Highly Reversible Open Framework Electrodes for Divalent Ion Batteries

Richard Y. Wang, Colin D. Wessells, Robert A. Huggins, and Yi Cui*,,

Department of Materials Science and Engineering, Stanford University, Stanford, California 94305, United States

Stanford Institute for Materials and Energy Sciences, SLAC National Accelerator Laboratory, 2575 Sand Hill
Road, Menlo Park, California 94025, United States

Supporting Information

7
1M Mg2+
6
1M Ca2+
5
1M Sr2+
0.1M Ba2+
Im(Z)

0
0 2 4 6 8 10 12 14 16
Re(Z)

0.1 0.1
1M Mg2+ 1M Ca2+
0.08 0.08

0.06 0.06
Im(Z)
Im(Z)

0.04 0.04

0.02 0.02

0 0
3.94 3.96 3.98 4 4.02 4.8 4.82 4.84 4.86 4.88
Re(Z) Re(Z)
0.1 1
1M Sr2+ 0.1M Ba2+
0.08 0.8

0.06 0.6
Im(Z)

Im(Z)

0.04 0.4

0.02 0.2

0 0
6.92 6.94 6.96 6.98 7 12.8 13 13.2 13.4 13.6
Re(Z) Re(Z)

Supporting Figure S1. Electrochemical impedance spectroscopy (EIS), measured at 50% charge

for each of the electrolytes, show increasing ohmic resistance going from Mg2+ to Ba2+. The

resistances for Ba2+ cannot be directly compared to the other results because the Ba2+ electrolyte

1
concentration is lower by an order of magnitude. EIS was collected with zero bias and a

frequency sweep from 100 kHz to 30 mHz with an amplitude of 10 mV.

0.3
2+
Ni
0.2
Specific current (A/g)

0.1

0.1

0.2

0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

Voltage (V) vs SHE

Supporting Figure S2. The CV curve (1 mV s-1 sweep rate) demonstrates reversible insertion of

Ni2+ ions in NiHCF. The electrode (with mass loading of approximately 10 mg cm-2) was cycled

in a 1 M solution of nickel nitrate at pH 2.

(A) (B)
0% charge 60% charge 0% charge 60% charge
20% charge 80% charge 20% charge 80% charge
40% charge 100% charge 40% charge 100% charge
Intensity
Intensity

10 20 30 40 50 60 70 10 20 30 40 50 60 70
2 2

2
(C)
0% charge 60% charge
20% charge 80% charge
40% charge 100% charge
Intensity

10 20 30 40 50 60 70
2

Supporting Figure S3. XRD spectra of NiHCF with varying concentrations of (A) K+, (B)

Mg2+, and (C) Ba2+ insertion ions show that the structure remains face-centered cubic and nearly

unchanged upon insertion and extraction of monovalent and divalent ions. A reference Prussian

Blue XRD is plotted at the bottom of each figure for comparison. 0% charge corresponds to a

fully reduced sample filled with insertion ions, and 100% charge corresponds to a fully oxidized

sample with no insertion ions present. XRD spectra were collected using a PANalytical XPert

PRO Diffractometer with Cu-K radiation.