Organic Based Aqueous Flow Batteries For Massive Electrical Energy Storage

Organic-Based Aqueous Flow Batteries
for Massive Electrical Energy Storage

Brian Huskinson1, Michael P. Marshak1, Changwon Suh2,
Süleyman Er2, Michael R. Gerhardt1, Cooper J. Galvin1,
Xudong Chen2, Qing Chen1, Liuchuan Tong2,
Alán Aspuru-Guzik2, Roy G. Gordon1,2 & Michael J. Aziz1
1 Harvard School of Engineering &

Applied Sciences
2 Dept. of Chemistry & Chemical
Biology, Harvard University
• Grid-scale storage
• Flow Batteries
• Quinones and hydroquinones
• Quinone-based flow batteries: First results
• Future prospects
Andlinger Center for Energy & Environment, Princeton University, 10/20/2014

Wind Power Becomes Competitive
The state’s biggest utilities, in a milestone for New England’s wind

power industry, have signed long-term contracts to buy wind-
generated electricity at prices below the costs of most conventional
sources, such as coal and nuclear plants.
The contracts, filed jointly Friday with the Department of Public
Utilities, represent the largest renewable energy purchase to be
considered by state regulators at one time. If approved, the contracts
would eventually save customers between 75 cents and $1 a month,
utilities estimated.
“This proves that competitively priced renewable power exists and
we can get it, and Massachusetts can benefit from it,” said Robert
Rio, a spokesman for Associated Industries of Massachusetts, a
trade group that represents some of the state’s biggest electricity
users.
The utilities — National Grid, Northeast Utilities, and Unitil Corp.
— would buy 565 megawatts of electricity from six wind farms in
Maine and New Hampshire, enough to power an estimated 170,000
homes.
... initial reaction to the price — on average, less than 8 cents per
kilowatt hour? “Wow.” ...
Boston Globe 9/23/2013, http://www.bostonglobe.com/business/2013/09/22/suddenly-
wind-competitive-with-conventional-power-sources/g3RBhfV440kJwC6UyVCjhI/story.html
Electricity Prices Go Negative (Europe)
10/12/2013
Electricity Prices Go Negative (US)
Slide courtesy of Prof. George Baker, HBS https://www.misoenergy.org/LMPContourMap/MISO_MidWest.html



Intermittency Causes California to Require Storage
10/17/2013
California adopts energy storage mandate for major utilities

California today became the first state in the country to require utilities to invest in energy storage, a move...
USA electric power

(Dec. 2013):
1100 GWe gen. capacity
24.6 GW (2.3%) storage:

= 23.37 GW PHES,
+1.23 GW other storage
Enersys Nickel-Cadmium
+ Valve-regulated Lead-Acid
1 MWh, 1.5 MW
http://www.windpowerengineering.com
/featured/business-news-projects
/improving-grid-lots-stored-mws/
Large-Scale Deployment of Off-Grid Storage
No access to grid: 1.4 Billion people (incl. 550 million in Africa, 400 million in India)
Photo courtesy of Prof. Sri Narayan,

http://www.raisinahill.org/2013/02/indo-us-dispute-on-solar-panel.html
University of Southern California
http://3.bp.blogspot.com/-beOrvaf2wzw/URT3ohD796I/AAAAAAAABkA/
9xwL0o5qO6I/s1600/Home+Lighting+System+in+a+hut+in+Jaisalmer+District+of+Rajasthan..jpg
Storage Makes Intermittent Renewables Dispatchable
3 weeks
Power
Wind supply
Solar supply
Power
Power
Grid demand
J. Rugolo and M.J. Aziz, “Electricity Storage for Intermittent Renewable Sources”, Energy Environ. Sci. 5, 7151 (2012)
Some Grid Supply Scenarios Enabled by Storage
Completely Levelized
Power
Grid minus baseload

Power
5 hr peak-consumption centered square wave

Power
Three storage scenarios: Power and energy
requirements, 1 MW nameplate production
supplied to grid
1 MW 
wind production
Power
Grid minus baseload (GMB)

STORAGE
1 MW  PV production
Constant output
Power
5 hr centered square wave

Electrochem storage: a distribution of instantaneous efficiencies
Requirement: high system efficiency
 1 MW nameplate PV requirement:
~?? MW peak power capacity; ?? MWh energy capacity (Energy/Power = ?? hr)
 1 MW nameplate wind requirement:
~?? MW peak power capacity; ?? MWh energy capacity (Energy/Power = ?? hr)
Storage: A Distribution of Efficiencies
Electrolytic Galvanic Linear Potential Approximation:

(Charging mode) (Discharging mode)
Power dens’y:
p, Power Density [mW/cm2]

Peaks at:

