废旧高镍正极材料酸性焙烧过程中的化学变化及金属回收

doi:10.16085/j.issn.1000-6613.2025-0766

化工进展 ›› 2025, Vol. 44 ›› Issue (S1): 528-540.DOI: 10.16085/j.issn.1000-6613.2025-0766

• 资源与环境化工 • 上一篇

废旧高镍正极材料酸性焙烧过程中的化学变化及金属回收

陈怀敬¹^,²(), 李彦强¹(), 王大辉¹(), 彭小平¹, 宋晓龙¹

^1.兰州理工大学省部共建有色金属先进加工与再利用国家重点实验室，甘肃兰州 730050
^2.兰州理工大学理学院，甘肃兰州 730050

收稿日期:2025-05-28 修回日期:2025-08-09 出版日期:2025-10-25 发布日期:2025-11-24
通讯作者: 王大辉
作者简介:陈怀敬（1974—），女，副教授，研究方向为资源循环利用。E-mail：120126498@qq.com
李彦强（1997—），男，硕士研究生，研究方向为资源循环利用。E-mail：3204893178@qq.com。
基金资助:
国家自然科学基金(51864032);沈阳材料科学国家（联合）实验室-有色金属加工与再利用国家重点实验室联合基金(18LHZD002);甘肃省科技重大专项(22ZD6GA008)

Chemical changes and metal recovery during sulfation roasting of spent high-nickel cathode materials

CHEN Huaijing¹^,²(), LI Yanqiang¹(), WANG Dahui¹(), PENG Xiaoping¹, SONG Xiaolong¹

^1.State Key Laboratory of Advance Processing and Recycling of Nonferrous Metals, Lanzhou University of Technology, Lanzhou 730050, Gansu, China
^2.College of Science, Lanzhou University of Technology, Lanzhou 730050, Gansu, China

Received:2025-05-28 Revised:2025-08-09 Online:2025-10-25 Published:2025-11-24
Contact: WANG Dahui

摘要/Abstract

摘要：

高镍正极材料LiNi_0.6Co_0.2Mn_0.2O₂具有更高的电化学容量并已开始应用于电动汽车动力电池，其报废后的回收利用受到广泛关注。本文采用热重-差示扫描量热法（TG-DSC）、X射线衍射（XRD）、X射线光电子能谱（XPS）、扫描电子显微镜-能量色散X射线谱（SEM-EDS）、热力学分析和电感耦合等离子体发射光谱（ICP-OES）等方法，系统研究了废旧高镍正极材料LiNi_0.6Co_0.2Mn_0.2O₂在酸性焙烧环境中的化学变化及金属回收。结果表明，高温作用下NaHSO₄·H₂O发生热分解产生气体SO₃、H₂O改变了焙烧过程气相组成。气相中SO₃、H₂O的存在有利于LiNi_0.6Co_0.2Mn_0.2O₂发生化学转变，并促使Li、Ni、Co及Mn元素中发生相应反应形成氢氧化物、氧化物及硫酸盐，金属硫酸盐是热力学最稳定的产物。NaHSO₄·H₂O的使用量对焙烧产物的组成有明显影响。随着NaHSO₄·H₂O使用量增加，焙烧产物中LiNi_0.6Co_0.2Mn_0.2O₂的量减少直至消失。当LiNi_0.6Co_0.2Mn_0.2O₂和NaHSO₄·H₂O混合质量比为1∶1.97时，焙烧产物物相组成为LiNaSO₄、Ni₆MnO₈、MnCo₂O₄、NiO、Na₂Ni(SO₄)₂、Na₂Mn(SO₄)₂和Na₂Co(SO₄)₂。焙烧过程中LiNi_0.6Co_0.2Mn_0.2O₂处于高价态的Ni、Co、Mn向低价态转变，焙烧产物的微观形貌呈现尺寸不一的块状并出现烧结现象。在LiNi_0.6Co_0.2Mn_0.2O₂与NaHSO₄·H₂O混合质量比为1∶1.97、600℃焙烧0.5h、60℃水浸出0.5h以及液固比25∶1(mL/g)的条件下，Li、Ni、Co、Mn的浸出率分别达到97.13%、16.72%、6.3%和19.38%，废旧高镍正极材料LiNi_0.6Co_0.2Mn_0.2O₂中的Li绝大部分已转移至水浸出液中。因此，将废旧高镍正极材料LiNi_0.6Co_0.2Mn_0.2O₂酸性焙烧并对焙烧产物进行水浸处理来实现有价金属的回收是可行的。

