• Review •
Shihao Zhou, Xianwen Wu, Yanhong Xiang, Ling Zhu, Zhixiong Liu, Caixian Zhao. Manganese-Based Cathode Materials for Aqueous Zinc Ion Batteries[J]. Progress in Chemistry, 2021, 33(4): 649-669.
Metal electrode | Ionic radius (Å) | Energy density (W·h·kg-1) | Discharge voltage plateau (V) | Specific capacity (mA·h·g-1) | Volumetric capacity (mA·h·cm-3) | Abundance in earth crust (ppm) | Cost (USD) kg-1 | Safety and recyclability | ||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
Lithium | 0.76 | 70~140 | 0.6~1.8 | 3860 | 2061 | 20 | 19.2 | low | ||||||
Zinc | 0.75 | 180~230 | 3.2~5.0 | 820 | 5855 | 70 | 2.2 | high |
Cathode | Morphology | Electrolyte | Voltage(V) | Capacity(mA·h·g-1) | Capacity retention/n cycles/y A·g-1 | ref |
---|---|---|---|---|---|---|
ɑ-MnO2 | nanorod | 1 M ZnSO4 | 1~1.8 | 233(83 mA·g-1) | 65%/50 cycles/0.083 | |
ɑ-MnO2 | nanorod | 2 M ZnSO4 + 0.1 M MnSO4 | 1~1.8 | 161(500 mA·g-1) | 92%/5000 cycles/5 C | |
ɑ-MnO2@Graphene | nanowire | 2 M ZnSO4 + 0.1 M MnSO4 | 1~1.85 | 382.2(300 mA·g-1) | 94%/3000 cycles/3 | |
α-MnO2@CNT | nanorod | 2 M ZnSO4 + 0.1 M MnSO4 | 0.8~1.8 | 306(61.6 mA·g-1) | 97%/1000/2.772 | |
α-MnO2@CNT HMs | microsphere | 2 M ZnSO4 + 0.1 M MnSO4 | 1.2~1.85 | 296(200 mA·g-1) | 97%/1000/2.772 | |
MnO2@porous-C | nanorod | 2 M ZnSO4 + 0.1 M MnSO4 | 0.8~1.8 | 239(100 mA·g-1) | 100%/1000 cycles/1 | |
α-MnO2@In2O3 | nanotube | 2 M ZnSO4 + 0.1 M MnSO4 | 1~1.8 | 425(100 mA·g-1) | 75 mA·h·g-1/3000 cycles/3 | |
Hollow MnO2/CC | nanosheet | 2 M ZnSO4 + 0.1 M MnSO4 | 0.8~1.8 | 263.9(1A·g-1) | 263.9/300 cycles/1 | |
β-MnO2 | nanorod | 1 M ZnSO4 | 1~1.8 | 270(100 mA·g-1) | 75%/200 cycles/0.2 | |
β-MnO2 | nanorod | 3 M Zn(CF3SO3)2+ 0.1 M Mn(CF3SO3)2 | 0.8~1.9 | 258(0.65 C) | 94%/2000 cycles/6.5C | |
β-MnO2@C | nanoparticle | 3 M Zn(CF3SO3)2 + 0.1 M MnSO4 | 1.0~1.8 | 150(200 mA·g-1) | 100%/400 cycles/0.3 | |
γ-MnO2 | mesoporous | 1 M ZnSO4 | 0.8~1.8 | 285(0.05 mA·c ) | 63%/40 cycles/0.5mA·c | |
γ-MnO2@C | nanorod | 2 M ZnSO4 + 0.4 M MnSO4 | 0.8~1.8 | 301(500 mA·g-1) | 64.1%/300 cycles/10 | |
Todorokite-MnO2 | nanoflake | 1 M ZnSO4 | 0.7~2.0 | 108(0.5 C) | 72%50 cycles/0.5C | |
δ-MnO2 | nanoflake | 1 M ZnSO4 | 1.0~1.8 | 252(83 mA·g-1) | 44%/100 cycles/0.1 | |
δ-MnO2 | nanoparticle | 1 M Zn(TFSI)2+0.1 M Mn(TFSI)2 | 0.9~1.8 | 238(0.2 C) | 93%/4000 cycles/20C | |
λ-MnO2 | nanoparticle | 1 M ZnSO4 | 1~1.8 | 136(100 mA·g-1) | - | |
ε-MnO2@CFP | nanoparticle | 2 M ZnSO4 + 0.2 M MnSO4 | 1~1.8 | 290(1 C) | 100%/10 000 cycles/6.5C | |
ɑ-Mn2O3 | nanoparticle | 2 M ZnSO4 + 0.1 M MnSO4 | 1~1.9 | 148(100 mA·g-1) | 51%/2000 cycles/0.1 | |
Mn2O3/Al2O3 | microbundle | 2 M ZnSO4 + 0.1 M MnSO4 | 1~1.8 | 289(300 mA·g-1) | 118 mAh·g-1/1100 cycle/1.5 | |
Mn3O4 | nanoparticle | 2 M ZnSO4 | 0.8~1.9 | 239.2(1 A·g-1) | 73%/300 cycles/0.5 | |
Porous cube-like Mn3O4 @C | porous nanocube | 2 M ZnSO4 + 0.1 M MnSO4 | 0.8~1.9 | 102.3(2 A·g-1) | 77.1%/200 cycles/0.5 | |
