Review on Synthesis, Characterization, and Electrochemical Properties of Fluorinated Nickel‐Cobalt‐Manganese Cathode Active Materials for Lithium‐Ion Batteries

Breddemann, Ulf; Krossing, Ingo

doi:10.1002/celc.202000029

Cited by 22 publications

(14 citation statements)

References 478 publications

(361 reference statements)

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“…It means that the fluoride ions are mainly clustered at the surface rather than at the inner part of cathode particles. In addition, the peak (∼685 eV) in Figure b closely coincides with metal fluorides such as LiF and TMF 2 (TM = Ni, Co, or Mn). , Moreover, with the increasing impurity concentration from 0.2 to 5 at. %, the peak intensity increases relatively.…”

Section: Results and Discussionmentioning

confidence: 65%

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Positive Role of Fluorine Impurity in Recovered LiNi_0.6Co_0.2Mn_0.2O₂ Cathode Materials

Zheng

Zhang

Vanaphuti

et al. 2021

ACS Appl. Mater. Interfaces

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Lithium-ion battery (LIB) recycling is considered as an important component to enable industry sustainability. A massive number of LIBs in portable electronics, electric vehicles, and grid storage will eventually end up as wastes, leading to serious economic and environmental problems. Hence, tremendous efforts have been made to improve the hydrometallurgical recycling process because it is the most promising option for handling end-of-life LIBs owing to its wide applicability, low cost, and high productivity. Despite these advantages, some extra elements (Al, Fe, C, F, and so forth) remain as impurities in the removal process and are retained in the solution, which is a great challenge to obtain high-quality cathode materials. In this work, the impacts caused by fluorine impurity on the LiNi0.6Co0.2Mn0.2O2 (NCM622) cathode are intensively investigated via hydrometallurgical coprecipitation for the first time. Our results show that up to 1 at. % fluorine impurity brings a positive influence on the recovered material due to a higher Ni2+ ratio on the surface of cathode particles. In addition, the presence of fluoride ions during coprecipitation could lead to the formation of holes in cathode particles, which improves the rate capability and cyclability dramatically. Compared to the virgin material, the capacity of the NCM622 material with 0.2 at. % fluorine impurity is boosted by ∼8% (167.7 mA h/g) with a remarkable capacity retention of 98.0% after 100 cycles at 0.33 C. Besides, the cathode with 0.2 at. % fluorine impurity shows a far better rate performance, especially at high rates (∼7% increased at 5 C) than that of virgin. These results convince that a low concentration of fluorine impurity is desirable in the hydrometallurgical recycling process. More importantly, this study offers implications in the design of high-performance NCM622 cathode materials via coprecipitation production with ion doping in the near future.

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Section: Results and Discussionmentioning

confidence: 65%

“…In addition, the peak (∼685 eV) in Figure 4b closely coincides with metal fluorides such as LiF and TMF 2 (TM = Ni, Co, or Mn). 38,39 Moreover, with the increasing impurity concentration from 0.2 to 5 at. %, the peak intensity increases relatively.…”

Section: Valence and Diffusion Analysismentioning

confidence: 96%

Positive Role of Fluorine Impurity in Recovered LiNi_0.6Co_0.2Mn_0.2O₂ Cathode Materials

Zheng

Zhang

Vanaphuti

et al. 2021

ACS Appl. Mater. Interfaces

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“…Therefore, no LiF layer was formed on the surface of the particles, and this result corroborates the substitution of O 2− for F − not only in the bulk, but also on the surface of the particles. An additional proof is given by the fact that the Mn 2p, Co 2p, and Ni 2p peaks of LiF-coated lamellar compounds show remarkable chemical shifts of the binding energy [ 53 , 54 ], which were not observed here. Both the pristine and co-doped samples had Co 2p, Ni 2p, and Mn 2p peaks without remarkable chemical shifts of the binding energy, which indicates that the chemical states of the TM elements in the layered LiNi 1/3 Mn 1/3 Co 1/3 O 2 structure did not change upon doping by F − and Na + .…”

Section: Resultsmentioning

confidence: 73%

Effect of Cationic (Na+) and Anionic (F−) Co-Doping on the Structural and Electrochemical Properties of LiNi1/3Mn1/3Co1/3O2 Cathode Material for Lithium-Ion Batteries

