The ternary transitional metal oxide NiCo_2O_4 is a promising anode material for sodium ion batteries due to its high theoretical capacity and superior electrical conductivity. However, its sodium storage capability i...The ternary transitional metal oxide NiCo_2O_4 is a promising anode material for sodium ion batteries due to its high theoretical capacity and superior electrical conductivity. However, its sodium storage capability is severely limited by the sluggish sodiation/desodiation reaction kinetics. Herein, NiCo_2O_4 double-shelled hollow spheres were synthesized via a microwave-assisted, fast solvothermal synthetic procedure in a mixture of isopropanol and glycerol, followed by annealing. Isopropanol played a vital role in the precipitation of nickel and cobalt,and the shrinkage of the glycerol quasi-emulsion under heat treatment was responsible for the formation of the double-shelled nanostructure. The as-synthesized productwas tested as an anode material in a sodium ion battery,was found to exhibit a high reversible specific capacity of 511 m Ahg^(-1) at 100 m Ag^(-1), and deliver high capacity retention after 100 cycles.展开更多
The overall electrochemical performances of Ni-Zn batteries are still far from satisfactory, specifically for rate performance and cycling stability Herein, we demonstrated a high-performance flexible Ni//Zn battery w...The overall electrochemical performances of Ni-Zn batteries are still far from satisfactory, specifically for rate performance and cycling stability Herein, we demonstrated a high-performance flexible Ni//Zn battery with outstanding durability and high power density based on selfsupported NiCo_2 O_4 nanosheets as cathode and Zn nanosheets as anode. This Ni//Zn battery is able to deliver a remarkable capacity of183.1 mAh g^(-1) and a good cycling performance(82.7% capacity retention after 3500 cycles). More importantly, this battery achieves an admirable power density of 49.0 kW kg^(-1) and energy density of 303.8 Wh kg^(-1), substantially higher than most recently reported batteries. With such excellent electrochemical performance, this battery will have great potential as an ultrafast power source in practical application.展开更多
Mesoporous NiCo_2O_4@MnO_2 nanoneedle arrays as electrode materials for supercapacitor grown on a conductive nickel foam were prepared by a facile hydrothermal route. The interconnected mesoporous structure of the NiC...Mesoporous NiCo_2O_4@MnO_2 nanoneedle arrays as electrode materials for supercapacitor grown on a conductive nickel foam were prepared by a facile hydrothermal route. The interconnected mesoporous structure of the NiCo_2O_4 nanoneedle arrays provides a large specific surface area for charge storage.The electrochemically active MnO_2 nanoparticles covered on the surface of NiCo_2O_4 nanoneedle result in a favorable synergistic storage effect because of charge redistribution at the NiCo_2O_4|MnO_2 interface,which reduces the interfacial polarization and facilitates ion diffusion. The initial specific capacitance of NiCo_2O_4@MnO_2(S2) is 1001 F g^(-1) at current density of 15 A g^(-1). The capacity retention of S2 is about87.4% after 4000 cycles, and the specific capacitance of S2 electrode only decreases from 1001 F g^(-1) to736 F g^(-1) even after 10,000 cycles. The first-principles calculations show that a chemical bonding between the NiCo_2O_4 and MnO_2 is not only helpful for stabilizing the composites but also leads to a charge redistribution at the interface, which may lead to a smaller interfacial polarization and thus beneficial for the interfacial capacity. The excellent electrochemical performance of NiCo_2O_4@MnO_2 composites(S2)can be ascribed to the high surface area, unique architecture, MnO_2 nanoparticle modification, reduced charge transfer resistance and stable interface between NiCo_2O_4 and MnO_2. The simple material synthesis and architectural design strategy provides new insights in opportunities to exhibit promising potential for practical application in energy storage.展开更多