E, Cell Potential [V]
Realistic
Thermo. limit Thermo. limit
How
much
A?
i, Current Density [mA/cm2]
Storage Requirements
for 1 MW Nameplate Production Capacity
Storage characteristics: Wind characteristics:
ηavg = 85% Nameplate = 1 MW
Supplied power to Max. power  = 0.480 MW CF = 32.5%
grid = 0.276 MW Stored energy = 23 MWhr
E/P ratio = 48 hr
Power [MW]
Storage characteristics: PV characteristics:

ηavg = 85% Nameplate = 1 MW
Supplied power to Max. power  = 0. 568 MW CF = 14%
Power [MW]
grid = 0.119 MW Stored energy = 8.0 MWhr

E/P ratio = 14 hr
Diminishing Returns on Buying Storage Power
Wind
Solar
Solar Wind
, Galvanic Power Capacity [MW] Energy/Power ratio [hr]
Three storage scenarios: Power and energy
requirements, 1 MW nameplate production
NiMH Batteries: 100x too little energy per power
Pb-acid
Li+ ion NiMH
Lead Acid
Lithium ion
25 50 75 25 50 75
Constant output (CONS) in blue Grid minus baseload (GMB) in red 5 hr centered (SW) in pink
Batteries Have Only About 1%
of the Required Energy for a Given Power
Requirements for Efficient

Storage, 1 MW nameplate
Solar Wind
Power 1 MW 1 MW
Energy 16 60
MWhr MWhr
energy 16 hr 60 hr
Ratio
power
Requirements for Efficient Available

Solar Wind Batteries
Power 1 MW 1 MW 1 MW
Energy 16 60 0.2 MWhr

MWhr MWhr
energy 16 hr 60 hr 12
Ratio
power minutes
1 MW
0.2 MWhr
$40k


MWhr MWhr
Ratio
power minutes
1 MW 1 MW
0.2 MWhr 0.2 MWhr
$40k


MWhr MWhr
Ratio
power minutes
1 MW 1 MW 1 MW
0.2 MWhr 0.2 MWhr 0.2 MWhr
$40k


MWhr MWhr
Ratio
power minutes
1 MW 1 MW 1 MW 1 MW
0.2 MWhr 0.2 MWhr 0.2 MWhr 0.2 MWhr
$40k


MWhr MWhr
Ratio
power minutes
1 MW 1 MW 1 MW 1 MW 1 MW
0.2 MWhr 0.2 MWhr 0.2 MWhr 0.2 MWhr 0.2 MWhr
$40k


