橄榄石LiFePO_4作为锂二次电池正极材料的研究
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摘要
为了缓解石油危机和减少内燃机交通工具给城市环境带来的污染,电动车从上世纪末开始,取得了飞速的发展。随着电动车对比能量要求的不断提高,高能锂二次电池日渐吸引着电动车生产商的目光,但安全性和价格成为其实际应用的两大主要问题。橄榄石结构的LiFePO4,由于其原料丰富、成本低、无毒、优异的热稳定性和安全性、较好的电化学性能和高比容量等优点,被认为是最有希望应用于电动车电池的正极材料。但LiFePO4在电子导电率和锂离子扩散速率上的不足是其大规模实用化必须首先解决的问题。鉴于LiFePO4材料巨大的应用潜力,本文以其为研究对象,在优化合成方法的基础上,进一步对电化学性能进行了研究。主要研究工作总结如下：
1.橄榄石结构LiMPO4的高温固相法合成及其电化学性能研究
采用高温固相法,在350℃预烧5h,650℃煅烧8h的最优条件下,所合成的纯LiFePO4材料在室温下首周可以给出136.4mAh/g,的容量；尽管在60℃下放电容量达到160.8mAh/g,但循环性能较差；CV和EIS结果表明,随着循环进行,电极的反应活性降低,电化学反应极化增加。通过研究不同掺杂离子对LiFePO4材料性能的影响发现,采用Mg2+取代1%Fe2+可以有效提高材料的循环性能,而这一改善主要归结于取代后材料的电化学反应活性得到提高。在LiFePO4材料表面包覆碳也可以有效提高其电化学性能,但是碳含量的不同,将对LiFePO4性能产生不同的影响,当碳含量为4.39wt%时,LiFePO4/C材料具有最佳的综合电化学性能。与以上掺杂元素不同,由于LiMnPO4具有与LiFePO4相同的橄榄石结构,LiFe1-xMnxPO4/C在0 2.LiFePO4材料的水热法合成
以LiOH·H2O、FeSO4·7H2O和H3P04为原料,添加抗坏血酸为抗氧化剂,采用水热法合成LiFePO4材料。在pH值7.01到9.53的范围内合成的样品均为纯相的LiFePO4,产物结晶度随水热温度的提高而增加,比较不同条件下得到的水热样品发现,当浓度是0.5M(以Fe2+浓度计)时,200℃下水热6h得到的样品具有较好的结晶度和电化学性能。TG结果表明水热合成的LiFePO4含有约0.72wt% H2O；高温煅烧可以有效除去水热样品中的吸附水和结晶水,并且能提高LiFePO4的结晶度和电化学活性；同时,若在高温煅烧时添加葡萄糖,可以进一步提高样品的电化学性能。在水热过程中,加入不同类型的表面活性剂对水热样品的形貌和电化学性能的影响不同,阳离子表面活性剂CTAB的添加效果较非离子表面活性剂PEG400或阴离子表面活性剂SDS好；随着CTAB浓度增加,合成的样品分散性变好,放电比容量提高,当CTAB浓度大于40mmol/L时,比容量基本不再增加；CTAB表面活性剂对材料性能的改善作用主要缘于它能够增加样品颗粒的分散性,并影响最终产物的形貌；通过改变水热原料发现,采用LiAc+NH4H2PO4+FeSO4为原料合成的样品中含有杂质；采用LiOH+H3PO4+FeSO4为原料所合成的LiFePO4样品首周比容量最高,而采用LiOH+NH4H2PO4+FeSO4为原料所合成的LiFePO4具有最好的循环性能。
3. LiFePO4/C材料的微波法合成
采用FePO4-4H2O与LiOH-H2O做原料,以葡萄糖做碳源和还原剂,微波加热2-7min即可以合成LiFePO4/C材料；合成样品的粒径随着微波时间的延长而烧结长大。其中微波加热4min的样品颗粒分布均一并具有最佳的电化学性能。与高温固相煅烧合成的样品相比,微波法合成的样品粒径更小,电化学反应电阻较低,并且容量更高；但由于微波加热时间短,包覆碳的石墨化程度低,导电性有所不足。微波法合成的LiFePO4/C材料中含有少量的三价铁杂质,随着微波加热时间的不同,杂质相也发生相应演变。微波加热时间2-4min得到的样品中杂质主要为三价铁反应中间物,随着微波加热时间延长到5min以上,三价铁中间体减少,而Li3Fe2(PO4)3杂质增多。进一步在650℃下煅烧1h可以有效除去这些三价铁杂质。采用Fe203与Li2CO3和NH4H2PO4为原料,以葡萄糖做为碳源和还原剂,微波加热5min可以合成LiFePO4/C材料,但是所得到的样品中含有一定的杂质,并且烧结成较大的颗粒,即使采用纳米Fe2O3前体也无法明显改善颗粒形貌；而以纳米FePO4为原料,可以得到纳米LiFePO4/C,但是性能并未显著提高。
4. LiFePO4和LiFePO4/C的储存性能研究
从结构和电化学两方面研究了包覆碳的LiFePO4/C和纯LiFePO4在不同条件下的储存性能。实验结果表明,环境的温度和湿度对LiFePO4/C样品存储后的物相和电化学性能起着关键作用。在50℃、Ar气或干燥空气,以及室温敞口存储时,LiFePO4/C样品的电化学性能变化不明显,而在50℃饱和蒸汽下存储12周后,样品在首周充放电中显示出较低的充电容量和异常的充放电效率。结构分析表明贮存后LiFePO4/C样品电化学行为的异常与杂质的生成有着直接联系。XRD和FTIR结果说明LiFePO4/C在50℃饱和蒸汽条件下存储时发生脱锂反应,LiFePO4脱锂生成橄榄石FePO4和Li3PO4杂质,并且杂质含量随着存储时间延长而增加。提高贮存温度,LiFePO4/C在存储时的脱锂反应速度加快,由此也带来了更多的负面影响,除杂质含量和首周效率进一步提升外,循环性也有所恶化。未包覆碳的LiFePO4与LiFePO4/C在贮存过程中的反应机理不同,尽管通过现有的结构分析,我们无法确认LiFePO4在湿热环境中贮存前后所发生的具体的结构变化,但是电化学测试的结果表明,80℃饱和蒸汽下的存储使LiFePO4的容量和循环性能均显著恶化,但这些电化学性质的衰退并非由橄榄石FePO4的生成而导致。结构和电化学表征都说明将存储后的样品在650℃下煅烧1h可以有效除去样品中的杂质,并使材料的结构和电化学性能基本得以恢复。在研究贮存稳定性的基础上,我们进一步研究了LiFePO4和LiFePO4/C的热稳定性,实验发现,两者的热稳定性明显不同,由于LiFePO4/C样品具有较高的比表面积和较小的原始颗粒,同样是300℃下、3h空气氛中的热处理,将使得LiFePO4/C的氧化程度更高,结构的破坏和电化学性能的衰退也更加显著。
