Chemistry evolution of LiNi1/3Co1/3Mn1/3O2-NaHSO4·H2O system during roasting

Xiaodong Zhang; Dahui Wang; Huaijing Chen; Lixin Yang; Yueshan Yu; Li Xu

doi:10.1016/j.ssi.2019.05.018

Chemistry evolution of LiNi_1/3Co_1/3Mn_1/3O₂-NaHSO₄·H₂O system during roasting

Xiaodong Zhang, Dahui Wang^*, Huaijing Chen, Lixin Yang, Yueshan Yu, Li Xu

^*Corresponding author for this work

Lanzhou University of Technology

Research output: Contribution to journal › Article › peer-review

29 Citations (Scopus)

Abstract

LiNi_1/3Co_1/3Mn_1/3O₂ is one of the key materials used in power lithium-ion batteries. At present, much attention is put on the study of chemical properties of LiNi_1/3Co_1/3Mn_1/3O₂ in acidic aqueous solutions. Different from the acidic aqueous solutions reaction system, this paper presents a study on the chemistry evolution of LiNi_1/3Co_1/3Mn_1/3O₂-NaHSO₄·H₂O system with stoichiometric mass ratio of 1:4.30 during roasting process, which is studied by thermogravimetry-differential scanning calorimetry, in-situ X-ray diffraction, X-ray diffraction and X-ray photoelectron spectroscopy. The experimental results show that the quondam phase composition of the mixture is disappeared and transformed to its corresponding sulfates (LiNaSO₄ and Na₂Ni(SO₄)₂ etc.). In the temperature range under 425 °C, the original structure of LiNi_1/3Co_1/3Mn_1/3O₂ is completely destroyed due to the lack of Li in the α-NaFeO₂ layered structure, and the bimetallic sulfates were transformed and existed in the form of Na₂M(SO₄)₂ (M = Ni, Co, Mn) from 425 °C to 550 °C. The occurrence of Li, Ni, Co, and Mn elements evolves as follows: LiNi_1/3Co_1/3Mn_1/3O₂ → Li₂SO₄ → LiNaSO₄, LiNi_1/3Co_1/3Mn_1/3O₂ → NiSO₄ → Na₆Ni(SO₄)₄ → Na₂Ni(SO₄)₂, LiNi_1/3Co_1/3Mn_1/3O₂ → CoSO₄ → Na₆Co(SO₄)₄ → Na₂Co(SO₄)₂, LiNi_1/3Co_1/3Mn_1/3O₂ → MnO₂ → Mn₂O₃ → MnSO₄ → Na₂Mn(SO₄)₂, and the change of valence state of Co and Mn is +3 → +2 and + 4 → +3 → +2, respectively. The chemistry reaction mechanism of this roasting process might be reactions as follows: 12LiNi_1/3Co_1/3Mn_1/3O₂ + 36NaHSO₄·H₂O → 18Na₂SO₄ + 6Li₂SO₄ + 4NiSO₄ + 4CoSO₄ + 4MnSO₄ + 54H₂O + 3O₂, Li₂SO₄ + Na₂SO₄ → 2LiNaSO₄, MeSO₄ + 3Na₂SO₄ → Na₆Me(SO₄)₄ (Me = Ni, Co), Na₆Me(SO₄)₄ → Na₂Me(SO₄)₂ + 2Na₂SO₄, MnSO₄ + Na₂SO₄ = Na₂Mn(SO₄)₂.

Original language	English
Article number	114983
Journal	Solid State Ionics
Volume	339
DOIs	https://doi.org/10.1016/j.ssi.2019.05.018
Publication status	Published - 15 Oct 2019
Externally published	Yes

