A Metal-Free Organic-Based Aqueous Flow Battery for ...
Transcript of A Metal-Free Organic-Based Aqueous Flow Battery for ...
Organic-Based Aqueous Flow Batteriesfor 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 & ChemicalBiology, 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
Electricity Prices Go Negative (US)
Slide courtesy of Prof. George Baker, HBS https://www.misoenergy.org/LMPContourMap/MISO_MidWest.html
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
California adopts energy storage mandate for major utilitiesCalifornia today became the first state in the country to require utilities to invest in energy storage, a move...
10/17/2013
Enersys Nickel-Cadmium + Valve-regulated Lead-Acid1 MWh, 1.5 MWhttp://www.windpowerengineering.com/featured/business-news-projects/improving-grid-lots-stored-mws/
USA electric power (Dec. 2013):
1100 GWe gen. capacity
24.6 GW (2.3%) storage:= 23.37 GW PHES,+1.23 GW other storage
Large-Scale Deployment of Off-Grid Storage
No access to grid: 1.4 Billion people (incl. 550 million in Africa, 400 million in India)
http://www.raisinahill.org/2013/02/indo-us-dispute-on-solar-panel.htmlhttp://3.bp.blogspot.com/-beOrvaf2wzw/URT3ohD796I/AAAAAAAABkA/
9xwL0o5qO6I/s1600/Home+Lighting+System+in+a+hut+in+Jaisalmer+District+of+Rajasthan..jpg
Photo courtesy of Prof. Sri Narayan,University of Southern California
Storage Makes Intermittent Renewables Dispatchable
Wind supply
Grid demand
Solar supply
J. Rugolo and M.J. Aziz, “Electricity Storage for Intermittent Renewable Sources”, Energy Environ. Sci. 5, 7151 (2012)
3 weeks
Pow
erP
ower
Pow
er
Some Grid Supply Scenarios Enabled by Storage
J. Rugolo and M.J. Aziz, “Electricity Storage for Intermittent Renewable Sources”, Energy Environ. Sci. 5, 7151 (2012)
Grid minus baseload
5 hr peak-consumption centered square wave
Completely Levelized
Pow
erP
ower
Pow
er
Electrochem storage: a distribution of instantaneous efficienciesRequirement: high system efficiency
Three storage scenarios: Power and energy requirements, 1 MW nameplate production
5 hr centered square wave
Grid minus baseload (GMB)
Constant output
J. Rugolo and M.J. Aziz, “Electricity Storage for Intermittent Renewable Sources”, Energy Environ. Sci. 5, 7151 (2012)
wind production
PV production
1 MW
1 MW
Pow
erP
ower
1 MW nameplate wind requirement:~?? MW peak power capacity; ?? MWh energy capacity (Energy/Power = ?? hr)
1 MW nameplate PV requirement:~?? MW peak power capacity; ?? MWh energy capacity (Energy/Power = ?? hr)
STORAGE
supplied to grid
Storage: A Distribution of Efficiencies
Realistic
Thermo. limitThermo. limit
Linear Potential Approximation:
Peaks at:
Electrolytic(Charging mode)
Galvanic(Discharging mode)
i, Current Density [mA/cm2]
E, C
ell P
oten
tial [
V]
p, P
ower
Den
sity
[mW
/cm
2 ]
Power dens’y:
HowmuchA?