关键词: 废旧高镍正极材料, 酸性焙烧, 化学变化, 金属回收, 水浸处理

Abstract:

High-nickel cathode material LiNi_0.6Co_0.2Mn_0.2O₂ has a higher electrochemical capacity and has begun to be applied in electric vehicle power batteries. The recycling and utilization of its scrap has received extensive attention. This paper adopted methods such as TG-DSC, XRD, XPS, SEM-EDS, thermodynamic analysis and ICP-OES to systematically study the chemical changes and metal recovery of the spent high-nickel cathode material LiNi_0.6Co_0.2Mn_0.2O₂ during sulfation roasting. The results showed that under high temperature, NaHSO₄·H₂O underwent thermal decomposition to produce gas SO₃ and H₂O, which changed the gas phase composition of the roasting process. The presence of SO₃ and H₂O in the gas phase was conducive to the chemical transformation of LiNi_0.6Co_0.2Mn_0.2O₂ and promoted the corresponding reactions of Li, Ni, Co, and Mn elements to form hydroxides, oxides and sulfates with metal sulfates being the thermodynamically most stable products. The amount of NaHSO₄·H₂O used had a significant effect on the composition of the roasting products. As the amount of NaHSO₄·H₂O used increased, the amount of LiNi_0.6Co_0.2Mn_0.2O₂ in the roasting products decreased until it disappeared. When the mixing ratio reached 1∶1.97, the phase composition was LiNaSO₄, Ni₆MnO₈, MnCo₂O₄, NiO, Na₂Ni(SO₄)₂, Na₂Mn(SO₄)₂ and Na₂Co(SO₄)₂. Under the conditions of a mixing ratio of 1∶1.97, roasting at 600℃ for 0.5h, water leaching at 60℃ for 0.5h and a liquid-to-solid ratio of 25∶1(mL/g), the leaching rates of Li, Ni, Co and Mn reached 97.13%, 16.72%, 6.3% and 19.38%, respectively, and most of the Li in LiNi_0.6Co_0.2Mn_0.2O₂ in the waste high-nickel cathode material was transferred to the water leaching solution. Roasting spent LiNi_0.6Co_0.2Mn_0.2O₂ and water leaching the roasting products to achieve the recovery of valuable metals was feasible.

Key words: spent high-nickel cathode materials, sulfation roasting, chemical changes, metal recovery, soaking in water treatment

中图分类号:

TM912.9

陈怀敬, 李彦强, 王大辉, 彭小平, 宋晓龙. 废旧高镍正极材料酸性焙烧过程中的化学变化及金属回收[J]. 化工进展, 2025, 44(S1): 528-540.

CHEN Huaijing, LI Yanqiang, WANG Dahui, PENG Xiaoping, SONG Xiaolong. Chemical changes and metal recovery during sulfation roasting of spent high-nickel cathode materials[J]. Chemical Industry and Engineering Progress, 2025, 44(S1): 528-540.