Keywords

Chemistry evolution
Element occurrence
In-situ XRD
LiNiCoMnO
Roasting

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10.1016/j.ssi.2019.05.018

Cite this

@article{3a805acba3a145f8a297c33e4ec15b8e,

title = "Chemistry evolution of LiNi1/3Co1/3Mn1/3O2-NaHSO4·H2O system during roasting",

abstract = "LiNi1/3Co1/3Mn1/3O2 is one of the key materials used in power lithium-ion batteries. At present, much attention is put on the study of chemical properties of LiNi1/3Co1/3Mn1/3O2 in acidic aqueous solutions. Different from the acidic aqueous solutions reaction system, this paper presents a study on the chemistry evolution of LiNi1/3Co1/3Mn1/3O2-NaHSO4·H2O system with stoichiometric mass ratio of 1:4.30 during roasting process, which is studied by thermogravimetry-differential scanning calorimetry, in-situ X-ray diffraction, X-ray diffraction and X-ray photoelectron spectroscopy. The experimental results show that the quondam phase composition of the mixture is disappeared and transformed to its corresponding sulfates (LiNaSO4 and Na2Ni(SO4)2 etc.). In the temperature range under 425 °C, the original structure of LiNi1/3Co1/3Mn1/3O2 is completely destroyed due to the lack of Li in the α-NaFeO2 layered structure, and the bimetallic sulfates were transformed and existed in the form of Na2M(SO4)2 (M = Ni, Co, Mn) from 425 °C to 550 °C. The occurrence of Li, Ni, Co, and Mn elements evolves as follows: LiNi1/3Co1/3Mn1/3O2 → Li2SO4 → LiNaSO4, LiNi1/3Co1/3Mn1/3O2 → NiSO4 → Na6Ni(SO4)4 → Na2Ni(SO4)2, LiNi1/3Co1/3Mn1/3O2 → CoSO4 → Na6Co(SO4)4 → Na2Co(SO4)2, LiNi1/3Co1/3Mn1/3O2 → MnO2 → Mn2O3 → MnSO4 → Na2Mn(SO4)2, and the change of valence state of Co and Mn is +3 → +2 and + 4 → +3 → +2, respectively. The chemistry reaction mechanism of this roasting process might be reactions as follows: 12LiNi1/3Co1/3Mn1/3O2 + 36NaHSO4·H2O → 18Na2SO4 + 6Li2SO4 + 4NiSO4 + 4CoSO4 + 4MnSO4 + 54H2O + 3O2, Li2SO4 + Na2SO4 → 2LiNaSO4, MeSO4 + 3Na2SO4 → Na6Me(SO4)4 (Me = Ni, Co), Na6Me(SO4)4 → Na2Me(SO4)2 + 2Na2SO4, MnSO4 + Na2SO4 = Na2Mn(SO4)2.",

keywords = "Chemistry evolution, Element occurrence, In-situ XRD, LiNiCoMnO, Roasting",

author = "Xiaodong Zhang and Dahui Wang and Huaijing Chen and Lixin Yang and Yueshan Yu and Li Xu",

note = "Publisher Copyright: {\textcopyright} 2019 Elsevier B.V.",

year = "2019",

month = oct,

day = "15",

doi = "10.1016/j.ssi.2019.05.018",

language = "English",

volume = "339",

journal = "Solid State Ionics",

issn = "0167-2738",

publisher = "Elsevier B.V.",

}

TY - JOUR

T1 - Chemistry evolution of LiNi1/3Co1/3Mn1/3O2-NaHSO4·H2O system during roasting

