Aqueous Soluble Organic (ASO) Flow Battery Development · Vanadium Redox Flow Batteries (VRFB)...
Transcript of Aqueous Soluble Organic (ASO) Flow Battery Development · Vanadium Redox Flow Batteries (VRFB)...
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Aqueous Soluble Organic (ASO) Flow Battery Development
Aaron Hollas, Vijayakumar Murugesan, Bin Li, Zimin Nie, Wei Wang, David Reed, Vince Sprenkle
Pacific Northwest National Laboratory
Support from DOE Office of Electricity Delivery & Energy Reliability
Energy Storage Program
DOE OE Energy Storage Peer Review 2018
Santa Fe, NM
September 2018
Why Redox Flow Batteries (RFB)
2Zhenguo Yang, et. al. Chemical Reviews, 111, 2011, 3577
Wei Wang, et. al. Advanced Functional Materials , 23, 2013, 970
➢ High safety
Spatial separation of reactive materials
Major constituent is water
Easy thermal management.
Battery health monitoring
➢ Easy recycling after service life
Consumption vs. Investment
➢ Decoupling of Power and Capacity
Tailor system to application
➢ 7 confirmed lithium-ion ESS fires in
Korea this summer alone.
Vanadium Redox Flow Batteries (VRFB)
3Zhenguo Yang, et. al. Chemical Reviews, 111, 2011, 3577
Wei Wang, et. al. Advanced Functional Materials , 23, 2013, 970
➢ Vanadium Redox Flow Battery (VRB)
Advantages
Current state-of-the-art, highly studied
High solubility
High cell voltage
MWh scale deployment
➢ …however…
High material cost
Capacity loss from crossover
Precipitation issues (temperature window)
Requires Nafion
V species -5°C 25°C 40°C
sulfate sulfate sulfate
V2+2M
(419 h)*
2M
(>30 d)
2M
(>30 d)
V3+2M
(634 h)
2M
(>30 d)
2M
(>30 d)
V4+ (VO2+)2M
(18 h)
2M
(95 h)
2M
(>30 d)
V5+ (VO2+)
2M
(>30 d)
2M
(>30 d)
2.2M
(95 h)
Vanadium Redox Flow Batteries (VRFB)
4Zhenguo Yang, et. al. Chemical Reviews, 111, 2011, 3577
Wei Wang, et. al. Advanced Functional Materials , 23, 2013, 970
➢ …however…
High material cost
Capacity loss from crossover
Precipitation issues (temperature window)
Requires Nafion
FY 2018 Milestone
➢ Evaluate new electrolyte composition on a pilot scale stack
capable of meeting $250/kWh cost target for a projected
1MW/4MWh system operating at 75 mA/cm2.
Aqueous-Soluble Organic (ASO) vs Vanadium
5Zhenguo Yang, et. al. Chemical Reviews, 111, 2011, 3577
Wei Wang, et. al. Advanced Functional Materials , 23, 2013, 970
➢ …however…
High material cost
Capacity loss from crossover
Precipitation issues (temperature window)
Requires Nafion
➢ Benefits of Organics vs Vanadium
Potentially lower cost
Vast library of candidates
Systems ranging from pH 0-14
Improved electrochemical kinetics
Candidates with 2e- redox events
J. Electrochem. Soc. 2016, 163 (7), A1442-A1449.
Nature Energy 1, Article number: 16102 (2016)Adv. Energy Mater. 2015, 1501449.Science 2015, 349 (6255), 1529.
Aqueous-Soluble Organic (ASO) RFB
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➢ Benefits of Organics vs Vanadium
Potentially lower cost
Vast library of candidates
Systems ranging from pH 0-14
Improved electrochemical kinetics
Candidates with 2e- redox events
J. Electrochem. Soc. 2016, 163 (7), A1442-A1449.
Nature Energy 1, Article number: 16102 (2016)Adv. Energy Mater. 2015, 1501449.Science 2015, 349 (6255), 1529.
➢ System Challenges
Moderate Solubility
Low Potential
Chemical Instability
Membrane Crossover
Identifying Potential Redox-Active Species
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➢ Selection Strategy
Identify redox-active core structure
Flavin-based
Quinone-based
Phenazine-based
Nature-inspired
redox-actives
Identifying Potential Redox-Active Species
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➢ Selection Strategy
Identify redox-active core structure
Target solubilizing groups (pH dependent) and
appropriate redox-tuning groups
Phenazine-based
Control Solubility
-SO3−, -CO2
−, -PO32 −, -NH2, -NR3
+, -OH
Tune Redox Potential - Withdrawing
-SO3−, -CO2
−, -PO32 −, -NR3
+
Tune Redox Potential - Donating
-NH2, -OH
Identifying Potential Redox-Active Species
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➢ Selection Strategy
Identify redox-active core structure
Target solubilizing groups (pH dependent) and
appropriate redox-tuning groups
Substitute core structure based on readily available
reagents and scalable synthetic methods
Phenazine-based
Control Solubility
-SO3−, -CO2
−, -PO32 −, -NH2, -NR3
+, -OH
Tune Redox Potential - Withdrawing
-SO3−, -CO2
−, -PO32 −, -NR3
+
Tune Redox Potential - Donating
-NH2, -OH
?