图/表 10

表1 废旧LiNi0.6Co0.2Mn0.2O2材料中金属元素的化学组成

元素	质量分数/%
Li	7.16
Ni	36.33
Co	12.16
Mn	11.34
Mg	0.005
Al	0.09

表2 LiNi0.6Co0.2Mn0.2O2与NaHSO4·H2O混合物在焙烧过程中可能发生的化学反应

编号	反应方程式	ΔG^⊖-T
式(2)	NaHSO₄+H₂O(g) $⇌$ NaHSO₄·H₂O	Δ_r $G T ⊖$ =-65.47+0.17T
式(3)	Na₂S₂O₇+H₂O(g) $⇌$ 2NaHSO₄	Δ_r $G T ⊖$ =-177.84+0.39T
式(4)	Na₂SO₄+SO₃(g) $⇌$ Na₂S₂O₇	Δ_r $G T ⊖$ =-154.72+0.24T
式(5)	2SO₂(g)+O₂(g) $⇌$ 2SO₃(g)	Δ_r $G T ⊖$ =-197.12+0.19T
式(6)	SO₃(g)+H₂O(g) $⇌$ H₂SO₄	Δ_r $G T ⊖$ =-169.35+0.27T
式(7)	6Li₂O+7.2NiO+2.4CoO+2.4MnO+3O₂(g) $⇌$ 12LiNi_0.6Co_0.2Mn_0.2O₂^[41]
式(8)	Li₂O+H₂O(g) $⇌$ 2LiOH	Δ_r $G T ⊖$ =-128.10+0.13T
式(9)	MnO+H₂O(g) $⇌$ Mn(OH)₂	Δ_r $G T ⊖$ =-29.41+0.05T
式(10)	NiO+H₂O(g) $⇌$ Ni(OH)₂	Δ_r $G T ⊖$ =-47.50+0.14T
式(11)	CoO+H₂O(g) $⇌$ Co(OH)₂	Δ_r $G T ⊖$ =-61.21+0.15T
式(12)	2LiOH+SO₃(g) $⇌$ Li₂SO₄+H₂O(g)	Δ_r $G T ⊖$ =-317.59+0.05T
式(13)	Mn(OH)₂+SO₃(g) $⇌$ MnSO₄+H₂O(g)	Δ_r $G T ⊖$ =-214.68+0.05T
式(14)	Ni(OH)₂+SO₃(g) $⇌$ NiSO₄+H₂O(g)	Δ_r $G T ⊖$ =-189.02+0.05T
式(15)	Co(OH)₂+SO₃(g) $⇌$ CoSO₄+H₂O(g)	Δ_r $G T ⊖$ =-229.41+0.13T
式(16)	2Mn₂O₃+O₂(g) $⇌$ 4MnO₂	Δ_r $G T ⊖$ =-111.97+0.21T
式(17)	4Mn₃O₄+O₂(g) $⇌$ 6Mn₂O₃	Δ_r $G T ⊖$ =-157.79+0.16T
式(18)	6MnO+O₂(g) $⇌$ 2Mn₃O₄	Δ_r $G T ⊖$ =-395.37+0.25T
式(19)	6CoO+O₂(g) $⇌$ 2Co₃O₄	Δ_r $G T ⊖$ =-407.39+0.34T
式(20)	Li₂O+SO₃(g) $⇌$ Li₂SO₄	Δ_r $G T ⊖$ =-393.56+0.18T
式(21)	CoO+SO₃(g) $⇌$ CoSO₄	Δ_r $G T ⊖$ =-202.00+0.19T
式(22)	NiO+SO₃(g) $⇌$ NiSO₄	Δ_r $G T ⊖$ =-184.58+0.19T
式(23)	MnO+SO₃(g) $⇌$ MnSO₄	Δ_r $G T ⊖$ =-228.44+0.20T
式(24)	1/3Co₃O₄+SO₃(g) $⇌$ CoSO₄+1/6O₂(g)	Δ_r $G T ⊖$ =-134.10+0.13T
式(25)	MnO₂+SO₃(g) $⇌$ MnSO₄+1/2O₂(g)	Δ_r $G T ⊖$ =-70.11+0.035T
式(26)	1/2Mn₂O₃+SO₃(g) $⇌$ MnSO₄+1/4O₂(g)	Δ_r $G T ⊖$ =-45.43+0.03T
式(27)	1/3Mn₃O₄+SO₃(g) $⇌$ MnSO₄+1/6O₂(g)	Δ_r $G T ⊖$ =-33.23+0.023T
式(28)	Li₂O+SO₂(g)+1/2O₂(g) $⇌$ Li₂SO₄	Δ_r $G T ⊖$ =-492.12+0.28T
式(29)	CoO+SO₂(g)+1/2O₂(g) $⇌$ CoSO₄	Δ_r $G T ⊖$ =-300.56+0.29T
式(30)	MnO+SO₂(g)+1/2O₂(g) $⇌$ MnSO₄	Δ_r $G T ⊖$ =-327.00+0.30T
式(31)	NiO+SO₂(g)+1/2O₂(g) $⇌$ NiSO₄	Δ_r $G T ⊖$ =-283.14+0.29T
式(32)	Li₂O+SO₂(g) $⇌$ Li₂SO₃	Δ_r $G T ⊖$ =-304.73+0.23T
式(33)	CoO+H₂SO₄ $⇌$ CoSO₄+H₂O(g)	Δ_r $G T ⊖$ =-85.88-0.07T
式(34)	NiO+H₂SO₄ $⇌$ NiSO₄+H₂O(g)	Δ_r $G T ⊖$ =-68.97-0.07T
式(35)	MnO+H₂SO₄ $⇌$ MnSO₄+H₂O(g)	Δ_r $G T ⊖$ =-114.80-0.06T
式(36)	Li₂O+H₂SO₄ $⇌$ Li₂SO₄+H₂O(g)	Δ_r $G T ⊖$ =-272.90-0.09T

