequent rearrangement of free Co_(6) octahedra.The as-formed CoOOH is stable upon cycling in alkaline electrolyte,exhibits conversion reaction mechanism with facile proton diffusion and is free of massive structural evolution,thus enables utilization of the bulk electrode material and realizes enhanced specific capacity as well as facilitated charge transfer and ion diffusion.In general,our work not only offers a feasible approach to deliberate modification of MnCo_(2)_(4)'s surface structure,but also provides an in-depth understanding of its charge storage mechanism,which enables rational design of the spinel oxides with promising charge storage properties.
基金supported by Hebei Province Higher Education Science and Technology Research Project(No.ZC2024031).
文摘The presence of toxic elements in manganese slag(MSG)poses a threat to the environment due to potential pollution.Utilizing CO_(2) curing on MS offers a promising approach to immobilize toxic substances within this material,thereby mitigating their release into the natural surroundings.This study investigates the impact of CO_(2) cured MS on various rheological parameters,including slump flow,plastic viscosity(η),and yield shear stress(τ).Additionally,it assesses flexural and compressive strengths(f_(t) and f_(cu)),drying shrinkage rates(DSR),durability indicators(chloride ion migration coefficient(CMC),carbonization depth(CD)),and the leaching behavior of heavy metal elements.Microscopic examination via scanning electron microscopy(SEM)is employed to elucidate the underlying mechanisms.The results indicate that CO_(2) curing significantly enhances the slump flow of ultra-high performance concrete(UHPC)by up to 51.2%.Moreover,it reduces UHPC’sηandτby rates ranging from 0%to 52.7%and 0%to 40.2%,respectively.The DSR exhibits a linear increase corresponding to the mass ratio of CO_(2) cured MS.Furthermore,CO_(2) curing enhances both f_(t) and f_(cu) of UHPC by up to 28.7%and 17.6%,respectively.The electrical resistance is also improved,showing an increase of up to 53.7%.The relationship between mechanical strengths and electrical resistance follows a cubic relationship.The CO_(2) cured MS demonstrates a notable decrease in the CMC and CD by rates ranging from 0%to 52.6%and 0%to 26.1%,respectively.The reductions of leached chromium(Cr)and manganese(Mn)are up to 576.3%and 1312.7%,respectively.Overall,CO_(2) curing also enhances the compactness of UHPC,thereby demonstrating its potential to improve both mechanical and durability properties.
基金supported by NSFC-20971085"973" programs (2007CB209701 and 2009CB930403)+1 种基金the Major Fundamental Research of Shanghai Science and Technology Committee (10dj1400102)the key project of State Education Ministry
文摘A homochrial manganese（Ⅱ） complex derived from chiral salen ligand （1R,2R）-（-）diaminocyclohexane-N,N-biscarboxyl-salicylidene） （1） has been synthesized through solvothermal procedure and characterized by IR,elemental analysis,TGA,circular dichroism （CD）,powder and single-crystal X-ray crystallography.It crystallizes in monoclinic,space group C2 with a=32.987（7）,b=7.4662（15）,c=17.931（4）,β=97.82（3）°,V=4375.0（15） 3,Z=8,D c=1.544 g/cm 3,F（000）=2096,M r=508.36,μ=0.658 mm-1,the final GOOF=0.975,R=0.0676 and wR=0.2068 for 6357 observed reflections with I 2σ（Ⅰ）.The coordination polymer 1 possesses a 1D infinite zigzag chain architecture constructed by the dicarboxyl-functionalized metallosalen ligand （MnSalen）,and the polymeric chains are further assembled into a 2D supramolecular network structure via strong intermolecular hydrogen bonding interactions between the adjacent zigzag chains.
基金supported by the Science and Technology Research Projects of the Education Department of Jilin Province (No. 2007. 213)
文摘A new metal-organic complex Mn2（cbba）4（phen）2 （Hcbba = 2-（4＇-chlorine-benzoyl）- benzoic acid, phen = 1,10-phenanthroline） 1 has been hydrotherrnally synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analyses and IR spectroscopy. The compound crystallizes in orthorhombic, space group Pbcn with α = 12.154（5）, b = 18.166（7）, c = 31.197（13） A, V = 6887（5） A^3, C80H48Cl4Mn2N4O12, Mr= 1508.90, Dc = 1.455 g/cm^3, μ（MoKα） = 0.591 mm^-1, F（000） = 3080, Z = 4, the final R = 0.0408 and wR = 0.0873 for 4033 observed reflections （I 〉 2σ（I））. In the crystal structure, the manganese atom is six-coordinated with four carboxylate oxygen atoms from three different cbba ligands and two nitrogen atoms from phen ligands, showing a distorted octahedral geometry. Furthermore, it exhibits a 3D supramolecular network through π-π interactions.
基金Project supported by the National Natural Science Foundation of China(No.51474086)Natural Science Foundation-Steel and Iron Foundation of Hebei Province(B2015209299)
文摘Two new three-dimensional coordination polymers, namely [Mn（L）（bpdc）]n（1）, [Mn（L）0.5（ndc）]n（2）（L = 1,4-bis（2-methylbenzimidazole）butane, H2 bpdc = 4,4＇-biphenyldicarboxylic acid, H2 ndc = 2,6-naphthalenedicarboxylic acid） have been successfully synthesized under hydrothermal conditions. Two complexes were characterized by physico-chemical, spectroscopic methods and single-crystal X-ray diffraction. Complex 1 shows a 3D → 3D 5-fold interpenetrated network with a 4-connected uninodal dia topology. Complex 2 possesses a 3D → 3D 3-fold interpenetrating architecture with a binodal（4,5）-connected xah topology. The fluorescence and thermal properties of the title complexes were discussed.
