High-performance Aqueous Redox Flow Battery (ARFB)
Kaixiang Lin, Qing Chen, Louise Eisenach, Alvaro Valle, Roy G. Gordon, Michael J. Aziz, Michael P. Marshak
250th American Chemical Society National Meeting & Exposition
Motivation- Wind and solar energy are widely and increasingly used for electricity generation
- Their intermittency leads to mismatch of peak energy production and demand
- Need a cheap and scalable method to capture intermittent energy and reuse it when wind
stops and sun sets.
Wind power
Solar power
Grid demand
Mismatch between peak electricity supply and demand
Time (hour)
3 weeks
A windy day
Sunny day
Cloudy day
Windless day
Peak electricity demand
Rugolo, J. and Aziz, M. Energy Environ. Sci. 5, 7151 (2012)
Existing Energy Storage Technology- Pumped hydro and compressed air energy storage (CAES) require special geology &
have high environmental costs.
- Solid-state battery systems have low discharge time due to coupled energy density (i.e.
kWh) and power density (i.e. kW).
How long electrical
energy gets
discharged
How much electrical energy
gets stored
Adapted from Dunn, B. et al., Science 334, 928 (2011)
High Power Supercapacitor
Compressed Air Energy Storage
ppressed Air ppppppprrrrrrrrrrrrrrrreeeeeeeeeessssssssssssssssssssssssssssssseeeeeeeeeeeeeeeeeeeeeeeeeedddddddddddddddddddddddd AAAAAAAAAAAAAAAAAAAAAAAiiiiiiiiiiiiirrrrrrrrrr
Pumped Hydro
Redox Flow Battery
Lithium-ion BatteryAdvanced Lead-Acid Batterytery
V2+
Aqueous Redox Flow Battery
Negative Electrolyte Positive Electrolyte
Electrical Cell
Pumps
EleleEE2
pp3 3
1 1
Pumps
Schematic of a redox flow battery during Charging:
e- e-SourceSSoSS4
1. VO2+ + 2H+ + e-
VO2+ + H2O
2. Cr3+ + e- Cr2+
3. AQDS + 2e-
AQDSH2
1. V2+ V3+ + e-
2. Fe2+ Fe3+ + e-
3. 2HBr Br2 + 2e-
2H+
VO2+
VO2+ + H2O V3+
VO2+ V2+
3
O
O
9,10-anthraquinone-2,7-disulfonic acid (AQDS)
-O3S SO3
-2H+, 2e
-
OH
OH-O3S SO3
-
AQDSH2
Aqueous Redox Flow BatteryAdvantage:
- Scalability: decoupled power and energy
- Cheap: commodity chemicals, widely used as dyes; no precious-metal catalyst
- Safety: room temperature operation; non-flammable aqueous solution
Challenge:
- Cross-over: Chemicals, i.e. bromine, vanadium, migrate across membrane causing
self-discharging/ capacity loss
- Corrosivity/ Toxicity: Chemicals such as bromine can be hazardous for residential
use.
Negative Electrolyte
O
OO
OO
OO
O
2e-
2,6-dihydroxyanthraquinone(2,6-DHAQ)
- Synthesized from cheap commodity
chemical
- Eeq = - 680 mV vs. SHE (in alkaline
solution)
- 2,6-DHAQ potassium salt solubility in 1
M KOH 0.6 M at r.t. and > 1 M at 40 ºC
O
OSO3Na
NaO3S
NaOHHeat
O
OONa
NaO
AQDS 2,6-DHAQ
Negative Electrolyte
Quinone/Ferrocyanide Redox Flow BatteryPositive Electrolyte
FeII
CN
CN CN
CN
CN
CN
FeIII
CN
CN CN
CN
CN
CN
-e-
4- 3-
FerricyanideFerrocyanide
- First used in Zinc/ferrocyanide hybrid
flow battery in 19851
- Food additive, anti-caking agent2
- Soluble and stable in alkaline solution
- Eeq = 500 mV vs. SHE (in alkaline
solution); independent of pH
1) R.P. Hollandsworth, et al. Zinc/ferricyanide battery development. Phase IV, SAND85-7195, Sandia National Laboratories, May 1985; 2) “Seventeenth Report of the Joint FAO/WHO Expert Committee on Food Additives. Report No. 539,” Wld Hlth Org. techn. Rep. Ser. (539, World Health Organization, 1974).
