锂离子电池LiMn_20_4/LiFePO_4和Li[Ni_(1/3)Co_(1/3)Mn_(1/3)]O_2/LiFePO_4复合电极的制备与性质研究
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摘要
自从1991年索尼公司率先推出第一块商品化锂离子电池以来，关于它的研究方兴未艾。目前，商业上广泛应用的锂离子正极材料主要有LiCoO_2层状材料、尖晶石型LiMn_2O_4材料、橄榄石型LiFePO_4材料和Li[Ni_(1/3)Co_(1/3)Mn_(1/3)]O_2三元层状材料。然而它们都有其自身不可忽略的缺点。近几年来，复合型电极材料的出现引起了研究人员的广泛关注。复合型电极指两种或者两种以上材料组成的电极，它通常具有单一型电极所不具备的更加优越的性能。LiMn_2O_4和LiFePO_4作为锂离子电池正极材料相互竞争并且彼此互补，特别是对混合动力汽车和纯电动汽车的应用。但是LiMn_2O_4由于二价Mn~(2+)离子的溶解和三价Mn~(3+)离子引起的Jahn-Taller畸变导致结构不稳定，使得电池容量衰减严重。 LiFePO_4材料最主要的问题是电子电导率低，以及由于LiFePO_4材料为两相反应， LiFePO_4/FePO_4相界面处的Li~+离子扩散缓慢而影响材料的倍率性能。因此，本论文的前半部分，我们选择LiMn_2O_4和LiFePO_4两个材料制备成复合电极，以复合后互相补偿各自缺点进而改善其电化学性能为研究目的，对LiMn_2O_4/LiFePO_4复合电极进行研究：
首先我们采用简单共混方法制备成五个不同比例的LiMn_2O_4/LiFePO_4复合电极，通过X射线衍射和扫描电子显微镜对复合材料的结构、颗粒尺寸以及颗粒表面形貌进行分析得知，质量比为1:1时， LiFePO_4纳米颗粒不仅粘附在微米尺寸的LiMn_2O_4颗粒表面，而且还填充在LiMn_2O_4颗粒与颗粒之间的间隙中，具有紧密填充状态。我们还对材料进行了电导率的分析，得知碳包覆的LiFePO_4材料具有更高的电子电导性，电导率高于LiMn_2O_4两个数量级。然后通过恒流充放电、循环伏安法以及电化学阻抗谱对复合材料进行电化学性能研究。该复合材料对应的电池具有较高的放电容量和良好的循环稳定性，是得益于这样特殊的表面形貌，材料具有良好的电子接触和振实密度。
然后，我们采用三种不同共混方式，即简单共混、球磨120rpm/5小时和球磨200rpm/10小时，制备质量比为1：1的LiMn_2O_4/LiFePO_4复合电极。通过对比XRD图谱可知，简单共混和球磨共混未改变材料原有晶体结构。扫描电镜分析得知，简单共混方法容易得到均匀分散的复合材料，而球磨共混方法严重破坏复合材料的均匀性。尤其是球磨能量达到200rpm/10小时，已经破坏了LiFePO_4原有的纺锤型颗粒形貌，且粘结在LiMn_2O_4颗粒表面，部分被包裹的LiMn_2O_4颗粒发生团聚。通过充放电、循环伏安法和电化学阻抗研究得知，简单共混的LiMn_2O_4/LiFePO_4复合电极具有较高的容量和循环稳定性，而球磨共混的LiMn_2O_4/LiFePO_4复合电极容量和循环性都有所减低，而且球磨能量越高，降低越多。这源于球磨使LiFePO_4紧密包裹在LiMn_2O_4颗粒表面，隔离了LiMn_2O_4颗粒与电解液之间的接触，LiMn_2O_4实际反应面积减小，并且使颗粒之间失去了物理接触的同时也失去了电子接触，因此导致了界面阻抗的急剧增加。
LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2三元层状材料结合了Ni、Co和Mn的各自优势，具有更高的可逆容量，较低的成本和较为温和的热稳定性。但是，该材料具有较低的电子传导性，限制了其倍率性能和容量保持率。而Padhi等人开发的碳包覆的LiFePO_4成为目前非常有应用前景的锂离子电池正极材料。其表面的碳涂层增强了LiFePO_4材料电子导电性，并且纳米颗粒有利于Li~+离子扩散。因此本文的后半部分，我们选择LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2和LiFePO_4材料制备成复合电极，我们以利用LiFePO_4提高层状LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2材料表面的电导率从而改善电池的倍率性、循环性能以及热稳定性为目的，对LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2/LiFePO_4复合电极进行研究：
首先我们采用共沉淀法合成了LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2层状材料，用机械球磨方法制备了LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2/LiFePO_4复合电极材料，采用X射线衍射对复合材料的结构分析得知，LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2为层状有序结构，与LiFePO_4复合后材料晶体结构未发生改变。使用扫描电镜观察到20wt%含量的LiFePO_4纳米颗粒均匀且完整地填充在LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2球体颗粒表面凹凸不平的凹槽中，与我们希望得到的形貌最为接近。得益于这样的表面形貌，使得该复合电极对应的电池在C/4倍率下，充电到4.4V时首次放电容量为178mAh/g，容量保持率为100%。对复合材料进行倍率性能测试，LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2/LiFePO_4复合电极表现出非常出色的循环稳定性明显优于单一的LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2电极。通过循环伏安法和电化学阻抗谱的分析，得知LiFePO_4包裹在LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2颗粒表面外，避免了LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2与电解液的直接接触，从而抑制了电解液与LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2之间不必要的副反应，因此降低了SEI膜的阻抗。另一方面LiFePO_4的表面碳层不仅有利于电子传导，而且有利于电极间的锂离子插入脱出并降低了电荷转移电阻。采用DSC分析仪对复合材料进行热稳定研究，发现电极的放热峰向高温区移动，并且释放的热量也明显减小。LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2/LiFePO_4复合电极安全性得到提高。
最后我们在2.5~4.8V电压区间，对LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2/LiFePO_4复合电极的循环性能和倍率性能进行分析，发现LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2/LiFePO_4复合电极在高电压下的放电容量、循环稳定性以及倍率性能都有所提高。通过循环伏安法和电化学阻抗谱分析，得出LiFePO_4颗粒避免了LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2与电解液的直接接触，抑制了电解液与LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2之间不必要的副反应，抵制了SEI膜的生长。同时， LiFePO_4表面的碳包覆层不仅有利于电子传导，而且有利于电极间锂离子插入脱出并降低了电荷转移电阻。采用DSC测试分析，得知LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2/LiFePO_4复合电极在高电压下安全性能有所改善。