The development of electric vehicle is recognized as one of the most effective way to alleviate the oil crisis and the urban air pollution originating from the internal-combustion engine. Because of its higher energy density, lithium ion battery is the preferred battery for the electric vehicle or hybrid electric vehicle, but the safety and cost are two main obstacles for its practical use. Because of the high abundance of raw materials and the low cost, non-toxicity, excellent thermal stability and safety, good electrochemical performance and high specific capacity, the olivine LiFePO4 is accepted as the most promising cathode material for the EV/HEV usage, but its shortcomings of low electric conductivity and slow lithium diffusion need to be overcome before its larger scale application. In view of its potential use in the near future, LiFePO4 material was chosen as our investigation object. The main results are summarized as follows:
1. Synthesis of olivine LiMPO4 by high temperature solid-state reaction and the investigation on its electrochemical properties
The phase-pure LiFePO4 was prepared by high temperature solid-state method. Presintering at 350℃for 5hrs followed by a final calcination at 650℃for 8hrs was revealed as the optimized preparation condition and thus-obtained sample can deliver 136.4mAh/g at the room temperature and 160.8mAh/g at 60℃in its first cycle. However, its capacity retentivity is poor; and the results from CV and EIS tests indicate that along with the repeated charge/discharge, the reactivity of the electrode decreases accompanied by the increased polarization. Substituting 1% Mg2+ for Fe2+ can effectively enhance the cycleability of LiFePO4 material because that doping improves the electrochemical reactivity of the material. Coating LiFePO4 with conductive carbon is another effective way to improve the electrochemical properties of LiFePO4, but the electrochemical property of LiFePO4/C is also greatly influenced by the content of carbon. Careful comparison indicates that the LiFePO4/C material with 4.39wt% carbon has the best performance. As LiMnPO4 has the same olivine structure as LiFePO4, it can form a homogeneous solid solution with LiFePO4 in a wide content range and the obtained sample shows increased cell parameters with increasing x value in the solid solution of LiMnxFe1-xP04. Electrochemical measurements show that the higher Mn content in the LiMnxFe1-xP04 phase results to a degraded electrochemical performance.
