金属（Mg、Al）微/纳米材料的制备及在一次电池中应用研究
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摘要
高能化学电源中,一次电池因具有高的能量密度、设计的灵活多样性及价格低廉等优势而备受关注。这类电池的阳极材料大都采用Li、Mg、Al、Zn等活泼金属,而阳极材料的性能提升将在很大程度上优化电池的综合性能,因此研究这些阳极关键材料具有极其重要的现实意义。金属Mg和Al材料作为阳极材料在电池中具有如下优点：(1)高的理论能量密度；(2)高的理论电压；(3)低成本；(4)环境友好、无污染；(5)安全可靠。但在实际电池体系中这些材料存在利用率低和实际放电能量密度低等不足,这些因素都影响其商品化的进程,其反映出来的科学问题主要可分为三部分：活性物质的活性低、阳极表面在电极反应过程中会形成钝化膜、电解液的不匹配问题导致阳极的腐蚀速率快。利用纳米材料的高反应活性、高比表面积以及独特的材料结构,可有效提高阳极材料的电化学性能。因此,电极材料微纳化和筛选适宜的电解液是提高一次电池性能的重要途径。
本论文开展了镁和铝微/纳米电极材料的制备、表征及其作为典型一次电池阳极材料的应用基础研究。主要内容如下：
(1)通过改变物理气相沉积法中的关键实验条件,制备了镁微米球及微米球/纳米球共混形貌,并测试了其在Mg/MnO2电池中的电化学性能。沉积产物的尺寸大小和形貌可通过调节加热温度、加热时间、载气流速、沉积温度等实验条件加以控制。采用扫描电子显微镜、粉末衍射、透射电镜及高分辨透射电镜、比表面积测试等技术对材料的微观组成及结构进行了分析。测试结果表明：镁材料的比表面积为0.61-1.92 m2 g-1,将这些制备出的镁材料和商业高纯镁分别进行了线性扫描、交流阻抗和放电性能测试。经过筛选不同的电解液防腐剂种类和浓度,发现Mg(NO3)2 (2.6 mol L-1)和NaNO2(2.6 mol L-1)的混合溶液因具有较慢的腐蚀速率和较小的电极极化,而适宜应用于高活性的镁电极。物理气相沉积法制备的镁材料可提高电极性能,尤其是镁微米球(直径1.5-3.0μm)和纳米球(直径50-150 nm)共混结构的电极性能最佳,其具有较负的起始电位(—1.08 V)、较高的电流密度(163 mA cm-2)、较小的表观活化能(5.1 kJ mol-1),主要原因在于电极材料可与电极膏中的导电剂有效接触,减小了电极极化,从而提高了电极的综合性能；另外,由镁微／纳米结构和γ-MnO2纳米线组装的Mg/MnO2电池展现出了平稳的放电平台及高的放电比容量等良好的电化学性能。
(2)采用物理气相沉积法通过蒸发商业高纯铝粉制备出了多种铝微／纳米材料。在制备过程中,采用多孔阳极氧化铝模板为衬底时,在750-950℃均易得到以微米球为主、纳米颗粒为辅的材料,主要原因是具有多孔结构的衬底会影响铝沉积初期的成核数量。经调节衬底种类、载气流速、加热时间等实验参数,摸索出了制备铝纳米棒的最优化实验条件：采用不锈钢网衬底、加热温度选用1000℃保温10小时、沉积温度300℃和载气流速1000 cm3 min-1。制得纳米棒的直径为30-90 nm,长度可达数微米。高分辨透射电镜表明,纳米棒具有良好的结晶度,晶格条纹间距为0.23 nm,对应铝晶体结构的(111)晶面,说明铝纳米棒是沿着[111]向生长的。当制备的铝纳米材料选用膏体配方为65 wt%活性物质、25 wt% Vulcan XC-72碳导电剂和10 wt%聚四氟乙烯(PTFE)干粉粘合剂时,电极性能可明显优于商业高纯铝粉。另外,铝纳米棒组装的铝／空气电池展现出了高的放电平台和放电比容量,其适合开发长寿命的电池体系。
Recently, electrochemical storage and generation of energy in primary batteries have attracted considerable research attention due to their high energy density, superior discharge performances, and low cost. Active metals (e.g., Li, Mg, Al and Zn) can be used in various primary batteries. Among the metallic materials, Mg and Al are especially suitable for being anodes in power devices because of the advantages of high theoretical energy density, high theoretical voltage, non-toxicity for the environment, and safety. However, some problems still remain for the two materials such as low anode utilization of Mg or Al sheet material, and low actual energy density, which hinder their widespread applications in the consumer market. The scientific issues associated with the practical problems can be grouped into three categories:low kinetics of active materials, passivation of the anode surfaces, and unsuitable electrolyte leading to a high corrosion rate of the anodes. In addition, micro/nanoscale materials own a series of specific physical and chemical properties that are different from their bulk counterparts because of unique crystallographic structure, which are paving a good way for the influence of the electrochemical capacity. Therefore, enhancing the electrochemical properties of the micro/nanoscale electrode materials and using an appropriate electrolyte can greatly improve the performances of primary batteries.