J. Rugolo and M.J. Aziz, “Electricity Storage for Intermittent Renewable Sources”, Energy Environ. Sci. 5, 7151 (2012)
Storage Requirements for 1 MW Nameplate Production Capacity
Pow
er [M
W]
Pow
er [M
W]
Supplied power to grid = 0.276 MW
Supplied power to grid = 0.119 MW
Storage characteristics:ηavg = 85%Max. power = 0.480 MWStored energy = 23 MWhrE/P ratio = 48 hr
Storage characteristics:ηavg = 85%Max. power = 0. 568 MWStored energy = 8.0 MWhrE/P ratio = 14 hr
Wind characteristics:Nameplate = 1 MW CF = 32.5%
PV characteristics:Nameplate = 1 MW CF = 14%
J. Rugolo and M.J. Aziz, “Electricity Storage for Intermittent Renewable Sources”, Energy Environ. Sci. 5, 7151 (2012)
Diminishing Returns on Buying Storage Power
SolarSolar
Wind
Wind
, Galvanic Power Capacity [MW]
J. Rugolo and M.J. Aziz, “Electricity Storage for Intermittent Renewable Sources”, Energy Environ. Sci. 5, 7151 (2012)
Energy/Power ratio [hr]
Lead Acid
Lithium ion
NiMH
Batteries: 100x too little energy per power
25 50 75
Three storage scenarios: Power and energy requirements, 1 MW nameplate production
5 hr centered (SW) in pinkGrid minus baseload (GMB) in redConstant output (CONS) in blue J. Rugolo and M.J. Aziz, “Electricity Storage for Intermittent Renewable Sources”, Energy Environ. Sci. 5, 7151 (2012)
25 50 75
NiMHPb-acidLi+ ion
Batteries Have Only About 1%of the Required Energy for a Given Power
J. Rugolo and M.J. Aziz, “Electricity Storage for Intermittent Renewable Sources”, Energy Environ. Sci. 5, 7151 (2012)
Requirements for Efficient Storage, 1 MW nameplate
Solar Wind
Power 1 MW 1 MW
Energy 16 MWhr
60 MWhr
16 hr 60 hrpower
energyRatio
Batteries Have Only About 1%of the Required Energy for a Given Power
J. Rugolo and M.J. Aziz, “Electricity Storage for Intermittent Renewable Sources”, Energy Environ. Sci. 5, 7151 (2012)
Requirements for Efficient Storage, 1 MW nameplate
Available
Solar Wind Batteries
Power 1 MW 1 MW 1 MW
Energy 16 MWhr
60 MWhr
0.2 MWhr
16 hr 60 hr 12minutespower
energyRatio
1 MW0.2 MWhr
$40k
Batteries Have Only About 1%of the Required Energy for a Given Power
J. Rugolo and M.J. Aziz, “Electricity Storage for Intermittent Renewable Sources”, Energy Environ. Sci. 5, 7151 (2012)
Requirements for Efficient Storage, 1 MW nameplate
Available
Solar Wind Batteries
Power 1 MW 1 MW 2 MW
Energy 16 MWhr
60 MWhr
0.4 MWhr
16 hr 60 hr 12minutespower
energyRatio
1 MW0.2 MWhr
1 MW0.2 MWhr
$40k
Batteries Have Only About 1%of the Required Energy for a Given Power
J. Rugolo and M.J. Aziz, “Electricity Storage for Intermittent Renewable Sources”, Energy Environ. Sci. 5, 7151 (2012)
Requirements for Efficient Storage, 1 MW nameplate
Available
Solar Wind Batteries
Power 1 MW 1 MW 3 MW
Energy 16 MWhr
60 MWhr
0.6 MWhr
16 hr 60 hr 12minutespower
energyRatio
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
$40k
Batteries Have Only About 1%of the Required Energy for a Given Power
J. Rugolo and M.J. Aziz, “Electricity Storage for Intermittent Renewable Sources”, Energy Environ. Sci. 5, 7151 (2012)
Requirements for Efficient Storage, 1 MW nameplate
Available
Solar Wind Batteries
Power 1 MW 1 MW 4 MW
Energy 16 MWhr
60 MWhr
0.8 MWhr
16 hr 60 hr 12minutespower
energyRatio
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
$40k
Batteries Have Only About 1%of the Required Energy for a Given Power
J. Rugolo and M.J. Aziz, “Electricity Storage for Intermittent Renewable Sources”, Energy Environ. Sci. 5, 7151 (2012)