MWhr MWhr
Ratio
power minutes
$40k


MWhr MWhr
Ratio
power minutes
$40k
1 MW 1 MW1 MW 1 MW 1 MW 1 MW 1 MW 1 MW 1 MW 1 MW
Requirements for Efficient Available 0.2 MWhr 0.21 MWhr
1 MW0.2 MWhr 0.21 MWhr
MW0.2 MWhr 0.21 MWhr
MW0.2 MWhr 0.21MWhr
MW0.2 MWhrMW 0.2 M
1 MW 1 MW1 MW 1 MW 1 MW 1 MW 1 MW 1 MW 1 MW 1 MW
Solar Wind Batteries 0.2 MWhr 0.21 MWhr
MW0.2 MWhr 0.21MWhr
MW0.2 MWhr MW 0.2 M
0.2 MWhr 1 0.2
MWMWhr 1 0.2MWMWhr 1 MW 0.2 MWhr 1 MW0.2 MWhr 1 MW
1 MW 1 MW MWhr1 MW 1 MW 1 MW
Power 1 MW 1 MW 300 MW 1 MW 1 MW10.2
MW 1 MW 10.2
MW MWhr
1 MW 10.2
MW MWhr
1 MW 10.2
MW MWhr 10.2
MWM
0.2 MWhr 0.21 MWhr
MW0.2 MWhr 0.21MWhr
MW0.2 MWhr MW 0.2 M
0.2 MWhr 1 0.2
MWMWhr 1 0.2
MWMWhr 0.2 MWhr 1 MW0.2 MWhr 1 MW
Energy 16 60 60 MWhr 1 MW
1 MW 1 MW 1 MW 1 MW
1 MW 1 MW
1
1 MW
MW 1 MW
1 MW
0.20.2
MWhr 0.2 MWhr 0.2 MWhr 0.2 MWhr 0.2 MWhr 0.2 M
MWhr MWhr MWhr0.20.2
MWhr
MWhr0.20.2
MWhrMWhr0.20.2
MWhrMWhr0.20.2
MWhrMWhr
energy 16 hr 60 hr 12 1 MW
1 MW 1 MW 11MW
1 MW 1 MW1 MW 1 MW1 MW 1 MW1 MW
MW 1 MW
1 MW 1 MW
1 MW 1 1MW
MW 1 MW
1 MW
Ratio 0.20.2
MWhr
MWhr0.2
0.2 MWhr
MWhr
MWhr0.2
0.2 MWhr
MWhr
MWhr0.2
0.2 MWhr
MWhr
MWhr0.2
0.2 MWhr 0.2 M
MWhr
power minutes 0.2
0.2MWhr 0.2 MWhr
0.2 0.2 MWhr
0.2 0.2 MWhr
0.2 MWhr 0.2 MW
1 MW 1 MW 1 1MW 1 1MW 1 1MW
1 MW 1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW 0.2 MWhr1 1MW
0.2 MWhr 1 MW
1 MW MW 1 MW MW 1 MWMW MW 1 MW
0.21MWhr
MW 0.21MWhr
MW
0.2MWhr 0.2
MWhr 0.2 1MWhr
MW
0.2MWhr 0.2
MWhr 0.2 1MWhr
MW
0.2MWhr 0.2 1MWhr
MW
MWhr 0.2 MWhr 0.2 MW
0.2 MWhr 0.2 MWhr 0.2 MWhr 0.2 MWhr 0.20.2 MWhr 1 0.2
MWhr MW MWhr 1 0.2
0.2 MWhr MW 1 MW
0.2 MWhr 1 MW
0.2 MWhr 1 MW
0.2 MWhr
1 MW 1 MW 1 MW 1 MW 1 MW 1 MW 1 MW 1 MW0.2 MWhr1 MW
$40k 1 MW 1 MW 1 MW 1 MW 0.2 MWhr
1 MW 0.2 MWhr 0.2 MWhr 0.2 MWhr 0.2 MWhr
0.2 MWhr 0.2 MWhr 0.2 MWhr 0.2 MWhr 0.2 MWhr 0.2 MWhr 0.2 MWhr 0.2 MWhr 0.2 MWhr
0.2 MWhr 0.2 MWhr 0.2 MWhr 1 0.2
MW MWhr 1 0.2
MW MWhr 1 1MW
MW 11MW MW 11MWMW 1 MW 1 MW
1 MW 1 MW 1 MW 1 MW 1 MW 1 MW 1 MW 1 MW 1 MW 1 MW
0.2MWhr
MWhr 0.20.2MWhr
MWhr 0.20.2MWhr
MWhr 0.2 MWhr 0.2 MW
MWhr MW MWhr 1 0.2
0.2 MWhr MW 1 MW
0.2 MWhr 0.2 1 MW
MWhr 1 MW
1 MW 1 MW 1 MW 1 MW 1 MW 1 MW 1 MW MWhr
0.2 1 MW0.2 MWhr1 MW
1 MW 1 MW 1 MW 1 MW 0.2 MWhr
1 MW 0.2 MWhr 0.2 MWhr 0.2 MWhr 0.2 MWhr
1 MW 1 MW 0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr 1
1 MW 0.2
MW MWhr 1 0.2
MW MWhr 1 MW 1 MW 1 MW
MWhr MW MWhr 1 0.2
MW MWhr 1 MW
0.2 MWhr 0.2 MWhr
0.2 MWhr 1 MW0.2 MWhr 1 MW
1 MW 1 MW 1 MW 1 MW 1 MW 1 MW0.2 MWhr 1 MW0.2 MWhr1 MW0.2 MWhr1 MW
Flow Batteries Independently Size Energy and Power
Requirements for Efficient energy 1 MW power energy

Storage, 1 MW nameplate storage conversion unit storage
unit unit
Solar Wind
ion-transport
electrode separator
Power 1 MW 1 MW
Energy 16 60 Electrolyte Electrolyte

MWhr MWhr
1 1
energy
energy 16 hr 60 hr MWhr MWhr
Ratio
Ratio
power
power
pump Power source pump

and load
based on image from vrbpower.com

unit unit
Solar Wind
ion-transport
electrode separator
Power 1 MW 1 MW

MWhr MWhr 10 10
energy MWhr MWhr
energy
Ratio
16 hr 60 hr
Ratio
power
power

and load

unit unit
Solar Wind
ion-transport
electrode separator
Power 1 MW 1 MW

MWhr MWhr
60 60
energy
Ratio
Ratio
power
power

and load

unit unit
Solar Wind
ion-transport
electrode separator
Power 1 MW 1 MW

MWhr MWhr
100 100
energy
Ratio
Ratio
power
power

and load
“Hope and Change” for Electrical Energy Storage
Vanadium Redox Flow Battery:
the Most Commercialized RFB
Power source
and load
Red Red
Ox Ox
Quinones for Battery Storage
Plastoquinone simplest
in photosynthesis quinone
oxidized
+2 H+,
+2 e– +2 H+, +2 H+, +2 H+,
+2 e– +2 e– +2 e–
reduced
Quinones/Hydroquinones: Reversible
proton and electron addition reactions
O–
with known and estimated pKa’s
O
“pBQ”
para-
-e- -e-
Q2- Q- Q benzo-
+e- +e- quinone
O– O
11.84 +H+ 4.1 +H+ ~ -7 +H+

