Enhancement of Electrochemical Performance of Aqueous Zinc Ion Batteries by Structural and Interfacial Design of MnO2 Cathodes: The Metal Ion Doping and Introduction of Conducting Polymers †
Abstract
:1. Introduction
2. Metal-Ions-Doped Manganese-Dioxide-Based Cathode Materials
2.1. Alkali and Alkaline-Earth Metal Ions
2.2. Transition and Rare-Earth-Metal Ions
2.2.1. Light Transition Metal Ions
2.2.2. Heavy Transition Metal Ions
2.2.3. Rare-Earth-Metal Ions
2.3. Post-Transition Metal Ions
3. Manganese-Oxide-Conducting Polymer Composite Cathodes for AZIBs
3.1. Polyaniline-Modified MnO2 Cathodes
3.2. Polypyrrole-Modified MnO2 Cathodes
3.3. Poly(3,4-Ethylenedioxythiophene)-Modified MnO2 Cathodes
4. On the Charge–Discharge Mechanism in Rechargeable Zn//MnO2 Batteries
- (i)
- Reversible (de)intercalation of Zn2+ ions,
- (ii)
- Reversible (de)intercalation of H+,
- (iii)
- Co-(de)intercalation of Zn2+ and H+,
- (iv)
- Electrolytic deposition/dissolution of MnO2.
5. Summary and Outlook
Author Contributions
Funding
Data Availability Statement
Conflicts of Interest
References
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Material | Synthesis Method | Morphology | Electrolyte | Specific Capacity, mAh g−1 (Current Density, A·g−1) | Capacity Retention, (Number of Cycles and Current, A·g−1) | Ref. |
---|---|---|---|---|---|---|
K-δ-MnO2 | precipitation | two-dimensional nanosheets | 2 M ZnSO4 + 0.1 M MnSO4 | 270.5 (0.1); 220.1 (1); 95.1 (3) | 104.6% (100, 0.3) | [23] |
Li0.023Mn0.87O2 | two-stage hydrothermal method (140/110 °C) | nanorods | 2 M ZnSO4 + 0.1 M MnSO4 | 184 (0.1); 0.54 (2) | 89% (1000, 1) 100% (100, 0.1) | [32] |
Na-δ-MnO2 | redox reaction | nanoplates | 2 M ZnSO4 + 0.2 M MnSO4 | 278 (0.308) 161 (1.85) 103 (6.16) | ~100% (2000, 2.46/3.08) | [60] |
Na:MnO2/GCF | electrochemical deposition on graphene-like carbon foam | nanosheets | 2 M ZnSO4 + 0.1 M MnSO4 | 381.8 (0.1) 258.5 (1) 94.8 (3) | ~80% (100, 0.1) ~75% (1000, 1) | [33] |
K0.19MnO2·0.56H2O | one-pot hydrothermal method (180 °C) | nanosheets | 3 M Zn(CF3SO3)2 | 107 (1) | 87.5% (2000, 10) | [28] |
K-δ-MnO2-V | one-pot hydrothermal method (160 °C) | layered structure | 2 M ZnSO4 + 0.1 M MnSO4 + 0.1 M K2SO4 | 288.8 (0.1) 85.7 (1) | 91.9% (1500, 1) 89.4% (500, 0.6) | [35] |
K0.29MnO2 0.67H2O | one-pot hydrothermal method (180 °C) | nanosheets | 2.5 M ZnSO4 + 0.2 M MnSO4 | 300 (0.2) 219 (1) 136 (3) | 92 % (500, 0.2) | [36] |
α-K0.19MnO2 | self-sacrificial template method | nanotubes | 3 M Zn(CF3SO3)2 + 0.2 M Mn(CF3SO3)2 + 3 M K(CF3SO3) | 270 (0.308) 222.8 (0.616) 200 (1.54) | 98.5% (50, 0.308) 92% (200, 0.616) 90% (400, 1.54) | [37] |
LGP@K0.15MnO2 | in-situ hydrothermal synthesis (150 °C) | nanosheets | 2 M ZnSO4 + 0.1 M MnSO4 | 402.6 (0.05) 196.1 (0.8) 116.1 (2) | 92.5% (100, 0.2) 83.3% (1000, 1) | [38] |
KMO-CNT/graphene | polyol reduction method | nanowires | 2 M ZnSO4 + 0.4 M MnSO4 | 373.1 (0.1) 213.6 (1) 108.8 (3) | 82.5% (350, 0.5) 77% (1000, 3) | [39] |