Requirements for Efficient Storage, 1 MW nameplate
Available
Solar Wind Batteries
Power 1 MW 1 MW 5 MW
Energy 16 MWhr
60 MWhr
1.0 MWhr
16 hr 60 hr 12minutespower
energyRatio
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
$40k
Batteries Have Only About 1%of the Required Energy for a Given Power
J. Rugolo and M.J. Aziz, “Electricity Storage for Intermittent Renewable Sources”, Energy Environ. Sci. 5, 7151 (2012)
Requirements for Efficient Storage, 1 MW nameplate
Available
Solar Wind Batteries
Power 1 MW 1 MW 10 MW
Energy 16 MWhr
60 MWhr
2.0 MWhr
16 hr 60 hr 12minutespower
energyRatio
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
$40k
Batteries Have Only About 1%of the Required Energy for a Given Power
J. Rugolo and M.J. Aziz, “Electricity Storage for Intermittent Renewable Sources”, Energy Environ. Sci. 5, 7151 (2012)
Requirements for Efficient Storage, 1 MW nameplate
Available
Solar Wind Batteries
Power 1 MW 1 MW 15 MW
Energy 16 MWhr
60 MWhr
3.0 MWhr
16 hr 60 hr 12minutespower
energyRatio
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
$40k
Batteries Have Only About 1%of the Required Energy for a Given Power
J. Rugolo and M.J. Aziz, “Electricity Storage for Intermittent Renewable Sources”, Energy Environ. Sci. 5, 7151 (2012)
Requirements for Efficient Storage, 1 MW nameplate
Available
Solar Wind Batteries
Power 1 MW 1 MW 300 MW
Energy 16 MWhr
60 MWhr
60 MWhr
16 hr 60 hr 12minutespower
energyRatio
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
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1 MW0.2 MW
1 MW0.2 MW
1 MW0.2 MW
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
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1 MW0.2 MWhr
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1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 M
1 MW0.2 M
1 MW0.2 M1 MW
0.2 MWhr1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
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1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 M
1 MW0.2 M
1 MW0.2 M
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
1 MW0.2 MWhr
$40k
Flow Batteries Independently Size Energy and Power
J. Rugolo and M.J. Aziz, “Electricity Storage for Intermittent Renewable Sources”, Energy Environ. Sci. 5, 7151 (2012)
power
energyRatio
energystorageunit
pump pump
electrodeion-transport
separator
1 MW powerconversion unit
energystorageunit
Power sourceand load
1MWhr
1MWhr
Electrolyte Electrolyte
Requirements for Efficient Storage, 1 MW nameplate
Solar Wind
Power 1 MW 1 MW
Energy 16 MWhr
60 MWhr
16 hr 60 hr
based on image from vrbpower.com
power
energyRatio
Flow Batteries Independently Size Energy and Power
J. Rugolo and M.J. Aziz, “Electricity Storage for Intermittent Renewable Sources”, Energy Environ. Sci. 5, 7151 (2012)
energystorageunit
pump pump
electrodeion-transport
separator
1 MW powerconversion unit
energystorageunit
power
energyRatio
Power sourceand load
Electrolyte Electrolyte
Requirements for Efficient Storage, 1 MW nameplate
Solar Wind
Power 1 MW 1 MW
Energy 16 MWhr
60 MWhr
16 hr 60 hr
10MWhr
10MWhr
based on image from vrbpower.com
power
energyRatio
Flow Batteries Independently Size Energy and Power
J. Rugolo and M.J. Aziz, “Electricity Storage for Intermittent Renewable Sources”, Energy Environ. Sci. 5, 7151 (2012)
energystorageunit
pump pump
electrodeion-transport
separator
1 MW powerconversion unit
energystorageunit
power
energyRatio
Power sourceand load