总之，通过本文的研究我们进一步加深了对LiMn_2O_4/LiFePO_4和LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2/LiFePO_4两种复合电极材料制备工艺、结构特征与电化学性质的理解，这为上述复合材料的基础研究和实际应用提供了必要的理论基础和技术指导。
Great efforts have been made on the lithium-ion batteries since SONY companyfirstly applied lithium-ion batteries for the commercial use in1991. Nowadays, themost popular cathode materials are layered LiCoO_2and Li[Ni_(1/3)Co_(1/3)Mn_(1/3)]O_2, spinelLiMn_2O_4, and olivine LiFePO_4. Recently, blend electrode materials, which containstwo or more electrodes, have attracted wide attention, due to the superior performancethan single-type electrode. LiMn_2O_4and LiFePO_4are competitive andcomplementary to each other as cathode materials, especially for the electric vehiclesor hybrid electric vehicles. However, LiMn_2O_4undergoes a gradual capacity fadingduring charge-discharge cycling because of the dissolution of Mn~(2+)and the structuraldistortion by the Jahn-Teller effect of Mn~(3+)ions. One of the main problems of LiFePO_4is the low electronic conductivity and slow lithium ion diffusion across the LiFePO_4/FePO4boundary. Therefore, in the first part of this work, we selectedLiMn_2O_4/LiFePO_4as a blend electrode in order to compensate their respectivedisadvantageous and improve its electrochemical performances:
Firstly, we successfully prepared LiMn_2O_4/LiFePO_4blend cathodes using asimple blending technique with five different mass ratios. Structural preoperty,particle size and particle surface morphology were examined by XRD and SEM.When the mass ratio of LiMn_2O_4: LiFePO_4equalled to1:1, the nano-sized LiFePO_4powders not only uniformly adhered to the micron-sized LiMn_2O_4particlesbut also effectively filled into the cavities of the LiMn_2O_4space as a close-packedstate. We also found that carbon-coated LiFePO_4had a higher electron conductivityand was two orders of magnitude larger than that of LiMn_2O_4. Then we studied theelectrochemical properties of the blend cathodes by charge-discharge cycling, cyclicvoltammetry (CV) and electrochemical impedance spectroscopy (EIS). This blendmaterial had a high discharge capacity and good cycle stability, because the special surface morphology could induce a good electrical contact and tap density
Secondly, we prepared LiMn_2O_4/LiFePO_4blend cathodes with mass ratio of1:1,using different blending techniques, i.e. hand-milling and ball-milling for5h/120rpmand10h/rpm. XRD showed that the samples did not change the originalcrystalstructures after hand milling or ball milling. While SEM indicated thathand-milling method was easy to get a uniform dispersion of the blend materials, butball-milling methods seriously damaged to the uniformity of the blend materials. Inparticular, when the ball-milling energy reached200rpm/10h, the spindle-shapedmorphology of LiFePO_4was destroyed and bonded on LiMn_2O_4particle surface withthe result of LiMn_2O_4particles reunion. We also studied the electrochemicalproperties of the material by charge-discharge cycling, CV and EIS. It was shown thatLiMn_2O_4/LiFePO_4blend cathodes using hand-milling method had a higher capacityand cycle stability in comparison with other methods. While ball-milling methodwould reduce electrode capacity and cycle resistance, and the higher milling energy,the more capacity fading. Because ball-milling would result in a tight wrap on theLiMn_2O_4particle surface by LiFePO_4, isolate the contact between LiMn_2O_4particlesand the electrolyte, reduce the actual reaction area of LiMn_2O_4, and lose the contactbetween the particles both from the physical and the electronic aspects. Thus all theseeffects would result in a increase of the interfacial impedance dramatically.