表2 LiNi0.6Co0.2Mn0.2O2与NaHSO4·H2O混合物在焙烧过程中可能发生的化学反应

编号	反应方程式	ΔG^⊖-T
式(2)	NaHSO₄+H₂O(g) $⇌$ NaHSO₄·H₂O	Δ_r $G T ⊖$ =-65.47+0.17T
式(3)	Na₂S₂O₇+H₂O(g) $⇌$ 2NaHSO₄	Δ_r $G T ⊖$ =-177.84+0.39T
式(4)	Na₂SO₄+SO₃(g) $⇌$ Na₂S₂O₇	Δ_r $G T ⊖$ =-154.72+0.24T
式(5)	2SO₂(g)+O₂(g) $⇌$ 2SO₃(g)	Δ_r $G T ⊖$ =-197.12+0.19T
式(6)	SO₃(g)+H₂O(g) $⇌$ H₂SO₄	Δ_r $G T ⊖$ =-169.35+0.27T
式(7)	6Li₂O+7.2NiO+2.4CoO+2.4MnO+3O₂(g) $⇌$ 12LiNi_0.6Co_0.2Mn_0.2O₂^[41]
式(8)	Li₂O+H₂O(g) $⇌$ 2LiOH	Δ_r $G T ⊖$ =-128.10+0.13T
式(9)	MnO+H₂O(g) $⇌$ Mn(OH)₂	Δ_r $G T ⊖$ =-29.41+0.05T
式(10)	NiO+H₂O(g) $⇌$ Ni(OH)₂	Δ_r $G T ⊖$ =-47.50+0.14T
式(11)	CoO+H₂O(g) $⇌$ Co(OH)₂	Δ_r $G T ⊖$ =-61.21+0.15T
式(12)	2LiOH+SO₃(g) $⇌$ Li₂SO₄+H₂O(g)	Δ_r $G T ⊖$ =-317.59+0.05T
式(13)	Mn(OH)₂+SO₃(g) $⇌$ MnSO₄+H₂O(g)	Δ_r $G T ⊖$ =-214.68+0.05T
式(14)	Ni(OH)₂+SO₃(g) $⇌$ NiSO₄+H₂O(g)	Δ_r $G T ⊖$ =-189.02+0.05T
式(15)	Co(OH)₂+SO₃(g) $⇌$ CoSO₄+H₂O(g)	Δ_r $G T ⊖$ =-229.41+0.13T
式(16)	2Mn₂O₃+O₂(g) $⇌$ 4MnO₂	Δ_r $G T ⊖$ =-111.97+0.21T
式(17)	4Mn₃O₄+O₂(g) $⇌$ 6Mn₂O₃	Δ_r $G T ⊖$ =-157.79+0.16T
式(18)	6MnO+O₂(g) $⇌$ 2Mn₃O₄	Δ_r $G T ⊖$ =-395.37+0.25T
式(19)	6CoO+O₂(g) $⇌$ 2Co₃O₄	Δ_r $G T ⊖$ =-407.39+0.34T
式(20)	Li₂O+SO₃(g) $⇌$ Li₂SO₄	Δ_r $G T ⊖$ =-393.56+0.18T
式(21)	CoO+SO₃(g) $⇌$ CoSO₄	Δ_r $G T ⊖$ =-202.00+0.19T
式(22)	NiO+SO₃(g) $⇌$ NiSO₄	Δ_r $G T ⊖$ =-184.58+0.19T
式(23)	MnO+SO₃(g) $⇌$ MnSO₄	Δ_r $G T ⊖$ =-228.44+0.20T
式(24)	1/3Co₃O₄+SO₃(g) $⇌$ CoSO₄+1/6O₂(g)	Δ_r $G T ⊖$ =-134.10+0.13T
式(25)	MnO₂+SO₃(g) $⇌$ MnSO₄+1/2O₂(g)	Δ_r $G T ⊖$ =-70.11+0.035T
式(26)	1/2Mn₂O₃+SO₃(g) $⇌$ MnSO₄+1/4O₂(g)	Δ_r $G T ⊖$ =-45.43+0.03T
式(27)	1/3Mn₃O₄+SO₃(g) $⇌$ MnSO₄+1/6O₂(g)	Δ_r $G T ⊖$ =-33.23+0.023T
式(28)	Li₂O+SO₂(g)+1/2O₂(g) $⇌$ Li₂SO₄	Δ_r $G T ⊖$ =-492.12+0.28T
式(29)	CoO+SO₂(g)+1/2O₂(g) $⇌$ CoSO₄	Δ_r $G T ⊖$ =-300.56+0.29T
式(30)	MnO+SO₂(g)+1/2O₂(g) $⇌$ MnSO₄	Δ_r $G T ⊖$ =-327.00+0.30T
式(31)	NiO+SO₂(g)+1/2O₂(g) $⇌$ NiSO₄	Δ_r $G T ⊖$ =-283.14+0.29T
式(32)	Li₂O+SO₂(g) $⇌$ Li₂SO₃	Δ_r $G T ⊖$ =-304.73+0.23T
式(33)	CoO+H₂SO₄ $⇌$ CoSO₄+H₂O(g)	Δ_r $G T ⊖$ =-85.88-0.07T
式(34)	NiO+H₂SO₄ $⇌$ NiSO₄+H₂O(g)	Δ_r $G T ⊖$ =-68.97-0.07T
式(35)	MnO+H₂SO₄ $⇌$ MnSO₄+H₂O(g)	Δ_r $G T ⊖$ =-114.80-0.06T
式(36)	Li₂O+H₂SO₄ $⇌$ Li₂SO₄+H₂O(g)	Δ_r $G T ⊖$ =-272.90-0.09T

