Novel three-dimensional （3D） concentration-gradient Ni-Co hydroxide nanostructures （3DCGNC） have been directly grown on nickel foam by a facile stepwise electrochemical deposition method and intensively investigat...Novel three-dimensional （3D） concentration-gradient Ni-Co hydroxide nanostructures （3DCGNC） have been directly grown on nickel foam by a facile stepwise electrochemical deposition method and intensively investigated as binder- and conductor-free electrode for supercapacitors. Based on a three- electrode electrochemical characterization technique, the obtained 3DCGNC electrodes demonstrated a high specific capacitance of 1,760 F·g^-1 and a remarkable rate capability whereby more than 62.5% capacitance was retained when the current density was raised from 1 to 100 A·g^-1. More importantly, asymmetric supercapacitors were assembled by using the obtained 3DCGNC as the cathode and Ketjenblack as a conventional activated carbon anode. The fabricated asymmetric supercapacitors exhibited very promising electrochemical performances with an excellent combination of high energy density of 103.0 Wh·kg^-1 at a power density of 3.0 kW·kg^-1, and excellent rate capability-energy densities of about 70.4 and 26.0 Wh·kg^-1 were achieved when the average power densities were increased to 26.2 and 133.4 kW·kg^-1, respectively. Moreover, an extremely stable cycling life with only 2.7% capacitance loss after 20,000 cycles at a current density of 5 A·g^-1 was achieved, which compares very well with the traditional doublelayer supercapacitors.展开更多
A well-ordered and spherical LiNi0.6Co0.2Mn0.2O2 cathode material was successfully synthesized from Ni and Mn concentration-gradient precursors via co-precipitation. The crystal structure, morphology and electrochemic...A well-ordered and spherical LiNi0.6Co0.2Mn0.2O2 cathode material was successfully synthesized from Ni and Mn concentration-gradient precursors via co-precipitation. The crystal structure, morphology and electrochemical properties of LiNi0.6Co0.2Mn0.2O2 were characterized by X-ray diffraction, scanning electron microscopy, energy-dispersive spectroscopy, and charge-discharge tests. The material delivered an initial discharge capacity of 174.3 mAh/g at 180 mA/g （1 C rate） between 2.8 and 4.3 V and more than 93.1% of that was retained after 100 cycles. In addition, it also exhibited excellent rate capability, high cut-off voltage and temperature performance.展开更多
The exploration of low-strain and high-performance electrode is a crucial issue for aqueous potassiumion battery(AKIB).Herein,a novel potassium mediated iron/manganese binary hexacyanoferrate nanocuboid,i.e.,K_(x)Fe_(...The exploration of low-strain and high-performance electrode is a crucial issue for aqueous potassiumion battery(AKIB).Herein,a novel potassium mediated iron/manganese binary hexacyanoferrate nanocuboid,i.e.,K_(x)Fe_(y)Mn_(1-y)[Fe(CN)_(6)]·nH_(2)O(KFeMnHCF)nanocuboid,with the concentration-gradient(CG)structure is designed as a high-performance cathode for AKIB.Internal the CG-KFeMnHCF nanocuboids,the manganese content gradually decreases from the interior to the surface and the iron content changes reverse,resulting in the concentration-gradient structure.Both experimental and finite element simulation(FEA)results demonstrate the lower internal stress and better mechanical characteristics of CG structured nanocuboid than the homogenous structured one upon ion intercalation/deintercalation processes.Meanwhile,the electrochemical testing and theoretical calculation(DFT)results disclose the substitution of Fe to Mn in the KMnHCF crystal results in the enhanced electronic conductivity,potassium migration and electrochemical kinetics.Taken