In this thesis, the developments of typical primary batteries were reviewed, especially for magnesium based and aluminum based batteries. The aims of the present study were to focus on the preparation processes, the structural characterization and the electrochemical properties of microscale and nanoscale Mg and Al as anode materials. The main content follows:
(1) The morphology-controlled synthesis of magnesium micro/nanomaterials and their electrochemical performance as the anode of primary Mg/MnO2 batteries have been reported. Mg micro/nanoscale materials with controllable shapes have been prepared via a conventional vapor-transport method under an inert atmosphere by adjusting the heating temperatures, heating time, flow-rates of argon gas, and the deposition temperatures. Extensive analyzing techniques including SEM, XRD, TEM/HRTEM, and BET were carried out to characterize the as-obtained samples. The results show that the as-prepared Mg samples are microspheres or micro/nanospheres with specific surface areas of 0.61-1.92 m2 g-1. The electrochemical properties of the as-prepared Mg and commercial Mg powders were further studied in terms of linear sweep voltammograms, impedance spectra, and discharge capabilities. By comparing the performances of different inhibitors in electrolytes, it was found that NaNO2 (2.6 mol L-1) as an inhibitor in the Mg(NO3)2 (2.6 mol L-1) electrolyte affords an Mg electrode with high current density and low corrosion rate. In particular, the Mg sample consisting of microspheres with a diameter of 1.5-3.0μm and nanospheres with a diameter of 50-150 nm exhibited superior electrode properties including negative initial potential (—1.08 V), high current density (163 mA cm-2), low apparent activation energy (5.1 kJ mol-1), and high discharge specific capacity (784 mAh g-1). The mixture of Mg microspheres and nanospheres is promising for the application in Mg/MnO2 primary batteries because of the sufficient contact with the electrolyte and greatly reduced charge transfer impedance and polarization.
(2) Various Al micro/nanoscale materials were successfully prepared via a conventional physical vapor deposition through the evaporation of commercial Al powders at certain experimental conditions. The mixture of microspheres and nanoparticles were fabricated via using anodic aluminum oxide (AAO) template as substrate even at a wide range of heating temperatures of 750-950℃, because the AAO substrate can play a crucial role in affecting the amount of nucleation in the initial depositing stage. After studying the effect of experimental parameters on the morphologies of micro/nanoscale materials, the optimal condition for synthesizing Al nanorods with uniform diameters of 30-90 nm were selected at a heating temperature of 1000℃for 10 h, a depositing temperature of 300℃with a constant argon gas of 1000 cm3·min-1 on the stainless steel mesh substrate. The HRTEM image of part of an Al nanorod shows that clear fringes with an interplanar spacing is 0.23 nm, which is in accordance with the d-spacings between the (111) crystal planes, indicating that the Al nanorod grows along the [111] direction. The electrode made from the as-deposited Al nanorods with the composition of 65 wt% Al,25 wt% carbon, and 10 wt% PTFE exhibits superior electrochemical properties to that made from commercial Al powders. Furthermore, the laboratorymade Al/air battery with the as-prepared Al nanorods displays high operating voltage and discharge specific capacity, which is important for developing long-life battery systems.
本论文开展了镁和铝微/纳米电极材料的制备、表征及其作为典型一次电池阳极材料的应用基础研究。主要内容如下：
(1)通过改变物理气相沉积法中的关键实验条件,制备了镁微米球及微米球/纳米球共混形貌,并测试了其在Mg/MnO2电池中的电化学性能。沉积产物的尺寸大小和形貌可通过调节加热温度、加热时间、载气流速、沉积温度等实验条件加以控制。采用扫描电子显微镜、粉末衍射、透射电镜及高分辨透射电镜、比表面积测试等技术对材料的微观组成及结构进行了分析。测试结果表明：镁材料的比表面积为0.61-1.92 m2 g-1,将这些制备出的镁材料和商业高纯镁分别进行了线性扫描、交流阻抗和放电性能测试。经过筛选不同的电解液防腐剂种类和浓度,发现Mg(NO3)2 (2.6 mol L-1)和NaNO2(2.6 mol L-1)的混合溶液因具有较慢的腐蚀速率和较小的电极极化,而适宜应用于高活性的镁电极。物理气相沉积法制备的镁材料可提高电极性能,尤其是镁微米球(直径1.5-3.0μm)和纳米球(直径50-150 nm)共混结构的电极性能最佳,其具有较负的起始电位(—1.08 V)、较高的电流密度(163 mA cm-2)、较小的表观活化能(5.1 kJ mol-1),主要原因在于电极材料可与电极膏中的导电剂有效接触,减小了电极极化,从而提高了电极的综合性能；另外,由镁微／纳米结构和γ-MnO2纳米线组装的Mg/MnO2电池展现出了平稳的放电平台及高的放电比容量等良好的电化学性能。
(2)采用物理气相沉积法通过蒸发商业高纯铝粉制备出了多种铝微／纳米材料。在制备过程中,采用多孔阳极氧化铝模板为衬底时,在750-950℃均易得到以微米球为主、纳米颗粒为辅的材料,主要原因是具有多孔结构的衬底会影响铝沉积初期的成核数量。经调节衬底种类、载气流速、加热时间等实验参数,摸索出了制备铝纳米棒的最优化实验条件：采用不锈钢网衬底、加热温度选用1000℃保温10小时、沉积温度300℃和载气流速1000 cm3 min-1。制得纳米棒的直径为30-90 nm,长度可达数微米。高分辨透射电镜表明,纳米棒具有良好的结晶度,晶格条纹间距为0.23 nm,对应铝晶体结构的(111)晶面,说明铝纳米棒是沿着[111]向生长的。当制备的铝纳米材料选用膏体配方为65 wt%活性物质、25 wt% Vulcan XC-72碳导电剂和10 wt%聚四氟乙烯(PTFE)干粉粘合剂时,电极性能可明显优于商业高纯铝粉。另外,铝纳米棒组装的铝／空气电池展现出了高的放电平台和放电比容量,其适合开发长寿命的电池体系。
