锂离子电池层状复合正极材料的制备与改性
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摘要
锂离子电池具有输出电压高、能量密度高、循环寿命长、自放电率低等众多优点,因此其在便携式电子设备、移动通讯等领域获得广泛应用,并被认为是最有希望成为电动汽车大功率的动力电池。目前LiCoO_2仍占据锂离子电池正极材料市场的主导地位,但由于其自身缺陷及资源限制,迫切需要开发一种新型的正极材料。锂离子电池层状复合正极材料LiNi_xCo_yMn_(1-x-y)O_2具有价格低廉、结构稳定、比容量高等优点,这使它被认为是最佳的LiCoO_2替代品之一,但制备困难,振实密度低,高倍率放电性能差等缺点限制了其商品化的进程。因此,提高层状复合正极材料的振实密度以及电化学性能特别是其在高倍率充放电条件下的循环性能是相关科研工作者的研究目标。本文概述了锂离子电池及其正极材料的研究进展,重点介绍了层状正极材料LiNi_xCo_yMn_(1-x-y)O_2的研究现状,作者通过改进制备方法,优化材料中钴镍锰配比,元素体相掺杂以及表面包覆等手段实现了对锂离子电池层状正极材料LiNi_xCo_yMn_(1-x-y)O_2的改性。主要研究内容和实验结论包括以下几个方面:
首先,对层状材料LiNi_xCo_yMn_(1-x-y)O_2部分合成方法进行了工艺优化。使用低热固相法,溶胶凝胶法,水热法制备了正极材料LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2,利用X射线粉末晶体衍射(XRD) ,扫描电子显微镜(SEM)以及恒流充放电测试等手段分析了所得材料的微观结构,形貌以及电化学性能,确定了各方法的最优合成工艺,研究表明低热固相法中高温煅烧后600℃回火2h所得材料性能最优,溶胶凝胶法中以草酸为配体且配比是1:2时所得材料性能最优,水热法的最佳合成工艺为160℃水热反应12h。其次,对层状材料LiNi_xCo_yMn_(1-x-y)O_2进行了钴镍锰配比优化研究。使用优化的低热固相法,溶胶凝胶法,水热法等合成系列锂离子电池层状正极材料LiNi_xCo_(1-2x)Mn_xO_2 (x=n, n/9, n/10, n/11, n/12, n/13, n/14, n/15, n/16, n/17),采用X射线衍射等表征手段和充放电等电化学性能测试手段,实现各系列材料中钴镍锰配比的优化。结果表明,LiCo_(5/9)Ni_(2/9)Mn_(2/9)O_2,LiCo_(4/10)Ni_(3/10)Mn_(3/10)O_2,LiCo_(5/11)Ni_(3/11)Mn_(3/11)O_2等材料表现出优异的结构,形貌和电化学性能。
再次,对层状材料LiNi_xCo_yMn_(1-x-y)O_2进行了掺杂改性研究。使用各种合成方法制备材料LiNi_(1/3)Co_(1/3-y)Mn_(1/3)M_yO_2-zNz (M:一种或几种金属阳离子,N:一种或几种阴离子;y和z为0,0.01,0.02,0.04,0.06,0.08,0.10等不同配比),实现了在阳离子位置上(Co原子位置)掺入一种或几种金属阳离子(Al,Cr, Fe,Zr,La),或在阴离子位置上(氧原子位置)掺入一种或几种阴离子(F,Cl,Br),或在阴阳离子位置上共掺入一种或几种离子,研究了掺杂对其结构,形貌以及电化学性能的影响。结果表明,掺杂材料的结晶度和粒度的均匀性均有提高,掺杂材料的倍率性能和循环性能均有明显提升。
最后,对层状材料LiNi_xCo_yMn_(1-x-y)O_2进行了包覆改性研究。在正极材料LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2表面实现了C和Al2O3的单层和双层包覆,考察了包覆方法,包覆材料和包覆量对产物结构,形貌和电化学性能的影响。XRD,SEM和电化学性能测试等分析手段表明,适量的无机氧化物,单质等材料包覆可以降低极化度,改善材料的循环稳定性,倍率性能,进一步改善材料的电化学性能。
Lithium-ion batteries, with the advantages as high voltage, high energy density, good cycling property, low self discharge, have been widely used in mobile communication devices, portable electronics and military equipments. At the moment, LiCoO_2 still dominates the lithium-ion batteries cathode material market, but owing to its own shortcomings and resource constraints, there is an urgent need to develop a new cathode material. Due to its low cost, good structure stability, and high specific capacity, the layered multiple cathode material of LiNi_xCo_yMn_(1-x-y)O_2 has been regarded as one of the most promising alternative material for LiCoO_2. However, some problems, including hard to synthesize, low tap density and low rate capability, restrict the procedure of its commercial availability. The improvement of tap density and electrochemical properties, especially its cyclability at high rate, is the main research target of scientists. In this paper, the researches on lithium-ion batteries and its cathode material especially the layered cathode material LiNi_xCo_yMn_(1-x-y)O_2 in recent years were analyzed. Some modification method such as improved synthesis methods, doping and coating were carried out by author to improve the tap density and electrochemical performances of them. The main contents and results of this study were described below:
First of all, some synthesis methods for LiNi_xCo_yMn_(1-x-y)O_2 were mended. Cathode material powders of layered LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 were synthesized using the method of low-heat solid-state reaction, sol-gel method and hydrothermal method. The evolution of the structural properties and electrochemical performances of LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 were investigated by X-ray diffraction (XRD), scanning electronic microscopy (SEM) and galvanostatic charge and discharge cycle. It was found that the optimum parameters for temper of low-heat solid-state reaction technique were 600℃and 2h, the optimal chelating agent in sol-gel method was oxalic acid and the optimal ratio was 1:2, the optimum conditions for hydrothermal reaction was 160℃and 12h.