2. Hydrothermal synthesis of LiFePO4 and its relative investigation
The LiFePO4 material can be successfully synthesized by hydrothermal method using LiOH-H2O、FeSO4·7H2O and H3PO4 as the raw materials and the ascorbic acid as the antioxidant addition. The phase-pure LiFePO4 can be prepared when the pH value is between 7.01 and 9.53, and the crystallinity of the final product increases as the hydrothermal temperature increases. Comparison of the LiFePO4 samples prepared under different conditions shows that when the mixture solution with the Fe2+ concentration of 0.5M was hydrothermally heated at 200℃for 6h, the best electrochemical performance can be achieved. The TG analysis tells that LiFePO4 prepared by the hydrothermal method contains 0.72wt% H2O. A calcination of the hydrothermal sample can effectively remove the water, it also brings an increased crystallinity and improved electrochemical reactivity of LiFePO4. Further investigation shows that if the hydrothermal sample is calcined with glucose, the electrochemical performance of the final product can be greatly enhanced. Addition of the surfactants in the hydrothermal solution has some effects on the morphology and the electrochemical performance of the LiFePO4 sample. It is revealed that among different surfactants, such as CTAB, PEG400 or SDS, adding the cationic surfactant of CTAB in the hydrothermal solution leads to the most notable improvement in the particle morphology. It is found that the addition of CTAB helps to better disperse the particles, and with the increasing CTAB concentration, the discharge capacity of the final product gradually increases until the CTAB concentration reaches 40mmol/L. The influence of different starting material was also studied. It is shown that when choosing LiAc+NH4H2PO4+FeSO4 as the raw materials, impurities are generated in the final product; while using LiOH+H3PO4+FeSO4 or LiOH+NH4H2PO4+FeSO4 as the raw materials leads to the highest first discharge capacity or best cycleability, respectively.
3. Microwave synthesis of LiFePO4/C materials and its relative investigation
LiFePO4/C was synthesized by microwave heating for 2-7minutes, using the FePO4·4H2O and LiOH·H2O as the starting materials and the glucose as the reductant. A longer microwave heating time results to a larger particle size. SEM and particle size analysis tell that 4min-microwave heating leads to the formation of LiFePO4/C sample with narrowly distributed particle size and good electrochemical performance. Comparing with the LiFePO4/C prepared by solid-state reaction, the sample derived by the microwave method has a smaller particle size, smaller reactive resistance (Rct) and a larger discharge capacity. However, it is also found that the short microwave heating time also results to the relatively lower degree of graphitization and the obtaining of less conductive carbon. The LiFePO4/C synthesized by microwave method usually contains some ferric impurities, and the type of the impurity changes with the heating time. During a short microwave heating, the ferric intermediate is the major impurity phase; while the microwave heating longer than 5min favors the formation of Li3Fe2(PO4)3 impurity. These ferric impurities can be effectively removed by a further calcination at 650℃for 1h. Microwave heating the mixture of Fe2O3, Li2CO3, NH4H2PO4 and glucose also leads to the formation of LiFePOVC, but the product has large particle size and contains some impurities even starting from the nanosized precursor. Replacing nano-Fe2O3 by nano-FePO4 precursor results to the obtaining of nano-sized LiFePO4/C, but the electrochemical property does not greatly change.
