硫酸盐法制浆黑液基多孔碳的制备及其在锂离子电池负极材料中的应用

Preparation of Multi-pore Carbon Based on Black Liquor from Kraft Pulping and Its Application in Lithium Ion Battery Anode Materials

关键词:  制浆黑液  多孔碳  自活化  硫掺杂  锂离子电池

Key Words:pulping black liquor  porous carbon  self-activation  S-doped  lithium-ion batteries

摘要:为了提高造纸废液的利用价值，在未加硫源和活化剂的前提下，以桉木硫酸盐废液为原料，在不同煅烧温度下制备了硫掺杂多孔碳材料，并将其应用于锂离子电池负极材料。在600℃下煅烧制备的多孔碳材料（黑液-600）初始放电比容量高达688 mAh/g，首次库伦效率53.96%，在较大的充放电电流密度下（2 A/g），仍然可以保持150 mAh/g左右的充放电比容量，1 A/g的电流密度下循环1000次比容量保持率为68%，展现了良好的循环和倍率性能。通过X射线衍射仪（XRD）、拉曼光谱仪（Raman）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）、元素分析、比表面积及孔径分布、X射线光电子能谱仪（XPS）等表征，结果显示黑液-600具有较大层间距（0.392 nm），2.94%的硫掺杂，含有丰富的缺陷、孔结构且具有190.8 m²/g的比表面积，这种多孔结构和元素掺杂使得碳材料具有优异的电化学活性和稳定性。

Abstract:In order to increase the utilization value of papermaking waste liquid， sulfur-doped porous carbon using black liquor from kraft pulping as raw material， was prepared at different calcination temperatures without adding sulfur source and activator， and subsequently utilized as anode material for lithium ion batteries. The specific discharge capacity of porous carbon material calcinated at 600℃ （black liquor-600） was as high as 688 mAh/g and the first time coulomb efficiency was 53.96%. At charge and discharge current density of 2 A/g， black liquor-600 could maintain a specific charge and discharge capacity of approximately 150 mAh/g； at current density of 1 A/g the capacity retention rate after 1000 cycles of which was 68%， showing good cycle and rate performance. After further characterized by XRD， Raman spectroscopy， SEM， TEM， elemental analysis， surface area and pore size distribution， and XPS， it was revealed that black liquor-600 had large layer spacing of 0.392 nm， sulfur doping of 2.94%， specific surface area of 190.8 m²/g， as well as abundant defects and pore structure ， endowing such carbon materials with excellent electrochemical activity and stability.