And secondly, the content ratios of Co, Ni, Mn of LiNi_xCo_yMn_(1-x-y)O_2 were optimized. Improved low-heat solid-state reaction method, sol-gel technique and hydrothermal method were used to prepare the several series of layered cathode material LiNixCo1-2xMnxO_2 (x=n, n/9, n/10, n/11, n/12, n/13, n/14, n/15, n/16, n/17) for lithium-ion batteries, the content ratio of Co, Ni, Mn of various series materials was ameliorated via XRD, SEM, galvanostatic charge and discharge test. The results implied that the materials LiCo_(5/9)Ni_(2/9)Mn_(2/9)O_2, LiCo_(4/10)Ni_(3/10)Mn_(3/10)O_2, LiCo5/11Ni3/11Mn3/11O_2 and so on exhibited outstanding structural properties and electrochemical performances.
Afterwards, LiNi_xCo_yMn_(1-x-y)O_2 materials were modified by doping. LiNi_(1/3)Co_(1/3-y)Mn_(1/3)M_yO_2-zNz were prepared using low-heat solid-state reaction method, sol-gel technique, hydrothermal method and so on, with one or more cation (Al, Cr, Fe, Zr, La) and/or anion (F, Cl, Br) doped in the cation (Co) and anion (O) site. The effects of doping on the structure, morphology and electrochemical performances were investigated. XRD tests exhibited that the formation of moliclinic structure improved. SEM results implied the uniformity of particles size was increased. The charge-discharge tests showed that the appropriate doping could greatly improve the performances of the as-prepared materials in rate ability and cycle capability.
Finally, the layered LiNi_xCo_yMn_(1-x-y)O_2 materials were modified via surface coating. Cathode materials LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 were coated with C and Al2O3. The effects of method, raw material and amount on the structure, morphology and electrochemical performances were investigated. The XRD, SEM and electrochemical evaluation results showed that coating with proper amount of inorganic oxide and elemental could reduce the polarization, improve cyclic stability and high-rate ability of material.
首先,对层状材料LiNi_xCo_yMn_(1-x-y)O_2部分合成方法进行了工艺优化。使用低热固相法,溶胶凝胶法,水热法制备了正极材料LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2,利用X射线粉末晶体衍射(XRD) ,扫描电子显微镜(SEM)以及恒流充放电测试等手段分析了所得材料的微观结构,形貌以及电化学性能,确定了各方法的最优合成工艺,研究表明低热固相法中高温煅烧后600℃回火2h所得材料性能最优,溶胶凝胶法中以草酸为配体且配比是1:2时所得材料性能最优,水热法的最佳合成工艺为160℃水热反应12h。其次,对层状材料LiNi_xCo_yMn_(1-x-y)O_2进行了钴镍锰配比优化研究。使用优化的低热固相法,溶胶凝胶法,水热法等合成系列锂离子电池层状正极材料LiNi_xCo_(1-2x)Mn_xO_2 (x=n, n/9, n/10, n/11, n/12, n/13, n/14, n/15, n/16, n/17),采用X射线衍射等表征手段和充放电等电化学性能测试手段,实现各系列材料中钴镍锰配比的优化。结果表明,LiCo_(5/9)Ni_(2/9)Mn_(2/9)O_2,LiCo_(4/10)Ni_(3/10)Mn_(3/10)O_2,LiCo_(5/11)Ni_(3/11)Mn_(3/11)O_2等材料表现出优异的结构,形貌和电化学性能。
再次,对层状材料LiNi_xCo_yMn_(1-x-y)O_2进行了掺杂改性研究。使用各种合成方法制备材料LiNi_(1/3)Co_(1/3-y)Mn_(1/3)M_yO_2-zNz (M:一种或几种金属阳离子,N:一种或几种阴离子;y和z为0,0.01,0.02,0.04,0.06,0.08,0.10等不同配比),实现了在阳离子位置上(Co原子位置)掺入一种或几种金属阳离子(Al,Cr, Fe,Zr,La),或在阴离子位置上(氧原子位置)掺入一种或几种阴离子(F,Cl,Br),或在阴阳离子位置上共掺入一种或几种离子,研究了掺杂对其结构,形貌以及电化学性能的影响。结果表明,掺杂材料的结晶度和粒度的均匀性均有提高,掺杂材料的倍率性能和循环性能均有明显提升。
最后,对层状材料LiNi_xCo_yMn_(1-x-y)O_2进行了包覆改性研究。在正极材料LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2表面实现了C和Al2O3的单层和双层包覆,考察了包覆方法,包覆材料和包覆量对产物结构,形貌和电化学性能的影响。XRD,SEM和电化学性能测试等分析手段表明,适量的无机氧化物,单质等材料包覆可以降低极化度,改善材料的循环稳定性,倍率性能,进一步改善材料的电化学性能。