Wang

Hashem

Abdel-Ghany

et al. 2022

IJMS

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Elemental doping for substituting lithium or oxygen sites has become a simple and effective technique to improve the electrochemical performance of layered cathode materials. Compared with single-element doping, this work presents an unprecedented contribution to the study of the effect of Na+/F- co-doping on the structure and electrochemical performance of LiNi1/3Mn1/3Co1/3O2. The co-doped Li1-zNazNi1/3Mn1/3Co1/3O2-zFz (z = 0.025) and pristine LiNi1/3Co1/3Mn1/3O2 materials were synthesized via the sol–gel method using EDTA as a chelating agent. Structural analyses, carried out by X-ray diffraction, Raman spectroscopy, and X-ray photoelectron spectroscopy, revealed that the Na+ and F- dopants were successfully incorporated into the Li and O sites, respectively. The co-doping resulted in larger Li-slab spacing, a lower degree of cation mixing, and the stabilization of the surface structure, which substantially enhanced the cycling stability and rate capability of the cathode material. The Na/F co-doped LiNi1/3Mn1/3Co1/3O2 electrode delivered an initial specific capacity of 142 mAh g−1 at a 1C rate (178 mAh g−1 at 0.1C), and it maintained 50% of its initial capacity after 1000 charge–discharge cycles at a 1C rate.

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“…One option to improve methanol production from CO 2 tested here is oxidative fluorination that changes the catalyst surface . Note that oxidative fluorination was also used to improve interfaces of chemically related cathode active battery materials, , similarly prepared by coprecipitation at a constant pH.…”

Section: Introductionmentioning

confidence: 99%

Enhancement of Methanol Synthesis by Oxidative Fluorination of Cu/ZnO Catalysts─Insights from Surface Analyses

et al. 2021

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A Cu/ZnO catalyst system for methanol synthesis promoted by oxidative fluorination was studied. Gaseous F2 reacts in a first step mainly with CuO to give CuF2 (XPS, thermodynamics). In the active system, the entire fluoride content transforms to ZnF2 and the catalyst system should be formulated as Cu/ZnO1–x /ZnF2 (XPS). Tested for methanol production using a (1 + x) H2/CO x syngas (x = 1, ..., 2, eight steps@40 bar, 473 and 513 K), the fluorinated systems have optimal performance at x = 2, that is, a 3H2/CO2 mixture, and inhibit CO2 promotion at low CO2 concentrations. The number of surface ZnO1–x oxygen defect sites and the number of active sites for methanol synthesis increased in the fluorinated systems after H2 reduction (refined chemisorption measurements, XPS, and BET analysis). Concomitantly, the number of active sites for the (reverse) water–gas shift reaction decreased. Both account for the increased methanol activity and selectivity of the fluorinated catalyst systems and imply negligible water inhibition for the fluorinated case.

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Review on Synthesis, Characterization, and Electrochemical Properties of Fluorinated Nickel‐Cobalt‐Manganese Cathode Active Materials for Lithium‐Ion Batteries

Cited by 22 publications

References 478 publications

Positive Role of Fluorine Impurity in Recovered LiNi_0.6Co_0.2Mn_0.2O₂ Cathode Materials

Positive Role of Fluorine Impurity in Recovered LiNi_0.6Co_0.2Mn_0.2O₂ Cathode Materials

Effect of Cationic (Na+) and Anionic (F−) Co-Doping on the Structural and Electrochemical Properties of LiNi1/3Mn1/3Co1/3O2 Cathode Material for Lithium-Ion Batteries

Enhancement of Methanol Synthesis by Oxidative Fluorination of Cu/ZnO Catalysts─Insights from Surface Analyses

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Review on Synthesis, Characterization, and Electrochemical Properties of Fluorinated Nickel‐Cobalt‐Manganese Cathode Active Materials for Lithium‐Ion Batteries

Cited by 22 publications

References 478 publications

Positive Role of Fluorine Impurity in Recovered LiNi0.6Co0.2Mn0.2O2 Cathode Materials

Positive Role of Fluorine Impurity in Recovered LiNi0.6Co0.2Mn0.2O2 Cathode Materials

Effect of Cationic (Na+) and Anionic (F−) Co-Doping on the Structural and Electrochemical Properties of LiNi1/3Mn1/3Co1/3O2 Cathode Material for Lithium-Ion Batteries

Enhancement of Methanol Synthesis by Oxidative Fluorination of Cu/ZnO Catalysts─Insights from Surface Analyses

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Positive Role of Fluorine Impurity in Recovered LiNi_0.6Co_0.2Mn_0.2O₂ Cathode Materials

Positive Role of Fluorine Impurity in Recovered LiNi_0.6Co_0.2Mn_0.2O₂ Cathode Materials