OH OH+
-e- -e-
QH- +e- QH +e- QH+
O– O
9.85 +H+ ~ -1 +H+ < -7 +H+
OH OH+
-e- -e-
QH2 +e- QH2+ +e- QH22+
hydro-
quinone
OH OH+
Quan, Sanchez, Wasylkiw, Smith, “Voltammetry of Quinones in Unbuffered Aqueous Solution...”, JACS 129, 12847 (2007)
Quinones/Hydroquinones: Reversible or Irreversible
proton and electron addition reactions
O–
with known and estimated pKa’s
O
“pBQ”
para-
-e- -e-
Q2- Q- Q benzo-
+e- +e- quinone
O– O
11.84 +H+ 4.1 +H+ ~ -7 +H+

OH OH+
-e- -e-
QH- +e- QH +e- QH+
O– O
9.85 +H+ ~ -1 +H+ < -7 +H+
OH OH+
-e- -e-
QH2 +e- QH2+ +e- QH22+
hydro-
quinone
OH OH+
Quan, Sanchez, Wasylkiw, Smith, “Voltammetry of Quinones in Unbuffered Aqueous Solution...”, JACS 129, 12847 (2007)
Quinone-Based Flow Batteries
Primary requirements:
• Reduction potential
• Solubility
• Redox kinetics
• Stability
• Cost
Cost of Chemicals Sets Floor on System Cost / kWh
Compound $/kg Source $/kAh $/kWh

per side per side
Vanadium
14.37 USGS (2011) 48.77 40.64
pentoxide (V2O5)
Anthraquinone <4.74 eBioChem <18.41 <21.46
Benzoquinone 5.27 Shanghai Smart Chemicals Co. 10.63 10.63
USGS (2006)
Bromine 1.76 5.25 6.12
“I wish I could
get that price!”
Full Cell $/kAh $/kWh
Anthraquinone with Bromine <23.66 <27.58
Anthraquinone with Benzoquinone <29.04 <32.09
Vanadium with Vanadium 97.54 81.28
Anthraquinone Di-sulfonate (AQDS)
Ox
AQDS AQDSH2 Red
AQDS + 2H+ + 2e-
O
SO3H SO3H 200 Oxidation
34 mV
Current Density (A cm )

100
–2
O
Potentiostat 0
O
Working Reference SO3H SO3H
Counter
electrode electrode -100
electrode
glassy C Ag/AgCl Pt
O
OH
SO3H SO3H
-200
OH Reduction
-300
1 M H2SO4, pH 0, -100 0 100 200 300 400 500
20 oC, 1 mM AQDS
Potential (mV vs. SHE)
B. Huskinson, M.P. Marshak, C. Suh, S. Er, M.R. Gerhardt, C.J. Galvin, X. Chen, A. Aspuru-Guzik, R.G. Gordon and
M.J. Aziz, “A metal-free organic-inorganic aqueous flow battery”, Nature 505, 195 (2014) 61
AQDS Pourbaix Diagram
1 mM Quinone
2 electrons,
2 protons
2 electrons,
1 proton
2 electrons,
0 protons
M.J. Aziz, “A metal-free organic-inorganic aqueous flow battery”, Nature 505, 195 (2014)
AQDS: Rotating Disk Electrode Response
-100
0
-90
-200 -80
–2
200 RPM
Limiting Current (A)

-70
-400
-60
-600
-50
-800 -40
-30
-1000
-20
3600 RPM
-1200
-10
-1400 0
50 100 150 200 250 300 0 2 4 6 8 10 12 14 16 18 20
1/2 1/2
Potential (mV vs. SHE)  (Rad/s)
Levich Equation:
iL = Current limited iL = 0.62n F A D2/3 ω1/2 1/6 CO*
by mass transport D = 3.8 × 10−6 cm2/s.
-60
0
-200 -50
–2
200 RPM
-400
-40
i (mA )
-600
–1
-30  / mV
13
-800 18
–1
23
-20 28
-1000 33
1
38
3600 RPM -10 363
-1200
-1400 iK 0
50 100 150 200 250 300 0.00 0.04 0.08 0.12 0.16 0.20 0.24
Potential (mV vs. SHE) –1/2 1/2 –1/2
 (s rad )
Current is limited
by mass transport Koutecký-Levich Plot:
and electrode kinetics Extrapolate to infinite rotation rate
Gives the kinetically-limited current, iK
exchange current density ik0 

rate const k0 = ik0/(FAC) = 7.2 × 10−3 cm/s -60
F = Faraday’s constant
-50
A = surface area
C = concentration
-40
Redox k0 [cm/s] (electrode)
i (mA )
–1
-30  / mV
couple 13
18
–1
23
-20
AQDS/ 7.2 x 10-3 (carbon) 28
33
1
38
AQDSH2 -10 363
Br2/Br- 5.8 X 10-4 (carbon)* iK 0