图1 LiNi0.6Co0.2Mn0.2O2-NaHSO4∙H2O体系焙烧过程反应的ΔG⊖-T图

图2 LiNi0.6Co0.2Mn0.2O2与NaHSO4·H2O不同质量比混合样品的TG-DSC曲线

图3 LiNi0.6Co0.2Mn0.2O2与NaHSO4·H2O按不同质量比混合焙烧产物的XRD图谱

图4 LiNi0.6Co0.2Mn0.2O2与NaHSO4·H2O不同质量比混合样焙烧-水浸后水浸渣的XRD图谱

图5 LiNi0.6Co0.2Mn0.2O2及混合样品焙烧产物中Ni、Co和Mn元素的XPS图谱

图6 LiNi0.6Co0.2Mn0.2O2及混合样品焙烧产物的SEM-EDS图像

图7 LiNi0.6Co0.2Mn0.2O2与NaHSO4·H2O混合物焙烧过程的机理

图8 LiNi0.6Co0.2Mn0.2O2与NaHSO4·H2O混合样焙烧-水浸后Li、Ni、Co和Mn的浸出率变化

参考文献 49

[1]	VIROLAINEN Sami, FALLAH FINI Mojtaba, LAITINEN Antero, et al. Solvent extraction fractionation of Li-ion battery leachate containing Li, Ni, and Co[J]. Separation and Purification Technology, 2017, 179: 274-282.
[2]	FAN Ersha, LI Li, WANG Zhenpo, et al. Sustainable recycling technology for Li-ion batteries and beyond: Challenges and future prospects[J]. Chemical Reviews, 2020, 120(14): 7020-7063.
[3]	HUANG Bin, PAN Zhefei, SU Xiangyu, et al. Recycling of lithium-ion batteries: Recent advances and perspectives[J]. Journal of Power Sources, 2018, 399: 274-286.
[4]	HUANG Tao, LIU Longfei, ZHANG Shuwen. Recovery of cobalt, lithium, and manganese from the cathode active materials of spent lithium-ion batteries in a bio-electro-hydrometallurgical process[J]. Hydrometallurgy, 2019, 188: 101-111.
[5]	NIE Xuejiao, XI Xiaotong, YANG Yang, et al. Recycled LiMn₂O₄ from the spent lithium ion batteries as cathode material for sodium ion batteries: Electrochemical properties, structural evolution and electrode kinetics[J]. Electrochimica Acta, 2019, 320: 134626.
[6]	WU Guozhen, CHEN Huaijing, WANG Dahui, et al. Chemistry evolution of LiFePO₄-NaHSO₄·H₂O system during roasting and recovery of Li and Fe[J]. Journal of Alloys and Compounds, 2024, 1007: 176376.
[7]	LI Li, FAN Ersha, GUAN Yibiao, et al. Sustainable recovery of cathode materials from spent lithium-ion batteries using lactic acid leaching system[J]. ACS Sustainable Chemistry & Engineering, 2017, 5(6): 5224-5233.
[8]	ZHANG Xihua, CAO Hongbin, XIE Yongbing, et al. A closed-loop process for recycling LiNi_1/3Co_1/3Mn_1/3O₂ from the cathode scraps of lithium-ion batteries: Process optimization and kinetics analysis[J]. Separation and Purification Technology, 2015, 150: 186-195.
[9]	HE Tao, DAI Junjie, DONG Yangtao, et al. Green closed-loop regeneration of ternary cathode materials from spent lithium-ion batteries through deep eutectic solvent[J]. Ionics, 2023, 29(5): 1721-1729.
[10]	CHI Zhexi, LI Jian, WANG Lihua, et al. Direct regeneration method of spent LiNi_1/3Co_1/3Mn_1/3O₂ cathode materials via surface lithium residues[J]. Green Chemistry, 2021, 23(22): 9099-9108.
[11]	ZHANG Xiaodong, WANG Dahui, CHEN Huaijing, et al. Chemistry evolution of LiNi_1/3Co_1/3Mn_1/3O₂-NaHSO₄·H₂O system during roasting[J]. Solid State Ionics, 2019, 339: 114983.
[12]	ZENG Xianlai, LI Jinhui, LIU Lili. Solving spent lithium-ion battery problems in China: Opportunities and challenges[J]. Renewable and Sustainable Energy Reviews, 2015, 52: 1759-1767.
