PVC 塑料协同热解回收再生锂离子电池正 极材料工艺的研究

通过高效且绿色的方法从退役锂离子电池正极材料中回收有价金属一
直是环境领域的重大挑战，对于基于火法冶金的回收工艺来说，降低能耗
和材料消耗是目前的主要方向。此外，聚氯乙烯（PVC）塑料作为另一种
引起严重环境问题的固体废弃物，其合理的处理方式也是目前亟待深入研
究 的 课 题 。 因 此 本 研 究 分 别 选 取 了 层状结 构 的 镍 钴 锰 酸 锂
（Li(Ni1/3Co1/3Mn1/3)O2，NCM）和尖晶石结构的锰酸锂（LiMn2O4，LMO）作为回收技术的研究对象，提出 PVC 协同热解以回收电池材料中有价金属的工艺。为了减少处理步骤，最大化金属利用率，本研究进一步提出基于
热解产物的高温固相的再生处理。
结果表明，对于 NCM 的回收研究，当 NCM/PVC 以质量比为 1:0.35 混
合后，在 550C 下热解 90min 可以获得 Li2CO3、MnO、NixCo1-x 以及金属氯化物，Li、Ni、Co、Mn 的平均回收率分别为 91.3%、93.47%、93.59%、
94.51%。与文献中记载的相关热解体系相比，完全反应所需的温度明显降
低。研究进一步结合材料表征和密度泛函计算，首先说明了 PVC 上 Cl 与
NCM 表面金属形成多种吸附构型，其中以 Cl-plane 构型最为稳定，同时
PVC 自身受热裂解会产生多种碳氢小分子，这两者是驱动协同热解进行的
关键因素。Li2CO3、MnO、NixCo1-x 等主要热解产物在经过高温固相处理后，
能再生出在结构形貌和电化学性能上均与商业 NCM 相似的正极材料。
对于 LMO 的回收研究，当 LMO/PVC 在配料比为 1:0.75，热解温度为
600C 时热解 60min 可以完全反应，此时 LMO 的分解产物为 Li2CO3、MnO
和少量金属氯化物，Li 和 Mn 的平均回收率分别为 91.2%和 93.1%。其反应
路径和 NCM-PVC 体系相似。同时相比于文献报导的其他 LMO 热解体系，
本研究因 Li2CO3 在 500C 即出现而说明具有更好的处理效果。对 Li2CO3、
MnO 等热解产物进行高温固相再生后，再生材料也表现出理想的晶体结构
和电化学性能。
综上所述，基于 PVC 协同热解的回收工艺能够达到降低温度和以废治
废的目的，为锂离子电池回收提供了一种经济、绿色的回收策略。
 

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