Recently, electrochemical storage and generation of energy in primary batteries have attracted considerable research attention due to their high energy density, superior discharge performances, and low cost. Active metals (e.g., Li, Mg, Al and Zn) can be used in various primary batteries. Among the metallic materials, Mg and Al are especially suitable for being anodes in power devices because of the advantages of high theoretical energy density, high theoretical voltage, non-toxicity for the environment, and safety. However, some problems still remain for the two materials such as low anode utilization of Mg or Al sheet material, and low actual energy density, which hinder their widespread applications in the consumer market. The scientific issues associated with the practical problems can be grouped into three categories:low kinetics of active materials, passivation of the anode surfaces, and unsuitable electrolyte leading to a high corrosion rate of the anodes. In addition, micro/nanoscale materials own a series of specific physical and chemical properties that are different from their bulk counterparts because of unique crystallographic structure, which are paving a good way for the influence of the electrochemical capacity. Therefore, enhancing the electrochemical properties of the micro/nanoscale electrode materials and using an appropriate electrolyte can greatly improve the performances of primary batteries.
In this thesis, the developments of typical primary batteries were reviewed, especially for magnesium based and aluminum based batteries. The aims of the present study were to focus on the preparation processes, the structural characterization and the electrochemical properties of microscale and nanoscale Mg and Al as anode materials. The main content follows:
(1) The morphology-controlled synthesis of magnesium micro/nanomaterials and their electrochemical performance as the anode of primary Mg/MnO2 batteries have been reported. Mg micro/nanoscale materials with controllable shapes have been prepared via a conventional vapor-transport method under an inert atmosphere by adjusting the heating temperatures, heating time, flow-rates of argon gas, and the deposition temperatures. Extensive analyzing techniques including SEM, XRD, TEM/HRTEM, and BET were carried out to characterize the as-obtained samples. The results show that the as-prepared Mg samples are microspheres or micro/nanospheres with specific surface areas of 0.61-1.92 m2 g-1. The electrochemical properties of the as-prepared Mg and commercial Mg powders were further studied in terms of linear sweep voltammograms, impedance spectra, and discharge capabilities. By comparing the performances of different inhibitors in electrolytes, it was found that NaNO2 (2.6 mol L-1) as an inhibitor in the Mg(NO3)2 (2.6 mol L-1) electrolyte affords an Mg electrode with high current density and low corrosion rate. In particular, the Mg sample consisting of microspheres with a diameter of 1.5-3.0μm and nanospheres with a diameter of 50-150 nm exhibited superior electrode properties including negative initial potential (—1.08 V), high current density (163 mA cm-2), low apparent activation energy (5.1 kJ mol-1), and high discharge specific capacity (784 mAh g-1). The mixture of Mg microspheres and nanospheres is promising for the application in Mg/MnO2 primary batteries because of the sufficient contact with the electrolyte and greatly reduced charge transfer impedance and polarization.
(2) Various Al micro/nanoscale materials were successfully prepared via a conventional physical vapor deposition through the evaporation of commercial Al powders at certain experimental conditions. The mixture of microspheres and nanoparticles were fabricated via using anodic aluminum oxide (AAO) template as substrate even at a wide range of heating temperatures of 750-950℃, because the AAO substrate can play a crucial role in affecting the amount of nucleation in the initial depositing stage. After studying the effect of experimental parameters on the morphologies of micro/nanoscale materials, the optimal condition for synthesizing Al nanorods with uniform diameters of 30-90 nm were selected at a heating temperature of 1000℃for 10 h, a depositing temperature of 300℃with a constant argon gas of 1000 cm3·min-1 on the stainless steel mesh substrate. The HRTEM image of part of an Al nanorod shows that clear fringes with an interplanar spacing is 0.23 nm, which is in accordance with the d-spacings between the (111) crystal planes, indicating that the Al nanorod grows along the [111] direction. The electrode made from the as-deposited Al nanorods with the composition of 65 wt% Al,25 wt% carbon, and 10 wt% PTFE exhibits superior electrochemical properties to that made from commercial Al powders. Furthermore, the laboratorymade Al/air battery with the as-prepared Al nanorods displays high operating voltage and discharge specific capacity, which is important for developing long-life battery systems.
引文
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