ElectrolyteElectrolyte
Requirements for Efficient Storage, 1 MW nameplate
Solar Wind
Power 1 MW 1 MW
Energy 16 MWhr
60 MWhr
16 hr 60 hr60
MWhr60
MWhr
based on image from vrbpower.com
power
energyRatio
Flow Batteries Independently Size Energy and Power
J. Rugolo and M.J. Aziz, “Electricity Storage for Intermittent Renewable Sources”, Energy Environ. Sci. 5, 7151 (2012)
energystorageunit
pump pump
electrodeion-transport
separator
1 MW powerconversion unit
energystorageunit
power
energyRatio
Power sourceand load
Electrolyte Electrolyte
Requirements for Efficient Storage, 1 MW nameplate
Solar Wind
Power 1 MW 1 MW
Energy 16 MWhr
60 MWhr
16 hr 60 hr100
MWhr100
MWhr
based on image from vrbpower.com
power
energyRatio
“Hope and Change” for Electrical Energy Storage
Vanadium Redox Flow Battery:the Most Commercialized RFB
Power sourceand load
Red
Ox
Red
Ox
Quinones for Battery Storage
+2 H+,+2 e–
+2 H+,+2 e–
+2 H+,+2 e– +2 H+,
+2 e–
Plastoquinonein photosynthesis
simplestquinone
oxidized
reduced
Quinones/Hydroquinones: Reversible
Quan, Sanchez, Wasylkiw, Smith, “Voltammetry of Quinones in Unbuffered Aqueous Solution...”, JACS 129, 12847 (2007)
proton and electron addition reactionswith known and estimated pKa’s
QH
para-benzo-quinone
hydro-quinone
OH
OH
O–
O–
OH
O–
O
O
OH+
OH+
OH+
O
QQ-Q2-
QH- QH+
QH22+QH2 QH2
+
-e-
+H+
-e-
-e--e-
-e--e-
+H+
+H+
+H+
+H+
+H+
~ -7~ -7
< -7
4.1
~ -1
4.1
~ -1
11.84
9.85
+H+
+H+
+e-+e-
+e-+e-
+e-+e-
“pBQ”
QH
Quinones/Hydroquinones: Reversible or Irreversible
Quan, Sanchez, Wasylkiw, Smith, “Voltammetry of Quinones in Unbuffered Aqueous Solution...”, JACS 129, 12847 (2007)
proton and electron addition reactionswith known and estimated pKa’s
hydro-quinone
OH
OH
O–
O–
OH
O–
O
O
OH+
OH+
OH+
O
QQ-Q2-
QH- QH+
QH22+QH2 QH2
+
-e-
+H+
-e-
-e--e-
-e--e-
+H+
+H+
+H+
+H+
+H+
~ -7~ -7
< -7
4.1
~ -1
4.1
~ -1
11.84
9.85
+H+
+H+
+e-+e-
+e-+e-
+e-+e-
para-benzo-quinone
“pBQ”
Quinone-Based Flow Batteries
Primary requirements:• Reduction potential• Solubility• Redox kinetics• Stability• Cost
Compound $/kg Source $/kAhper side
$/kWh per side
Vanadium pentoxide (V2O5)
14.37 USGS (2011) 48.77 40.64
Anthraquinone <4.74 eBioChem <18.41 <21.46
Benzoquinone 5.27 Shanghai Smart Chemicals Co. 10.63 10.63
Bromine 1.76 USGS (2006) 5.25 6.12
Full Cell $/kAh $/kWhAnthraquinone with Bromine <23.66 <27.58Anthraquinone with Benzoquinone <29.04 <32.09Vanadium with Vanadium 97.54 81.28
Cost of Chemicals Sets Floor on System Cost / kWh
“I wish I could get that price!”
-100 0 100 200 300 400 500-300
-200
-100
0
100
200
Cur
rent
Den
sity
(A
cm–2
)
Potential (mV vs. SHE)
Anthraquinone Di-sulfonate (AQDS)+ 2H+ + 2e-
Potentiostat
Working electrodeglassy C
Counterelectrode
Pt
ReferenceelectrodeAg/AgCl
34 mV
1 M H2SO4, pH 0, 20 oC, 1 mM AQDS
AQDSAQDSH2
61
Red
Ox
Reduction
Oxidation
AQDS
OH
OH
SO3HSO3H
O
O
SO3HSO3H
O
O
SO3HSO3H
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)
2 electrons,2 protons
2 electrons,1 proton
2 electrons,0 protons
AQDS Pourbaix Diagram
1 mM Quinone
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)
AQDS: Rotating Disk Electrode Response
50 100 150 200 250 300-1400
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-1000
-800
-600
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-200
0
Cur
rent
Den
sity
(A
cm–2
)
Potential (mV vs. SHE)
200 RPM
3600 RPM
iL = Current limited by mass transport
Levich Equation:iL = 0.62n F A D2/3 ω1/2 1/6 CO*D = 3.8 × 10−6 cm2/s.
