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Inorganic Nanowire-Modified Polyelectrolytes for
Vanadium Flow Battery Membranes
Brandon Clark1,2, Dr. Amy Peterson1, Dr. Yousef Mahmoud2
1Department of Chemical Engineering, Worcester Polytechnic Institute
2Department of Electrical and Computer Engineering, Worcester Polytechnic Institute
Project Goals/Methods
Results: ZnO-PSS DLS
Background
Recent Work
Acknowledgements
References
Future Work
Crosslinking strategies for insolubility
1. PSS-Maleic Acid: Fischer
esterification with hydroquinone
2. UV light5
Vanadium Redox Flow Battery (VRFB): currently used for
grid energy storage, especially for transient renewables1
Nafion: proton exchange membrane2
Pros
1. High chemical stability
Cons
1. Expensive
2. High vanadium permeability
a) Due to ion channel bulk transport
b) Leads to capacity losses
Current membranes (PBI3 and SPEEK4)
1. Improved selectivity
2. Still expensive
3. Sacrifices some conductivity
a) Poor ion channel self assembly
Inorganic Nanowires4
1. Believed to block vanadium further
by plugging ion channels
1. Confirm electrostatic adhesion of ZnO and TiO2
nanowires onto Polystyrene sulfonate (PSS)
2. Compare membrane performance to current
popular battery membranes
a) ion exchange capacity
b) water and vanadium ion permeability
c) proton conductivity
3. Build a battery prototype
a) Study voltage and coulombic efficiency
through charge-discharge cycling
PSS
ZnO
TiO2
Polybenzimidazole
Poly ether ether ketone
Battery
Prototype
Permeability Test
Nafion
Particle Size: No
appreciable trend
1. PSS is small
0
100
200
300
400
500
600
700
0 5 10 15 20 25 30
Size(nm)
Adsorption Time
PSS-ZnO
ZnO Control
PSS Control
-80
-70
-60
-50
-40
-30
-20
0 5 10 15 20 25 30
ZetaPotential(mV)
Adsorption Time (min)
PSS-ZnO
ZnO Control
PSS Control
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
0.45
0.5
0 5 10 15 20 25 30
Conductivity(mS/cm)
Adsorption Time (min)
PSS-ZnO
ZnO Control
PSS Control
Zeta Potential: more negative
as absorption time increased
1. PSS: preferential
electrostatic absorption
compared to Na+
Conductivity: only high at
zero absorption time
1. electrostatic bonding
may prevent electron
mobility
1. Chen, C. L.; Yeoh, H. K.; Chakrabartia, M. H. An enhanced one-dimensional stationary model for the all-
vanadium redox flow battery; Proceedings of the 6th International Conference on Process Systems
Engineering (PSE ASIA); 2013; Vol. 25, pp 27.
2. Tung, S.; Hwang, B. Synthesis and characterization of hydrated phosphor–silicate glass membrane
prepared by an accelerated sol–gel process with water/vapor management. Journal of Materials
Chemistry 2005, 15, 3532-3538.
3. Yuan, Z.; Duan, Y.; Zhang, H.; Li, X.; Zhang, H.; Vankelecom, I. Advanced porous membranes with ultra-high
selectivity and stability for vanadium flow batteries. Energy & Environmental Science 2016, 9, 441-447.
4. Ji, Y.; Tay, Z. Y.; Li, S. F. Y. Highly selective sulfonated poly (ether ether ketone)/titanium oxide composite
membranes for vanadium redox flow batteries. J. Membr. Sci. 2017, 539, 197-205.
5. Hong, K.; Kim, S. H.; Yang, C.; Yun, W. M.; Nam, S.; Jang, J.; Park, C.; Park, C. E. Photopatternable Poly (4-
styrene sulfonic acid)-wrapped MWNT thin-film source/drain electrodes for use in organic field-effect
transistors. ACS applied materials & interfaces 2010, 3, 74-79.
This work is funded by the WPI departments of Chemical Engineering
and Electrical and Computer Engineering. I would like to thank Dr.
Amy Peterson, Dr. Yousef Mahmoud, Ivan Ding, Anthony D’Amico,
and Lv Xuejian for their support and mentorship.