both advantages from the well-designed architecture and optimized crystal structure,the CG-KFeMnHCF achieves the superior rate capability and ultrahigh stability in aqueous potassium ion system.In particular,the CG-KFe_(0.31)Mn_(0.69)HCF achieves the best comprehensive properties among all the samples.The full AKIBs based on CG-KFe_(0.31)Mn_(0.69)HCF cathode achieves the high energy density(83 Wh kg^(-1)),superior power density,high capacity retention(83%)over high-rate long-term cycles,good adaptation to a wide temperature range(-20 to 40℃)and high reliability even under outside deformations.Therefore,this work not only provides a new clue to design the highperformance cathode,but also promotes the applications of AKIBs for diverse electronics and wide working environments.展开更多
采用"两步"进料方式实现进料口浓度的连续梯度变换,并根据数学微积分公式完成材料的浓度梯度设计.通过共沉淀方法和"管道式合成"技术合成了浓度梯度前驱体,并与过量6.5%的Li OH·H2O在氧气气氛下混合煅烧得到...采用"两步"进料方式实现进料口浓度的连续梯度变换,并根据数学微积分公式完成材料的浓度梯度设计.通过共沉淀方法和"管道式合成"技术合成了浓度梯度前驱体,并与过量6.5%的Li OH·H2O在氧气气氛下混合煅烧得到浓度梯度正极材料.浓度梯度正极材料的平均化学成分由ICP-AES测得为LiNi_(0.643)Co_(0.055)Mn_(0.302)O_2.SEM照片显示,浓度梯度LiNi_(0.643)Co_(0.055)Mn_(0.302)O_2正极材料呈球状,粒径大小约5μm,其振实密度为2.029 g/cm3.XRD谱图表明,LiNi_(0.643)Co_(0.055)Mn_(0.302)O_2具有良好的α-Na Fe O2层状结构;最小二乘法Rietveld精修得晶格参数a=0.2877(5)nm,c=1.4242(24)nm,V=0.102088(31)nm3.EDS和元素分布图共同验证了浓度梯度正极材料中Ni,Co,Mn的梯度变化.电化学测试结果表明,LiNi_(0.643)Co_(0.055)Mn_(0.302)O_2初始放电容量为187.68 m A·h·g-1,库仑效率为84.76%;1C倍率下充放电循环200周后放电容量为146.45 m A·h·g-1,容量保留率为86.90%.展开更多
通过控制结晶法和浓度梯度进料的方式制备了Ni、Co和Mn三元素组分含量呈全梯度分布的类球形Ni_(0.7)Co_(0.15)Mn_(0.15)(OH)_2前驱体,与LiOH·H_2O均匀混合并焙烧后获得LiNi_(0.7)Co_(0.15)Mn_(0.15)O_2正极材料,系统研究了不同焙...通过控制结晶法和浓度梯度进料的方式制备了Ni、Co和Mn三元素组分含量呈全梯度分布的类球形Ni_(0.7)Co_(0.15)Mn_(0.15)(OH)_2前驱体,与LiOH·H_2O均匀混合并焙烧后获得LiNi_(0.7)Co_(0.15)Mn_(0.15)O_2正极材料,系统研究了不同焙烧温度对材料Ni、Co和Mn三元素扩散情况、晶体结构及电化学性能的影响规律。通过能谱仪(EDXS)分析不同焙烧温度下材料颗粒中Ni、Co、Mn三元素的扩散程度。研究结果表明,在800℃下焙烧得到的正极材料梯度分布特征明显且电化学性能最佳,首次放电比容量为186.1 m Ah·g^(-1)(2.8~4.3 V,0.2C),2C大倍率充放电条件下循环200次后容量保持率为90.1%。这种材料兼具高比容量及良好的循环稳定性,可以用作下一代高能量密度锂离子电池正极材料。展开更多
Al80Ni6 Y8 Co4 Cu2 amorphous ribbons were isothermally annealed and a mixed structure consisting of α-Al particle with a size of less than 15nm and Al3Ni compound with a size of about 30nm was obtained. The crystall...Al80Ni6 Y8 Co4 Cu2 amorphous ribbons were isothermally annealed and a mixed structure consisting of α-Al particle with a size of less than 15nm and Al3Ni compound with a size of about 30nm was obtained. The crystallization kinetics of Al80Ni6 Y8 Co4 Cu2 amorphous alloy shows that the precipitation of α-Al particles is the growth process controlled by diffusion of the solute elements rejected from the growing crystals. By quenching at different cooling rates, a mixed structure consisting of nanoscale α-Al particles and the remaining glass matrix or structure consisting of nanoscale particle (Al phase or Al3Ni compound) with a size of about 100nm was formed. The addition of Co elements and Cu elements to Al-Ni-Y alloy systems increases the glass formation ability of the alloy and the thermal stability of the supercooled liquid region against crystallization, which results from significant difference of atomic size, strong bonding nature among constituent elements and the low diffisivity of the solute elements due to the concentration gradient in the growing front of crystals.展开更多
基金This work was supported by the National Natural Science Foundation of China （No. 21001117）, the Shenzhen Peacock Plan （No. KQCX20140522150815065）, and the Starting-Up Funds of South University of Science and Technology of China （SUSTC） through the Talent Plan of the Shenzhen Government. H. T. L. acknowledges the support from a Key Project of the Hunan Provincial Science and Technology Plan （No. 2014FJ2007）.