0 2 4 6 8 10 12 14 16 18 200
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-30
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-60
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-80
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Lim
iting
Cur
rent
(A)
1/2 (Rad/s)1/2
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)
AQDS: Rotating Disk Electrode Response
Koutecký-Levich Plot:Extrapolate to infinite rotation rateGives the kinetically-limited current, iK
50 100 150 200 250 300-1400
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-1000
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0
Cur
rent
Den
sity
(A
cm–2
)
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200 RPM
3600 RPM
0.00 0.04 0.08 0.12 0.16 0.20 0.240
-10
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-60
/ mV 13 18 23 28 33 38 363
i–1 (m
A–1)
–1/2 (s1/2 rad–1/2)
Current is limited by mass transportand electrode kinetics
iK1
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)
AQDS: Rotating Disk Electrode Response
Koutecký-Levich Plot:Extrapolate to infinite rotation rateGives the kinetically-limited current, iK
0.00 0.04 0.08 0.12 0.16 0.20 0.240
-10
-20
-30
-40
-50
-60
/ mV 13 18 23 28 33 38 363
i–1 (m
A–1)
–1/2 (s1/2 rad–1/2)
iK1
exchange current density ik0 rate const k0 = ik0/(FAC) = 7.2 × 10−3 cm/s
*Weber, A. Z.; Mench, M. M.; Meyers, J. P.; Ross, P. N.; Gostick, J. T.; Liu, Q. J. Appl. Electrochem. 2011, 41, 1137
Redox couple
k0 [cm/s] (electrode)
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)*
F = Faraday’s constantA = surface areaC = concentration
Quinone-Bromide Flow Battery
Porous carbonpaper electrode(no catalyst)
AQDSH2
AQDS
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)
AQDS
+ 2H+ + 2e-AQDSAQDSH2 Red
Ox
OH
OH
SO3HSO3H
O
O
SO3HSO3H
AQDSH2
E0: +0.21 V +1.09 V
Cell AssemblyCarbon paper Nafion membrane
Teflon gasket
Serpentineflow field
Interdigitatedflow fieldor
Assembled single-cell stack
Cell Performance
• 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
State of Charge (SOC)
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)
Cell Performance
• 40 oC• posolyte: 3 M HBr + 0.5 M Br2• negolyte: 1 M AQDS + 1 M H2SO4
spans decades of VRB developmentin 1 year
Peak galvanic power density > 0.6 W cm-2 SOC
Galvanic power density
Electrolytic power density of 3.3 W cm-2
at 2.25 A cm-2
Electrolytic power density
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)
now 1.0 W/cm2
Voltage Efficiency
-0.7 -0.6 -0.5 -0.4 -0.3 -0.2 -0.1 0.0 0.1 0.2 0.3 0.40.70
0.75
0.80
0.85
0.90
0.95
1.00
Vol
tage
Effi
cien
cy
Power Density (W cm-2)
charge discharge
10% SOC25%50%75%90%
Discharge:75-150 mW cm-2
at 90% voltage efficiency
Charge:125-200 mW cm-2 at 90% voltage efficiency
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)
Cycling to ~102
75
0 20 40 60 80 100 120 140 160 180 2000.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
Cel
l Pot
entia
l (V
)
Time (hrs)
0 20 40 60 80 100
80
82
84
86
88
90
92
94
96
98
100
Cycle Number
Dis
char
ge C
apac
ity R
eten
tion
(%)
100 102 104 106 1080.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
Cel
l Pot
entia
l (V
)
Time (hrs)
49 50 51 52 53
80
82
84
86
88
90
92
94
96
98
100
Dis
char
ge C
apac
ity R
eten
tion
(%)
Cycle Number
99.986% average
• 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
Capacity Retention = (Coulombs of discharge) / (immediately preceding coulombs of discharge)
Impose ±0.25 A/cm2 square wave, switched at 0, +1.5 V
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)
0 100 200 300 400 500 600 7000.0
0.2
0.4
0.6
0.8
1.0
Cur
rent
Effi
cien
cy (%
)
Cycle Number
0.0
0.2
0.4
0.6
0.8
1.0
Dis
char
ge C
apac
ity R
eten
tion
(%)
