机械活化—碳热还原法LiFePO_4/C材料的制备、结构与性能
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摘要
橄榄石型的LiFePO4用作锂离子二次电池正极材料具有工作电压稳、容量较高、结构稳定、高温性能和循环性能好、安全无毒以及成本低廉等优点,已成为国内外的研究热点。但是目前LiFePO4实用化生产所需要解决的3个问题是：(1)找到一种低成本,规模化生产的制备方法；(2)大幅度改善LiFePO4的导电性；(3)有效的控制LiFePO4的粒径分布和表面形貌,提高其填充密度。相对于其它制备方法,碳热还原法由于其具有低成本、工艺简单的优点,被认为是最有望实现产业化的制备方法。然而,碳热还原法在高温下制备时颗粒容易聚集长大,粒径大小不容易控制,从而大大地影响了其产业化发展的进程。本文在传统的机械球磨的基础上,采用机械活化法与碳热还原法相结合制备了LiFePO4/C复合材料,研究了前驱体的机械活化工艺(球料比、球磨介质、球磨气氛、球磨温度和时间等)对LiFePO4/C复合材料颗粒尺寸及电性能的影响,并系统的考察了原料配比、煅烧温度、煅烧时间、升温速率等工艺条件对LiFePO4正极材料晶体结构、表观形貌及电化学性能的影响。主要研究工作的结论如下：
(1)研究了前驱体的机械活化工艺(球料比、球磨介质、球磨气氛、球磨温度和时间等)对LiFePO4/C复合材料颗粒尺寸及电性能的影响。结果表明,球料比为6：1的机械活化工艺所制备的LiFePO4/C的颗粒细小均匀,平均粒径约为500nm,其1C首次放电比容量最优,达到134mAh/g,循环20次后容量保持率为99.2%；利用玛瑙球磨罐球磨所制LiFePO4/C材料为类球形,颗粒粒径较小,平均粒径约500-600nm,1 C首次放电比容量达到136mAh/g,循环20次后容量保持率为99%；在氩气气氛保护下的前驱体机械活化工艺制备的样品的含碳量最高(5.27%),比表面积最大(30.452m2／g),其1C首次放电比容量为132mAh/g,循环20次后容量保持率为99.3%；在25℃下球磨6h所制备的LiFePO4/C的比表面积达29.152m2／g,其1 C首次放电比容量可达136mAh/g,循环20次后容量保持率为98.9%。
(2)研究了合成条件(煅烧温度、煅烧时间、原料配比和升温速率)对材料的粒径分布、颗粒形貌、晶体结构以及电性能的影响。研究结果表明,随着煅烧温度的增加,LiFePO4/C材料的放电比容量和循环性能先增加后减小,其中煅烧温度为650。C所制备的LiFePO4/C材料同时具有较小的颗粒尺寸和较高的结晶度,其1C充放电倍率下的首次放电比容量达到138mAh·g-1,循环20次后放电比容量为138.6mAh／g,容量保持率为99.7%；随着煅烧时间的增加,LiFePO4/C材料的放电比容量和循环性能呈现先增加后减小的趋势。其中煅烧时间为12h所制备的LiFePO4/C材料具有较小的颗粒尺寸(400nm左右)和较高的结晶度,其1C充放电倍率下的首次放电比容量达到137mAh·g-1,循环20次后放电比容量为136.2mAh/g,容量保持率分别为99.4%；当原料中Li、Fe和P的物质的量比为1.02：1：1时,所合成的材料具有较高的放电比容量(137mAh.g-1)和最高的放电平台(3.36V),循环20次以后,放电比容量为134.6mAh/g,容量保持率为99%；升温速率为2℃／min所制备的LiFePO4/C材料具有最优的放电比容量和最高的库仑效率,其1C充放电倍率下的首次放电比容量为134.6mAh·g-1;在最佳工艺、配比条件下所制备的LiFePO4/C材料在0.1C充放电倍率下首次放电比容量为158.7mAh/g。其在0.2C、0.5C、1.0C和2.0C倍率放电下,首次放电比容量分别为150.9mAh/g、143.2mAh/g、135.9mAh/g和128.8mAh/g,分别相当于0.1C容量的95.1%、90.2%、85.6%和81.1%。经过20次循环后,其1C和2C倍率的放电比容量分别为137.6mAh/g和126mAh/g,容量保持率高达99.6%和98.3%,具有良好的倍率性能和循环性能。
Olivine-type LiFePO4 have been known as an interesting cathode material for lithium ion batteries due to its flat potential plateau, high thermal and chemical stability and high specific capability, as well as good cycle performance, non-toxicity and low cost. However, there are three main things to do to put LiFePO4 into commercially used. The first one is to find a low-cost preparation method which could be large-scale produced. The second one is to find an effective way to improve its ion and electrochemical conductivity. The third one is to synthesize fine and homogeneous particle sizes of LiFePO4 and improve its tap-density. Compared with other synthesis techniques, CTR (carbothermal reduction method) is the most promising method for industry producing with its low cost and simple process. However, the hard-controlled particle size during the calcination at high temperatures makes it an obstacle for its practical applications. In this paper, LiFePO4/C composite cathode materials have been synthesized by mechanical activation combined with carbothermal reduction method. The influences of parameters of mechanical activation (ball-to-power weight ratio, milling media, the atmosphere, temperature and time of ball-milling) on the structure and performance of the material were investigated. The structure, morphology and electrochemical properties of LiFePO4/C prepared at different temperature, time, proportion ratio and heating rate were also studied. The main results and conclusions were listed as following:
(1) Studied the processing conditions of the precursor including ball-to-power weight ratio, milling media, the atmosphere, temperature and time of ball-milling on the performance of the prepared LiFePO4/C. The result indicated that, LiFePO4/C having an average particle size of about 500nm can be prepared by ball-milling the forerunner with ball-to-powder ration at 6:1, and the powder exhibits a capacity of 134mAh/g at 1C rate. The cycling retention rate of it after 20 cycles was about 99.2% of its maximum capacity. LiFePO4/C material prepared by ball-milling the precursor in agate tank are spherical with average particle size of about 500-600nm. The discharge capacity of it reaches 134mAh/g at 1C rate and the capacity retention after 20 cycles is 99%. LiFePO4/C material prepared by ball-milling the precursor in Ar atmosphere with the highest specific surface area of 30.452m2/g and carbon content of 5.27% has an excellent discharge capacity of 132mAh/g at 1C rate. LiFePO4/C material prepared by ball-milling the precursor at 25℃for 6h can deliver 136mAh/g of reversible capacity at 1C rate with a low capacity fading after 20 cycles.
(2) Studied the allocated proportion of the precursor (FePO4 and Li2CO3), calcining temperature, the calcine time and heating rate on the performance of the prepared LiFePO4/C. The result indicated that increasing the sintering temperature and extending sintering time resulted in higher crystallinity but a larger particle size. In the range of 600～750℃and 6～24h, 650℃and 12h are the optimum synthetic temperature and sintering time for the LiFePO4/C with small particle sizes and perfect crystal. The specific discharge capacity reaches as high as 138mAh/g at 1C rate. When the raw material mole ratio (nLi:nFe:nP) is 1.02:1:1, the LiFePO4/C showed the highest potential plateau at 3.36V and the best capacity of 137mAh/g at 1C rate with capacity retention of 99% after 20 cycles. When the heating rate is 2℃/min, LiFePO4/C reaches the best specific discharge capacity and Coulomb's efficiency with 134.6mAh/g at 1C rate In the present case, LiFePO4/C synthesized at 650℃for 12h with raw material mole ratio (nLi:nFe:nP) of 1.02:1:1 and heating rate of 2℃/min shows best electrochemical performances. Under this condition, the obtained LiFePO4/C shows an initial discharge capacity of 158.7 mAh/g,150.9.2 mAh/g,143.2mAh/g and 135.9mAh/g at 0.1C, 0.2C,0.5C and 1.0C rate, respectively. After 20 cycles, the composite cathode retains 99.6% and 98.3% of the first cycle discharge capacity at 1.0C and 2C, respectively.
(1)研究了前驱体的机械活化工艺(球料比、球磨介质、球磨气氛、球磨温度和时间等)对LiFePO4/C复合材料颗粒尺寸及电性能的影响。结果表明,球料比为6：1的机械活化工艺所制备的LiFePO4/C的颗粒细小均匀,平均粒径约为500nm,其1C首次放电比容量最优,达到134mAh/g,循环20次后容量保持率为99.2%；利用玛瑙球磨罐球磨所制LiFePO4/C材料为类球形,颗粒粒径较小,平均粒径约500-600nm,1 C首次放电比容量达到136mAh/g,循环20次后容量保持率为99%；在氩气气氛保护下的前驱体机械活化工艺制备的样品的含碳量最高(5.27%),比表面积最大(30.452m2／g),其1C首次放电比容量为132mAh/g,循环20次后容量保持率为99.3%；在25℃下球磨6h所制备的LiFePO4/C的比表面积达29.152m2／g,其1 C首次放电比容量可达136mAh/g,循环20次后容量保持率为98.9%。
(2)研究了合成条件(煅烧温度、煅烧时间、原料配比和升温速率)对材料的粒径分布、颗粒形貌、晶体结构以及电性能的影响。研究结果表明,随着煅烧温度的增加,LiFePO4/C材料的放电比容量和循环性能先增加后减小,其中煅烧温度为650。C所制备的LiFePO4/C材料同时具有较小的颗粒尺寸和较高的结晶度,其1C充放电倍率下的首次放电比容量达到138mAh·g-1,循环20次后放电比容量为138.6mAh／g,容量保持率为99.7%；随着煅烧时间的增加,LiFePO4/C材料的放电比容量和循环性能呈现先增加后减小的趋势。其中煅烧时间为12h所制备的LiFePO4/C材料具有较小的颗粒尺寸(400nm左右)和较高的结晶度,其1C充放电倍率下的首次放电比容量达到137mAh·g-1,循环20次后放电比容量为136.2mAh/g,容量保持率分别为99.4%；当原料中Li、Fe和P的物质的量比为1.02：1：1时,所合成的材料具有较高的放电比容量(137mAh.g-1)和最高的放电平台(3.36V),循环20次以后,放电比容量为134.6mAh/g,容量保持率为99%；升温速率为2℃／min所制备的LiFePO4/C材料具有最优的放电比容量和最高的库仑效率,其1C充放电倍率下的首次放电比容量为134.6mAh·g-1;在最佳工艺、配比条件下所制备的LiFePO4/C材料在0.1C充放电倍率下首次放电比容量为158.7mAh/g。其在0.2C、0.5C、1.0C和2.0C倍率放电下,首次放电比容量分别为150.9mAh/g、143.2mAh/g、135.9mAh/g和128.8mAh/g,分别相当于0.1C容量的95.1%、90.2%、85.6%和81.1%。经过20次循环后,其1C和2C倍率的放电比容量分别为137.6mAh/g和126mAh/g,容量保持率高达99.6%和98.3%,具有良好的倍率性能和循环性能。