Spinel oxide(NiCo_(2)O_(4))has demonstrated great potential to replace noble metal catalysts for the oxidation reaction of air pollutants.To further boost the oxidation ability of such catalysts,in this study,a facile...Spinel oxide(NiCo_(2)O_(4))has demonstrated great potential to replace noble metal catalysts for the oxidation reaction of air pollutants.To further boost the oxidation ability of such catalysts,in this study,a facile surface-engineering strategy wherein NiCo_(2)O_(4) was treated with different alkali solvents was developed.The obtained catalyst(NiCo_(2)O_(4)-OH)showed a higher surface alkalinity and more surface defects compared to the pristine spinel oxide,including enhanced structural distortion as well as promoted oxygen vacancies.The propane oxidation ability of NiCo_(2)O_(4)-OH was greatly enhanced,with a propane conversion rate that was approximately 6.4 times higher than that of pristine NiCo_(2)O_(4) at a reaction temperature 193℃.This work sets a valuable paradigm for the surface modulation of spinel oxide via alkali treatment to ensure a high-performance oxidation catalyst.展开更多
甘油是生物质精炼的主要副产物(约占10%),年过剩量与低利用率导致其市场价格(0.24-0.6 US kg^(-1))较低.甘油是具有三个活性羟基的多元醇,被认为是生产高价值产品的理想原料.甲酸作为甘油转化最重要的产品之一,广泛应用于农药、皮革、...甘油是生物质精炼的主要副产物(约占10%),年过剩量与低利用率导致其市场价格(0.24-0.6 US kg^(-1))较低.甘油是具有三个活性羟基的多元醇,被认为是生产高价值产品的理想原料.甲酸作为甘油转化最重要的产品之一,广泛应用于农药、皮革、染料和医药行业,将甘油电氧化(EGOR)为甲酸(FA)不仅能有效避免资源过剩造成浪费,而且能满足未来对甲酸燃料电池的需求.然而甘油电催化氧化途径较为复杂,涉及反应中间产物的脱氢、吸附/解吸和C-C键裂解.本文将密度泛函理论(DFT)与实验相结合,研究了在精细构建的NiCo_(2)O_(4)纳米片上通过EGOR生产FA的反应机制.DFT计算结果表明,活性羟基(OH^(*))物种可以改变EGOR生产FA过程的决速步骤(RDS),通过调节吸附中间体的吸附能可获得理想的FA产率.其中,高度羟基化的NiCo_(2)O_(4)纳米片(311)-OH^(*)晶面上具有最低的吉布斯自由能,能显著提升反应过程动力学.在理论分析的基础上,通过简易的电沉积方法精准制备了超薄NiCo_(2)O_(4)纳米片(~1.7 nm),并采用X射线吸收精细结构谱和高分辨透射电镜对催化剂进行了结构分析.结果表明,NiCo_(2)O_(4)纳米片中四面体(A_(Td))和八面体(B_(Oh))配位具有内角共享的A_(Td)-O-B_(Oh)和边共享的B_(Oh)-O-B_(Oh)构型,金属间的协同作用有效改善了材料的电子效应,有利于提供更多的吸附位点并促进EGOR过程中的电荷转移.NiCo_(2)O_(4)纳米片在EGOR中的电荷转移电阻仅为0.94Ω,电化学活性表面积高达10.25 cm^(2).相比较电催化析氧反应,NiCo_(2)O_(4)纳米片表现出了较好的EGOR性能,在10 mA cm^(-2)的电流密度下阳极功耗降低了320 mV,在100 mA cm^(-2)的电流密度时的阳极电势仅为1.46 VRHE.此外,在120 h的稳定性测试中,甘油的转化率和FA的选择性可分别保持在89%和70%.多电位步骤实验、原位电化学阻抗谱和电子顺磁共振谱结果表明,NiCo_(2)O_(4)纳米片上原位产生的OH^(*)物种是EGOR过程中的直接活性中心,有利于将RDS从甘油酸脱氢裂解转化为甘油醛的脱氢步骤,并进一步促进C-C键的裂解.进一步结合理论预测,证实了OH^(*)物种是EGOR过程中的直接活性中心.综上,采用绿色高效的电催化手段促进甘油生产高附加值化学品是生物质链升级的重要举措,有效避免了传统的高温高压,以水为介质,原位利用OH^(*).本文为新型催化剂的未来设计和理解生物质基原料电氧化升级反应机制提供了新思路.展开更多
矩形片状介孔NiCo_2O_4催化剂被首次同时用于非酶葡萄糖传感器和非酶葡萄糖燃料电池中.结果表明:在传感器上,介孔NiCo_2O_4催化剂对葡萄糖具有优异的传感特性,如超快的响应时间(小于1 s),超高的灵敏度(662.31μA(mmol L-1)-1cm-2)以及...矩形片状介孔NiCo_2O_4催化剂被首次同时用于非酶葡萄糖传感器和非酶葡萄糖燃料电池中.结果表明:在传感器上,介孔NiCo_2O_4催化剂对葡萄糖具有优异的传感特性,如超快的响应时间(小于1 s),超高的灵敏度(662.31μA(mmol L-1)-1cm-2)以及超低的检测限(0.3 nmol L-1at S/N=3);在燃料电池上,介孔Ni Co2O催化剂作为负极材料展示出了良好的应用前景,包括0.63 V的开路电压,0.092 m W cm-24的最大输出功率和1.3 mA cm^-2的极限电流密度.该材料对葡萄糖优异的催化能力归因于介孔结构引起的巨大比表面积能够提供更多的活性位点和NiCo_2O_4本身具有的良好的催化能力.本研究为促进非酶葡萄糖超敏感检测和丰富非酶葡萄糖燃料电池负极催化材料的发展提供了有利的依据.展开更多