0.00 0.04 0.08 0.12 0.16 0.20 0.24
Fe3+/Fe2+ 2.2 x 10-5 (gold)* 

–1/2
(s
1/2 –1/2
rad )
Cr3+/Cr2+ 2 x 10-4 (mercury)*

VO2+/VO2+ 3 x 10-6 (carbon)* Koutecký-Levich Plot:
V3+/V2+ 4 x 10-3 (mercury)* Extrapolate to infinite rotation rate
Gives the kinetically-limited current, iK
*Weber, A. Z.; Mench, M. M.; Meyers, J. P.; Ross, P. N.; Gostick, J. T.; Liu, Q. J. Appl. Electrochem. 2011, 41, 1137
Quinone-Bromide Flow Battery
Ox
AQDSH2 Red
AQDS + 2H+ + 2e-
OH
SO3H SO3H
AQDSH2
OH AQDSH2
O
SO3H SO3H
AQDS AQDS
O
E0: +0.21 V +1.09 V
Porous carbon
paper electrode
(no catalyst)
Cell Assembly
Serpentine Interdigitated Carbon paper Nafion membrane
or
flow field flow field
Teflon gasket
Assembled single-cell stack
Cell Performance
State of Charge (SOC) • Interdigitated flow

fields
• Toray carbon paper
electrodes (pretreated,
6 layers/side,
no added catalyst)
• Nafion 212 (50 um),
40 oC
• posolyte: 3 M HBr
+ 0.5 M Br2
• negolyte:
1 M 2,7-AQDS
+ 1 M H2SO4
Cell Performance now 1.0 W/cm2
Electrolytic power density Galvanic power density
Peak galvanic power

SOC
density > 0.6 W cm-2
Electrolytic power
density of 3.3 W cm-2
at 2.25 A cm-2
spans decades of • 40 oC
VRB development • posolyte: 3 M HBr + 0.5 M Br2
in 1 year • negolyte: 1 M AQDS + 1 M H2SO4
Voltage Efficiency
1.00
Discharge:
Charge: 75-150 mW cm-2
0.95 125-200 mW cm-2 at at 90% voltage
90% voltage efficiency efficiency
0.90
Voltage Efficiency
10% SOC
25%
0.85 50%
75%
0.80 90%
0.75
charge discharge
0.70
-0.7 -0.6 -0.5 -0.4 -0.3 -0.2 -0.1 0.0 0.1 0.2 0.3 0.4
-2
Power Density (W cm )
75
Cycling to ~102
Impose ±0.25 A/cm2 square wave, switched at 0, +1.5 V

Cycle Number Cycle Number
0 20 40 60 80 100 49 50 51 52 53
1.8
1.8
100 100
1.6
99.986% average
Discharge Capacity Retention (%)

1.6

98 98
1.4 96 1.4
96
94 1.2
Cell Potential (V)
1.2 94
Cell Potential (V)

92
1.0 1.0 92
90
0.8 0.8 90
88
0.6 88
86 0.6
0.4 86
84 0.4
84
0.2 82
0.2 82
0.0 80
0 20 40 60 80 100 120 140 160 180 200 0.0 80
Time (hrs) 100 102 104 106 108
Time (hrs)
Capacity Retention = (Coulombs of discharge) / (immediately preceding coulombs of discharge)
• Nafion 115 (125 um); 30 oC
• Toray carbon electrodes 2 cm2, 6 layers, no catalyst
• Negolyte: 1 M AQDS in 1 M H2SO4
• Posolyte: 3 M HBr + 0.5 M Br2 in H2O B. Huskinson, M.P. Marshak, M.R. Gerhardt and M.J. Aziz,
“Cycling of a quinone-bromide flow battery for large-scale electrochemical energy storage”, ECS Trans. 61, 27 (2014)
76
Cycling to ~103
Capacity Retention = (Coulombs of discharge) / (immediately preceding coulombs of discharge)

Current Efficiency = (Coulombs of discharge) / (immediately preceding coulombs of charge)
99.84% avg. discharge capacity retention