750 cycles0.75 A cm-2
Cycling to ~103
76
99.84% avg. discharge capacity retention
98.35% avg. current efficiency
Capacity Retention = (Coulombs of discharge) / (immediately preceding coulombs of discharge)Current Efficiency = (Coulombs of discharge) / (immediately preceding coulombs of charge)
• ±0.75 A/cm2 square wave, switched at 0, +1.5 V• Nafion 115 (125 um); 40 oC• Toray carbon electrodes, 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)
current efficiency loss:• Br2 crossover?• O2 permeation?• H2 evolution?
0.00 0.25 0.50 0.75 1.00
0.98
0.99
1.00
Current density (A/cm2)
Cur
rent
Effi
cien
cy
Current Efficiency
0.0
0.2
0.4
0.6
0.8
1.0
Volta
ge E
ffici
ency
Voltage Efficiency
0.00 0.25 0.50 0.75 1.00
0.98
0.99
1.00
Cur
rent
Effi
cien
cy
Current density (mA/cm2)
Current Efficiency
0.0
0.2
0.4
0.6
0.8
1.0
Voltage Efficiency
Volta
ge E
ffici
ency
0.00 0.25 0.50 0.75 1.000.0
0.2
0.4
0.6
0.8
1.0
Current density (A/cm2)
Ener
gy E
ffici
ency Energy Efficiency
0.00 0.25 0.50 0.75 1.000.0
0.2
0.4
0.6
0.8
1.0
Current density (A/cm2)
Ener
gy E
ffici
ency
Energy Efficiency
Efficiency vs. Current Density
Nafion 212 Nafion 115
Negolyte: 20 mL (1M AQDS + 1M H2SO4)Posolyte: 125 mL (3.5M HBr + 0.5M Br2)Electrode Area: 5 cm2
Additional Advantages of Quinones for Energy Storage
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
Low chemicals cost: Enables low cost/kWhRapid redox kinetics: Enable low cost/kW
Additional Advantages of Quinones for Energy Storage
• 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
Low chemicals cost: Enables low cost/kWhRapid redox kinetics: Enable low cost/kWSmall organic molecules: Enable inexpensive separator
Quinones as an Energy Storage Medium
Low chemicals cost: Enables low cost/kWhRapid redox kinetics: Enable low cost/kWSmall organic molecules: Enable inexpensive separatorAll-liquid storage: Enables inexpensive BOS and high cycle life
Quinones as an Energy Storage Medium
Low chemicals cost: Enables low cost/kWhRapid redox kinetics: Enable low cost/kWSmall organic molecules: Enable inexpensive separatorAll-liquid storage: Enables inexpensive BOS and high cycle lifeAqueous electrolyte: Enables fireproof operation
• Damaged/overheated Li‐ion cells can ignite spontaneously & create fierce fires
9‐Nov‐2008—Li‐ion fire destroys Pearl Harbor‐docked Advanced SEAL Delivery System (ASDL); $237M in damage
3‐Sep‐2010—Li battery fire ignites aboard UPS 747 departing Dubai; crash kills both pilots
7‐Jan‐2013—fire ignites in Li-ion battery pack (2×size of a car battery) of auxiliary power unit in 787 Dreamliner while on the ground in Boston
Li-ion batteries ubiquitous. . . but safety concerns are not going away
Li-ion batteries ubiquitous. . . but safety concerns are not going away
May‐2011—fire ignites in battery pack 3 weeks after crash test of Chevy Volt
• 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)
Slide courtesy of Dr. Debra Rolison, NRL
Quinones as an Energy Storage Medium
Low chemicals cost: Enables low cost/kWhRapid redox kinetics: Enable low cost/kWSmall organic molecules: Enable inexpensive separatorAll-liquid storage: Enables inexpensive BOS and high cycle lifeAqueous electrolyte: Enables fireproof operationNon-toxic: Ideal for commercial, residential markets
Quinones as an Energy Storage Medium
Low chemicals cost: Enables low cost/kWhRapid redox kinetics: Enable low cost/kWSmall organic molecules: Enable inexpensive separatorAll-liquid storage: Enables inexpensive BOS and high cycle lifeAqueous electrolyte: Enables fireproof operationNon-toxic: Ideal for commercial, residential marketsScalability: 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 BrGives <$27/kWh cost of chemicals for QBFB.