Cobalt nickel bimetallic oxides(NiCo_(2)O_(4))have received numerous attentions in terms of their controllable morphology,high temperature,corrosion resistance and strong electromagnetic wave(EMW)absorption capability...Cobalt nickel bimetallic oxides(NiCo_(2)O_(4))have received numerous attentions in terms of their controllable morphology,high temperature,corrosion resistance and strong electromagnetic wave(EMW)absorption capability.However,broadening the absorption bandwidth is still a huge challenge for NiCo_(2)O_(4)-based absorbers.Herein,the unique NiCo_(2)O_(4)@C core-shell microcubes with hollow structures were fabricated via a facile sacrificial template strategy.The concentration of oxygen vacancies and morphologies of the three-dimensional(3D)cubic hollow core-shell NiCo_(2)O_(4)@C framework were effectively optimized by adjusting the calcination temperature.The specially designed 3D framework structure facilitated the multiple reflections of incident electromagnetic waves and provided rich interfaces between multiple components,generating significant interfacial polarization losses.Dipole polarizations induced by oxygen vacancies could further enhance the attenuation ability for the incident EM waves.The optimized NiCo_(2)O_(4)@C hollow microcubes exhibit superior EMW absorption capability with minimum RL(RLmin)of-84.45 dB at 8.4 GHz for the thickness of 3.0 mm.Moreover,ultrabroad effective absorption bandwidth(EAB)as large as 12.48 GHz(5.52-18 GHz)is obtained.This work is believed to illuminate the path to synthesis of high-performance cobalt nickel bimetallic oxides for EMW absorbers with excellent EMW absorption capability,especially in broadening effective absorption bandwidth.展开更多
基金financially supported by the Science Foundation of Sichuan Province(Grant No.2016FZ0070)the Natural Science Foundation of China(NSFC,201476145)the technical support for Materials Characterization from The Analytical and Testing Center of Sichuan University
文摘The ternary transitional metal oxide NiCo_2O_4 is a promising anode material for sodium ion batteries due to its high theoretical capacity and superior electrical conductivity. However, its sodium storage capability is severely limited by the sluggish sodiation/desodiation reaction kinetics. Herein, NiCo_2O_4 double-shelled hollow spheres were synthesized via a microwave-assisted, fast solvothermal synthetic procedure in a mixture of isopropanol and glycerol, followed by annealing. Isopropanol played a vital role in the precipitation of nickel and cobalt,and the shrinkage of the glycerol quasi-emulsion under heat treatment was responsible for the formation of the double-shelled nanostructure. The as-synthesized productwas tested as an anode material in a sodium ion battery,was found to exhibit a high reversible specific capacity of 511 m Ahg^(-1) at 100 m Ag^(-1), and deliver high capacity retention after 100 cycles.
基金supported by the Guangdong Natural Science Funds for Distinguished Young Scholar (2014A030306048)National Natural Science Foundation of China (21403306)+3 种基金Tip-top Scientific and Technical Innovative Youth Talents of Guangdong Special Support Program (2015TQO1C205)Pearl River Nova Program of Guangzhou (201610010080)Open Fund of Jiangsu Key Laboratory of Materials and Technology for Energy Conversion (MTEC-2015M05)Training Program of Scientific and Technological Innovation for Undergraduates (pdjh2017a0003)
文摘The overall electrochemical performances of Ni-Zn batteries are still far from satisfactory, specifically for rate performance and cycling stability Herein, we demonstrated a high-performance flexible Ni//Zn battery with outstanding durability and high power density based on selfsupported NiCo_2 O_4 nanosheets as cathode and Zn nanosheets as anode. This Ni//Zn battery is able to deliver a remarkable capacity of183.1 mAh g^(-1) and a good cycling performance(82.7% capacity retention after 3500 cycles). More importantly, this battery achieves an admirable power density of 49.0 kW kg^(-1) and energy density of 303.8 Wh kg^(-1), substantially higher than most recently reported batteries. With such excellent electrochemical performance, this battery will have great potential as an ultrafast power source in practical application.
