锂离子电池正极材料LiNi_(0.5)Mn_(1.5)O_4的制备及改性研究
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摘要
动力锂离子电池的开发对电池的比能量、寿命、安全性提出了更高的要求。尖晶石LiNio.5Mn1.5O4具有高电压、高功率、低成本等优势,引起很多科研工作者的兴趣。目前,限制该材料应用的主要因素是其高压下氧化分解电解液严重,导致高倍率下循环稳定性不佳。本文以改善LiNio.5Mn1.5O4高倍率下循环性为目标,研究了LiNio.5Mn1.5O4高温固相合成中煅烧温度对容量和倍率性能的影响,然后分别通过F掺杂、Cr与F复合掺杂、Co与F复合掺杂对LiNio.5Mn1.5O4进行了改性研究,取得如下主要创新性成果：
煅烧温度对LiNio.5Mn1.5O4放电容量和倍率性能的影响研究结果显示,800℃-900℃煅烧所制样品均具有较理想的尖晶石结构。随着煅烧温度的升高,样品的晶粒不断长大,0.2C倍率下的放电初始容量呈下降趋势,800℃煅烧所制样品的容量最高,可达129.1mAh·g-1。然而,1C-5C高倍率循环时,900℃所制样品的容量较高,2C放电容量达100.8mAh·g-1。随着煅烧温度的升高,晶粒增大,电解液分解受到一定抑制,Mn3+含量提高,降低了LiNio.5Mn1.5O4的膜电阻和电荷传递阻抗,这是改善LiNio.5Mn1.5O4样品高倍率循环性能的原因。然而,由于增大了锂离子扩散路径,导致其初始容量下降,高倍率下的容量改善程度不是太大。
F掺杂改性研究结果显示,800℃-900℃煅烧所制LiNi0.5Mn1.5O4-xFx样品均为较理想的尖晶石结构,F掺杂可抑制杂质相NiO或LixNi1-xO的生成。F掺杂量和煅烧温度是影响样品晶粒发育、颗粒形貌与大小、电性能的两个主要因素。850℃煅烧所制F掺杂量x=0.05样品晶粒发育完善、颗粒大小适中且均匀,抑制电解液氧化分解效果好,具有最小的膜阻抗和电荷传递阻抗,显著改善倍率循环稳定性。该样品0.2C放电容量为125mAh·g-1左右；0.2C、0.5C、1C、2C各循环10轮后,容量仍保持在120 mAh·g-1左右。过高温度和过多F离子掺杂使得样品烧结过度而形成较大的异形颗粒,对电性能不利。
首次对LiNi0.5Mn1.5O4进行了Cr与F复合掺杂改性研究,结果显示,800℃-900℃煅烧所制LiNi0.5Mn1.5-xCrxO4-xFx均为较理想的尖晶石结构,NiO或LixNi1-xO杂相峰基本消失。800℃、850℃煅烧温度下,复合掺杂样品可有效抑制电解液氧化分解,使得膜阻抗和电荷传递阻抗都明显下降,倍率性能有了明显改善。其中,850℃煅烧所制Cr、F掺杂量为0.025的样品颗粒分布均匀,形态清晰,晶粒生长趋于完整,具有最小的电化学阻抗,电性能最佳,其0.2C的放电容量为124.1 mAh·g-,经0.2C、0.5C、1C、2C各循环10轮后的容量仍保持在120 mAh·g-1左右。而900℃煅烧时晶粒熔融烧结长大严重,所制样品性能无改善。
首次对LiNio.5Mn1.5O4进行了Co与F复合掺杂改性研究,结果显示,800℃-900℃煅烧所制LiNi0.5Mn1.5-xCoxO4-xFx也为较纯的尖晶石结构,几乎没有LixNi1-xO、NiO等杂相的生成。掺杂对产品颗粒形貌影响甚小。相比未掺杂样品,800℃下所制掺杂量x=0.04的样品阻抗有所降低,其0.2C倍率下放电容量达132.4mAh·g-1,倍率循环性能有所改善,但效果不是很显著。随着Co、F复合掺杂量增大,对高压下电解液分解的加速作用增大,其电荷传递阻抗和膜阻抗呈增加趋势,电池内阻增大,电性能恶化。
对比以上三种改性手段的效果,对LiNi0.5Mn1.5O4进行F掺杂或Cr与F复合掺杂,通过优化煅烧温度和掺杂量,可以制备得到晶粒发育完善、颗粒大小适中且均匀,抑制电解液分解效果好,膜阻抗和电荷传递阻抗小的改性材料,从而显著改善高倍率循环性能。
Rapid development of EV or HEV requests high power Li-ion batteries (LIBs) to have higher energy, longer life and better safety than before. Recently, spinel LiNi0.5Mn1.5O4 attracts more attention of many researchers due to its lower cost, higher voltage and rate capability. However, severer electrolyte decomposition on higher voltage leads to unsatisfactory cycling stability at high rate, which limits its use. In order to improve the rate cycling capability of LiNi0.5Mn1.5O4,the effects of annealing temperature on the capacity and rate capability of LiNio.5Mn1.5O4 were studied, and modification of LiNi0.5Mn1.5O4 by F-doping, Cr- and F- co-doping, Co- and F- co-doping were investigated in this paper.