Layered LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2material showed a high reversible capacity, a lowcost and moderate thermal stability because it combines the advantages of Ni, Co andMn. However, the low electronic conductivity limited the rate capability and capacityretention rate of LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2. Padhi et al. developed a method ofcarbon-coated LiFePO_4and was considered to have a good application prospect. Thecarbon-coating on the particle surface would enhance the electronic conductivity ofthe LiFePO_4material, and the nanoparticles benefited to Li~+ion diffusion. Therefore,in the latter part of this paper, we choose LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2/LiFePO_4blendcathodes in order to improve the rate capability, cycle characteristics and thermalstability of LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2material by the surface conductivity of particles:
Firstly, we synthesized LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2material using a co-precipitationmethod, then prepared LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2/LiFePO_4blend material by mechanical ball milling. XRD showed that LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2is a layered structure. Afterblending with LiFePO_4, the crystal structure of LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2did not change.SEM pictures showed that LiFePO_4nanoparticles uniformly and completely filledinto the uneven spherical particles of LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2surface, when the contentwas20wt%, and the morphology was what we expected. Thanks to such kind ofsurface morphology, the blend cathode had a initial discharge capacity of178mAh/gand a capacity retention rate of100%when it charged to4.4V at C/4rate. Rateperformance test showed that LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2/LiFePO_4blend cathodes exhibitedexcellent cycle stability which was significantly better than singleLiNi_(1/3)Co_(1/3)Mn_(1/3)O_2cathode. Then, CV and EIS measurement showed that LiFePO_4wrapped on the particle surfaces of LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2, avoided the direct contactbetween LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2and the electrolyte, and inhibited the unwanted sidereaction between the electrolyte and LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2with the results of thereduced impedance of the SEI film. On the other hand, the surface carbon layer of LiFePO_4benefited to both electron conductivity and lithium ion insertion/extractionand reduced the charge transfer resistance. Hence, DSC measurement showed that theexothermic peak of the electrode moved to the high-temperature region, and therelease of heat was also reduced. Therefore, the safety performance ofLiNi_(1/3)Co_(1/3)Mn_(1/3)O_2/LiFePO_4blend cathodes could be improved.