文摘Novel three-dimensional （3D） concentration-gradient Ni-Co hydroxide nanostructures （3DCGNC） have been directly grown on nickel foam by a facile stepwise electrochemical deposition method and intensively investigated as binder- and conductor-free electrode for supercapacitors. Based on a three- electrode electrochemical characterization technique, the obtained 3DCGNC electrodes demonstrated a high specific capacitance of 1,760 F·g^-1 and a remarkable rate capability whereby more than 62.5% capacitance was retained when the current density was raised from 1 to 100 A·g^-1. More importantly, asymmetric supercapacitors were assembled by using the obtained 3DCGNC as the cathode and Ketjenblack as a conventional activated carbon anode. The fabricated asymmetric supercapacitors exhibited very promising electrochemical performances with an excellent combination of high energy density of 103.0 Wh·kg^-1 at a power density of 3.0 kW·kg^-1, and excellent rate capability-energy densities of about 70.4 and 26.0 Wh·kg^-1 were achieved when the average power densities were increased to 26.2 and 133.4 kW·kg^-1, respectively. Moreover, an extremely stable cycling life with only 2.7% capacitance loss after 20,000 cycles at a current density of 5 A·g^-1 was achieved, which compares very well with the traditional doublelayer supercapacitors.
文摘A well-ordered and spherical LiNi0.6Co0.2Mn0.2O2 cathode material was successfully synthesized from Ni and Mn concentration-gradient precursors via co-precipitation. The crystal structure, morphology and electrochemical properties of LiNi0.6Co0.2Mn0.2O2 were characterized by X-ray diffraction, scanning electron microscopy, energy-dispersive spectroscopy, and charge-discharge tests. The material delivered an initial discharge capacity of 174.3 mAh/g at 180 mA/g （1 C rate） between 2.8 and 4.3 V and more than 93.1% of that was retained after 100 cycles. In addition, it also exhibited excellent rate capability, high cut-off voltage and temperature performance.
基金supported by the Innovation Foundation of Graduate Student of Harbin Normal University(Grant No.HSDSSCX2020-18)the Natural Science Foundation of Heilongjiang Province,China(Grant No.TD2020B001)the Opening Project of State Key Laboratory of Advanced Chemical Power Sources(Grant No.SKL-ACPS-C-25)。
文摘The exploration of low-strain and high-performance electrode is a crucial issue for aqueous potassiumion battery(AKIB).Herein,a novel potassium mediated iron/manganese binary hexacyanoferrate nanocuboid,i.e.,K_(x)Fe_(y)Mn_(1-y)[Fe(CN)_(6)]·nH_(2)O(KFeMnHCF)nanocuboid,with the concentration-gradient(CG)structure is designed as a high-performance cathode for AKIB.Internal the CG-KFeMnHCF nanocuboids,the manganese content gradually decreases from the interior to the surface and the iron content changes reverse,resulting in the concentration-gradient structure.Both experimental and finite element simulation(FEA)results demonstrate the lower internal stress and better mechanical characteristics of CG structured nanocuboid than the homogenous structured one upon ion intercalation/deintercalation processes.Meanwhile,the electrochemical testing and theoretical calculation(DFT)results disclose the substitution of Fe to Mn in the KMnHCF crystal results in the enhanced electronic conductivity,potassium migration and electrochemical kinetics.Taken both advantages from the well-designed architecture and optimized crystal structure,the CG-KFeMnHCF achieves the superior rate capability and ultrahigh stability in aqueous potassium ion system.In particular,the CG-KFe_(0.31)Mn_(0.69)HCF achieves the best comprehensive properties among all the samples.The full AKIBs based on CG-KFe_(0.31)Mn_(0.69)HCF cathode achieves the high energy density(83 Wh kg^(-1)),superior power density,high capacity retention(83%)over high-rate long-term cycles,good adaptation to a wide temperature range(-20 to 40℃)and high reliability even under outside deformations.Therefore,this work not only provides a new clue to design the highperformance cathode,but also promotes the applications of AKIBs for diverse electronics and wide working environments.