The effects of annealing temperatures on capacity and rate capability of LiNio.5Mn1.5O4 were investigated. The results show that the all samples prepared at 800℃～900℃showed better spinel structure. With increasing the temperatures, the crystal particles grew gradually, but the initial discharge capacity at 0.2C decreased. The sample prepared at 800℃showed the highest capacity of 129.1 mAh·g-1. However when discharged at 1C～5C, the sample prepared at 900℃exhibited higher capacity. Its capacity reached 100.8 mAh·g-1 at 2C. Increasing annealing temperatures made crystal particles grow bigger, the electrolyte decomposition reduce and the Mn3+ content increase, which reduced the film impedance and charge transfer impedance, and then improved the rate capability of LiNio.5Mn1.5O4. However, the improvement was limited due to the enlarged Li+ diffusion path and decrease of initial capacity.
The studies on the modification of LiNi0.5Mn1.5O4 by F-doping show that all LiNi0.5Mn1.5O4-xFx samples prepared at 800℃～900℃showed better spinel structure. F-doping can reduce the impure phase NiO or LixNi1-xO. The doped F amount and annealing temperatures were two major factors affecting the crystal particles growth, morphology and electrochemical properties of samples. The sample with x=0.05 prepared at 850℃revealed better crystalline morphology, suitable particle size distribution, better reduce of electrolyte decomposition, the smallest film impedance and charge transfer impedance, leading to remarkable improvement of rate capability. Its capacity reached about 125 mAh·g-1 at 0.2C, and retained at about 120 mAh·g-1 after charge-discharged at 0.2C,0.5C,1C and 2C each 10 cycles. Too high annealing temperatures and too more doped F made the sample agglomerate seriously to form too big particles, and then deteriorate its electrochemical performance.
The investigation of Cr- and F- co-doped LiNio.5Mn1.5O4 has been carried out first to our knowledge. The results show that all LiNio.5Mn1.5-xCrxO4-xFx samples prepared at 800℃～900℃showed better spinel structure. Impure phase NiO or LixNi1-xO was not observed. The co-doped samples prepared at 800℃and 850℃exhibited effective reducing electrolyte decomposition, leading to remarkable decrease of film impedance and charge transfer impedance, and then improving the rate capability significantly. Among the samples, the sample with x=0.025 prepared at 850℃showed uniform particle size, better crystalline morphology, the smallest electrochemical impedance and the best electrochemical performance. Its capacity reached about 124.1 mAh·g-1 at 0.2C, and retained at about 120 mAh·g-1 after charge-discharged at 0.2C,0.5C,1C and 2C each 10 cycles. Annealing at 900℃made the sample agglomerate seriously to form too big particles, and then deteriorate its electrochemical performance.
The effects of Co- and F- co-doping on the electrochemical performance of LiNi0.5Mn1.5O4 also have been investigated first to our knowledge. The results show that all LiNi0.5Mn1.5-xCoxO4-xFx samples prepared at 800℃～900℃displayed better spinel structure. No NiO or LixNi1-xO impure phase was formed. Co-doping had little effect on the particle morphology of samples. Compared with base sample, the co-doped sample with x=0.04 prepareed at 800℃showed a little decreased impedance and smaller improved rate capability. Its discharge capacity reached 132.4mAh·g-1 at 0.2C. However, increasing the co-doped ion amount accelerated the electrolyte decomposition, enhanced the film impedance and charge transfer impedance, leading to deterioration of electrochemical performance.