Olivine-type LiFePO4 have been known as an interesting cathode material for lithium ion batteries due to its flat potential plateau, high thermal and chemical stability and high specific capability, as well as good cycle performance, non-toxicity and low cost. However, there are three main things to do to put LiFePO4 into commercially used. The first one is to find a low-cost preparation method which could be large-scale produced. The second one is to find an effective way to improve its ion and electrochemical conductivity. The third one is to synthesize fine and homogeneous particle sizes of LiFePO4 and improve its tap-density. Compared with other synthesis techniques, CTR (carbothermal reduction method) is the most promising method for industry producing with its low cost and simple process. However, the hard-controlled particle size during the calcination at high temperatures makes it an obstacle for its practical applications. In this paper, LiFePO4/C composite cathode materials have been synthesized by mechanical activation combined with carbothermal reduction method. The influences of parameters of mechanical activation (ball-to-power weight ratio, milling media, the atmosphere, temperature and time of ball-milling) on the structure and performance of the material were investigated. The structure, morphology and electrochemical properties of LiFePO4/C prepared at different temperature, time, proportion ratio and heating rate were also studied. The main results and conclusions were listed as following:
(1) Studied the processing conditions of the precursor including ball-to-power weight ratio, milling media, the atmosphere, temperature and time of ball-milling on the performance of the prepared LiFePO4/C. The result indicated that, LiFePO4/C having an average particle size of about 500nm can be prepared by ball-milling the forerunner with ball-to-powder ration at 6:1, and the powder exhibits a capacity of 134mAh/g at 1C rate. The cycling retention rate of it after 20 cycles was about 99.2% of its maximum capacity. LiFePO4/C material prepared by ball-milling the precursor in agate tank are spherical with average particle size of about 500-600nm. The discharge capacity of it reaches 134mAh/g at 1C rate and the capacity retention after 20 cycles is 99%. LiFePO4/C material prepared by ball-milling the precursor in Ar atmosphere with the highest specific surface area of 30.452m2/g and carbon content of 5.27% has an excellent discharge capacity of 132mAh/g at 1C rate. LiFePO4/C material prepared by ball-milling the precursor at 25℃for 6h can deliver 136mAh/g of reversible capacity at 1C rate with a low capacity fading after 20 cycles.
(2) Studied the allocated proportion of the precursor (FePO4 and Li2CO3), calcining temperature, the calcine time and heating rate on the performance of the prepared LiFePO4/C. The result indicated that increasing the sintering temperature and extending sintering time resulted in higher crystallinity but a larger particle size. In the range of 600～750℃and 6～24h, 650℃and 12h are the optimum synthetic temperature and sintering time for the LiFePO4/C with small particle sizes and perfect crystal. The specific discharge capacity reaches as high as 138mAh/g at 1C rate. When the raw material mole ratio (nLi:nFe:nP) is 1.02:1:1, the LiFePO4/C showed the highest potential plateau at 3.36V and the best capacity of 137mAh/g at 1C rate with capacity retention of 99% after 20 cycles. When the heating rate is 2℃/min, LiFePO4/C reaches the best specific discharge capacity and Coulomb's efficiency with 134.6mAh/g at 1C rate In the present case, LiFePO4/C synthesized at 650℃for 12h with raw material mole ratio (nLi:nFe:nP) of 1.02:1:1 and heating rate of 2℃/min shows best electrochemical performances. Under this condition, the obtained LiFePO4/C shows an initial discharge capacity of 158.7 mAh/g,150.9.2 mAh/g,143.2mAh/g and 135.9mAh/g at 0.1C, 0.2C,0.5C and 1.0C rate, respectively. After 20 cycles, the composite cathode retains 99.6% and 98.3% of the first cycle discharge capacity at 1.0C and 2C, respectively.
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