1.0 1.0
98.35% avg. current efficiency

0.8 0.8
Current Efficiency (%)
0.6 0.6
0.4
• ±0.75 A/cm2 square wave, switched at 0, +1.5 V 0.4
• Nafion 115 (125 um); 40 oC
• Toray carbon electrodes, 6 layers, no catalyst
0.2 • Negolyte: 1 M AQDS in 1 M H2SO4 0.2
750 cycles
• Posolyte:
-2
3 M HBr + 0.5 M Br2 in H2O
0.75 A cm
0.0 0.0
0 100 200 300 400 500 600 700
Cycle Number B. Huskinson, M.P. Marshak, M.R. Gerhardt and M.J. Aziz,
“Cycling of a quinone-bromide flow battery for large-scale electrochemical energy storage”, ECS Trans. 61, 27 (2014)
Efficiency vs. Current Density
Nafion 212 Nafion 115

1.00 1.0
1.00 1.0
0.8
0.8
Current Efficiency
Voltage Efficiency
Current Efficiency
0.99
Voltage Efficiency
0.6
0.99 0.6 Current Efficiency
Voltage Efficiency
0.4
0.4
Current Efficiency 0.98 0.2

0.98 Voltage Efficiency 0.2
current efficiency loss:
0.0
• Br2 crossover? 0.0
0.00 0.25 0.50 0.75 1.00 0.00 0.25 0.50 0.75 1.00
2
Current density (A/cm ) • O2 permeation? Current density (mA/cm2)
• H2 evolution?
1.0 1.0
0.8 0.8
Energy Efficiency
Energy Efficiency
Energy Efficiency
Energy Efficiency
0.6 0.6
Negolyte: 20 mL
0.4 (1M AQDS + 1M H2SO4) 0.4
Posolyte: 125 mL
0.2 (3.5M HBr + 0.5M Br2) 0.2
Electrode Area: 5 cm2

0.0 0.0
0.00 0.25 0.50 0.75 1.00 0.00 0.25 0.50 0.75 2
1.00
Current density (A/cm )
2 Current density (A/cm )
Additional Advantages of Quinones for Energy Storage
Low chemicals cost: Enables low cost/kWh
Rapid redox kinetics: Enable low cost/kW
Redox couple k0 [cm/s] (electrode material)

AQDS/AQDSH2 7.2 x 10-3 (carbon)
Br2/Br- 5.8 X 10-4 (carbon)
Fe3+/Fe2+ 2.2 x 10-5 (gold)
Cr3+/Cr2+ 2 x 10-4 (mercury)
VO2+/VO2+ 3 x 10-6 (carbon)
V3+/V2+ 4 x 10-3 (mercury)
Quinone kinetics on glassy carbon exceed those of most other battery redox couples
Additional Advantages of Quinones for Energy Storage
Small organic molecules: Enable inexpensive separator
• Dianions: reduced crossover through cation-exchange membranes

• Quinones on both sides would eliminate Br2 exposure and Br2 crossover
 hydrocarbon membranes
• Bulky molecules may enable inexpensive separator
• Possibility of functionalizing with additional R groups for physical or chemical membrane
exclusion
Quinones as an Energy Storage Medium
All-liquid storage: Enables inexpensive BOS and high cycle life
Aqueous electrolyte: Enables fireproof operation
Li-ion batteries  ubiquitous
. . . but safety concerns are not going away
• Damaged/overheated Li‐ion cells can ignite
spontaneously & create fierce fires
• Li cells have been implicated in at least 24
combustion incidents on or around aircraft in
2010‐2012, both in cargo and carry‐on bags
(Wall Street Journal, 12/30/2012)
• Li‐ion batteries containing more than 25 grams
(0.88 oz) equivalent lithium content (ELC) are
forbidden in air travel (safetravel.dot.gov)
7‐Jan‐2013—fire ignites in
9‐Nov‐2008—Li‐ion fire Li-ion battery pack (2×
destroys Pearl Harbor‐ May‐2011—fire ignites in 3‐Sep‐2010—Li battery size of a car battery) of
docked Advanced SEAL battery pack 3 weeks fire ignites aboard UPS auxiliary power unit in
Delivery System after crash test of Chevy 747 departing Dubai; 787 Dreamliner while on
(ASDL); $237M in Volt crash kills both pilots the ground in Boston
damage Slide courtesy of Dr. Debra Rolison, NRL
Non-toxic: Ideal for commercial, residential markets
Scalability: Enables rapid chemistry scaleup
Scalability
Bulk synthesis of AQDS mixtures

without purification leads to nearly
identical half-cell performance.
Estimated electrolyte cost of

<$21/kWh for AQDS and $6 for Br
Gives <$27/kWh cost of chemicals
for QBFB.
Scalability: Enables rapid chemistry scaleup
Tunability: Enables performance improvements
Computational Screening
Electron-donating –OH groups