Based on above results, it is concluded that modification of LiNi0.5Mn1.5O4 by F-doping or Cr-and F- co-doping can improve rate capability remarkably. In the cases, optimizing the annealing temperatures and doped ion amounts can make sure to prepare modified higher rate LiNi0.5Mn1.5O4 with well crystalline, uniform particle size distribution, better reduce of electrolyte decomposition and smaller film impedance and charge transfer impedance.
煅烧温度对LiNio.5Mn1.5O4放电容量和倍率性能的影响研究结果显示,800℃-900℃煅烧所制样品均具有较理想的尖晶石结构。随着煅烧温度的升高,样品的晶粒不断长大,0.2C倍率下的放电初始容量呈下降趋势,800℃煅烧所制样品的容量最高,可达129.1mAh·g-1。然而,1C-5C高倍率循环时,900℃所制样品的容量较高,2C放电容量达100.8mAh·g-1。随着煅烧温度的升高,晶粒增大,电解液分解受到一定抑制,Mn3+含量提高,降低了LiNio.5Mn1.5O4的膜电阻和电荷传递阻抗,这是改善LiNio.5Mn1.5O4样品高倍率循环性能的原因。然而,由于增大了锂离子扩散路径,导致其初始容量下降,高倍率下的容量改善程度不是太大。
F掺杂改性研究结果显示,800℃-900℃煅烧所制LiNi0.5Mn1.5O4-xFx样品均为较理想的尖晶石结构,F掺杂可抑制杂质相NiO或LixNi1-xO的生成。F掺杂量和煅烧温度是影响样品晶粒发育、颗粒形貌与大小、电性能的两个主要因素。850℃煅烧所制F掺杂量x=0.05样品晶粒发育完善、颗粒大小适中且均匀,抑制电解液氧化分解效果好,具有最小的膜阻抗和电荷传递阻抗,显著改善倍率循环稳定性。该样品0.2C放电容量为125mAh·g-1左右；0.2C、0.5C、1C、2C各循环10轮后,容量仍保持在120 mAh·g-1左右。过高温度和过多F离子掺杂使得样品烧结过度而形成较大的异形颗粒,对电性能不利。
首次对LiNi0.5Mn1.5O4进行了Cr与F复合掺杂改性研究,结果显示,800℃-900℃煅烧所制LiNi0.5Mn1.5-xCrxO4-xFx均为较理想的尖晶石结构,NiO或LixNi1-xO杂相峰基本消失。800℃、850℃煅烧温度下,复合掺杂样品可有效抑制电解液氧化分解,使得膜阻抗和电荷传递阻抗都明显下降,倍率性能有了明显改善。其中,850℃煅烧所制Cr、F掺杂量为0.025的样品颗粒分布均匀,形态清晰,晶粒生长趋于完整,具有最小的电化学阻抗,电性能最佳,其0.2C的放电容量为124.1 mAh·g-,经0.2C、0.5C、1C、2C各循环10轮后的容量仍保持在120 mAh·g-1左右。而900℃煅烧时晶粒熔融烧结长大严重,所制样品性能无改善。
首次对LiNio.5Mn1.5O4进行了Co与F复合掺杂改性研究,结果显示,800℃-900℃煅烧所制LiNi0.5Mn1.5-xCoxO4-xFx也为较纯的尖晶石结构,几乎没有LixNi1-xO、NiO等杂相的生成。掺杂对产品颗粒形貌影响甚小。相比未掺杂样品,800℃下所制掺杂量x=0.04的样品阻抗有所降低,其0.2C倍率下放电容量达132.4mAh·g-1,倍率循环性能有所改善,但效果不是很显著。随着Co、F复合掺杂量增大,对高压下电解液分解的加速作用增大,其电荷传递阻抗和膜阻抗呈增加趋势,电池内阻增大,电性能恶化。
对比以上三种改性手段的效果,对LiNi0.5Mn1.5O4进行F掺杂或Cr与F复合掺杂,通过优化煅烧温度和掺杂量,可以制备得到晶粒发育完善、颗粒大小适中且均匀,抑制电解液分解效果好,膜阻抗和电荷传递阻抗小的改性材料,从而显著改善高倍率循环性能。
Rapid development of EV or HEV requests high power Li-ion batteries (LIBs) to have higher energy, longer life and better safety than before. Recently, spinel LiNi0.5Mn1.5O4 attracts more attention of many researchers due to its lower cost, higher voltage and rate capability. However, severer electrolyte decomposition on higher voltage leads to unsatisfactory cycling stability at high rate, which limits its use. In order to improve the rate cycling capability of LiNi0.5Mn1.5O4,the effects of annealing temperature on the capacity and rate capability of LiNio.5Mn1.5O4 were studied, and modification of LiNi0.5Mn1.5O4 by F-doping, Cr- and F- co-doping, Co- and F- co-doping were investigated in this paper.
