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
Abstract
:1. Introduction
2. Results and Discussion
2.1. Structure and Morphology
2.2. Electrochemical Behavior
3. Conclusions
4. Materials and Methods
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Crystal Data | NMC333 | Na/F-NMC333 |
---|---|---|
Lattice parameters | ||
a (Å) | 2.857(3) | 2.859(7) |
c(Å) | 14.205(3) | 14.221(6) |
V (Å3) | 100.43 | 100.72 |
c/a | 4.971(9) | 4.974(1) |
Lc (nm) | 42 | 34 |
ε × 10−2 (rd) | 1.84 | 1.16 |
I(003)/I(104) | 1.24 | 1.32 |
Reliability factors | ||
Rp (%) | 9.8 | 7.8 |
Rwp (%) | 11.9 | 12.2 |
χ2 | 1.22 | 1.61 |
Occupancy (Occ) | ||
Ni2+ on Li-site% | 2.08 | 1.28 |
Na on Li-site% | 0 | 2.47 |
F on O-site% | 0 | 2.39 |
Zoxy | 0.24056 | 0.24499 |
S(MO2) (Å) a | 2.636 | 2.513 |
I(LiO2) (Å) b | 2.099 | 2.251 |
Nominal Formula | Mole Fraction | |||||
---|---|---|---|---|---|---|
Na | F | Ni | Mn | Co | O | |
LiNi0.33Mn0.33Co0.33 O2 | - | - | 0.3411 | 0.3305 | 0.3284 | 1.998 |
Li0.975Na0.025Ni0.33Mn0.33Co0.33O1.975F0.025 | 0.028 | 0.026 | 0.3240 | 0.3310 | 0.3454 | 1.972 |
Material | Specific Surface Area (m2 g−1) | Average Pore Radius (nm) | Pore Volume (cm3 g−1) | LBET (nm) |
---|---|---|---|---|
NMC333 | 6.7 | 2.8 | 0.0075 | 196 |
Na/F-NMC333 | 7.1 | 3.0 | 0.0086 | 185 |
Modes | Band Position (cm−1) | Band Width (cm−1) | Band Area | |
---|---|---|---|---|
NMC333 | ||||
ν1 | Eg (Ni) | 477 | 52 | 5678.4 |
ν2 | A1g Ni) | 539 | 31 | 3226.7 |
ν3 | Eg (Co) | 512 | 37 | 2371.7 |
ν4 | A1g (Co) | 600 | 45 | 25,298.9 |
ν5 | Eg (Mn) | 566 | 41 | 5950.3 |
ν6 | A1g (Mn) | 640 | 51 | 9213.5 |
Na/F-NMC333 | ||||
ν1 | Eg (Ni) | 480 | 45 | 6151.7 |
ν2 | A1g (Ni) | 544 | 27 | 4840.6 |
ν3 | Eg (Co) | 514 | 34 | 3556.9 |
ν4 | A1g (Co) | 601 | 44 | 23,604.8 |
ν5 | Eg (Mn) | 571 | 39 | 6241.5 |
ν6 | A1g (Mn) | 638 | 49 | 12,607.1 |
Element | Core Level | Binding Energy (eV) | |
---|---|---|---|
NMC333 | Na/F-NMC333 | ||
Ni 2p | 2p3/2 | 845.4 | 845.4 |
2p1/2 | 871.8 | 871.6 | |
Satellite | 861.6 | 876.7 | |
ΔBE | 17.4 | 17.2 | |
Co 2p | 2p3/2 | 780.0 | 780.0 |
2p1/2 | 795.0 | 795.0 | |
Satellite | 789.4 | 790.0 | |
ΔBE | 15.0 | 15.0 | |
Mn 2p | 2p3/2 | 742.8 | 742.8 |
2p1/2 | 754.4 | 754.4 | |
ΔBE | 11.6 | 11.6 | |
O 1s | 1s | 529.6 | 529.3 |
531.3 | 531.0 | ||
F 1s | 1s | - | 685.4 |
Na 1s | 1s | - | 1071.8 |
Dopant | Specific Capacity (mAh g−1) | Cycles | Decay per Cycle (%) | Ref. |
---|---|---|---|---|
0.05 Na | 120 @ 1C | 10 | 2.51 | [15] |
0.03 Na | 133 @ 0.5C | 50 | 0.09 | [16] |
0.05 Na | 177 @ 0.1C | 30 | 0.42 | [17] |
0.1 Na | 95 @ 0.2C | 100 | 0.37 | [18] |
0.08 F | 136 @ 1.2 mA cm−2 | 50 | 0.21 | [20] |
0.04 F | 172 @ 0.2C | 30 | 0.15 | [21] |
0.04 Al + 0.05 F | 148 @ 0.1C | 20 | 0.3 | [22] |
0.02 Al + 0.02 B + 0.02 F | 157 @ 1C | 30 | 0.02 | [23] |
0.025 Na + 0.025 F | 70 @ 1C | 1000 | 0.05 | this work |
Electrode | Specific Capacity (mAh g−1) | Coulombic Efficiency 200th Cycle (%) | |||
---|---|---|---|---|---|
1st Cycle | 500th Cycle | Capacity Decay | 1000th Cycle | ||
NMC333 | 136 | 17 | 0.24 | 2.5 | 99.4 |
Na/F-NMC333 | 142 | 86 | 0.11 | 70 | 99.5 |
Parameters | NMC333 | Na/F-NMC333 | ||
---|---|---|---|---|
Fresh Cell | After Cycling | Fresh Cell | After Cycling | |
Rs (Ω) | 45.4 | 18.1 | 29.4 | 51.7 |
RSEI (Ω) | - | 164.7 | - | 95 |
CPESEI-T | - | 1.2 × 10−5 | - | 1.4 × 10−5 |
CPESEI-P | - | 0.82 | - | 0.81 |
Rct (Ω) | 61.6 | 321.3 | 62.8 | 242.5 |
CPEdl-T | 1.5 × 10−5 | 3 × 10−4 | 6.8 × 10−5 | 8.9 × 10−5 |
CPEdl-P | 0.85 | 0.65 | 0.74 | 0.73 |
Zw-R | 51.1 | 2073 | 46 | 950.6 |
Zw-T | 0.097 | 31.6 | 0.123 | 12.8 |
Zw-P | 0.58 | 0.56 | 0.78 | 0.57 |
DLi+ (cm2 s−1) | 1.3 × 10−11 | 8.3 × 10−15 | 1.7 × 10−11 | 4.0 × 10−14 |
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Wang, H.; Hashem, A.M.; Abdel-Ghany, A.E.; Abbas, S.M.; El-Tawil, R.S.; Li, T.; Li, X.; El-Mounayri, H.; Tovar, A.; Zhu, L.; et al. 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. Int. J. Mol. Sci. 2022, 23, 6755. https://doi.org/10.3390/ijms23126755
Wang H, Hashem AM, Abdel-Ghany AE, Abbas SM, El-Tawil RS, Li T, Li X, El-Mounayri H, Tovar A, Zhu L, et al. 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. International Journal of Molecular Sciences. 2022; 23(12):6755. https://doi.org/10.3390/ijms23126755
Chicago/Turabian StyleWang, Hua, Ahmed M. Hashem, Ashraf E. Abdel-Ghany, Somia M. Abbas, Rasha S. El-Tawil, Tianyi Li, Xintong Li, Hazim El-Mounayri, Andres Tovar, Likun Zhu, and et al. 2022. "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" International Journal of Molecular Sciences 23, no. 12: 6755. https://doi.org/10.3390/ijms23126755