6 Calc. lower the reduction potential.
Calc.
5 Exp.
Number of –OH Groups
DHAQDS
2
AQDS
0
-400 -300 -200 -100 0 100 200 300 400

Changwon Suh, Süleyman Er, Michael Marshak, Alán Aspuru-Guzik

Tunability
200
Oxidation Electron-donating –OH groups
100 lower the reduction potential.
–2
end
0
start
-100
AQDS
1,8-DHAQDS
-200 MH-AQDS
Reduction
-300
-100 0 100 200 300 400 500

AQDS
E0 = 0.210 V
Tunability
200
Oxidation
100
–2
end
0
start
-100
AQDS
1,8-DHAQDS
-200 MH-AQDS
Reduction
-300
-100 0 100 200 300 400 500

OH O OH
HO3S SO3H
1,8-DHAQDS AQDS Cooper Galvin

E0 = 0.118 V E0 = 0.210 V
Tunability
200
Oxidation • Addition of OH groups lowers
100
the reduction potential by
~170 mV
–2
end • Expect ~20% increase in OCV

0
start
of Quinone-Bromide cell
-100
AQDS
1,8-DHAQDS
-200 MH-AQDS
Reduction
-300
-100 0 100 200 300 400 500

OH O OH
HO3S SO3H
MH-AQDS 1,8-DHAQDS AQDS Cooper Galvin,

E0 = 0.039 V E0 = 0.118 V E0 = 0.210 V Michael Marshak
Tunability Demonstration in Quinone-Bromide Cell
1.10
Open Circuit Voltage (V)

1.05 0.5 M DHAQDS
0.5 M AQS
1.00 0.5 M AQDS
1 M AQDS
0.95
0.90
0.85
0.80
0.75
2
0.70 ln
2
0.65
0 20 40 60 80 100
State of Charge (%)
Preliminary results from DHAQDS and AQS

flow cells against HBr/Br2
AQDS show open circuit voltage rising above 1.0 V at
E0 = 0.210 V high state of charge.
Michael Gerhardt (unpublished)

1.10

1.05 0.5 M DHAQDS
0.5 M AQS
1.00 0.5 M AQDS
1 M AQDS
0.95
0.90
0.85
O 0.80
SO3H 0.75
AQS
0.70
E0 = 0.193 V
0.65
17 mV OCV gain O 0 20 40 60 80 100
State of Charge (%)


1.10

1.05 0.5 M DHAQDS
0.5 M AQS
DHAQDS 1.00 0.5 M AQDS
1 M AQDS
E0 = 0.118 V 0.95
92 mV OCV gain 0.90
0.85
O 0.80
SO3H 0.75
AQS
0.70
E0 = 0.193 V
0.65
17 mV OCV gain O 0 20 40 60 80 100
State of Charge (%)


1.0 V Quinone-Quinone Cell
0.1 M in H2O
Open Circuit Potential = 1.03 V
Peak power density = 50 mA cm−2
>99% current Efficiency
High cell resistance

due (primarily?) to low ion conc.
Michael Marshak, Liuchuan Tong (unpublished)

Are quinones special?
“[Quinones] seem to involve a different kind

of process from such irreversible reductions
as the hydrogenation of ethylene
derivatives, or the reduction of aldehydes,
ketones, and nitriles.”
hydroquinone benzoquinone
J. B. Conant
ethane ethylene
L. F. Fieser
J.B. Conant, H.M. Kahn, L.F. Fieser, S.S. Kurtz,, J. Am. Chem. Soc. 44, 1382 (1922).
Quinone Redox Scheme
QH2
Redox-Active Orbital of Quinone
HOMO SOMO LUMO
• Hydroquinone HOMO is π-type
e– e–
• Virtually identical to quinone LUMO
Q
• Zero electron density on O-H bond
H+ H+ H+
• Near zero motion of any other atoms
e– e–
H+ H+ H+
+ - + -
- + - + QH2 e– e–
DFT Calculations using Gaussian03; B3LYP functional / TZVP basis set (Michael Marshak)
Ethane/Ethylene Orbitals
C2H6
Degenerate HOMO of Ethane consists of C−H σ bonds
C2H4
LUMO of Ethylene is the π* (anti-bond)