The effects of annealing temperatures on capacity and rate capability of LiNio.5Mn1.5O4 were investigated. The results show that the all samples prepared at 800℃～900℃showed better spinel structure. With increasing the temperatures, the crystal particles grew gradually, but the initial discharge capacity at 0.2C decreased. The sample prepared at 800℃showed the highest capacity of 129.1 mAh·g-1. However when discharged at 1C～5C, the sample prepared at 900℃exhibited higher capacity. Its capacity reached 100.8 mAh·g-1 at 2C. Increasing annealing temperatures made crystal particles grow bigger, the electrolyte decomposition reduce and the Mn3+ content increase, which reduced the film impedance and charge transfer impedance, and then improved the rate capability of LiNio.5Mn1.5O4. However, the improvement was limited due to the enlarged Li+ diffusion path and decrease of initial capacity.
The studies on the modification of LiNi0.5Mn1.5O4 by F-doping show that all LiNi0.5Mn1.5O4-xFx samples prepared at 800℃～900℃showed better spinel structure. F-doping can reduce the impure phase NiO or LixNi1-xO. The doped F amount and annealing temperatures were two major factors affecting the crystal particles growth, morphology and electrochemical properties of samples. The sample with x=0.05 prepared at 850℃revealed better crystalline morphology, suitable particle size distribution, better reduce of electrolyte decomposition, the smallest film impedance and charge transfer impedance, leading to remarkable improvement of rate capability. Its capacity reached about 125 mAh·g-1 at 0.2C, and retained at about 120 mAh·g-1 after charge-discharged at 0.2C,0.5C,1C and 2C each 10 cycles. Too high annealing temperatures and too more doped F made the sample agglomerate seriously to form too big particles, and then deteriorate its electrochemical performance.
The investigation of Cr- and F- co-doped LiNio.5Mn1.5O4 has been carried out first to our knowledge. The results show that all LiNio.5Mn1.5-xCrxO4-xFx samples prepared at 800℃～900℃showed better spinel structure. Impure phase NiO or LixNi1-xO was not observed. The co-doped samples prepared at 800℃and 850℃exhibited effective reducing electrolyte decomposition, leading to remarkable decrease of film impedance and charge transfer impedance, and then improving the rate capability significantly. Among the samples, the sample with x=0.025 prepared at 850℃showed uniform particle size, better crystalline morphology, the smallest electrochemical impedance and the best electrochemical performance. Its capacity reached about 124.1 mAh·g-1 at 0.2C, and retained at about 120 mAh·g-1 after charge-discharged at 0.2C,0.5C,1C and 2C each 10 cycles. Annealing at 900℃made the sample agglomerate seriously to form too big particles, and then deteriorate its electrochemical performance.
The effects of Co- and F- co-doping on the electrochemical performance of LiNi0.5Mn1.5O4 also have been investigated first to our knowledge. The results show that all LiNi0.5Mn1.5-xCoxO4-xFx samples prepared at 800℃～900℃displayed better spinel structure. No NiO or LixNi1-xO impure phase was formed. Co-doping had little effect on the particle morphology of samples. Compared with base sample, the co-doped sample with x=0.04 prepareed at 800℃showed a little decreased impedance and smaller improved rate capability. Its discharge capacity reached 132.4mAh·g-1 at 0.2C. However, increasing the co-doped ion amount accelerated the electrolyte decomposition, enhanced the film impedance and charge transfer impedance, leading to deterioration of electrochemical performance.
Based on above results, it is concluded that modification of LiNi0.5Mn1.5O4 by F-doping or Cr-and F- co-doping can improve rate capability remarkably. In the cases, optimizing the annealing temperatures and doped ion amounts can make sure to prepare modified higher rate LiNi0.5Mn1.5O4 with well crystalline, uniform particle size distribution, better reduce of electrolyte decomposition and smaller film impedance and charge transfer impedance.
引文
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