At last, the electrochemical performance analysis ofLiNi_(1/3)Co_(1/3)Mn_(1/3)O_2/LiFePO_4blend cathodes in the voltage window of2.5~4.8Vfound that discharge capacity, cycle stability and rate capability ofLiNi_(1/3)Co_(1/3)Mn_(1/3)O_2/LiFePO_4blend cathodes had also been enhanced. CV and EISanalysis showed that LiFePO_4particles avoided the direct contact betweenLiNi_(1/3)Co_(1/3)Mn_(1/3)O_2and electrolyte, suppressed the unwanted side reaction betweenthe electrolyte and LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2, and resisted the growth of the SEI film at thesame time. The surface carbon layer of LiFePO_4benefited to both electronconductivity and lithium ion insertion/extraction, and reduced the charge transferresistance. DSC measurement showed that safety performance ofLiNi_(1/3)Co_(1/3)Mn_(1/3)O_2/LiFePO_4blend cathodes had been improved in high voltage.
In sum, this work provided a comprehensive understanding on the preparation, structural and electrochemical performances of two types of blend cathode materials:LiMn_2O_4/LiFePO_4and LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2/LiFePO_4, and offered a necessarytheoretical and technical guidance for the research of blend cathodes.
首先我们采用简单共混方法制备成五个不同比例的LiMn_2O_4/LiFePO_4复合电极，通过X射线衍射和扫描电子显微镜对复合材料的结构、颗粒尺寸以及颗粒表面形貌进行分析得知，质量比为1:1时， LiFePO_4纳米颗粒不仅粘附在微米尺寸的LiMn_2O_4颗粒表面，而且还填充在LiMn_2O_4颗粒与颗粒之间的间隙中，具有紧密填充状态。我们还对材料进行了电导率的分析，得知碳包覆的LiFePO_4材料具有更高的电子电导性，电导率高于LiMn_2O_4两个数量级。然后通过恒流充放电、循环伏安法以及电化学阻抗谱对复合材料进行电化学性能研究。该复合材料对应的电池具有较高的放电容量和良好的循环稳定性，是得益于这样特殊的表面形貌，材料具有良好的电子接触和振实密度。
然后，我们采用三种不同共混方式，即简单共混、球磨120rpm/5小时和球磨200rpm/10小时，制备质量比为1：1的LiMn_2O_4/LiFePO_4复合电极。通过对比XRD图谱可知，简单共混和球磨共混未改变材料原有晶体结构。扫描电镜分析得知，简单共混方法容易得到均匀分散的复合材料，而球磨共混方法严重破坏复合材料的均匀性。尤其是球磨能量达到200rpm/10小时，已经破坏了LiFePO_4原有的纺锤型颗粒形貌，且粘结在LiMn_2O_4颗粒表面，部分被包裹的LiMn_2O_4颗粒发生团聚。通过充放电、循环伏安法和电化学阻抗研究得知，简单共混的LiMn_2O_4/LiFePO_4复合电极具有较高的容量和循环稳定性，而球磨共混的LiMn_2O_4/LiFePO_4复合电极容量和循环性都有所减低，而且球磨能量越高，降低越多。这源于球磨使LiFePO_4紧密包裹在LiMn_2O_4颗粒表面，隔离了LiMn_2O_4颗粒与电解液之间的接触，LiMn_2O_4实际反应面积减小，并且使颗粒之间失去了物理接触的同时也失去了电子接触，因此导致了界面阻抗的急剧增加。
LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2三元层状材料结合了Ni、Co和Mn的各自优势，具有更高的可逆容量，较低的成本和较为温和的热稳定性。但是，该材料具有较低的电子传导性，限制了其倍率性能和容量保持率。而Padhi等人开发的碳包覆的LiFePO_4成为目前非常有应用前景的锂离子电池正极材料。其表面的碳涂层增强了LiFePO_4材料电子导电性，并且纳米颗粒有利于Li~+离子扩散。因此本文的后半部分，我们选择LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2和LiFePO_4材料制备成复合电极，我们以利用LiFePO_4提高层状LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2材料表面的电导率从而改善电池的倍率性、循环性能以及热稳定性为目的，对LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2/LiFePO_4复合电极进行研究：
首先我们采用共沉淀法合成了LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2层状材料，用机械球磨方法制备了LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2/LiFePO_4复合电极材料，采用X射线衍射对复合材料的结构分析得知，LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2为层状有序结构，与LiFePO_4复合后材料晶体结构未发生改变。使用扫描电镜观察到20wt%含量的LiFePO_4纳米颗粒均匀且完整地填充在LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2球体颗粒表面凹凸不平的凹槽中，与我们希望得到的形貌最为接近。得益于这样的表面形貌，使得该复合电极对应的电池在C/4倍率下，充电到4.4V时首次放电容量为178mAh/g，容量保持率为100%。对复合材料进行倍率性能测试，LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2/LiFePO_4复合电极表现出非常出色的循环稳定性明显优于单一的LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2电极。通过循环伏安法和电化学阻抗谱的分析，得知LiFePO_4包裹在LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2颗粒表面外，避免了LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2与电解液的直接接触，从而抑制了电解液与LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2之间不必要的副反应，因此降低了SEI膜的阻抗。另一方面LiFePO_4的表面碳层不仅有利于电子传导，而且有利于电极间的锂离子插入脱出并降低了电荷转移电阻。采用DSC分析仪对复合材料进行热稳定研究，发现电极的放热峰向高温区移动，并且释放的热量也明显减小。LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2/LiFePO_4复合电极安全性得到提高。
最后我们在2.5~4.8V电压区间，对LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2/LiFePO_4复合电极的循环性能和倍率性能进行分析，发现LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2/LiFePO_4复合电极在高电压下的放电容量、循环稳定性以及倍率性能都有所提高。通过循环伏安法和电化学阻抗谱分析，得出LiFePO_4颗粒避免了LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2与电解液的直接接触，抑制了电解液与LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2之间不必要的副反应，抵制了SEI膜的生长。同时， LiFePO_4表面的碳包覆层不仅有利于电子传导，而且有利于电极间锂离子插入脱出并降低了电荷转移电阻。采用DSC测试分析，得知LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2/LiFePO_4复合电极在高电压下安全性能有所改善。