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Clark NCSU Future Leaders Conference Poster

  • 1. Inorganic Nanowire-Modified Polyelectrolytes for Vanadium Flow Battery Membranes Brandon Clark1,2, Dr. Amy Peterson1, Dr. Yousef Mahmoud2 1Department of Chemical Engineering, Worcester Polytechnic Institute 2Department of Electrical and Computer Engineering, Worcester Polytechnic Institute Project Goals/Methods Results: ZnO-PSS DLS Background Recent Work Acknowledgements References Future Work Crosslinking strategies for insolubility 1. PSS-Maleic Acid: Fischer esterification with hydroquinone 2. UV light5 Vanadium Redox Flow Battery (VRFB): currently used for grid energy storage, especially for transient renewables1 Nafion: proton exchange membrane2 Pros 1. High chemical stability Cons 1. Expensive 2. High vanadium permeability a) Due to ion channel bulk transport b) Leads to capacity losses Current membranes (PBI3 and SPEEK4) 1. Improved selectivity 2. Still expensive 3. Sacrifices some conductivity a) Poor ion channel self assembly Inorganic Nanowires4 1. Believed to block vanadium further by plugging ion channels 1. Confirm electrostatic adhesion of ZnO and TiO2 nanowires onto Polystyrene sulfonate (PSS) 2. Compare membrane performance to current popular battery membranes a) ion exchange capacity b) water and vanadium ion permeability c) proton conductivity 3. Build a battery prototype a) Study voltage and coulombic efficiency through charge-discharge cycling PSS ZnO TiO2 Polybenzimidazole Poly ether ether ketone Battery Prototype Permeability Test Nafion Particle Size: No appreciable trend 1. PSS is small 0 100 200 300 400 500 600 700 0 5 10 15 20 25 30 Size(nm) Adsorption Time PSS-ZnO ZnO Control PSS Control -80 -70 -60 -50 -40 -30 -20 0 5 10 15 20 25 30 ZetaPotential(mV) Adsorption Time (min) PSS-ZnO ZnO Control PSS Control 0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.5 0 5 10 15 20 25 30 Conductivity(mS/cm) Adsorption Time (min) PSS-ZnO ZnO Control PSS Control Zeta Potential: more negative as absorption time increased 1. PSS: preferential electrostatic absorption compared to Na+ Conductivity: only high at zero absorption time 1. electrostatic bonding may prevent electron mobility 1. Chen, C. L.; Yeoh, H. K.; Chakrabartia, M. H. An enhanced one-dimensional stationary model for the all- vanadium redox flow battery; Proceedings of the 6th International Conference on Process Systems Engineering (PSE ASIA); 2013; Vol. 25, pp 27. 2. Tung, S.; Hwang, B. Synthesis and characterization of hydrated phosphor–silicate glass membrane prepared by an accelerated sol–gel process with water/vapor management. Journal of Materials Chemistry 2005, 15, 3532-3538. 3. Yuan, Z.; Duan, Y.; Zhang, H.; Li, X.; Zhang, H.; Vankelecom, I. Advanced porous membranes with ultra-high selectivity and stability for vanadium flow batteries. Energy & Environmental Science 2016, 9, 441-447. 4. Ji, Y.; Tay, Z. Y.; Li, S. F. Y. Highly selective sulfonated poly (ether ether ketone)/titanium oxide composite membranes for vanadium redox flow batteries. J. Membr. Sci. 2017, 539, 197-205. 5. Hong, K.; Kim, S. H.; Yang, C.; Yun, W. M.; Nam, S.; Jang, J.; Park, C.; Park, C. E. Photopatternable Poly (4- styrene sulfonic acid)-wrapped MWNT thin-film source/drain electrodes for use in organic field-effect transistors. ACS applied materials & interfaces 2010, 3, 74-79. This work is funded by the WPI departments of Chemical Engineering and Electrical and Computer Engineering. I would like to thank Dr. Amy Peterson, Dr. Yousef Mahmoud, Ivan Ding, Anthony D’Amico, and Lv Xuejian for their support and mentorship.