• Grid-scale storage
• Flow Batteries
• Quinones and hydroquinones
• Quinone-based flow batteries: First results
• Future prospects
10/12/2013
Electricity Prices Go Negative (US)
10/17/2013
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)
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
J. Rugolo and M.J. Aziz, “Electricity Storage for Intermittent Renewable Sources”, Energy Environ. Sci. 5, 7151 (2012)
Three storage scenarios: Power and energy
requirements, 1 MW nameplate production
supplied to grid
1 MW
wind production
Power
J. Rugolo and M.J. Aziz, “Electricity Storage for Intermittent Renewable Sources”, Energy Environ. Sci. 5, 7151 (2012)
Storage: A Distribution of Efficiencies
Power dens’y:
E, Cell Potential [V]
Realistic
How
much
A?
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
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]
J. Rugolo and M.J. Aziz, “Electricity Storage for Intermittent Renewable Sources”, Energy Environ. Sci. 5, 7151 (2012)
Diminishing Returns on Buying Storage Power
Wind
Solar
Solar Wind
J. Rugolo and M.J. Aziz, “Electricity Storage for Intermittent Renewable Sources”, Energy Environ. Sci. 5, 7151 (2012)
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
J. Rugolo and M.J. Aziz, “Electricity Storage for Intermittent Renewable Sources”, Energy Environ. Sci. 5, 7151 (2012)
Batteries Have Only About 1%
of the Required Energy for a Given Power
Power 1 MW 1 MW
Energy 16 60
MWhr MWhr
energy 16 hr 60 hr
Ratio
power
J. Rugolo and M.J. Aziz, “Electricity Storage for Intermittent Renewable Sources”, Energy Environ. Sci. 5, 7151 (2012)
Batteries Have Only About 1%
of the Required Energy for a Given Power
Power 1 MW 1 MW 1 MW
1 MW
0.2 MWhr
$40k
J. Rugolo and M.J. Aziz, “Electricity Storage for Intermittent Renewable Sources”, Energy Environ. Sci. 5, 7151 (2012)
Batteries Have Only About 1%
of the Required Energy for a Given Power
Power 1 MW 1 MW 2 MW
1 MW 1 MW
0.2 MWhr 0.2 MWhr
$40k
J. Rugolo and M.J. Aziz, “Electricity Storage for Intermittent Renewable Sources”, Energy Environ. Sci. 5, 7151 (2012)
Batteries Have Only About 1%
of the Required Energy for a Given Power
Power 1 MW 1 MW 3 MW
1 MW 1 MW 1 MW
0.2 MWhr 0.2 MWhr 0.2 MWhr
$40k
J. Rugolo and M.J. Aziz, “Electricity Storage for Intermittent Renewable Sources”, Energy Environ. Sci. 5, 7151 (2012)
Batteries Have Only About 1%
of the Required Energy for a Given Power
Power 1 MW 1 MW 4 MW
1 MW 1 MW 1 MW 1 MW
0.2 MWhr 0.2 MWhr 0.2 MWhr 0.2 MWhr
$40k
J. Rugolo and M.J. Aziz, “Electricity Storage for Intermittent Renewable Sources”, Energy Environ. Sci. 5, 7151 (2012)
Batteries Have Only About 1%
of the Required Energy for a Given Power
Power 1 MW 1 MW 5 MW
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
J. Rugolo and M.J. Aziz, “Electricity Storage for Intermittent Renewable Sources”, Energy Environ. Sci. 5, 7151 (2012)
Batteries Have Only About 1%
of the Required Energy for a Given Power
Power 1 MW 1 MW 10 MW
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
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
J. Rugolo and M.J. Aziz, “Electricity Storage for Intermittent Renewable Sources”, Energy Environ. Sci. 5, 7151 (2012)
Batteries Have Only About 1%
of the Required Energy for a Given Power
Power 1 MW 1 MW 15 MW
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
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
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
J. Rugolo and M.J. Aziz, “Electricity Storage for Intermittent Renewable Sources”, Energy Environ. Sci. 5, 7151 (2012)
Batteries Have Only About 1%
of the Required Energy for a Given Power
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
0.2 MWhr 0.2 MWhr 0.2 MWhr 0.2 MWhr 0.2 MWhr
Storage, 1 MW nameplate
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
1 MW0.2 MWhr 0.21 MWhr
MW0.2 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
0.2 MWhr 0.2 MWhr 0.2 MWhr 0.2 MWhr 0.2 MWhr
1 MW 10.2
MW MWhr 10.2
MWM
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 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 MW 1 MW 1 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
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 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
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 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
1 MW 1 MW 1 MW 1 MW 1 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
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
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
J. Rugolo and M.J. Aziz, “Electricity Storage for Intermittent Renewable Sources”, Energy Environ. Sci. 5, 7151 (2012)
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)
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)
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)
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)
“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
-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
-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
“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
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
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
-100
0
-90
-200 -80
Current Density (A cm )
–2
200 RPM
-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.
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
-60
0
-200 -50
Current Density (A cm )
–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
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
F = Faraday’s constant
-50
A = surface area
C = concentration
-40
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
*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
Porous carbon
paper electrode
(no catalyst)
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 Assembly
Serpentine Interdigitated Carbon paper Nafion membrane
or
flow field flow field
Teflon gasket
Assembled single-cell stack
Cell Performance
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 now 1.0 W/cm2
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
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)
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 )
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)
75
Cycling to ~102
1.2 94
Cycling to ~103
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
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
• 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
Quinone kinetics on glassy carbon exceed those of most other battery redox couples
Additional Advantages of Quinones for Energy Storage
Low chemicals cost: Enables low cost/kWh
Rapid redox kinetics: Enable low cost/kW
Small organic molecules: Enable inexpensive separator
• 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
Quinones as an Energy Storage Medium
Low chemicals cost: Enables low cost/kWh
Rapid redox kinetics: Enable low cost/kW
Small organic molecules: Enable inexpensive separator
All-liquid storage: Enables inexpensive BOS and high cycle life
Aqueous electrolyte: Enables fireproof operation
Non-toxic: Ideal for commercial, residential markets
Quinones as an Energy Storage Medium
Low chemicals cost: Enables low cost/kWh
Rapid redox kinetics: Enable low cost/kW
Small organic molecules: Enable inexpensive separator
All-liquid storage: Enables inexpensive BOS and high cycle life
Aqueous electrolyte: Enables fireproof operation
Non-toxic: Ideal for commercial, residential markets
Scalability: Enables rapid chemistry scaleup
Scalability
DHAQDS
2
AQDS
0
end
0
start
-100
AQDS
1,8-DHAQDS
-200 MH-AQDS
Reduction
-300
AQDS
E0 = 0.210 V
Tunability
200
Oxidation
100
Current Density (A cm )
–2
end
0
start
-100
AQDS
1,8-DHAQDS
-200 MH-AQDS
Reduction
-300
~170 mV
–2
-100
AQDS
1,8-DHAQDS
-200 MH-AQDS
Reduction
-300
1.10
0.90
0.85
0.80
0.75
2
0.70 ln
2
0.65
0 20 40 60 80 100
1.10
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
1.10
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
0.1 M in H2O
Open Circuit Potential = 1.03 V
Peak power density = 50 mA cm−2
>99% current Efficiency
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
C2H4