总之，通过本文的研究我们进一步加深了对LiMn_2O_4/LiFePO_4和LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2/LiFePO_4两种复合电极材料制备工艺、结构特征与电化学性质的理解，这为上述复合材料的基础研究和实际应用提供了必要的理论基础和技术指导。
Great efforts have been made on the lithium-ion batteries since SONY companyfirstly applied lithium-ion batteries for the commercial use in1991. Nowadays, themost popular cathode materials are layered LiCoO_2and Li[Ni_(1/3)Co_(1/3)Mn_(1/3)]O_2, spinelLiMn_2O_4, and olivine LiFePO_4. Recently, blend electrode materials, which containstwo or more electrodes, have attracted wide attention, due to the superior performancethan single-type electrode. LiMn_2O_4and LiFePO_4are competitive andcomplementary to each other as cathode materials, especially for the electric vehiclesor hybrid electric vehicles. However, LiMn_2O_4undergoes a gradual capacity fadingduring charge-discharge cycling because of the dissolution of Mn~(2+)and the structuraldistortion by the Jahn-Teller effect of Mn~(3+)ions. One of the main problems of LiFePO_4is the low electronic conductivity and slow lithium ion diffusion across the LiFePO_4/FePO4boundary. Therefore, in the first part of this work, we selectedLiMn_2O_4/LiFePO_4as a blend electrode in order to compensate their respectivedisadvantageous and improve its electrochemical performances:
Firstly, we successfully prepared LiMn_2O_4/LiFePO_4blend cathodes using asimple blending technique with five different mass ratios. Structural preoperty,particle size and particle surface morphology were examined by XRD and SEM.When the mass ratio of LiMn_2O_4: LiFePO_4equalled to1:1, the nano-sized LiFePO_4powders not only uniformly adhered to the micron-sized LiMn_2O_4particlesbut also effectively filled into the cavities of the LiMn_2O_4space as a close-packedstate. We also found that carbon-coated LiFePO_4had a higher electron conductivityand was two orders of magnitude larger than that of LiMn_2O_4. Then we studied theelectrochemical properties of the blend cathodes by charge-discharge cycling, cyclicvoltammetry (CV) and electrochemical impedance spectroscopy (EIS). This blendmaterial had a high discharge capacity and good cycle stability, because the special surface morphology could induce a good electrical contact and tap density
Secondly, we prepared LiMn_2O_4/LiFePO_4blend cathodes with mass ratio of1:1,using different blending techniques, i.e. hand-milling and ball-milling for5h/120rpmand10h/rpm. XRD showed that the samples did not change the originalcrystalstructures after hand milling or ball milling. While SEM indicated thathand-milling method was easy to get a uniform dispersion of the blend materials, butball-milling methods seriously damaged to the uniformity of the blend materials. Inparticular, when the ball-milling energy reached200rpm/10h, the spindle-shapedmorphology of LiFePO_4was destroyed and bonded on LiMn_2O_4particle surface withthe result of LiMn_2O_4particles reunion. We also studied the electrochemicalproperties of the material by charge-discharge cycling, CV and EIS. It was shown thatLiMn_2O_4/LiFePO_4blend cathodes using hand-milling method had a higher capacityand cycle stability in comparison with other methods. While ball-milling methodwould reduce electrode capacity and cycle resistance, and the higher milling energy,the more capacity fading. Because ball-milling would result in a tight wrap on theLiMn_2O_4particle surface by LiFePO_4, isolate the contact between LiMn_2O_4particlesand the electrolyte, reduce the actual reaction area of LiMn_2O_4, and lose the contactbetween the particles both from the physical and the electronic aspects. Thus all theseeffects would result in a increase of the interfacial impedance dramatically.