Ca0.28MnO2·0.5H2O | one-step hydrothermal method | interconnected nanoflakes | 1 M ZnSO4 + 0.1 M MnSO4 | 298 (0.175) 277.7 (0.35) 124.5 (3.5) | 85% (1000, 4) 92% (5000, 3.5) | [40] |
Zn-δ-MnO2 | redox reaction | flower-like nanospheres | 2 M ZnSO4 + 0.1 M MnSO4 | 275 (0.3) 121 (3) | 100% (100, 0.3/0.6) 100% (500, 1) | [41] |
GQDs·ZnxMnO2 | redox reaction | nanoflowers | 1 M ZnSO4 | 403.6 (0.3) 211.5 (4) | 88.1% (500, 1) | [42] |
Zn-doped Mn3O4-MnO2-NSs | electrochemical deposition | vertical nanosheets | 2 M ZnSO4 + 0.1 M MnSO4 | 562.1 (0.3) 272.7 (6) | 69.4% (200, 3) | [27] |
V-doped δ-MnO2 | redox reaction | nanoparticles | 1 M ZnSO4 | 266 (0.066) 150 (0.266) 67 (1.064) | 52.4% (100, 0.066) | [25] |
V-doped δ-MnO2 | modified coprecipitation | nanosheets with aerogel-like morphology | 2 M ZnSO4 | 194 (0.2) 74 (2) | 71% (100, 0.3) 52% (600, 3) | [43] |
Fe-doped δ-MnO2 | one-step hydrothermal process (120 °C) | nanoflowers | 2 M ZnSO4 + 0.1 M MnSO4 | 390 (0.1) 320 (1) 160 (3) | 86.3% (200, 1) | [44] |
Co/Zn-doped δ-MnO2 on N-doped CC | electrochemical deposition | film on the carbon nanowires | 2 M ZnSO4 + 0.07 M MnSO4 | 280 (1.2) 30 (10.5) | ~100% (600, 1.2) | [26] |
Co-doped δ-MnO2 | molten-salt synthesis process | nanosheets | 2 M ZnSO4 + 0.2 M MnSO4 | 500 (0.1) 125 (5) | 63% (5000, 2) 100% (0.3, 100) | [45] |
Co-doped α-MnO2 on CC | one-step hydrothermal process (120 °C) + plasma treatment | nanowires | 2 M ZnSO4 + 0.1 M MnSO4 | 511 (0.5) 337 (1) 100 (5) | 98% (1000, 3) | [29] |
Co-doped σ-MnO2 | one-step electrodeposition | nanosheets | 2 M ZnSO4 + 0.2 M MnSO4 + 0.02 CoAc | 313.8 (0.5) | 91.8% (1000, 1) | [46] |
Ni-doped α-MnO2 (Ni0.052K0.119Mn0.948O2 0.208H2O) | one-step hydrothermal process (120 °C) | nanorods | 3 M ZnSO4 + 0.2 M MnSO4 | 303 (0.015) | 71.4% (2000, 1.232) | [47] |
Cu-doped δ–MnO2 on CC | one-step hydrothermal process (160 °C) | nanowires | 2 M ZnSO4 + 0.2 M MnSO4 | 398.2 (0.1) 224.9 (1) 124.9 (5) | 90.1% (700, 5) | [48] |
Cu0.06MnO2·1.7H2O (δ–MnO2) | one-step hydrothermal process (180 °C) | nanoflowers | 2 M ZnSO4 + 0.1 M MnSO4 | 493.3 (0.1) 350 (0.5) 125.8 (5) | 80% (150, 0.5) | [49] |
Bi0.09MnO2·1.5H2O (δ–MnO2) | one-step hydrothermal process (180 °C) | nanoflowers | 2 M ZnSO4 + 0.1 M MnSO4 | 175.5 (0.1) 65 (2) | 96% (1100, 1) 72.3 % (500, 0.5) | [49] |
Ag-doped α-MnO2 | one-step hydrothermal process (120 °C) | nanowires | 2 M ZnSO4 + 0.1 M MnSO4 | 315 (0.05) 177 (0.5) 85 (2) | 94.4% (500, 0.5) | [50] |
Mo-doped α-MnO2 | one-step hydrothermal process (120 °C) | nanorods | 2 M ZnSO4 + 0.2 M MnSO4 | 222.8 (0.1); 65.8 (5) | 82.6% (1000, 2) | [51] |
Mo-doped δ-MnO2 | one-step hydrothermal method (120 °C) | flower-like nanospheres | 2 M ZnSO4 + 0.1 M MnSO4 | 327 (0.2) 207 (1) 107 (3) | 76.8% (1000, 1) | [52] |
La3+-inserted δ -MnO2 | redox reaction | nanoflorets | 1 M ZnSO4 + 0.4 M MnSO4 | 278.5 (0.1) | 71% (200, 0.2) | [53] |
