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

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

Abstract

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

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

CLC Number:

TM912.9

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.

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.

Figures/Tables 10

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

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

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

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