4. Investigation on the storage properties of LiFePO4/C and bare LiFePO4
The storage properties of LiFePO4/C and bare LiFePO4 are investigated in detail. Storage tests under different conditions tell us that moisture and temperature in the storing environment has the most profound effect on the structure as well as the electrochemical property of LiFePO4/C. When storing LiFePO4/C in dry Ar or dry air, its structure or electrochemical almost remain unchanged; while exposing LiFePO4/C to saturated humidity air at 50℃for 12 weeks, its initial charging capacity decreases and the efficiency in the first cycle reaches 125%. This negative effect is found to be originated from the spontaneous delithiation and thus-resulted impurity formation. From FT-IR and XRD measurements, we directly observe the formation of olivine FePO4 and Li3PO4 during the storage in humid-hot air, and it is further confirmed that lithium extraction occurs in different degree depending on the storing time. Increasing temperature is found to favor the delithiation reaction. In the case that the LiFePO4/C sample is stored in saturated humidity air at 80℃, an 8-weeks storing will cause 18% delithiation, greatly shrunk initial charging capacity and degraded cycling stability. Storage tests of bare LiFePO4 indicate that unlike LiFePO4/C, exposing LiFePO4 to humid-hot air will not lead to the formation of olivine FePO4 and the aging mechanism for LiFePO4 differs from that of LiFePO4/C. XRD and FTIR measurements reveal no detectable structural changes in bare LiFePO4 after exposure to saturated humidity air at 80℃for 8 weeks; however, cycling tests show that the storage results in a notable degradation in the initial charging/discharging capacity and capacity retentivity. Although lithium extraction is unavoidable and significant once LiFePO4/C is stored in a humid-hot environment, thus-induced structure heterogeneity can be repaired by a re-calcination treatment. Re-calcining the stored LiFePO4/C sample at 650℃in H2/Ar for lhour, its structure and charging/discharging behavior both recover to the primitive state. Besides the storage behavior, we also investigated the thermal stability of LiFePO4 and LiFePO4/C. It is found that, comparing with bare LiFePO4 LiFePO4/C shows more serious structure damage and more notable deterioration in the electrochemical property after being heated at 300℃in air. These differences should be explained by different specific surface area.
1.橄榄石结构LiMPO4的高温固相法合成及其电化学性能研究
采用高温固相法,在350℃预烧5h,650℃煅烧8h的最优条件下,所合成的纯LiFePO4材料在室温下首周可以给出136.4mAh/g,的容量；尽管在60℃下放电容量达到160.8mAh/g,但循环性能较差；CV和EIS结果表明,随着循环进行,电极的反应活性降低,电化学反应极化增加。通过研究不同掺杂离子对LiFePO4材料性能的影响发现,采用Mg2+取代1%Fe2+可以有效提高材料的循环性能,而这一改善主要归结于取代后材料的电化学反应活性得到提高。在LiFePO4材料表面包覆碳也可以有效提高其电化学性能,但是碳含量的不同,将对LiFePO4性能产生不同的影响,当碳含量为4.39wt%时,LiFePO4/C材料具有最佳的综合电化学性能。与以上掺杂元素不同,由于LiMnPO4具有与LiFePO4相同的橄榄石结构,LiFe1-xMnxPO4/C在0