DFT-Directed Synthesis
➢ Selection Strategy
Identify redox-active core structure
Target solubilizing groups (pH dependent) and
appropriate redox-tuning groups
Substitute core structure based on readily available
reagents and scalable synthetic methods
Vijayakumar Murugesan10
Synthetic Methods for Phenazine Derivatives
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➢ Synthetic Strategy
Readily available precursors – Low cost
Straightforward synthetic procedures – Scalability
Modular syntheses – Readily access diverse derivatives
Synthetic Methods for Phenazine Derivatives
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➢ Synthetic Strategy
Readily available precursors – Low cost
Straightforward synthetic procedures – Scalability
Modular syntheses – Readily access diverse derivatives
➢ Yields >90%
➢ Reactions performed in water
➢ Simple product isolation
Down-Selected Candidates
131 M NaOH, 100 mV/s,GC electrode, saturated anolyte
-1.6 -1.4 -1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0.0
Potential (V vs Ag/AgCl)
phenazine
Solubility (M)
1M NaOH
E°’1/2 (V vs Ag/AgCl)
phenazine trace -0.56
Down-Selected Candidates
141 M NaOH, 100 mV/s,GC electrode, 8.5 mM anolyte
-1.6 -1.4 -1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0.0
Potential (V vs Ag/AgCl)
phenazine
R = CO2H
Solubility (M)
1M NaOH
E°’1/2 (V vs Ag/AgCl)
phenazine trace -0.56
R = CO2H 0.95 -1.08
Down-Selected Candidates
151 M NaOH, 100 mV/s,GC electrode, 8.5 mM anolyte
-1.6 -1.4 -1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0.0
Potential (V vs Ag/AgCl)
phenazine
R = CO2H
R = SO3H
Solubility (M)
1M NaOH
E°’1/2 (V vs Ag/AgCl)
phenazine trace -0.56
R = CO2H 0.95 -1.08
R = SO3H 1.45 -1.06
Down-Selected Candidates
161 M NaOH, 100 mV/s,GC electrode, 8.5 mM anolyte
-1.6 -1.4 -1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0.0
Potential (V vs Ag/AgCl)
phenazine
R = CO2H
R = SO3H
R = H
Solubility (M)
1M NaOH
E°’1/2 (V vs Ag/AgCl)
phenazine trace -0.56
R = CO2H 0.95 -1.08
R = SO3H 1.45 -1.06
R = H 1.6 -0.98
Down-Selected Candidates
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Solubility (M)
1M NaOH
E°’1/2 (V vs Ag/AgCl)
phenazine trace -0.56
R = CO2H 0.95 -1.08
R = SO3H 1.45 -1.06
R = H 1.6 -0.98
Fe(CN)6x- ----- 0.34
1 M NaOH, 100 mV/s,GC electrode, 8.5 mM anolyte
-1.6 -1.2 -0.8 -0.4 0.0 0.4 0.8
Potential (V vs Ag/AgCl)
phenazine
R = CO2H
R = SO3H
R = H
Fe(CN)6
x-
Down-Selected Candidate - DHPS
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Solubility (M)
1M NaOH
E°’1/2 (V vs Ag/AgCl) Solubility (M)
Charged State
phenazine trace -0.56 -----
R = CO2H 0.95 -1.08 -----
R = SO3H 1.45 -1.06 ≥1.4
R = H 1.6 -0.98 <0.1
Fe(CN)6x- ----- 0.34 -----
1 M NaOH, 100 mV/s,GC electrode, 8.5 mM anolyte
-1.6 -1.2 -0.8 -0.4 0.0 0.4 0.8
Potential (V vs Ag/AgCl)
R = SO3H (DHPS)
Fe(CN)6
x-
1.4 V Theoretical Potential
DHPS: 1.4 M Concentration, 10 cm2 Cell
191.4 M 5 + 3 equiv. NaOH in 5mL of 1M NaOH2 equiv. K4Fe(CN)6/2 equiv K3Fe(CN)6 in 45 mL 2M NaOHInterdigitated cell, 100 mL/min, ELAT/CP-ESA, N212, 100 mA/cm2
1.4 M DHPS → 2.8 M e−
90% capacity retention after 500 cycles
Scale-Up: 57 cm2 Cell
201M DHPS3- in 60 mL of 1M NaOH0.5M K4Fe(CN)6 and 0.125M K3Fe(CN)6 in 225 mL of 1M NaOHN212, ELAT/ESA, 100 mL/min
57 cm2 interdigitated cell design
1 M DHPS
70% EE at 75 mA/cm2
0.0 0.5 1.0 1.5 2.0 2.5 3.0
0.8
0.9
1.0
1.1
1.2
1.3
1.4
1.5
1.6
1.7
1.8
Voltage (
V)
Capacity (Ah)
75 mA/cm2
100 mA/cm2
125 mA/cm2
Summary & Acknowledgements
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Financial support from US DOE Office of Electricity Delivery & Energy Reliability
Pacific Northwest National Laboratory is a multi-program national laboratory
operated by Battelle Memorial Institute for the U.S. Department of Energy under
Contract DE-AC05-76RL01830.
Developed high energy anolyte: 1.4 M solubility, -1.06 V vs Ag/AgCl
Demonstrated promising performance at 10 cm2 cell: >80% EE and >1.2V at 100 mA/cm2
Initiated scale-up to 57 cm2 cell design: 70% EE at 75 mA/cm2 (early-stage)
➢ Improve cell performance at 57 cm2 cell and continue scale-up
➢ Develop full understanding of capacity loss mechanisms and address through
electrolyte composition, molecular design, and membrane/electrode choice.
Summary
FutureDirection
Support
Supplementary –DHPS Electrochemical Kinetics
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-1.4 -1.2 -1.0 -0.8 -0.6
Potential (V vs Ag/AgCl)
Ketjen black on glassy carbon
-1.4 -1.2 -1.0 -0.8 -0.6
Glassy Carbon
Potential (V vs Ag/AgCl)
Poor electrochemical kinetics at pristine glassy carbon
Facile kinetics with ketjen black deposit
Carbon paper electrodes in cell
Supplementary –Stability of DHPS in 1M NaOH
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* Diminished intensity a result of H/D exchange1.4 M in 1 M NaOH/D2O
Discharged State Charged State