AU - Zhang, Xiaodong

AU - Wang, Dahui

AU - Chen, Huaijing

AU - Yang, Lixin

AU - Yu, Yueshan

AU - Xu, Li

PY - 2019/10/15

Y1 - 2019/10/15

N2 - LiNi1/3Co1/3Mn1/3O2 is one of the key materials used in power lithium-ion batteries. At present, much attention is put on the study of chemical properties of LiNi1/3Co1/3Mn1/3O2 in acidic aqueous solutions. Different from the acidic aqueous solutions reaction system, this paper presents a study on the chemistry evolution of LiNi1/3Co1/3Mn1/3O2-NaHSO4·H2O system with stoichiometric mass ratio of 1:4.30 during roasting process, which is studied by thermogravimetry-differential scanning calorimetry, in-situ X-ray diffraction, X-ray diffraction and X-ray photoelectron spectroscopy. The experimental results show that the quondam phase composition of the mixture is disappeared and transformed to its corresponding sulfates (LiNaSO4 and Na2Ni(SO4)2 etc.). In the temperature range under 425 °C, the original structure of LiNi1/3Co1/3Mn1/3O2 is completely destroyed due to the lack of Li in the α-NaFeO2 layered structure, and the bimetallic sulfates were transformed and existed in the form of Na2M(SO4)2 (M = Ni, Co, Mn) from 425 °C to 550 °C. The occurrence of Li, Ni, Co, and Mn elements evolves as follows: LiNi1/3Co1/3Mn1/3O2 → Li2SO4 → LiNaSO4, LiNi1/3Co1/3Mn1/3O2 → NiSO4 → Na6Ni(SO4)4 → Na2Ni(SO4)2, LiNi1/3Co1/3Mn1/3O2 → CoSO4 → Na6Co(SO4)4 → Na2Co(SO4)2, LiNi1/3Co1/3Mn1/3O2 → MnO2 → Mn2O3 → MnSO4 → Na2Mn(SO4)2, and the change of valence state of Co and Mn is +3 → +2 and + 4 → +3 → +2, respectively. The chemistry reaction mechanism of this roasting process might be reactions as follows: 12LiNi1/3Co1/3Mn1/3O2 + 36NaHSO4·H2O → 18Na2SO4 + 6Li2SO4 + 4NiSO4 + 4CoSO4 + 4MnSO4 + 54H2O + 3O2, Li2SO4 + Na2SO4 → 2LiNaSO4, MeSO4 + 3Na2SO4 → Na6Me(SO4)4 (Me = Ni, Co), Na6Me(SO4)4 → Na2Me(SO4)2 + 2Na2SO4, MnSO4 + Na2SO4 = Na2Mn(SO4)2.

AB - LiNi1/3Co1/3Mn1/3O2 is one of the key materials used in power lithium-ion batteries. At present, much attention is put on the study of chemical properties of LiNi1/3Co1/3Mn1/3O2 in acidic aqueous solutions. Different from the acidic aqueous solutions reaction system, this paper presents a study on the chemistry evolution of LiNi1/3Co1/3Mn1/3O2-NaHSO4·H2O system with stoichiometric mass ratio of 1:4.30 during roasting process, which is studied by thermogravimetry-differential scanning calorimetry, in-situ X-ray diffraction, X-ray diffraction and X-ray photoelectron spectroscopy. The experimental results show that the quondam phase composition of the mixture is disappeared and transformed to its corresponding sulfates (LiNaSO4 and Na2Ni(SO4)2 etc.). In the temperature range under 425 °C, the original structure of LiNi1/3Co1/3Mn1/3O2 is completely destroyed due to the lack of Li in the α-NaFeO2 layered structure, and the bimetallic sulfates were transformed and existed in the form of Na2M(SO4)2 (M = Ni, Co, Mn) from 425 °C to 550 °C. The occurrence of Li, Ni, Co, and Mn elements evolves as follows: LiNi1/3Co1/3Mn1/3O2 → Li2SO4 → LiNaSO4, LiNi1/3Co1/3Mn1/3O2 → NiSO4 → Na6Ni(SO4)4 → Na2Ni(SO4)2, LiNi1/3Co1/3Mn1/3O2 → CoSO4 → Na6Co(SO4)4 → Na2Co(SO4)2, LiNi1/3Co1/3Mn1/3O2 → MnO2 → Mn2O3 → MnSO4 → Na2Mn(SO4)2, and the change of valence state of Co and Mn is +3 → +2 and + 4 → +3 → +2, respectively. The chemistry reaction mechanism of this roasting process might be reactions as follows: 12LiNi1/3Co1/3Mn1/3O2 + 36NaHSO4·H2O → 18Na2SO4 + 6Li2SO4 + 4NiSO4 + 4CoSO4 + 4MnSO4 + 54H2O + 3O2, Li2SO4 + Na2SO4 → 2LiNaSO4, MeSO4 + 3Na2SO4 → Na6Me(SO4)4 (Me = Ni, Co), Na6Me(SO4)4 → Na2Me(SO4)2 + 2Na2SO4, MnSO4 + Na2SO4 = Na2Mn(SO4)2.

KW - Chemistry evolution

KW - Element occurrence

KW - In-situ XRD

KW - LiNiCoMnO

KW - Roasting

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U2 - 10.1016/j.ssi.2019.05.018

DO - 10.1016/j.ssi.2019.05.018

M3 - Article

AN - SCOPUS:85067621186

SN - 0167-2738

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JO - Solid State Ionics

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