以LiOH·H2O、FeSO4·7H2O和H3P04为原料,添加抗坏血酸为抗氧化剂,采用水热法合成LiFePO4材料。在pH值7.01到9.53的范围内合成的样品均为纯相的LiFePO4,产物结晶度随水热温度的提高而增加,比较不同条件下得到的水热样品发现,当浓度是0.5M(以Fe2+浓度计)时,200℃下水热6h得到的样品具有较好的结晶度和电化学性能。TG结果表明水热合成的LiFePO4含有约0.72wt% H2O；高温煅烧可以有效除去水热样品中的吸附水和结晶水,并且能提高LiFePO4的结晶度和电化学活性；同时,若在高温煅烧时添加葡萄糖,可以进一步提高样品的电化学性能。在水热过程中,加入不同类型的表面活性剂对水热样品的形貌和电化学性能的影响不同,阳离子表面活性剂CTAB的添加效果较非离子表面活性剂PEG400或阴离子表面活性剂SDS好；随着CTAB浓度增加,合成的样品分散性变好,放电比容量提高,当CTAB浓度大于40mmol/L时,比容量基本不再增加；CTAB表面活性剂对材料性能的改善作用主要缘于它能够增加样品颗粒的分散性,并影响最终产物的形貌；通过改变水热原料发现,采用LiAc+NH4H2PO4+FeSO4为原料合成的样品中含有杂质；采用LiOH+H3PO4+FeSO4为原料所合成的LiFePO4样品首周比容量最高,而采用LiOH+NH4H2PO4+FeSO4为原料所合成的LiFePO4具有最好的循环性能。
3. LiFePO4/C材料的微波法合成
采用FePO4-4H2O与LiOH-H2O做原料,以葡萄糖做碳源和还原剂,微波加热2-7min即可以合成LiFePO4/C材料；合成样品的粒径随着微波时间的延长而烧结长大。其中微波加热4min的样品颗粒分布均一并具有最佳的电化学性能。与高温固相煅烧合成的样品相比,微波法合成的样品粒径更小,电化学反应电阻较低,并且容量更高；但由于微波加热时间短,包覆碳的石墨化程度低,导电性有所不足。微波法合成的LiFePO4/C材料中含有少量的三价铁杂质,随着微波加热时间的不同,杂质相也发生相应演变。微波加热时间2-4min得到的样品中杂质主要为三价铁反应中间物,随着微波加热时间延长到5min以上,三价铁中间体减少,而Li3Fe2(PO4)3杂质增多。进一步在650℃下煅烧1h可以有效除去这些三价铁杂质。采用Fe203与Li2CO3和NH4H2PO4为原料,以葡萄糖做为碳源和还原剂,微波加热5min可以合成LiFePO4/C材料,但是所得到的样品中含有一定的杂质,并且烧结成较大的颗粒,即使采用纳米Fe2O3前体也无法明显改善颗粒形貌；而以纳米FePO4为原料,可以得到纳米LiFePO4/C,但是性能并未显著提高。
4. LiFePO4和LiFePO4/C的储存性能研究
从结构和电化学两方面研究了包覆碳的LiFePO4/C和纯LiFePO4在不同条件下的储存性能。实验结果表明,环境的温度和湿度对LiFePO4/C样品存储后的物相和电化学性能起着关键作用。在50℃、Ar气或干燥空气,以及室温敞口存储时,LiFePO4/C样品的电化学性能变化不明显,而在50℃饱和蒸汽下存储12周后,样品在首周充放电中显示出较低的充电容量和异常的充放电效率。结构分析表明贮存后LiFePO4/C样品电化学行为的异常与杂质的生成有着直接联系。XRD和FTIR结果说明LiFePO4/C在50℃饱和蒸汽条件下存储时发生脱锂反应,LiFePO4脱锂生成橄榄石FePO4和Li3PO4杂质,并且杂质含量随着存储时间延长而增加。提高贮存温度,LiFePO4/C在存储时的脱锂反应速度加快,由此也带来了更多的负面影响,除杂质含量和首周效率进一步提升外,循环性也有所恶化。未包覆碳的LiFePO4与LiFePO4/C在贮存过程中的反应机理不同,尽管通过现有的结构分析,我们无法确认LiFePO4在湿热环境中贮存前后所发生的具体的结构变化,但是电化学测试的结果表明,80℃饱和蒸汽下的存储使LiFePO4的容量和循环性能均显著恶化,但这些电化学性质的衰退并非由橄榄石FePO4的生成而导致。结构和电化学表征都说明将存储后的样品在650℃下煅烧1h可以有效除去样品中的杂质,并使材料的结构和电化学性能基本得以恢复。在研究贮存稳定性的基础上,我们进一步研究了LiFePO4和LiFePO4/C的热稳定性,实验发现,两者的热稳定性明显不同,由于LiFePO4/C样品具有较高的比表面积和较小的原始颗粒,同样是300℃下、3h空气氛中的热处理,将使得LiFePO4/C的氧化程度更高,结构的破坏和电化学性能的衰退也更加显著。
The development of electric vehicle is recognized as one of the most effective way to alleviate the oil crisis and the urban air pollution originating from the internal-combustion engine. Because of its higher energy density, lithium ion battery is the preferred battery for the electric vehicle or hybrid electric vehicle, but the safety and cost are two main obstacles for its practical use. Because of the high abundance of raw materials and the low cost, non-toxicity, excellent thermal stability and safety, good electrochemical performance and high specific capacity, the olivine LiFePO4 is accepted as the most promising cathode material for the EV/HEV usage, but its shortcomings of low electric conductivity and slow lithium diffusion need to be overcome before its larger scale application. In view of its potential use in the near future, LiFePO4 material was chosen as our investigation object. The main results are summarized as follows:
1. Synthesis of olivine LiMPO4 by high temperature solid-state reaction and the investigation on its electrochemical properties