Layered LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2material showed a high reversible capacity, a lowcost and moderate thermal stability because it combines the advantages of Ni, Co andMn. However, the low electronic conductivity limited the rate capability and capacityretention rate of LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2. Padhi et al. developed a method ofcarbon-coated LiFePO_4and was considered to have a good application prospect. Thecarbon-coating on the particle surface would enhance the electronic conductivity ofthe LiFePO_4material, and the nanoparticles benefited to Li~+ion diffusion. Therefore,in the latter part of this paper, we choose LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2/LiFePO_4blendcathodes in order to improve the rate capability, cycle characteristics and thermalstability of LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2material by the surface conductivity of particles:
Firstly, we synthesized LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2material using a co-precipitationmethod, then prepared LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2/LiFePO_4blend material by mechanical ball milling. XRD showed that LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2is a layered structure. Afterblending with LiFePO_4, the crystal structure of LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2did not change.SEM pictures showed that LiFePO_4nanoparticles uniformly and completely filledinto the uneven spherical particles of LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2surface, when the contentwas20wt%, and the morphology was what we expected. Thanks to such kind ofsurface morphology, the blend cathode had a initial discharge capacity of178mAh/gand a capacity retention rate of100%when it charged to4.4V at C/4rate. Rateperformance test showed that LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2/LiFePO_4blend cathodes exhibitedexcellent cycle stability which was significantly better than singleLiNi_(1/3)Co_(1/3)Mn_(1/3)O_2cathode. Then, CV and EIS measurement showed that LiFePO_4wrapped on the particle surfaces of LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2, avoided the direct contactbetween LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2and the electrolyte, and inhibited the unwanted sidereaction between the electrolyte and LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2with the results of thereduced impedance of the SEI film. On the other hand, the surface carbon layer of LiFePO_4benefited to both electron conductivity and lithium ion insertion/extractionand reduced the charge transfer resistance. Hence, DSC measurement showed that theexothermic peak of the electrode moved to the high-temperature region, and therelease of heat was also reduced. Therefore, the safety performance ofLiNi_(1/3)Co_(1/3)Mn_(1/3)O_2/LiFePO_4blend cathodes could be improved.
At last, the electrochemical performance analysis ofLiNi_(1/3)Co_(1/3)Mn_(1/3)O_2/LiFePO_4blend cathodes in the voltage window of2.5~4.8Vfound that discharge capacity, cycle stability and rate capability ofLiNi_(1/3)Co_(1/3)Mn_(1/3)O_2/LiFePO_4blend cathodes had also been enhanced. CV and EISanalysis showed that LiFePO_4particles avoided the direct contact betweenLiNi_(1/3)Co_(1/3)Mn_(1/3)O_2and electrolyte, suppressed the unwanted side reaction betweenthe electrolyte and LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2, and resisted the growth of the SEI film at thesame time. The surface carbon layer of LiFePO_4benefited to both electronconductivity and lithium ion insertion/extraction, and reduced the charge transferresistance. DSC measurement showed that safety performance ofLiNi_(1/3)Co_(1/3)Mn_(1/3)O_2/LiFePO_4blend cathodes had been improved in high voltage.
In sum, this work provided a comprehensive understanding on the preparation, structural and electrochemical performances of two types of blend cathode materials:LiMn_2O_4/LiFePO_4and LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2/LiFePO_4, and offered a necessarytheoretical and technical guidance for the research of blend cathodes.
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