Outlook
• Cost and tunability of redox-active organics look promising

for E storage, other apps?
• High power density, low cost quinone-bromine Redox Flow Batt
proves the concept
• There is plenty of room for improvement
• molecules
• separators
• porous electrodes and fluidics
• How low can the capital cost be?
Fun Facts about Quinones
Hydroquinone cream is used to bleach Emodin is found in Aloe Vera
dark spots, moles, etc off of skin
Vitamin K1 is part of the electron Blatellaquinone is a sex pheromone

transport chain in photosystem I, female cockroaches use to attract males
found in all green plants
Acknowledgments
Harvard U Ctr for the Environment,
Harvard School of Engrg & Appl Sci
Harvard Physics Department,
NSF Grad Rsch Fellowship Program,
DOE ARPA-E award DE-AR0000348
Not pictured: Dr. Brian Huskinson,
Professor Theodore Betley, Saraf
Nawar, Rachel Burton, Cooper
Galvin, Sidharth Chand, Tyler Van
Valkenburg, Bilen Aküzüm, Ryan
Duncan, Dr. Süleyman Er, Dr.
Xudong Chen, Phil Baker, Dr. Trent
Molter
Top Row: Prof. Alán Aspuru-Guzik, Dr. Rafa Gómez-Bombarelli, Tim Hirzel, Louise Eisenach, Dr. Jorge Aguilera
Iparraguirre, Prof. Mauricio Salles
Second Row: Jessa Piaia, Drew Wong, Kaixiang Lin, Prof. Xin Li, Dr. David Hardee, Dr. Michael Marshak
Third Row: Jennifer Wei, Dr. Qing Chen, Michael Gerhardt, Liuchuan Tong, Xinyou Ke
Front Row: Dr. Ed Pyzer-Knapp, Dr. Changwon Suh, Lauren Hartle, Prof. Michael Aziz, Prof. Roy Gordon
Not pictured: Prof. Theodore Betley, Saraf Nawar, Bilen Aküzüm, Rachel Burton, Cooper Galvin, Sidharth Chand, Phil Baker,
Dr. Trent Molter, Dr. Brian Huskinson, Ryan Duncan, Dr. Süleyman Er, Dr. Xudong Chen

Organic Based Aqueous Flow Batteries For Massive Electrical Energy Storage

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Organic Based Aqueous Flow Batteries For Massive Electrical Energy Storage

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Organic-Based Aqueous Flow Batteries

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1 Harvard School of Engineering &

Biology, Harvard University

Andlinger Center for Energy & Environment, Princeton University, 10/20/2014

The state’s biggest utilities, in a milestone for New England’s wind

Slide courtesy of Prof. George Baker, HBS https://www.misoenergy.org/LMPContourMap/MISO_MidWest.html

Slide courtesy of Prof. George Baker, HBS https://www.misoenergy.org/LMPContourMap/MISO_MidWest.html

Slide courtesy of Prof. George Baker, HBS https://www.misoenergy.org/LMPContourMap/MISO_MidWest.html

California adopts energy storage mandate for major utilities

USA electric power

1100 GWe gen. capacity

24.6 GW (2.3%) storage:

Photo courtesy of Prof. Sri Narayan,

Grid minus baseload

5 hr peak-consumption centered square wave

Grid minus baseload (GMB)

5 hr centered square wave

Electrolytic Galvanic Linear Potential Approximation:

p, Power Density [mW/cm2]

Thermo. limit Thermo. limit

i, Current Density [mA/cm2]

Storage characteristics: PV characteristics:

grid = 0.119 MW Stored energy = 8.0 MWhr

, Galvanic Power Capacity [MW] Energy/Power ratio [hr]

Requirements for Efficient

Requirements for Efficient Available

Energy 16 60 0.2 MWhr

Requirements for Efficient Available

Energy 16 60 0.4 MWhr

Requirements for Efficient Available

Energy 16 60 0.6 MWhr

Requirements for Efficient Available

Energy 16 60 0.8 MWhr

Requirements for Efficient Available

Energy 16 60 1.0 MWhr

Requirements for Efficient Available

Energy 16 60 2.0 MWhr

Requirements for Efficient Available

Energy 16 60 3.0 MWhr

Requirements for Efficient energy 1 MW power energy

Energy 16 60 Electrolyte Electrolyte

pump Power source pump

Requirements for Efficient energy 1 MW power energy

Energy 16 60 Electrolyte Electrolyte

pump Power source pump

Requirements for Efficient energy 1 MW power energy

Energy 16 60 Electrolyte Electrolyte

pump Power source pump

Requirements for Efficient energy 1 MW power energy

Energy 16 60 Electrolyte Electrolyte

pump Power source pump

11.84 +H+ 4.1 +H+ ~ -7 +H+

11.84 +H+ 4.1 +H+ ~ -7 +H+

Compound $/kg Source $/kAh $/kWh

Current Density (A cm )

Limiting Current (A)

exchange current density ik0 

Redox k0 [cm/s] (electrode)

Br2/Br- 5.8 X 10-4 (carbon)* iK 0

Fe3+/Fe2+ 2.2 x 10-5 (gold)* 

Cr3+/Cr2+ 2 x 10-4 (mercury)*

E0: +0.21 V +1.09 V