[13]	KU Heesuk, JUNG Yeojin, Minsang JO, et al. Recycling of spent lithium-ion battery cathode materials by ammoniacal leaching[J]. Journal of Hazardous Materials, 2016, 313: 138-146.
[14]	王昊, 霍进达, 曲国瑞, 等. 退役锂电池正极材料资源化回收技术研究进展[J]. 化工进展, 2023, 42(5): 2702-2716.
	WANG Hao, HUO Jinda, QU Guorui, et al. Research progress of positive electrode material recycling technology for retired lithium batteries[J]. Chemical Industry and Engineering Progress, 2023, 42(5): 2702-2716.
[15]	HE Lipo, SUN Shuying, SONG Xingfu, et al. Leaching process for recovering valuable metals from the LiNi_1/3Co_1/3Mn_1/3O₂ cathode of lithium-ion batteries[J]. Waste Management, 2017, 64: 171-181.
[16]	MA Liwen, NIE Zuoren, XI Xiaoli, et al. Cobalt recovery from cobalt-bearing waste in sulphuric and citric acid systems[J]. Hydrometallurgy, 2013, 136: 1-7.
[17]	MESHRAM Pratima, PANDEY B D, MANKHAND T R. Hydrometallurgical processing of spent lithium ion batteries (LIBs) in the presence of a reducing agent with emphasis on kinetics of leaching[J]. Chemical Engineering Journal, 2015, 281: 418-427.
[18]	CHEN Xiangping, CHEN Yongbin, ZHOU Tao, et al. Hydrometallurgical recovery of metal values from sulfuric acid leaching liquor of spent lithium-ion batteries[J]. Waste Management, 2015, 38: 349-356.
[19]	ZHUANG Luqi, SUN Conghao, ZHOU Tao, et al. Recovery of valuable metals from LiNi_0.5Co_0.2Mn_0.3O₂ cathode materials of spent Li-ion batteries using mild mixed acid as leachant[J]. Waste Management, 2019, 85: 175-185.
[20]	LIU Yenchun, LIU Minchi. Reproduction of Li battery LiNi _x Mn _y Co_1- _x_- _y O₂ positive electrode material from the recycling of waste battery[J]. International Journal of Hydrogen Energy, 2017, 42(29): 18189-18195.
[21]	ZHENG Rujuan, WANG Wenhui, DAI Yunkun, et al. A closed-loop process for recycling LiNi _x Co _y Mn_(1- _x-y₎O₂ from mixed cathode materials of lithium-ion batteries[J]. Green Energy & Environment, 2017, 2(1): 42-50.
[22]	JOULIÉ M, LAUCOURNET R, BILLY E. Hydrometallurgical process for the recovery of high value metals from spent lithium nickel cobalt aluminum oxide based lithium-ion batteries[J]. Journal of Power Sources, 2014, 247: 551-555.
[23]	JI Guanjun, Xing OU, ZHAO Ruirui, et al. Efficient utilization of scrapped LiFePO₄ battery for novel synthesis of Fe₂P₂O₇/C as candidate anode materials[J]. Resources, Conservation and Recycling, 2021, 174: 105802.
[24]	LI Li, LU Jun, ZHAI Longyu, et al. A facile recovery process for cathodes from spent lithium iron phosphate batteries by using oxalic acid[J]. CSEE Journal of Power and Energy Systems, 2018, 4(2): 219-225.
[25]	刘子潇, 张家靓, 杨成, 等. 热力学研究在锂离子电池回收中的应用[J]. 化工进展, 2021, 40(10): 5325-5336.
	LIU Zixiao, ZHANG Jialiang, YANG Cheng, et al. Applications of thermodynamic research in recycling of lithium ion battery[J]. Chemical Industry and Engineering Progress, 2021, 40(10): 5325-5336.
