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Frontiers in Energy

Front. Energy    2017, Vol. 11 Issue (3) : 401-409
β-Nickel hydroxide cathode material for nano-suspension redox flow batteries
Yue LI1, Cheng HE1, Elena V. TIMOFEEVA2, Yujia DING2, Javier PARRONDO1, Carlo SEGRE2, Vijay RAMANI1()
1. Center for Solar Energy?and Energy Storage, Department of Energy,?Environmental and Chemical?Engineering, Washington University in St. Louis, 1 Brookings Dr., St. Louis, MO 63130, USA
2. Physics Department, Illinois Institute of Technology, Chicago, IL 60616, USA
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As part of an effort to build a prototype flow battery system using a nano-suspension containing β-Ni(OH)2 nanoparticles as the cathode material, nano-sized β-Ni(OH)2 particles with well-controlled particle size and morphology were synthesized via the one-step precipitation of a NiCl2 precursor. The composition and morphology of the nanoparticles were characterized by scanning electronic microscopy (SEM) and X-ray diffraction (XRD). The XRD patterns confirmed that β-Ni(OH)2 was successfully synthesized, while SEM results showed that the particle sizes range from 70 to 150 nm. To ensure that Ni(OH)2 could be employed in the nano-suspension flow battery, the electrochemical performance of the synthesized β-Ni(OH)2 was initially tested in pouch cells through charge/discharge cycling. The phase transformations occurring during charge/discharge were investigated usingin-situ X-ray absorption spectroscopy to obtain the shift in the oxidation state of Ni (X-ray adsorption near edge structure, XANES) and the distances between Ni and surrounding atoms in charged and discharged states (extended X-ray absorption fine structure, EXAFS). XANES results indicated that the electrode in the discharged state was a mixture of phases because the edge position did not shift back completely. XAFS results further proved that the discharge capacity was provided by β-NiOOH and the ratio between β-Ni(OH)2 and g-NiOOH in the electrode in the discharged state was 71:29. Preliminary nano-suspension tests in a lab-scale cell were conducted to understand the behavior of the nano-suspension during charge/discharge cycling and to optimize the operating conditions.

Keywords nano-suspension flow battery      β-Ni(OH)2      scanning electronic microscopy (SEM)      X-ray diffraction (XRD)      X-ray adsorption near edge structure (XANES)      extended X-ray absorption fine structure (EXAFS)     
Corresponding Authors: Vijay RAMANI   
Just Accepted Date: 18 July 2017   Online First Date: 25 August 2017    Issue Date: 07 September 2017
 Cite this article:   
Yue LI,Cheng HE,Elena V. TIMOFEEVA, et al. β-Nickel hydroxide cathode material for nano-suspension redox flow batteries[J]. Front. Energy, 2017, 11(3): 401-409.
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Fig.1  Schematic of the pouch cell used for in-situ XAFS measurement and the X-ray path through the cell
Fig.2  Histogram of the particle size distribution of the as-synthesized Ni(OH)2 particles
Fig.3  XRD patterns of as-synthesized Ni(OH)2 and b-Ni(OH)2 baseline
Fig.4  Charge and discharge curves for b-Ni(OH)2 pouch cells at a charge/discharge C-rate of C/2
Fig.5  Specific discharge capacity vs. cycle number
Fig.6  XAFS spectra for the Ni K-edge of as-synthesized Ni(OH)2 powder and for the Ni(OH)2 casted electrode in the pouch cell in charged and discharged states
Fig.7  EXAFS spectra in R-space for pristine Ni(OH)2 and for pouch cells in charged and discharged states
Sample Rf/% Model Amp. Path N R σ2
Pristine Ni(OH) 2 4.7 b-Ni(OH)2 0.77 Ni-O 6 2.07(2) 0.005(4)
Ni-Ni 6 3.11(2) 0.006(3)
Charged sample 1.2 b-NiOOH 0.73 Ni-O 6 1.91(1) 0.006(2)
Ni-Ni 6 2.83(2) 0.010(2)
Discharged sample 4.0 b-Ni(OH)2 0.59 Ni-O 6 2.08(3) 0.0055
Ni-Ni 6 3.12(3) 0.0061
g-NiOOH 0.24 Ni-O 6 1.94(5) 0.0059
Ni-Ni 6 2.83(5) 0.0096
Tab.1  EXAFS modelling results for Ni(OH)2 electrodes
Fig.8  Charge curves at 7.2 mA/cm2 for b-Ni(OH)2 nano-suspension
Fig.9  Discharge at 0.72 mA/cm2 for b-Ni(OH)2 nano-suspension
Fig.10  Comparison of XRD patterns of as-prepared Ni(OH)2 and nanoparticles recovered from nano-suspension after 13 cell charge/discharge cycles
Fig.11  Specific discharge capacities at a discharge current density of 0.72 mA/cm2 for b-Ni(OH)2 nano-suspension at different charge rates
Fig.12  Specific discharge capacity for b-Ni(OH)2 nano-suspension at a charge current density of 7.2 mA/cm2 and a discharge current density of 0.72 mA/cm2
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