Si-SiO_x-Sn/C复合负极材料的合成及电化学性能研究
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摘要
目前锂离子电池的应用越来越广泛。与其他类型的二次电池相比锂离子电池具有较多优点,比如,工作电压和能量密度高,循环寿命长,自放电率小,无记忆效应且电极材料不含有毒物质,是现代的“绿色电池”。广泛的应用于移动电话,笔记本电脑,电动车和混合电动车中。锂电池负极材料主要采用已经商业化的碳类材料,但由于它的理论比容量较低,且由于碳材料的嵌锂电位与金属锂接近,在快速充电时存在安全隐患,所以开发高比容量和性能安全的负极材料成为必要。由于硅和锡的理论比容量高(分别为4200 mAh g-1,994 mAh g-1),成为研究热点。但由于它们在充放电过程中存在严重的体积膨胀收缩,导致容量衰减较快,循环性能较差,极大的影响了材料的实用价值。利用硅锡的复合物或其合金,可以有效地改善它们的循环性能。本论文研究了一氧化硅和二氧化锡均匀混合后在碳的作用下于高温管式炉中发生反应,合成新的具有充放电效应的电极材料。考察了温度的影响,电化学性能及交流阻抗。通过实验研究得到以下结论：
1.将SiO、纳米Sn02和碳混合后湿磨,于氮气保护下在管式炉中加热到750℃,800℃,850℃,900℃,950℃和1000℃。经XRD分析得知,新合成的材料中温度在800℃及以上时,Sn02经碳还原转化为Sn金属,750℃时Sn02未发生变化。SiO高温下发生自身歧化反应,使得材料中含有Si02晶体和无定形硅,且在900℃时SiO2成无定形。由XRD分析得知在900℃合成的材料较理想。
2.将各个温度下合成的材料分别与金属锂组成半电池,进行电化学性能测试。由充放电数据得知与XRD分析结果保持一致。90℃时在225 mAg-1的电流密度下,其首次放电比容量高达1144.2 mAh g-1,具有较高的比容量。由此可确定最佳合成温度是900℃。
3.对900℃下合成的材料与金属锂组成半电池进行倍率性能测试。结果表明0.5 C、1 C、5 C、10C倍率下材料的首次放电比容量分别1144.2 mAh g-1,715.8 mAh g-1,359.0 mAh g-1和282.9 mAh g-1。倍率越大,首次放电比容量越小。
4.900℃时合成的材料与金属锂组成的半电池在225 mA g-1电流密度下,分别在循环至第一次,第三次和第三十次时在0.02 V电压下进行交流阻抗研究。阻抗图谱曲线随着循环次数的增多,高频区的半圆逐渐增大,表明材料的充放电越来越难。电极界面和活性物质间电阻的增大也可能是造成容量衰减的一个原因。
Lithium-ion cells are considered presently the best choice for rechargeable batteries. Lithium-ion cells have many advantageous compared with other secondary batteries. Lithium-ion battery has high voltage, high energy density, long cycle life, self-discharge rate is small, no memory effect and also the electrode material does not contain toxic substances, is the modern "green battery." It is widely used in mobile phones, notebook computers, electric vehicles and hybrid electric vehicles. Since the first commercialization of Li-ion batteries by Sony in 1991, graphite carbon has been the favorable anode material for its good reversibility and stability with thousands of cycles. However since the theoretical capacity (372 mAh g-1) of graphite is limited, new anode materials with high specific capacity are searched to satisfy the requirement of advanced power sources in such applications as electric vehicles with extended range.
The search for next-generation anode materials of Li-ion batteries has focused on Si- and Sn-based oxide materials that offer a considerably larger specific (4200 mAh g-1 and 994 mAh g-1) and volumetric capacity than conventional carbonaceous materials. Such studies indicate that silicone monoxide, SiO, has a large discharge specific capacity. However, due to their serious volume change when charging and discharging, leading to fast capacity fading and poor cycle performance, it is a great impact to the material of its practical value. The composite of Si- and Sn-based compounds or alloys can effectively improve their cycling performance. In this work, we studied Si-SiOx-Sn/C composite which was prepared by thermal reduction method, and tested it as anode material for Li-ion battery. The composites were synthesized by heating the milled mixture of SiO, SnO2 and carbon in an inert gas filled furnace. The effects of temperature, electrochemical properties and impedance were researched, and the results were as follows:
1. Si-SiOx-Sn/C composites were prepared in following steps:the mixture of SiO powder, carbon powder and Nano-SnO2 powder was milled in a planetary ball mill for 5 h. The milled composites were dispersed into the acetone solvent. The dried solid mixtures were heated to 750℃,800℃,850℃,900℃,950℃and 1000℃for 2 h respectively in a furnace tube under an inert atmosphere. The XRD results show that SnO2 can be reduced into Sn metal above 800℃, and silicon-mono-oxide is transformed into silicon and silicon dioxide (2SiO→Si+SiO2). Further results indicated that the composite heated at 900℃for 2 h is better in performance.
2. Charge and discharge measurements were carried out employing a two-electrode 2025 coin cell. Lithium metal was used as the counter electrode. When the composite was heated at 900℃for 2 h, the first discharge capacity of the composite anode can reach as high as 1144.2 mAh g-1 under a constant current density of 225 mA g-1.