Ce-doped α- MnO2 | one-step hydrothermal method (140 °C) | nanorod-like structure | 2 M ZnSO4 + 0.1 M MnSO4 | 134 (1.54) | 74% (100, 1.54) | [54] |
Ce-MnO2@CC | one-step electrodeposition | porous lamellar structures | PAM/2 M ZnSO4 + 0.1 M MnSO4 | 292 (0.1) 212 (0.5) 106 (2) | 64% (450, 0.1) | [55] |
Al-intercalated α-MnO2 | one-step hydrothermal method (140 °C) | nanorods | PVA: 1 M ZnSO4 (1:4) | 333.6 (1) 198.6 (4) | 94.5% (2000, 2) | [24] |
Al-Doped α-MnO2 coated by Lignin | one-step hydrothermal process (200 °C) | 1D nanorod structures | 2 M ZnSO4 + 0.2 M MnSO4 | ~420 (0.1) 180 (1.5) | 66.7% (3000, 1.5) | [56] |
Al3+ pre-intercalated K0.27MnO2·0.54H2O (δ-MnO2) | modified hydrothermal method (160 °C) | spherical microflowers | 2 M ZnSO4 + 0.1 M MnSO4 | 323.7 (0.1) 250 (0.5) 191.7 (2) | 99% (300, 0.5) | [57] |
α-MnO2@KCoAl | co-precipitation method | irregular lumpy particles with agglomeration | 2 M ZnSO4 + 0.05 M MnSO4 | 524 (0.5) 431 (1) 221 (5) | ~66.4% (100, 0.5) | [58] |
Bi-doped α-MnO2 | redox process followed by annealing | nanoparticles | 2 M ZnSO4 + 0.2 M MnSO4 | 363 (0.1) 286 (0.6) 197 (1) | 93% (10,000, 1) | [59] |
Sn-doped α-MnO2 | hydrothermal process (180 °C) with further calcination | nanorods | 2 M ZnSO4 + 0.1 M MnSO4 | 210 (0.1) 106 (1) | 80 % (500, 1) | [30] |
Material | Synthesis Method | Morphology | Electrolyte | Specific Capacity, mAh g−1 (Current Density, A·g−1) | Capacity Retention, (Number of Cycles and Current, A·g−1) | Ref. |
---|---|---|---|---|---|---|
δ-MnO2@polyaniline | gas/liquid interface reaction | mesoporous nanohybrids | 2 M ZnSO4 + 0.2 M MnSO4 | 313 (0.1) 145 (1) 88 (3) | ~100% (500, 0.5) | [65] |
Polyaniline- intercalated δ-MnO2 | one-step inorganic/ organic interface reaction | nanolayers with spongiform structure | 2 M ZnSO4 + 0.1 M MnSO4 | 298 (0.05) 280 (0.2) 110 (3) | 90% (200, 0.2) 40% (5000, 2) | [66] |
Polyaniline-coated β-MnO2/rGO | MnO2 ball-milling + hydrothermal process with rGO (160 °C) + in situ polymerization | aerogel-supported | 2 M ZnSO4 | 241.1 (0.1) 111.7 (1) | 82.7% (600, 1) | [67] |
PANI-δ-MnO2/CC | hydrothermal method (150 °C) + in situ polymerization | nanosheets | 2 M ZnSO4 + 0.1 M MnSO4 | 286 (0.5) 233 (2) 177 (4) | 96.9% (9000, 4) | [68] |
α-MnO2@PANI | hydrothermal process (160 °C) + in situ interfacial polymerization | core-shell | 2 M ZnSO4 + 0.1 M MnSO4 | 342 (0.2) 100 (3) | 82% (2000, 2) | [69] |
α-MnO2/PPy | hydrothermal process (160 °C) + in situ polymerization | nanorods | 2 M ZnSO4 + 0.1 M MnSO4 | 256 (0.1) 104 (1) | 100% (500, 1) 100% (50, 0.1) | [78] |
β-MnO2/PPy | one-step hydrothermal process (120 °C) | micro-spherical structure of nanowires and clusters of nanorods | 2 M ZnSO4 + 0.1 M MnSO4 | 215.4 (0.1) 214.1 (0.2) 171.5 (0.5) 69.9 (1.5) | 100% (160, 0.2) | [79] |
CNT/α-MnO2-PPy | in situ reactive self- assembly and following vacuum filtration | core-shell structure and rod-shaped morphology | 2 M ZnSO4 + 0.1 M MnSO4 | 253.9 (0.3) 83.3 (2) | 87.4% (1000, 1) 75.5% (200, 0.3) | [81] |