The phase-pure LiFePO4 was prepared by high temperature solid-state method. Presintering at 350℃for 5hrs followed by a final calcination at 650℃for 8hrs was revealed as the optimized preparation condition and thus-obtained sample can deliver 136.4mAh/g at the room temperature and 160.8mAh/g at 60℃in its first cycle. However, its capacity retentivity is poor; and the results from CV and EIS tests indicate that along with the repeated charge/discharge, the reactivity of the electrode decreases accompanied by the increased polarization. Substituting 1% Mg2+ for Fe2+ can effectively enhance the cycleability of LiFePO4 material because that doping improves the electrochemical reactivity of the material. Coating LiFePO4 with conductive carbon is another effective way to improve the electrochemical properties of LiFePO4, but the electrochemical property of LiFePO4/C is also greatly influenced by the content of carbon. Careful comparison indicates that the LiFePO4/C material with 4.39wt% carbon has the best performance. As LiMnPO4 has the same olivine structure as LiFePO4, it can form a homogeneous solid solution with LiFePO4 in a wide content range and the obtained sample shows increased cell parameters with increasing x value in the solid solution of LiMnxFe1-xP04. Electrochemical measurements show that the higher Mn content in the LiMnxFe1-xP04 phase results to a degraded electrochemical performance.
2. Hydrothermal synthesis of LiFePO4 and its relative investigation
The LiFePO4 material can be successfully synthesized by hydrothermal method using LiOH-H2O、FeSO4·7H2O and H3PO4 as the raw materials and the ascorbic acid as the antioxidant addition. The phase-pure LiFePO4 can be prepared when the pH value is between 7.01 and 9.53, and the crystallinity of the final product increases as the hydrothermal temperature increases. Comparison of the LiFePO4 samples prepared under different conditions shows that when the mixture solution with the Fe2+ concentration of 0.5M was hydrothermally heated at 200℃for 6h, the best electrochemical performance can be achieved. The TG analysis tells that LiFePO4 prepared by the hydrothermal method contains 0.72wt% H2O. A calcination of the hydrothermal sample can effectively remove the water, it also brings an increased crystallinity and improved electrochemical reactivity of LiFePO4. Further investigation shows that if the hydrothermal sample is calcined with glucose, the electrochemical performance of the final product can be greatly enhanced. Addition of the surfactants in the hydrothermal solution has some effects on the morphology and the electrochemical performance of the LiFePO4 sample. It is revealed that among different surfactants, such as CTAB, PEG400 or SDS, adding the cationic surfactant of CTAB in the hydrothermal solution leads to the most notable improvement in the particle morphology. It is found that the addition of CTAB helps to better disperse the particles, and with the increasing CTAB concentration, the discharge capacity of the final product gradually increases until the CTAB concentration reaches 40mmol/L. The influence of different starting material was also studied. It is shown that when choosing LiAc+NH4H2PO4+FeSO4 as the raw materials, impurities are generated in the final product; while using LiOH+H3PO4+FeSO4 or LiOH+NH4H2PO4+FeSO4 as the raw materials leads to the highest first discharge capacity or best cycleability, respectively.
