Supporting Information P2-Type Na x Cu 0.15 Ni 0.20 Mn 0.65 O 2 Cathodes with High Voltage for High-Power and Long-Life Sodium-Ion Batteries

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1 Supporting Information P2-Type Na x Cu 0.15 Ni 0.20 Mn 0.65 O 2 Cathodes with High Voltage for High-Power and Long-Life Sodium-Ion Batteries Wenpei Kang,, Denis Y. W. Yu, *, Pui-Kit Lee, Zhenyu Zhang, Haidong Bian, Wenyue Li, Tsz-Wai Ng, Wenjun Zhang and Chun-Sing Lee * Center of Super-Diamond and Advanced Films (COSDAF), City University of Hong Kong, Hong Kong SAR, China School of Energy and Environment, City University of Hong Kong, Hong Kong SAR, People s Republic of China. State Key Laboratory of Heavy Oil Processing, College of Science, China University of Petroleum (East China), Qingdao , P. R. China * Corresponding Author: denisyu@cityu.edu.hk; apcslee@cityu.edu.hk S-1

2 Figure S1 (a) XRD and (b, c) SEM images of the as-prepared Cu 0.15 Ni 0.20 Mn 0.65 C 2 O 4 2H 2 O precursor. S-2

3 (a) (b) Figure S2 (a) Survey spectra of the Na x Cu 0.15 Ni 0.20 Mn 0.65 O 2 (x = 0.50, 0.67 and 0.75) samples; (b) O 1s core level spectra. S-3

4 Figure S3 The magnified Na0.67Cu0.15Ni0.20Mn0.65O2. HRTEM images S-4 for (a) Na0.50Cu0.15Ni0.20Mn0.65O2 and (b)

5 Figure S4 CV curves of Na 0.75 Cu 0.15 Ni 0.20 Mn 0.65 O 2 sample at a scan rate of 0.1 mv s 1. S-5

6 Figure S5 Representative charge discharge curves of Na 0.75 Cu 0.15 Ni 0.20 Mn 0.65 O 2 electrode; (a) The electrodes are cycled at 10 ma g -1 in the initial two cycles and 1000 ma g -1 in the following cycles; (b) The electrodes are cycled at various current densities for 10 cycles each. S-6

7 Figure S6 Representative charge discharge curves of (a) Na 0.50 Cu 0.15 Ni 0.20 Mn 0.65 O 2 and (b) Na 0.67 Cu 0.15 Ni 0.20 Mn 0.65 O 2 electrodes cycled at 10 ma g -1 in the initial two cycles and 1000 ma g -1 in the following cycles over the voltage range of V. S-7

8 Table S1 ICP-AES results and lattice parameters of Na x Cu 0.15 Ni 0.20 Mn 0.65 O 2. x Na (mg L -1 ) M/T [1] / / / Cu (mg L -1 ) M/T 3.546/ / / Ni (mg L -1 ) M/T 4.386/ / / Mn (mg L -1 ) M/T / / / [1] M represents the measured value and T represents the theoretical value. Na:Cu:Ni:Mn a (Å) c (Å) V (Å 3 ) 0.51:0.15:0.20: :0.15:0.20: :0.15:0.20: S-8

9 Table S2 Average oxidation states of Mn and estimated oxygen deficiency of Na x Cu 0.15 Ni 0.20 Mn 0.65 O 2-δ from redox titration. x Estimated avg Mn oxidation state Oxygen deficiency (δ) S-9

10 Table S3 Electrochemical performance comparison of Mn- based cathode materials substituted by different cations in the literature Material Na x Cu 0.15 Ni 0.20 Mn 0.65 O 2 Na x MnO 2+z Na 0.7 MnO 2 Na 0.66 Li 0.18 Mn 0.71 Ni 0.21 Co 0.08 O 2+δ Na 2/3 Fe 1/2 Mn 1/2 O 2 Na 0.67 Ni 0.25 Mg 0.1 Mn 0.65 O 2 Initial capacity (mah g -1 ) ~ Test current (ma g -1 ) Capacity (mah g -1 ) 65/1000th 84/100th ~70/50th 110/150 th ~50/40 th 87/100th capacity retention 81.6% 60% 56% 75% 51% 87% Ref This Work Na 2/3 Co 1/2 Mn 1/2 O /30th 69% 6 Na 2/3 Fe 1/3 Mn 2/3 O /40th 80% 7 Na 2/3 Fe 1/2 Mn 1/2 O ~150/30th 79% 8 Na 0.67 Mg 0.1 Mn 0.9 O ~130/25th 76% 9 Na 2/3 [Mg 0.28 Mn 0.72 ]O ~150/30 th 71% 10 Na x Ni 0.22 Co 0.11 Mn 0.66 O 2 Na 0.67 Mn 0.67 Ni 0.15 Mg 0.18 O 2 Na 7/9 Cu 2/9 Fe 1/9 Mn 2/3 O ~ /200th 78/100 th 59.5/150th Na 0.67 Cu 0.33 Mn 0.67 O /500th 76.6% 14 Na 0.68 Cu 0.34 Mn 0.66 O 2 70 ~20 43/1000th 61% 15 Na 0.5 [Ni 0.23 Fe 0.13 Mn 0.63 ]O /100th 69% 16 Na x Ni 0.22 Co 0.11 Mn 0.66 O ~99/200th 76% 17 Na 0.66 Ni 0.26 Zn 0.07 Mn 0.67 O /30th 89% 18 76% 92% 87% References [1] Bucher, N.; Hartung, S.; Nagasubramanian, A.; Cheah, Y. L.; Hoster, H. E.; Madhavi, S. Layered Na x MnO 2+z in Sodium Ion Batteries-Influence of Morphology on Cycle Performance. ACS Appl. Mater. Interfaces 2014, 6, [2] Su, D. W.; Wang, C. Y.; Ahn, H. J.; Wang, G. X. Single Crystalline Na 0.7 MnO 2 Nanoplates as Cathode Materials for Sodium-Ion Batteries with Enhanced Performance. Chem. - Eur. J. 2013, 19, [3] Guo, S. H.; Liu, P.; Yu, H. J.; Zhu, Y. B.; Chen, M. W.; Ishidaand, M.; Zhou, H. S. A Layered P2- and O3-Type Composite as a High-Energy Cathode for Rechargeable Sodium-Ion Batteries. Angew. Chem., Int. Ed. 2015, 54, S-10

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