Mn3O4@NC | nanorod | 2 M ZnSO4 + 0.1 M MnSO4 | 0.8~1.9 | 280(100 mA·g-1) | 77.6%/700 cycles/1 | |
MnO | nanoparticle | 2 M ZnSO4 + 0.1 M MnSO4 | 1.0~1.9 | 330(100 mA·g-1) | 300 mAh·g-1/300 cycles/0.3 | |
Mn0.61□0.39O @C | nanoparticle | 2 M ZnSO4 + 0.1 M MnSO4 | 0.8~1.8 | 117.2(1 A·g-1) | 99%/1500 cycles/1 | |
ZnMn2O4 | microrod | 1 M ZnSO4 + 0.1 M MnSO4 | 0.6~1.9 | 240(200 mA·g-1) | 79%/1000 cycles/2 | |
Hollow ZnMn2O4 | hollow microsphere | 2 M ZnSO4 + 0.1 M MnSO4 | 0.8~1.9 | 220(100 mA·g-1) | 106.5 mAh·g-1/300 cycles/0.1 | |
ZnMn2O4/C | nanoparticle | 3 M Zn(CF3SO3)2 | 0.8~1.9 | 150(50 mA·g-1) | 94%/500 cycles/0.5 | |
ZnMn2O4@PCPs | nanoparticle | 1 M ZnSO4 +0.05 M MnSO4 | 0.8~1.8 | 145.2(1000 mA·g-1) | 86.5%/2000 cycles/1 | |
HM-ZnMn2O4@rGO | hollow nanosphere | 2 M ZnSO4 + 0.1 M MnSO4 | 0.8~1.8 | 147(300 mA·g-1) | 72.7/6500 cycles/1 | |
OD-ZnMn2O4@PEDOT | nanofiber | PVA/LiCl/ZnCl2/MnSO4Gel | 0.8~1.9 | 221(0.5 mA·c ) | 93.8%/300 cycles/8 mA·c | |
MnS | nanoparticle | 2 M ZnSO4 | 1~1.8 | 110(500 mA·g-1) | 63.6%/100 cycles/0.5 | |
MnOx@N-C | nanorod | 2 M ZnSO4 + 0.1 M MnSO4 | 0.8~1.8 | 100(2 A·g-1) | 100 mA·h·g-1/1600 cycles/2 | |
V-doped MnO2 | nanoparticle | 1 M ZnSO4 | 1~1.8 | 266(66 mA·g-1) | 49%/100 cycles/0.066 | |
Ce-doped α-MnO 2 | nanorod | 2 M ZnSO4 + 0.1 M MnSO4 | 1~1.8 | 134(5 C) | 70%/100 cycles/5 C | |
Ti-MnO2 | nanowire | 3 M Zn(CF3SO3)2+ 0.1 M Mn(CF3SO3)2 | ~ | 259(100 mA·g-1) | 86%/4000 cycles/1 | |
NixMn3-xO4@C | nanoparticle | 2M ZnSO4 + 0.15 M MnSO4 | 1~1.85 | 133.7(200 mA·g-1) | 91.9%/850 cycles/0.4 | |
ZnNixCoyMn2-x-yO4@N-GO | nanoparticle | 2 M ZnSO4 +0.1 M MnSO4 | 0.7~1.7 | 3.5(1.5 A·g-1) | 79%/900 cycles/1 | |
H2O-intercalated δ-MnO 2 | nanoflake | 1 M ZnSO4 | 1~1.9 | 154(3 A·g-1) | 75.3%/200 cycles | |
Na0.46Mn2O4·1.4H2O | nanoplates | 2 M ZnSO4 + 0.2 M MnSO4 | 0.9~1.9 | 159(2 A·g-1) | 98%/10 000 cycles/20 C | |
La+-intercalated δ-MnO 2 | nanofloret | 1 M ZnSO4 + 0.4 M MnSO4 | 0.8~1.9 | 278.5(100 mA·g-1) | - | |
K0.8Mn8O16 | nanorod | 2 M ZnSO4 + 0.2 M MnSO4 | 1~1.8 | 330(100 mA·g-1) | 150 mAh·g-1/1000 cycles/1 | |
KxMn8-xO16 | nanodendrite | 1 M Zn(CF3SO3)2 + 0.05 M MnSO4 | 0.8~1.8 | 116(100 mA·g-1) | 74%/300 cycles/0.1 | |
P-MnO2-x@VMG | nanosheet | PVA/ZnCl2/MnSO4 Gel | 1~1.8 | 302.8(500 mA·g-1) | 90%/1000 cycles/2 | |
ZnMn2O4/NG | nanoparticle | 1 M ZnSO4 +0.05 M MnSO4 | 0.8~1.8 | 221(100 mA·g-1) | 97.4%/2500 cycles/1 | |
MnOx/PPy | nanoparticle | 2 M ZnSO4 + 0.1 M MnSO4 | 0.4~1.9 | 302(150 mA·g-1) | 114 mAh·g-1/1000 cycles/6 | |
ZnMn2O4/Mn2O3 | microsphere | 1 M ZnSO4 | 0.8~1.9 | 82.6(500 mA·g-1) | 112 mAh·g-1/300 cycles/0.5 | |
Binder-free Mn3O4 | nanoflower | 2 M ZnSO4 + 0.1 M MnSO4 | 1~1.8 | 296(100 mA·g-1) | 100%/100 cycles/0.5 | |
oxygen-deficient δ-MnO 2 | nanosheet | 1 M ZnSO4 + 0.2 M MnSO4 | 1~1.8 | 159(200 mA·g-1) | 80%/3000 cycles/5 | |
oxygen-deficient β-MnO 2 | nanowire | 2 M ZnSO4 + 0.1 M MnSO4 | 0.8~1.8 | 302(50 mA·g-1) | 94%/3000 cycles/5 |
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