基金financially supported by the National Natural Science Foundation of China (nos. 51774002 and 21773060)Anhui Provincial Science Fund for Excellent Young Scholars (no. gxyqZD2016066)
文摘Mesoporous NiCo_2O_4@MnO_2 nanoneedle arrays as electrode materials for supercapacitor grown on a conductive nickel foam were prepared by a facile hydrothermal route. The interconnected mesoporous structure of the NiCo_2O_4 nanoneedle arrays provides a large specific surface area for charge storage.The electrochemically active MnO_2 nanoparticles covered on the surface of NiCo_2O_4 nanoneedle result in a favorable synergistic storage effect because of charge redistribution at the NiCo_2O_4|MnO_2 interface,which reduces the interfacial polarization and facilitates ion diffusion. The initial specific capacitance of NiCo_2O_4@MnO_2(S2) is 1001 F g^(-1) at current density of 15 A g^(-1). The capacity retention of S2 is about87.4% after 4000 cycles, and the specific capacitance of S2 electrode only decreases from 1001 F g^(-1) to736 F g^(-1) even after 10,000 cycles. The first-principles calculations show that a chemical bonding between the NiCo_2O_4 and MnO_2 is not only helpful for stabilizing the composites but also leads to a charge redistribution at the interface, which may lead to a smaller interfacial polarization and thus beneficial for the interfacial capacity. The excellent electrochemical performance of NiCo_2O_4@MnO_2 composites(S2)can be ascribed to the high surface area, unique architecture, MnO_2 nanoparticle modification, reduced charge transfer resistance and stable interface between NiCo_2O_4 and MnO_2. The simple material synthesis and architectural design strategy provides new insights in opportunities to exhibit promising potential for practical application in energy storage.
基金financially supported by the National Natural Science Foundation of China(No.22072069)the Key Laboratory of Hubei Province for Coal Conversion and New Carbon Materials(Wuhan University of Science and Technology No.WKDM202303).
文摘Spinel oxide(NiCo_(2)O_(4))has demonstrated great potential to replace noble metal catalysts for the oxidation reaction of air pollutants.To further boost the oxidation ability of such catalysts,in this study,a facile surface-engineering strategy wherein NiCo_(2)O_(4) was treated with different alkali solvents was developed.The obtained catalyst(NiCo_(2)O_(4)-OH)showed a higher surface alkalinity and more surface defects compared to the pristine spinel oxide,including enhanced structural distortion as well as promoted oxygen vacancies.The propane oxidation ability of NiCo_(2)O_(4)-OH was greatly enhanced,with a propane conversion rate that was approximately 6.4 times higher than that of pristine NiCo_(2)O_(4) at a reaction temperature 193℃.This work sets a valuable paradigm for the surface modulation of spinel oxide via alkali treatment to ensure a high-performance oxidation catalyst.