3. Microwave synthesis of LiFePO4/C materials and its relative investigation
LiFePO4/C was synthesized by microwave heating for 2-7minutes, using the FePO4·4H2O and LiOH·H2O as the starting materials and the glucose as the reductant. A longer microwave heating time results to a larger particle size. SEM and particle size analysis tell that 4min-microwave heating leads to the formation of LiFePO4/C sample with narrowly distributed particle size and good electrochemical performance. Comparing with the LiFePO4/C prepared by solid-state reaction, the sample derived by the microwave method has a smaller particle size, smaller reactive resistance (Rct) and a larger discharge capacity. However, it is also found that the short microwave heating time also results to the relatively lower degree of graphitization and the obtaining of less conductive carbon. The LiFePO4/C synthesized by microwave method usually contains some ferric impurities, and the type of the impurity changes with the heating time. During a short microwave heating, the ferric intermediate is the major impurity phase; while the microwave heating longer than 5min favors the formation of Li3Fe2(PO4)3 impurity. These ferric impurities can be effectively removed by a further calcination at 650℃for 1h. Microwave heating the mixture of Fe2O3, Li2CO3, NH4H2PO4 and glucose also leads to the formation of LiFePOVC, but the product has large particle size and contains some impurities even starting from the nanosized precursor. Replacing nano-Fe2O3 by nano-FePO4 precursor results to the obtaining of nano-sized LiFePO4/C, but the electrochemical property does not greatly change.
4. Investigation on the storage properties of LiFePO4/C and bare LiFePO4
The storage properties of LiFePO4/C and bare LiFePO4 are investigated in detail. Storage tests under different conditions tell us that moisture and temperature in the storing environment has the most profound effect on the structure as well as the electrochemical property of LiFePO4/C. When storing LiFePO4/C in dry Ar or dry air, its structure or electrochemical almost remain unchanged; while exposing LiFePO4/C to saturated humidity air at 50℃for 12 weeks, its initial charging capacity decreases and the efficiency in the first cycle reaches 125%. This negative effect is found to be originated from the spontaneous delithiation and thus-resulted impurity formation. From FT-IR and XRD measurements, we directly observe the formation of olivine FePO4 and Li3PO4 during the storage in humid-hot air, and it is further confirmed that lithium extraction occurs in different degree depending on the storing time. Increasing temperature is found to favor the delithiation reaction. In the case that the LiFePO4/C sample is stored in saturated humidity air at 80℃, an 8-weeks storing will cause 18% delithiation, greatly shrunk initial charging capacity and degraded cycling stability. Storage tests of bare LiFePO4 indicate that unlike LiFePO4/C, exposing LiFePO4 to humid-hot air will not lead to the formation of olivine FePO4 and the aging mechanism for LiFePO4 differs from that of LiFePO4/C. XRD and FTIR measurements reveal no detectable structural changes in bare LiFePO4 after exposure to saturated humidity air at 80℃for 8 weeks; however, cycling tests show that the storage results in a notable degradation in the initial charging/discharging capacity and capacity retentivity. Although lithium extraction is unavoidable and significant once LiFePO4/C is stored in a humid-hot environment, thus-induced structure heterogeneity can be repaired by a re-calcination treatment. Re-calcining the stored LiFePO4/C sample at 650℃in H2/Ar for lhour, its structure and charging/discharging behavior both recover to the primitive state. Besides the storage behavior, we also investigated the thermal stability of LiFePO4 and LiFePO4/C. It is found that, comparing with bare LiFePO4 LiFePO4/C shows more serious structure damage and more notable deterioration in the electrochemical property after being heated at 300℃in air. These differences should be explained by different specific surface area.
引文
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