文摘采用"两步"进料方式实现进料口浓度的连续梯度变换,并根据数学微积分公式完成材料的浓度梯度设计.通过共沉淀方法和"管道式合成"技术合成了浓度梯度前驱体,并与过量6.5%的Li OH·H2O在氧气气氛下混合煅烧得到浓度梯度正极材料.浓度梯度正极材料的平均化学成分由ICP-AES测得为LiNi_(0.643)Co_(0.055)Mn_(0.302)O_2.SEM照片显示,浓度梯度LiNi_(0.643)Co_(0.055)Mn_(0.302)O_2正极材料呈球状,粒径大小约5μm,其振实密度为2.029 g/cm3.XRD谱图表明,LiNi_(0.643)Co_(0.055)Mn_(0.302)O_2具有良好的α-Na Fe O2层状结构;最小二乘法Rietveld精修得晶格参数a=0.2877(5)nm,c=1.4242(24)nm,V=0.102088(31)nm3.EDS和元素分布图共同验证了浓度梯度正极材料中Ni,Co,Mn的梯度变化.电化学测试结果表明,LiNi_(0.643)Co_(0.055)Mn_(0.302)O_2初始放电容量为187.68 m A·h·g-1,库仑效率为84.76%;1C倍率下充放电循环200周后放电容量为146.45 m A·h·g-1,容量保留率为86.90%.
文摘通过控制结晶法和浓度梯度进料的方式制备了Ni、Co和Mn三元素组分含量呈全梯度分布的类球形Ni_(0.7)Co_(0.15)Mn_(0.15)(OH)_2前驱体,与LiOH·H_2O均匀混合并焙烧后获得LiNi_(0.7)Co_(0.15)Mn_(0.15)O_2正极材料,系统研究了不同焙烧温度对材料Ni、Co和Mn三元素扩散情况、晶体结构及电化学性能的影响规律。通过能谱仪(EDXS)分析不同焙烧温度下材料颗粒中Ni、Co、Mn三元素的扩散程度。研究结果表明,在800℃下焙烧得到的正极材料梯度分布特征明显且电化学性能最佳,首次放电比容量为186.1 m Ah·g^(-1)(2.8~4.3 V,0.2C),2C大倍率充放电条件下循环200次后容量保持率为90.1%。这种材料兼具高比容量及良好的循环稳定性,可以用作下一代高能量密度锂离子电池正极材料。
文摘Al80Ni6 Y8 Co4 Cu2 amorphous ribbons were isothermally annealed and a mixed structure consisting of α-Al particle with a size of less than 15nm and Al3Ni compound with a size of about 30nm was obtained. The crystallization kinetics of Al80Ni6 Y8 Co4 Cu2 amorphous alloy shows that the precipitation of α-Al particles is the growth process controlled by diffusion of the solute elements rejected from the growing crystals. By quenching at different cooling rates, a mixed structure consisting of nanoscale α-Al particles and the remaining glass matrix or structure consisting of nanoscale particle (Al phase or Al3Ni compound) with a size of about 100nm was formed. The addition of Co elements and Cu elements to Al-Ni-Y alloy systems increases the glass formation ability of the alloy and the thermal stability of the supercooled liquid region against crystallization, which results from significant difference of atomic size, strong bonding nature among constituent elements and the low diffisivity of the solute elements due to the concentration gradient in the growing front of crystals.