文摘甘油是生物质精炼的主要副产物(约占10%),年过剩量与低利用率导致其市场价格(0.24-0.6 US kg^(-1))较低.甘油是具有三个活性羟基的多元醇,被认为是生产高价值产品的理想原料.甲酸作为甘油转化最重要的产品之一,广泛应用于农药、皮革、染料和医药行业,将甘油电氧化(EGOR)为甲酸(FA)不仅能有效避免资源过剩造成浪费,而且能满足未来对甲酸燃料电池的需求.然而甘油电催化氧化途径较为复杂,涉及反应中间产物的脱氢、吸附/解吸和C-C键裂解.本文将密度泛函理论(DFT)与实验相结合,研究了在精细构建的NiCo_(2)O_(4)纳米片上通过EGOR生产FA的反应机制.DFT计算结果表明,活性羟基(OH^(*))物种可以改变EGOR生产FA过程的决速步骤(RDS),通过调节吸附中间体的吸附能可获得理想的FA产率.其中,高度羟基化的NiCo_(2)O_(4)纳米片(311)-OH^(*)晶面上具有最低的吉布斯自由能,能显著提升反应过程动力学.在理论分析的基础上,通过简易的电沉积方法精准制备了超薄NiCo_(2)O_(4)纳米片(~1.7 nm),并采用X射线吸收精细结构谱和高分辨透射电镜对催化剂进行了结构分析.结果表明,NiCo_(2)O_(4)纳米片中四面体(A_(Td))和八面体(B_(Oh))配位具有内角共享的A_(Td)-O-B_(Oh)和边共享的B_(Oh)-O-B_(Oh)构型,金属间的协同作用有效改善了材料的电子效应,有利于提供更多的吸附位点并促进EGOR过程中的电荷转移.NiCo_(2)O_(4)纳米片在EGOR中的电荷转移电阻仅为0.94Ω,电化学活性表面积高达10.25 cm^(2).相比较电催化析氧反应,NiCo_(2)O_(4)纳米片表现出了较好的EGOR性能,在10 mA cm^(-2)的电流密度下阳极功耗降低了320 mV,在100 mA cm^(-2)的电流密度时的阳极电势仅为1.46 VRHE.此外,在120 h的稳定性测试中,甘油的转化率和FA的选择性可分别保持在89%和70%.多电位步骤实验、原位电化学阻抗谱和电子顺磁共振谱结果表明,NiCo_(2)O_(4)纳米片上原位产生的OH^(*)物种是EGOR过程中的直接活性中心,有利于将RDS从甘油酸脱氢裂解转化为甘油醛的脱氢步骤,并进一步促进C-C键的裂解.进一步结合理论预测,证实了OH^(*)物种是EGOR过程中的直接活性中心.综上,采用绿色高效的电催化手段促进甘油生产高附加值化学品是生物质链升级的重要举措,有效避免了传统的高温高压,以水为介质,原位利用OH^(*).本文为新型催化剂的未来设计和理解生物质基原料电氧化升级反应机制提供了新思路.
基金supported by the National Natural Science Foundation of China (21671132 and 81301345)Shanghai Natural Science Foundation (14ZR1450000)support from Shanghai Key Laboratory of High Temperature Superconductors, Shanghai University
文摘矩形片状介孔NiCo_2O_4催化剂被首次同时用于非酶葡萄糖传感器和非酶葡萄糖燃料电池中.结果表明:在传感器上,介孔NiCo_2O_4催化剂对葡萄糖具有优异的传感特性,如超快的响应时间(小于1 s),超高的灵敏度(662.31μA(mmol L-1)-1cm-2)以及超低的检测限(0.3 nmol L-1at S/N=3);在燃料电池上,介孔Ni Co2O催化剂作为负极材料展示出了良好的应用前景,包括0.63 V的开路电压,0.092 m W cm-24的最大输出功率和1.3 mA cm^-2的极限电流密度.该材料对葡萄糖优异的催化能力归因于介孔结构引起的巨大比表面积能够提供更多的活性位点和NiCo_2O_4本身具有的良好的催化能力.本研究为促进非酶葡萄糖超敏感检测和丰富非酶葡萄糖燃料电池负极催化材料的发展提供了有利的依据.
基金This work was supported by Natural Science Foundation of Shandong Province(ZR2022ME089)National Natural Science Foundation of China(52207249)Yantai Basic Research Project(2022JCYJ04).
文摘Cobalt nickel bimetallic oxides(NiCo_(2)O_(4))have received numerous attentions in terms of their controllable morphology,high temperature,corrosion resistance and strong electromagnetic wave(EMW)absorption capability.However,broadening the absorption bandwidth is still a huge challenge for NiCo_(2)O_(4)-based absorbers.Herein,the unique NiCo_(2)O_(4)@C core-shell microcubes with hollow structures were fabricated via a facile sacrificial template strategy.The concentration of oxygen vacancies and morphologies of the three-dimensional(3D)cubic hollow core-shell NiCo_(2)O_(4)@C framework were effectively optimized by adjusting the calcination temperature.The specially designed 3D framework structure facilitated the multiple reflections of incident electromagnetic waves and provided rich interfaces between multiple components,generating significant interfacial polarization losses.Dipole polarizations induced by oxygen vacancies could further enhance the attenuation ability for the incident EM waves.The optimized NiCo_(2)O_(4)@C hollow microcubes exhibit superior EMW absorption capability with minimum RL(RLmin)of-84.45 dB at 8.4 GHz for the thickness of 3.0 mm.Moreover,ultrabroad effective absorption bandwidth(EAB)as large as 12.48 GHz(5.52-18 GHz)is obtained.This work is believed to illuminate the path to synthesis of high-performance cobalt nickel bimetallic oxides for EMW absorbers with excellent EMW absorption capability,especially in broadening effective absorption bandwidth.