Cell Performance – Setup N
egat
ive
Elec
trol
yte Positive Electrolyte
Electrical Cell
Pumps Pumps
Cell Configuration:
- Graphite plates with serpentine flow pattern
- Pretreated SGL porous carbon electrodes
- Pretreated Nafion 212 membrane
- Gear Pump
Electrolyte Composition:
Positive: 0.4 M ferricyanide at r.t. and
0.8 M at 45 ºC both in 1 M KOH
Negative: 0.5 M K+ salt of 2,6-DHAQ
and 1 M K+ salt of 2,6-DHAQ at 45 ºC
both in 1 M KOH
O
OO
O
O
OO
O
2e-
2K+
FeII
CN
CN CN
CN
CN
CN
FeIII
CN
CN CN
CN
CN
CN
- e-
4-
3-
Nafion 212Porous Carbon Electrode
Serpentine Graphite Flow Plates
Cell Performance – Power DensityCell Configuration:
- Graphite plates with serpentine flow pattern
- Pretreated SGL porous carbon electrodes
- Pretreated Nafion 212 membrane
- Gear Pump
Electrolyte Composition:
Positive: 0.4 M ferricyanide at r.t. and
0.8 M at 45 ºC both in 1 M KOH
Negative: 0.5 M K+ salt of 2,6-DHAQ
and 1 M K+ salt of 2,6-DHAQ at 45 ºC
both in 1 M KOH
- Average current and energy efficiency over 100 cycles is > 99% and 84%
respectively.
- Cell showed ~ 0.1% 0.067% capacity loss per cycle; this is mainly due to
electrolyte leakage
Cell Performance – Cycling, Capacity Retention and Efficiency
-1.0 -0.8 -0.6 -0.4-8
-6
-4
-2
0
2
4
7.6 mM 2,6-DHAQ added
3.9 mM 2,6-DHAQ added
Curr
ent D
ensi
ty (m
A/cm
2 )
Potential (V vs. SHE)
Cycled Posolyte
-1.5 -1.0 -0.5 0.0 0.5 1.0 1.5
-60
-40
-20
0
20
40
60
80
Curr
ent D
ensi
ty (m
A/cm
2 )
Potential (V vs. SHE)
ferri/ferrocyanide
2,6-DHAQ
4
Cell Performance – Membrane Crossover
-1.00 -0.88 -000000........66666666 ---888
----666666
-4
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0
0
0
0
0
0
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ferrrrrrrrriiiiiiii/iiiiiiii ferrocyayyy nide
2,22,2222,22,2,22,222222222222,22222,6666666666-666-66666 DHDHDHDHHHHHHHHHHHDHHHHHHHHHHHHHDHHHHHHHHHHAAAAAAQAQAQAQAAAAAAAA
- CV result suggested less than 0.8% of 2,6-DHAQ cross over after 100 charge-
discharge cycles
- Showed crossover rate at least 3 orders of magnitude lower than bromine and
vanadium ions
- The result showed possibility of using cheaper membrane or even separator for
future batteriesM. C. Tucker, et al. Impact of membrane characteristics on the performance and cycling of the Br2–H2 redox flow cell. Journal of Power Sources. 284, 212–221 (2015).; S. Jeong, et al. Effect of nafion membrane thickness on performance of vanadium redox flow battery. Korean Journal of Chemical Engineering. 31, 2081–2087 (2014).
2,6-DHAQ Recrystallized:
2,6-DHAQ Boiled in 5 M KOH for 1 month:
Negative electrolyte after 100 charge-discharge cycles:
O
OOH
HO
2,6-DHAQ
O
Chemical and Electrochemical Stability of 2,6-DHAQ
Future Work
O
1,5-dimethyldihydroxyanthraquinone
HO
O
OH
O
2,3,6,7-tetrahydroxyanthraquinone
HO
O
OHHO
OH
i. condensation with acetaldehyde; ii. oxidation by Na2Cr2O7; iii. Hydrolysis by HBr
i-iii. Sulfonate followed by hydrolysis iv. Dimerization in AlCl3:NaCl molten salt
- H. Behre, F. et al. Method for producing 3-hydroxy-2-methylbenzoic acid (2004), WO2003080542A3.
- T. S. Balaban, et al. Helv. Chim.Acta. 89, 333–351 (2006)
O
O
1,2-dimethoxybenzene
i,ii iii
O
O
O
OO
O
2,3,6,7-tetramethoxyanthraquinone
naphthalene
O
OH
3-hydroxy-2-methylbenzoic acid
HOi - iii iv
Acknowledgement- I want to specially thank Prof. Michael Aziz, Prof.
Roy Gordon and Prof. Alan Aspuru-Guzik (1st row from left to right respectively) for their inspiration and guidance to move this project forward and Dr. Qing Chen (2nd row next to me) for helping with electrochemical analysis and cell cycling experiment.
- Finally I want to thank the entire team and financial support from ARPA-E.
Conclusion- Quinone molecules can be utilized in both acidic and alkaline flow batteries- Non-toxic and low corrosive electrolyte- High cell voltage and peak power density- High current and energy efficiency and small capacity loss- Low membrane crossover rate- High chemical and electrochemical stability- Explore new hydroxylated anthraquinones to achieve higher cell performance
n
Conclusion and Acknowledgement