α-MnO2/rGO-PPy | hydrothermal process (140 °C) + in situ polymerization | nanowires wrapped by PPy | 3 M Zn(CF3SO3)2 | 438.3 (0.1) 248.8 (0.5) | ~85.9% (100, 0.5) | [82] |
Mn2O3/α-MnO2@PPy | molten salt method + self-initiated polymerization | nanobelts and nanoparticles | 2 M ZnSO4 + 0.2 M MnSO4 | 289.9 (0.2) 252.6 (1) 199.8 (3) | ~100% (1000, 3) 96.7% (1000, 1) | [83] |
Fe-doped α-MnO2 coated by PPy | chemical precipitation method + in situ polymerization | nanoparticles | 2 M ZnSO4 + 0.1 M MnSO4 | 270 (0.1) 164 (0.4) 73 (1) | 99.6% (100, 0.1) | [84] |
α-MnO2/PPy@SS | electrodeposition | nanocrystallites | 1 M ZnSO4 + 0.1 M MnSO4 | 143.2 (0.308) 102.2 (0.924) 86.8 (1.54) | 74.2% (850, 1.54) | [85] |
MnO2@PEDOT | electrodeposition | nanosheets | 2 M ZnCl2 + 0.4 M MnSO4 | 366.6 (0.74) 143 (7.43) | 83.7% (300, 1.11) | [90] |
PEDOT@Co-MnO2 | low-temperature hydrothermal process + electrochemical polymerization | nanoflakes | 2 M ZnSO4 | 298.9 (1) | 92.3% (1000, 5.0) | [92] |
δ-MnO2/α-MnO2 /PEDOT | decomposition (δ -MnO2) + hydrothermal process (150 °C, α-MnO2) + electrodeposition (PEDOT) | nanowires of δ-MnO2 and nanoflakes of α-MnO2 | 2 M ZnSO4 + 0.1 M MnSO4 | 360.5 (0.031) 174.5 (0.308) 94 (1.54) | 78% (860, 0.308) | [93] |
δ-MnO2@PEDOT | redox reaction | nanowires | 2 M ZnSO4 + 0.2 M MnSO4 | 242 (0.2) 133 (1) 120.7 (2) | 85.1% (1000, 2) | [95] |
VG-α-MnO2 coated with PEDOT:PSS | hydrothermal process (150 °C) | MnO2 nano- particles on VG nanosheets with 3D porous structure | 1 M ZnSO4 + 0.1 M MnSO4 | 367.4 (0.5) 280.5 (1) 148.2 (6) | 73.7% (1000, 5) | [98] |
K0.46Mn2O4·1.55 H2O (δ-MnO2)/PEDOT:PSS | hydrothermal method (160 °C) +mechanical mixing with PEDOT:PSS | nanoflowers | 2 M ZnSO4 + 0.1 M MnSO4 | 380 (0.3) 243 (1) 40 (5) | 100% (120, 0.3) | [97] |
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Kamenskii, M.A.; Volkov, F.S.; Eliseeva, S.N.; Tolstopyatova, E.G.; Kondratiev, V.V. Enhancement of Electrochemical Performance of Aqueous Zinc Ion Batteries by Structural and Interfacial Design of MnO2 Cathodes: The Metal Ion Doping and Introduction of Conducting Polymers. Energies 2023, 16, 3221. https://doi.org/10.3390/en16073221
Kamenskii MA, Volkov FS, Eliseeva SN, Tolstopyatova EG, Kondratiev VV. Enhancement of Electrochemical Performance of Aqueous Zinc Ion Batteries by Structural and Interfacial Design of MnO2 Cathodes: The Metal Ion Doping and Introduction of Conducting Polymers. Energies. 2023; 16(7):3221. https://doi.org/10.3390/en16073221
Chicago/Turabian StyleKamenskii, Mikhail A., Filipp S. Volkov, Svetlana N. Eliseeva, Elena G. Tolstopyatova, and Veniamin V. Kondratiev. 2023. "Enhancement of Electrochemical Performance of Aqueous Zinc Ion Batteries by Structural and Interfacial Design of MnO2 Cathodes: The Metal Ion Doping and Introduction of Conducting Polymers" Energies 16, no. 7: 3221. https://doi.org/10.3390/en16073221