[26]	ALMEIDA Jenifer Rigo, MOURA Mayra Nicoli, BARRADA Renan Vicente, et al. Composition analysis of the cathode active material of spent Li-ion batteries leached in citric acid solution: A study to monitor and assist recycling processes[J]. Science of the Total Environment, 2019, 685: 589-595.
[27]	LI Li, BIAN Yifan, ZHANG Xiaoxiao, et al. Process for recycling mixed-cathode materials from spent lithium-ion batteries and kinetics of leaching[J]. Waste Management, 2018, 71: 362-371.
[28]	ZHANG Jialiang, HU Juntao, ZHANG Wenjuan, et al. Efficient and economical recovery of lithium, cobalt, nickel, manganese from cathode scrap of spent lithium-ion batteries[J]. Journal of Cleaner Production, 2018, 204: 437-446.
[29]	LIU Fupeng, PENG Chao, MA Quanxin, et al. Selective lithium recovery and integrated preparation of high-purity lithium hydroxide products from spent lithium-ion batteries[J]. Separation and Purification Technology, 2021, 259: 118181.
[30]	HOSSAIN Rumana, KUMAR Uttam, SAHAJWALLA Veena. Selective thermal transformation of value added cobalt from spent lithium-ion batteries[J]. Journal of Cleaner Production, 2021, 293: 126140.
[31]	XIAO Jiefeng, LI Jia, XU Zhenming. Novel approach for in situ recovery of lithium carbonate from spent lithium ion batteries using vacuum metallurgy[J]. Environmental Science & Technology, 2017, 51(20): 11960-11966.
[32]	YANG Yue, HUANG Guoyong, XU Shengming, et al. Thermal treatment process for the recovery of valuable metals from spent lithium-ion batteries[J]. Hydrometallurgy, 2016, 165: 390-396.
[33]	LIU Pengcheng, XIAO Li, CHEN Yifeng, et al. Recovering valuable metals from LiNi _x Mn _y Co_1- _x_- _y O₂ cathode materials of spent lithium ion batteries via a combination of reduction roasting and stepwise leaching[J]. Journal of Alloys and Compounds, 2019, 783: 743-752.
[34]	FEI Zitong, SU Yongyou, ZHA Yunchun, et al. Selective lithium extraction of cathode materials from spent lithium-ion batteries via low-valent salt assisted roasting[J]. Chemical Engineering Journal, 2023, 464: 142534.
[35]	TANG Yiqi, ZHANG Beilei, XIE Hongwei, et al. Recovery and regeneration of lithium cobalt oxide from spent lithium-ion batteries through a low-temperature ammonium sulfate roasting approach[J]. Journal of Power Sources, 2020, 474: 228596.
[36]	DING Hongbing, SU Yang, WANG Xinlu, et al. Enhancing the cycling stability of nickel-rich oxide cathode materials through a multifunctional CeO₂ coating[J]. Journal of Colloid and Interface Science, 2025, 687: 118-130.
[37]	郭学益, 蔡海燕, 毛高强, 等. 富镍三元正极材料的研究进展[J]. 工程科学学报, 2025, 47(4): 697-716.
	GUO Xueyi, CAI Haiyan, MAO Gaoqiang, et al. Research progress of Ni-rich ternary cathode materials[J]. Chinese Journal of Engineering, 2025, 47(4): 697-716.
[38]	LIU Lixia, LI Xiaoqing, ZHOU Kuan, et al. Highly improved cyclic stability of high voltage LiNi_0.6Co_0.2Mn_0.2O₂/graphite pouch cells via a silicon-based electrolyte additive[J]. ACS Applied Materials & Interfaces, 2025, 17(8): 12105-12116.
