锂离子电池在储能和电动汽车领域扮演着重要角色，在能量密度不断增长的需求下，高比能量密度的新型活性材料被广泛研究。其中，传统石墨负极的实际比能量已经接近理论极限，因此新型负极材料成为研究的热点。单质磷具有比容量高、原料丰富、价格低廉的优点，是一种具有发展潜力的新型高比能量锂电负极材料。本文利用气相沉积法，将红磷沉积入活性炭孔内形成纳米颗粒，解决了红磷导电性差、充放电循环体积变化大、化学稳定性差的问题，制备出了具有较好应用前景的磷-碳复合负极材料，并系统研究了碳基体对材料的性能影响以及材料的应用技术，为磷-碳复合负极材料产业技术的研发提供了理论和实验依据。 通过选取不同孔道结构的活性炭制备磷-碳复合材料，研究碳基体对磷-碳复合材料性能的影响，探究适合红磷吸附沉积的孔径范围。研究表明，微孔碳比介孔碳更适合红磷的吸附沉积，制备出的磷-碳复合材料具有更高的磷负载量和比容量；活性炭内部孔径并未被完全利用，通过减小粒径或延长沉积时间的方法可以进一步提高磷负载量；制备出的磷-碳复合材料，第5次循环比容量最大超过1200 mAh/g，第5至第50次循环容量保持率最好为92.8%，比容量高，循环稳定性好。 选取两种碳源制备材料进行实验，对比研究磷-碳复合材料对不同电解液的相容性以及低温性能，对磷-碳复合材料的电化学特性进行研究。研究表明，磷-碳复合材料与碳酸酯类电解液和醚类电解液均显示出较好的相容性。两种材料中低温性能更优组，在0℃时倍率性能仅比常温时略微下降，在-20℃、0.2C条件下仍能保持50%以上的初始比容量（常温、0.1C）。低温预处理结果显示，材料的循环性能在0℃以下开始出现明显降低。 使用石墨和磷-碳复合材料，选取不同导电剂和粘结剂，刮涂制备不同极片配方双活性材料混合负极，探讨石墨-磷碳复合材料极片制备工艺。研究表明，增加磷-碳复合材料的比例，对极片的电解液浸润和电子导电率产生负面影响；在磷-碳复合材料占活性物质质量28.6%的条件下，可制备出比容量、循环性俱佳的极片，首次充电比容量为530 mAh/g，50次循环容量保持率为91.5%；该混合负极中石墨与红磷拥有各自的电化学性能；全电池充放电曲线表明该混合负极在电池能量管理方面具有较好的应用前景。
Li-ion battery plays an important role in the field of power storage and electric vehicles. New active materials with high energy density are researched extensively with the growing demand of it. The capacity of traditional graphite anode has been close to the theoretical limit. New anode material has been researched hotly. Phosphorus is a kind of new potential anode material for high capacity Li-ion batteries, having the advantages of high specific capacity, abundant reserves and low price. In this paper, the P@C composite material prepared by Chemical Vapor Deposition (CVD) with a micro-nano structure, has effectively solved the problems of the use of red phosphorus, including low electronic conductivity, large volume change during lithium insertion and extraction and poor chemical stability. That makes P@C composite material a promising anode active material of lithium-ion battery. The influences of carbon matrix on the properties of P@C material and applied technologies are studied systematically, providing theoretical and experimental bases for the research of P@C material’s industrial technology. Selected different kinds of activated carbon, which had different pore structures, to prepare P@C composite material, to explore the impact of carbon matrix on the properties of materials and suitable pore size range for phosphorus adsorption. The research showed that micropore carbon was better than mesopore carbon for adsorption, preparing the P@C material with higher phosphorus load and higher capacity. The internal pore of active carbon had not been fully used. Reducing the size of carbon or increasing the time of deposition could improve the phosphorus load further. The P@C composite material had a high capacity and good cycle stability. The highest capacity of 5th cycle was more than 1200 mAh/g. The best conservation rate from 5th cycle to 50th cycle was 92.8%. Selected two kinds of carbon preparing P@C material, studying the electrochemical performance of P@C composite material consisted of compatibility of electrolyte and low temperature performance. The result of compatibility of electrolyte research showed that carbonic acid ester and ether electrolyte were available. In the low temperature experiment, the better group had a slight decrease at 0℃ in rate performance than 20℃. The specific capacity in -20℃, 0.2C still remained more than 50% compared with that in 20℃, 0.1C. The cycle performance after pretreatment were tested, showing a significant decrease below 0℃. Prepared different proportion of double anode active material mixed with the graphite using scrape coating preparation method, with different kinds of conductive agent and binder, to study the electrode technology of P@C composite material. The results showed that P@C composite material had a negative impact on the infiltration of electrolyte and reduced the electronic conductivity. The quality score of the P@C composite materials in active material was 28.6%, it could achieve a high capacity and great cycle performance. The initial charge capacity was 530mAh/g and the capacity retention rate after 50 cycles was 91.5%. Red phosphorus and graphite had the corresponding electrochemical performance in the anode. The charge and discharge curves of full battery showed that the hybrid anode had a good application prospect in the battery energy management.