3. Further results show that the first discharge capacity of the composite anode heated at 900℃for 2 h can reach 1144.2 mAh g-1、715.8 mAh g-1、359.0 mAh g-1 and 282.9 mAh g-1 under 0.5 C、1 C、5 C、10 C.
4. We researched the typical EIS Nyquist plots of composite anode heated at 900℃, after the first, third and 30 th cycles. The diameter of the semicircle becomes larger with the increase of cycle number, which indicates that the charge transfer reaction process becomes more difficult as charge and discharge cycles proceed. Increase of interface and particle contact resistance could be a cause of the capacity decay.
1.将SiO、纳米Sn02和碳混合后湿磨,于氮气保护下在管式炉中加热到750℃,800℃,850℃,900℃,950℃和1000℃。经XRD分析得知,新合成的材料中温度在800℃及以上时,Sn02经碳还原转化为Sn金属,750℃时Sn02未发生变化。SiO高温下发生自身歧化反应,使得材料中含有Si02晶体和无定形硅,且在900℃时SiO2成无定形。由XRD分析得知在900℃合成的材料较理想。
2.将各个温度下合成的材料分别与金属锂组成半电池,进行电化学性能测试。由充放电数据得知与XRD分析结果保持一致。90℃时在225 mAg-1的电流密度下,其首次放电比容量高达1144.2 mAh g-1,具有较高的比容量。由此可确定最佳合成温度是900℃。
3.对900℃下合成的材料与金属锂组成半电池进行倍率性能测试。结果表明0.5 C、1 C、5 C、10C倍率下材料的首次放电比容量分别1144.2 mAh g-1,715.8 mAh g-1,359.0 mAh g-1和282.9 mAh g-1。倍率越大,首次放电比容量越小。
4.900℃时合成的材料与金属锂组成的半电池在225 mA g-1电流密度下,分别在循环至第一次,第三次和第三十次时在0.02 V电压下进行交流阻抗研究。阻抗图谱曲线随着循环次数的增多,高频区的半圆逐渐增大,表明材料的充放电越来越难。电极界面和活性物质间电阻的增大也可能是造成容量衰减的一个原因。
Lithium-ion cells are considered presently the best choice for rechargeable batteries. Lithium-ion cells have many advantageous compared with other secondary batteries. Lithium-ion battery has high voltage, high energy density, long cycle life, self-discharge rate is small, no memory effect and also the electrode material does not contain toxic substances, is the modern "green battery." It is widely used in mobile phones, notebook computers, electric vehicles and hybrid electric vehicles. Since the first commercialization of Li-ion batteries by Sony in 1991, graphite carbon has been the favorable anode material for its good reversibility and stability with thousands of cycles. However since the theoretical capacity (372 mAh g-1) of graphite is limited, new anode materials with high specific capacity are searched to satisfy the requirement of advanced power sources in such applications as electric vehicles with extended range.
The search for next-generation anode materials of Li-ion batteries has focused on Si- and Sn-based oxide materials that offer a considerably larger specific (4200 mAh g-1 and 994 mAh g-1) and volumetric capacity than conventional carbonaceous materials. Such studies indicate that silicone monoxide, SiO, has a large discharge specific capacity. However, due to their serious volume change when charging and discharging, leading to fast capacity fading and poor cycle performance, it is a great impact to the material of its practical value. The composite of Si- and Sn-based compounds or alloys can effectively improve their cycling performance. In this work, we studied Si-SiOx-Sn/C composite which was prepared by thermal reduction method, and tested it as anode material for Li-ion battery. The composites were synthesized by heating the milled mixture of SiO, SnO2 and carbon in an inert gas filled furnace. The effects of temperature, electrochemical properties and impedance were researched, and the results were as follows:
1. Si-SiOx-Sn/C composites were prepared in following steps:the mixture of SiO powder, carbon powder and Nano-SnO2 powder was milled in a planetary ball mill for 5 h. The milled composites were dispersed into the acetone solvent. The dried solid mixtures were heated to 750℃,800℃,850℃,900℃,950℃and 1000℃for 2 h respectively in a furnace tube under an inert atmosphere. The XRD results show that SnO2 can be reduced into Sn metal above 800℃, and silicon-mono-oxide is transformed into silicon and silicon dioxide (2SiO→Si+SiO2). Further results indicated that the composite heated at 900℃for 2 h is better in performance.
2. Charge and discharge measurements were carried out employing a two-electrode 2025 coin cell. Lithium metal was used as the counter electrode. When the composite was heated at 900℃for 2 h, the first discharge capacity of the composite anode can reach as high as 1144.2 mAh g-1 under a constant current density of 225 mA g-1.
3. Further results show that the first discharge capacity of the composite anode heated at 900℃for 2 h can reach 1144.2 mAh g-1、715.8 mAh g-1、359.0 mAh g-1 and 282.9 mAh g-1 under 0.5 C、1 C、5 C、10 C.
4. We researched the typical EIS Nyquist plots of composite anode heated at 900℃, after the first, third and 30 th cycles. The diameter of the semicircle becomes larger with the increase of cycle number, which indicates that the charge transfer reaction process becomes more difficult as charge and discharge cycles proceed. Increase of interface and particle contact resistance could be a cause of the capacity decay.
引文
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