二氧化锰电极材料制备与性能研究
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摘要
能源永远是人类发展的首要问题。随着矿石燃料的枯竭和自然环境的恶化,高能量、高功率的储能装置成为研究的热点。超级电容器作为一种很有前景的储能器件,虽然具有很高的功率密度,但跟其它储能器件(例如锂离子电池)相比其能量密度仍然较低,特别是在高功率大电流放电时,能量密度不能满足市场的需求。因此,采用简单工艺和低廉的成本制备性能优良的电化学电容器电极材料就显得格外的重要。
二氧化锰(MnO2)是一种重要的过渡金属氧化物,由于具有高理论容量、价格低廉、环境友好的特点,适合作为储能材料,例如锂离子电池和电化学电容器。我们在60-80℃下采用温和的化学浴反应制备出α-和δ-的混相结构Mn02。相同体系下通过简单的改变反应参数,分别得到纯相的α-,δ-和γ-MnO2。发现MnO2的不同晶体结构是由反应温度、pH值和时间决定的。电化学测试结果表明混相Mn02与其它纯相Mn02相比,具有优良的电化学性能。这种混相Mn02结构中存在着大量的晶界,利于电子和离子扩散,提供了额外的电化学活性点。此工作中,我们不仅仅有目的的优化化学浴合成参数制备高性能的混相MnO2材料,更重要的是为提高粉末电极电化学电容性能提供了一条有效的途径。
论文在无模板情况下,采用了两种阴极电沉积路径,分别制备出MnO2微米棒阵列和纳米墙阵列。实验结果表明F-离子的刻蚀作用是形成微米棒阵列的决定因素,而另-种纳米墙阵列的形貌是在电解水的基础上形成的。其中MnO2纳米墙阵列具有较高的比容量,适合作为电极材料。另外,两种无模板合成方法的工艺简单,为电沉积制备微/纳米阵列材料提供了有益的参考。
Energy is always a priority issue for human being. The high-energy, high-power energy storage devices are widely investigated, owing to the decreasing availability of fossil and climate change. Although electrochemical capacitor has a high power density as a promising energy storage device, it cannot content the market demands due to its low energy density compared with other energy storage devices (e. g. lithium-ion batteries). Consequently, Choosing effective technology and low costing to prepare electrode materials with excellent electrochemical performance has become critical issue.
Manganese dioxide (MnO2) is an important transition oxide, of particular interest for its potential applications in energy storage devices, such as lithium-ion batteries and supercapacitors, on account of its high theoretical capacitance, low cost and environmental friendliness. We used mild chemical bath route at 60-80℃to synthesize MnO2, which was confirmed as a mixed phase of bothα- andδ-phases. Pureα-,δ-, and y-phase MnO2 can also be chemically prepared in the same solution system by adjusting reaction parameters slightly. The crystallographic structure of MnO2 was found to be determined by the chemical bath reaction temperature, pH value and time. The electrochemical test results indicate that mixed-phase MnO2 have better capacitance properties than other pure phase MnO2. The mixed-phase MnO2 possessing lots of phase interface can provide extra electrochemically active boundaries and is propitious to electron/ionic transmission. In the current work, we not only purposefully designed the optimum reaction parameters to synthesize high performance mixed-phase MnO2 through mild chemical bath route, but also provides an effectives approach to enhance the capacitance of powder-based electrodes.
MnO2 microrod arrays and nanowall arrays were prepared through two template-free cathodic electrodeposition processes. The experiment results indicate that the etching effect of F- is a key factor to form microrod arrays and the growth of nanowall arrays is based on the electrolysis of water. MnO2 nanowall arrays have a larger specific capacitance as electrode materials. Moreover, the template-free synthesis methods are simple in preparation, which provide a referential example for electrodeposition of micro/nano-array materials.
二氧化锰(MnO2)是一种重要的过渡金属氧化物,由于具有高理论容量、价格低廉、环境友好的特点,适合作为储能材料,例如锂离子电池和电化学电容器。我们在60-80℃下采用温和的化学浴反应制备出α-和δ-的混相结构Mn02。相同体系下通过简单的改变反应参数,分别得到纯相的α-,δ-和γ-MnO2。发现MnO2的不同晶体结构是由反应温度、pH值和时间决定的。电化学测试结果表明混相Mn02与其它纯相Mn02相比,具有优良的电化学性能。这种混相Mn02结构中存在着大量的晶界,利于电子和离子扩散,提供了额外的电化学活性点。此工作中,我们不仅仅有目的的优化化学浴合成参数制备高性能的混相MnO2材料,更重要的是为提高粉末电极电化学电容性能提供了一条有效的途径。
论文在无模板情况下,采用了两种阴极电沉积路径,分别制备出MnO2微米棒阵列和纳米墙阵列。实验结果表明F-离子的刻蚀作用是形成微米棒阵列的决定因素,而另-种纳米墙阵列的形貌是在电解水的基础上形成的。其中MnO2纳米墙阵列具有较高的比容量,适合作为电极材料。另外,两种无模板合成方法的工艺简单,为电沉积制备微/纳米阵列材料提供了有益的参考。
Energy is always a priority issue for human being. The high-energy, high-power energy storage devices are widely investigated, owing to the decreasing availability of fossil and climate change. Although electrochemical capacitor has a high power density as a promising energy storage device, it cannot content the market demands due to its low energy density compared with other energy storage devices (e. g. lithium-ion batteries). Consequently, Choosing effective technology and low costing to prepare electrode materials with excellent electrochemical performance has become critical issue.
Manganese dioxide (MnO2) is an important transition oxide, of particular interest for its potential applications in energy storage devices, such as lithium-ion batteries and supercapacitors, on account of its high theoretical capacitance, low cost and environmental friendliness. We used mild chemical bath route at 60-80℃to synthesize MnO2, which was confirmed as a mixed phase of bothα- andδ-phases. Pureα-,δ-, and y-phase MnO2 can also be chemically prepared in the same solution system by adjusting reaction parameters slightly. The crystallographic structure of MnO2 was found to be determined by the chemical bath reaction temperature, pH value and time. The electrochemical test results indicate that mixed-phase MnO2 have better capacitance properties than other pure phase MnO2. The mixed-phase MnO2 possessing lots of phase interface can provide extra electrochemically active boundaries and is propitious to electron/ionic transmission. In the current work, we not only purposefully designed the optimum reaction parameters to synthesize high performance mixed-phase MnO2 through mild chemical bath route, but also provides an effectives approach to enhance the capacitance of powder-based electrodes.
MnO2 microrod arrays and nanowall arrays were prepared through two template-free cathodic electrodeposition processes. The experiment results indicate that the etching effect of F- is a key factor to form microrod arrays and the growth of nanowall arrays is based on the electrolysis of water. MnO2 nanowall arrays have a larger specific capacitance as electrode materials. Moreover, the template-free synthesis methods are simple in preparation, which provide a referential example for electrodeposition of micro/nano-array materials.
引文
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