Quinones as an Energy Storage Medium
Low chemicals cost: Enables low cost/kWhRapid redox kinetics: Enable low cost/kWSmall organic molecules: Enable inexpensive separatorAll-liquid storage: Enables inexpensive BOS and high cycle lifeAqueous electrolyte: Enables fireproof operationNon-toxic: Ideal for commercial, residential marketsScalability: Enables rapid chemistry scaleupTunability: Enables performance improvements
Computational Screening
Electron-donating –OH groups lower the reduction potential.
-400 -300 -200 -100 0 100 200 300 400
0
1
2
3
4
5
6 Calc. Calc. Exp.
Num
ber o
f –O
H G
roup
s
Potential (mV vs. SHE)
AQDS
DHAQDS
Changwon Suh, Süleyman Er, Michael Marshak, Alán Aspuru-Guzik
-100 0 100 200 300 400 500
-300
-200
-100
0
100
200
Cur
rent
Den
sity
(A
cm–2
)
Potential (mV vs. SHE)
AQDS 1,8-DHAQDS MH-AQDS
Tunability
Reduction
Oxidation
AQDSE0 = 0.210 V
end
start
Electron-donating –OH groups lower the reduction potential.
-100 0 100 200 300 400 500
-300
-200
-100
0
100
200
Cur
rent
Den
sity
(A
cm–2
)
Potential (mV vs. SHE)
AQDS 1,8-DHAQDS MH-AQDS
Tunability
HO3SO
O
SO3HOH OH
Reduction
Oxidation
AQDSE0 = 0.210 V
1,8-DHAQDSE0 = 0.118 V
end
start
Cooper Galvin
-100 0 100 200 300 400 500
-300
-200
-100
0
100
200
Cur
rent
Den
sity
(A
cm–2
)
Potential (mV vs. SHE)
AQDS 1,8-DHAQDS MH-AQDS
Tunability
HO3SO
O
SO3HOH OH
Reduction
Oxidation
AQDSE0 = 0.210 V
1,8-DHAQDSE0 = 0.118 V
end
start
• Addition of OH groups lowers the reduction potential by ~170 mV
• Expect ~20% increase in OCV of Quinone-Bromide cell
MH-AQDSE0 = 0.039 V
Cooper Galvin,Michael Marshak
Tunability Demonstration in Quinone-Bromide Cell
Michael Gerhardt (unpublished)
AQDSE0 = 0.210 V
State of Charge (%)0 20 40 60 80 100
0.65
0.70
0.75
0.80
0.85
0.90
0.95
1.00
1.05
1.10
0.5 M DHAQDS 0.5 M AQS 0.5 M AQDS 1 M AQDS
Preliminary results from DHAQDS and AQS flow cells against HBr/Br2show open circuit voltage rising above 1.0 V at high state of charge.