Lithium-ion batteries, with the advantages as high voltage, high energy density, good cycling property, low self discharge, have been widely used in mobile communication devices, portable electronics and military equipments. At the moment, LiCoO_2 still dominates the lithium-ion batteries cathode material market, but owing to its own shortcomings and resource constraints, there is an urgent need to develop a new cathode material. Due to its low cost, good structure stability, and high specific capacity, the layered multiple cathode material of LiNi_xCo_yMn_(1-x-y)O_2 has been regarded as one of the most promising alternative material for LiCoO_2. However, some problems, including hard to synthesize, low tap density and low rate capability, restrict the procedure of its commercial availability. The improvement of tap density and electrochemical properties, especially its cyclability at high rate, is the main research target of scientists. In this paper, the researches on lithium-ion batteries and its cathode material especially the layered cathode material LiNi_xCo_yMn_(1-x-y)O_2 in recent years were analyzed. Some modification method such as improved synthesis methods, doping and coating were carried out by author to improve the tap density and electrochemical performances of them. The main contents and results of this study were described below:
First of all, some synthesis methods for LiNi_xCo_yMn_(1-x-y)O_2 were mended. Cathode material powders of layered LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 were synthesized using the method of low-heat solid-state reaction, sol-gel method and hydrothermal method. The evolution of the structural properties and electrochemical performances of LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 were investigated by X-ray diffraction (XRD), scanning electronic microscopy (SEM) and galvanostatic charge and discharge cycle. It was found that the optimum parameters for temper of low-heat solid-state reaction technique were 600℃and 2h, the optimal chelating agent in sol-gel method was oxalic acid and the optimal ratio was 1:2, the optimum conditions for hydrothermal reaction was 160℃and 12h.
And secondly, the content ratios of Co, Ni, Mn of LiNi_xCo_yMn_(1-x-y)O_2 were optimized. Improved low-heat solid-state reaction method, sol-gel technique and hydrothermal method were used to prepare the several series of layered cathode material LiNixCo1-2xMnxO_2 (x=n, n/9, n/10, n/11, n/12, n/13, n/14, n/15, n/16, n/17) for lithium-ion batteries, the content ratio of Co, Ni, Mn of various series materials was ameliorated via XRD, SEM, galvanostatic charge and discharge test. The results implied that the materials LiCo_(5/9)Ni_(2/9)Mn_(2/9)O_2, LiCo_(4/10)Ni_(3/10)Mn_(3/10)O_2, LiCo5/11Ni3/11Mn3/11O_2 and so on exhibited outstanding structural properties and electrochemical performances.
Afterwards, LiNi_xCo_yMn_(1-x-y)O_2 materials were modified by doping. LiNi_(1/3)Co_(1/3-y)Mn_(1/3)M_yO_2-zNz were prepared using low-heat solid-state reaction method, sol-gel technique, hydrothermal method and so on, with one or more cation (Al, Cr, Fe, Zr, La) and/or anion (F, Cl, Br) doped in the cation (Co) and anion (O) site. The effects of doping on the structure, morphology and electrochemical performances were investigated. XRD tests exhibited that the formation of moliclinic structure improved. SEM results implied the uniformity of particles size was increased. The charge-discharge tests showed that the appropriate doping could greatly improve the performances of the as-prepared materials in rate ability and cycle capability.
Finally, the layered LiNi_xCo_yMn_(1-x-y)O_2 materials were modified via surface coating. Cathode materials LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 were coated with C and Al2O3. The effects of method, raw material and amount on the structure, morphology and electrochemical performances were investigated. The XRD, SEM and electrochemical evaluation results showed that coating with proper amount of inorganic oxide and elemental could reduce the polarization, improve cyclic stability and high-rate ability of material.
引文
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