[39]	牛萍健, 谢天, 袁安, 等. 锂离子电池正极材料LiNi_0.6Co_0.2Mn_0.2O₂的研究进展[J]. 功能材料, 2018, 49(12): 12007-12016.
	NIU Pingjian, XIE Tian, YUAN An, et al. Research progress of the LiNi_0.6Co_0.2Mn_0.2O₂ as a cathode material of lithium ion batteries[J]. Journal of Functional Materials, 2018, 49(12): 12007-12016.
[40]	姚凤仪, 郭德威, 桂明德.氧硫硒分族[M]. 北京: 科学出版社, 1990.
	YAO Fengyi, GUO Dewei, GUI Deming. Oxygen, Sulfur, Selenium Subgroups[M]. Beijing: Science Press, 1990.
[41]	LIANG Longwei, DU Ke, LU Wei, et al. Synthesis and characterization of concentration-gradient LiNi_0.6Co_0.2Mn_0.2O₂ cathode material for lithium ion batteries[J]. Journal of Alloys and Compounds, 2014, 613: 296-305.
[42]	CHEN Bo, LIU Tianhui, JIAO Huan, et al. Phase transitions and energy storage properties of some compositions in the (1-x)Li₂SO_4– _x Na₂SO₄ system[J]. Phase Transitions, 2014, 87(7): 629-640.
[43]	TALLMAN Killian R, WHEELER Garrett P, KERN Christopher J, et al. Nickel-rich nickel manganese cobalt (NMC622) cathode lithiation mechanism and extended cycling effects using operando X-ray absorption spectroscopy[J]. The Journal of Physical Chemistry C, 2021, 125(1): 58-73.
[44]	YUE Peng, WANG Zhixing, GUO Huajun, et al. A low temperature fluorine substitution on the electrochemical performance of layered LiNi_0.8Co_0.1Mn_0.1O_2- _z F _z cathode materials[J]. Electrochimica Acta, 2013, 92: 1-8.
[45]	SOHN Jong Rack. Correlation between acidic properties of nickel catalysts and catalytic activities for ethylene dimerization and butene isomerization[J]. Catalysis Surveys from Asia, 2004, 8(4): 249-263.
[46]	PARK Sanghyuk, KIM Duho, KU Heesuk, et al. The effect of Fe as an impurity element for sustainable resynthesis of Li [Ni_1/3Co_1/3Mn_1/3]O₂ cathode material from spent lithium-ion batteries[J]. Electrochimica Acta, 2019, 296: 814-822.
[47]	OKAZAKI Noriyasu, OSADA Seiji, TADA Akio. Deactivation by sulfur dioxide of alumina-based catalysts for selective catalytic reduction of nitrogen monoxide by ethene[J]. Applied Surface Science, 1997, 121/122: 396-399.
[48]	Katana NGALA J, CHERNOVA Natasha A, MA Miaomiao, et al. The synthesis, characterization and electrochemical behavior of the layered LiNi_0.4Mn_0.4Co_0.2O₂ compound[J]. Journal of Materials Chemistry, 2004, 14(2): 214-220.
[49]	MAO Jiakai, LI Jia, XU Zhengming. Coupling reactions and collapsing model in the roasting process of recycling metals from LiCoO₂ batteries[J]. Journal of Cleaner Production, 2018, 205: 923-929.

废旧高镍正极材料酸性焙烧过程中的化学变化及金属回收

Chemical changes and metal recovery during sulfation roasting of spent high-nickel cathode materials

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 10

参考文献 49

相关文章 3

编辑推荐

Metrics

本文评价

[1]	侯学军, 章小明, 程文博, 王馨, 王春霞, 徐盛明, 黄国勇. 废钒钛基SCR催化剂的处置方法研究进展[J]. 化工进展, 2021, 40(10): 5313-5324.
[2]	陈庆云，王云海. 微生物燃料电池阴极功能的研究进展[J]. 化工进展, 2013, 32(10): 2352-2360.
[3]	张海燕，张安贵. 乳化液膜技术研究进展 [J]. 化工进展, 2007, 26(2): 180-.