Ope
n C
ircui
t Vol
tage
(V)
2 ln 2
Tunability Demonstration in Quinone-Bromide Cell
Michael Gerhardt (unpublished)
O
O
SO3H
AQDSE0 = 0.210 V
AQSE0 = 0.193 V
17 mV OCV gainState of Charge (%)
0 20 40 60 80 1000.65
0.70
0.75
0.80
0.85
0.90
0.95
1.00
1.05
1.10
0.5 M DHAQDS 0.5 M AQS 0.5 M AQDS 1 M AQDS
Preliminary results from DHAQDS and AQS flow cells against HBr/Br2show open circuit voltage rising above 1.0 V at high state of charge.
Ope
n C
ircui
t Vol
tage
(V)
Tunability Demonstration in Quinone-Bromide Cell
Michael Gerhardt (unpublished)
O
O
SO3H
AQDSE0 = 0.210 V
AQSE0 = 0.193 V
17 mV OCV gain
DHAQDSE0 = 0.118 V
92 mV OCV gain
State of Charge (%)0 20 40 60 80 100
0.65
0.70
0.75
0.80
0.85
0.90
0.95
1.00
1.05
1.10
0.5 M DHAQDS 0.5 M AQS 0.5 M AQDS 1 M AQDS
Preliminary results from DHAQDS and AQS flow cells against HBr/Br2show open circuit voltage rising above 1.0 V at high state of charge.
Ope
n C
ircui
t Vol
tage
(V)
1.0 V Quinone-Quinone Cell
0.1 M in H2OOpen Circuit Potential = 1.03 VPeak 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.”
J.B. Conant, H.M. Kahn, L.F. Fieser, S.S. Kurtz,, J. Am. Chem. Soc. 44, 1382 (1922).
ethane ethylene
hydroquinone benzoquinoneJ. B. Conant
L. F. Fieser
Quinone Redox Scheme
QH2
Q
Redox-Active Orbital of Quinone
e– e–
e– e–
e– e–
H+
H+
H+
H+
H+
H+
LUMOHOMO SOMO
• Hydroquinone HOMO is π-type
• Virtually identical to quinone LUMO
• Zero electron density on O-H bond
• Near zero motion of any other atoms
Q
DFT Calculations using Gaussian03; B3LYP functional / TZVP basis set (Michael Marshak)
-+ -+- +-+ QH2
Ethane/Ethylene Orbitals
Degenerate HOMO of Ethane consists of C−H σ bonds
LUMO of Ethylene is the π* (anti-bond)
C2H6
C2H4
Outlook
• Cost and tunability of redox-active organics look promising for E storage, other apps?
• High power density, low cost quinone-bromine Redox Flow Battproves 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 bleachdark spots, moles, etc off of skin
Blatellaquinone is a sex pheromone female cockroaches use to attract males
Emodin is found in Aloe Vera
Vitamin K1 is part of the electron transport chain in photosystem I,found in all green plants
Acknowledgments
Not pictured: Dr. Brian Huskinson, Professor Theodore Betley, SarafNawar, Rachel Burton, Cooper Galvin, Sidharth Chand, Tyler Van Valkenburg, Bilen Aküzüm, Ryan Duncan, Dr. Süleyman Er, Dr. Xudong Chen, Phil Baker, Dr. Trent MolterTop Row: Prof. Alán Aspuru-Guzik, Dr. Rafa Gómez-Bombarelli, Tim Hirzel, Louise Eisenach, Dr. Jorge Aguilera Iparraguirre, Prof. Mauricio SallesSecond Row: Jessa Piaia, Drew Wong, Kaixiang Lin, Prof. Xin Li, Dr. David Hardee, Dr. Michael MarshakThird Row: Jennifer Wei, Dr. Qing Chen, Michael Gerhardt, Liuchuan Tong, Xinyou KeFront Row: Dr. Ed Pyzer-Knapp, Dr. Changwon Suh, Lauren Hartle, Prof. Michael Aziz, Prof. Roy GordonNot 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
Harvard U Ctr for the Environment, Harvard School of Engrg & Appl SciHarvard Physics Department,NSF Grad Rsch Fellowship Program, DOE ARPA-E award DE-AR0000348