Quinone electrochemistry in acidic and alkaline solutions & its - PowerPoint PPT Presentation

Quinone electrochemistry in acidic and alkaline solutions & its application in large scale energy storage Michael R. Gerhardt 1 , Kaixiang Lin 2 , Qing Chen 1 , Michael P. Marshak 1,3 , Liuchuan Tong 2 , Roy G. Gordon 1,2 , Michael J. Aziz 1 1) Harvard School of Engineering and Applied Sciences, Cambridge, MA 02138 2) Department of Chemistry and Chemical Biology, Harvard University, Cambridge MA 02138 1 3) Department of Chemistry and Biochemistry, University of Colorado, Boulder CO 80309

Energy Storage (kWh) Power Generation (kW) 2 Photo: Eliza Grinnell, SEAS Communications

O OH + 2H + , 2e ‐ OH O In aqueous acidic solution Huskinson, B., Marshak, M. P., Suh, C., Er, S., Gerhardt, M.R., Galvin, C.J., Chen, X., Aspuru ‐ Guzik, A., Gordon, R.G., and Aziz, M.J. (2014). 3 3 Nature , 505 (7482), 195–198.

O OH Chemistry Solution Cost ($/kWh) Quinone ‐ Bromide <$27 + 2H + , 2e ‐ Vanadium Redox $50 – $180 “I wish I could get that price!” OH O In aqueous acidic solution Huskinson, B., Marshak, M. P., Suh, C., Er, S., Gerhardt, M.R., Galvin, C.J., Chen, X., Aspuru ‐ Guzik, A., Gordon, R.G., and Aziz, M.J. (2014). 4 4 Nature , 505 (7482), 195–198.

O OH Chemistry Solution Cost ($/kWh) Quinone ‐ Bromide <$27 + 2H + , 2e ‐ Vanadium Redox $50 – $180 “I wish I could get that price!” OH O In aqueous acidic solution Customizable Huskinson, B., Marshak, M. P., Suh, C., Er, S., Gerhardt, M.R., Galvin, C.J., Chen, X., Aspuru ‐ Guzik, A., Gordon, R.G., and Aziz, M.J. (2014). 5 5 Nature , 505 (7482), 195–198.

O OH Chemistry Solution Cost ($/kWh) Quinone ‐ Bromide <$27 + 2H + , 2e ‐ Vanadium Redox $50 – $180 “I wish I could get that price!” OH O In aqueous acidic solution Customizable Long cycle life Huskinson, B., Marshak, M. P., Suh, C., Er, S., Gerhardt, M.R., Galvin, C.J., Chen, X., Aspuru ‐ Guzik, A., Gordon, R.G., and Aziz, M.J. (2014). 6 6 Nature , 505 (7482), 195–198.

0.2 AQDS 2 ) Potentiostat Current Density (mA/cm 0.1 0.0 O HO 3 S SO 3 H -0.1 O Electrolyte Solution -0.2 E 0 = 0.210 V vs SHE -0.3 -0.3 -0.2 -0.1 0.0 0.1 0.2 0.3 Overpotential (V) [1] K. B. Oldham, J. C. Myland, Electrochim. Acta . 56 , 10612–10625 (2011). 7 7 [2] B. Huskinson et al. , Nature . 505 , 195–198 (2014).

0.2 AQDS Model 2 ) Current Density (mA/cm Reversible 2 ‐ electron model: 0.1 assume AQDS concentration at electrode surface is dictated by 0.0 Nernst equation [1]. Reaction rate is mass transport limited. O HO 3 S SO 3 H -0.1 Measured rate constant k 0 = 7.2 × 10 − 3 cm/s [2] O -0.2 E 0 = 0.210 V vs SHE -0.3 -0.3 -0.2 -0.1 0.0 0.1 0.2 0.3 Overpotential (V) [1] K. B. Oldham, J. C. Myland, Electrochim. Acta . 56 , 10612–10625 (2011). 8 8 [2] B. Huskinson et al. , Nature . 505 , 195–198 (2014).

O HO 3 S SO 3 H O No catalyst required 9 Huskinson, B., Marshak, M. P., et al. (2014). Nature , 505 (7482), 195–198.

1.4 1.2 1.0 Voltage (V) 0.8 0.6 State of Charge 10% 30% 0.4 50% 70% 0.2 90% 0.0 -2 -1 0 1 2 3 -2 ) Current Density (A cm 0.7 State of Charge 10% 0.6 -2 ) 30% Power Density (W cm 50% 0.5 70% 90% 0.4 0.3 0.2 0.1 0.0 0.0 0.5 1.0 1.5 2.0 2.5 3.0 -2 ) 10 Current Density (A cm Data: Qing Chen

O HO 3 S SO 3 H 0.2 “AQDS” –2 ) O Current Density (mA cm 0.1 9,10 ‐ anthraquinone 2,7 ‐ disulfonic acid 0.0 -0.1 AQDS -0.2 -0.3 -0.1 0.0 0.1 0.2 0.3 0.4 0.5 Potential (V vs. SHE) Glassy carbon electrode, 3 mm dia, 25 mV/s scan rate, 25 °C. Ag/AgCl reference. Pt coil counter electrode. Supporting electrolyte 1 M H 2 SO 4 11 11 Quinone concentration 1 mM

O HO 3 S SO 3 H 0.2 “AQDS” 2 ) O Current Density (mA/cm 0.1 0.0 -0.1 AQDS “AQS” AQS -0.2 9,10 ‐ anthraquinone 2 ‐ sulfonic acid -0.3 -0.1 0.0 0.1 0.2 0.3 0.4 0.5 Potential (V vs. SHE) Glassy carbon electrode, 3 mm dia, 25 mV/s scan rate, 25 °C. Ag/AgCl reference. Pt coil counter electrode. Supporting electrolyte 1 M H 2 SO 4 12 12 Quinone concentration 1 mM

O HO 3 S SO 3 H 0.2 “AQDS” 2 ) O Current Density (mA/cm 0.1 0.0 -0.1 AQDS “AQS” AQS DHAQDS -0.2 -0.3 -0.1 0.0 0.1 0.2 0.3 0.4 0.5 Potential (V vs. SHE) “DHAQDS” 1,8 ‐ dihydroxy 9,10 ‐ anthraquinone Glassy carbon electrode, 3 mm dia, 25 mV/s scan rate, 25 °C. Ag/AgCl reference. Pt coil counter electrode. Supporting electrolyte 1 M H 2 SO 4 2,7 ‐ disulfonic acid 13 13 Quinone concentration 1 mM

O HO 3 S SO 3 H 1.05 “AQDS” 1.00 DHAQDS O Open Circuit Potential (V) AQS 0.95 AQDS 0.90 0.85 “AQS” 0.80 0.75 0.70 0.65 0 20 40 60 80 100 State of Charge (%) “DHAQDS” Posolyte: 0.5 M Br 2 , 3 M HBr 14 14 Negolyte: 1 M quinone, 1 to 2 M H 2 SO 4 (3 M total proton concentration)

O HO 3 S SO 3 H 1.05 “AQDS” 1.00 DHAQDS O Open Circuit Potential (V) AQS 0.95 AQDS 0.90 0.85 “AQS” 0.80 0.75 0.70 0.65 0 20 40 60 80 100 State of Charge (%) “DHAQDS” Posolyte: 0.5 M Br 2 , 3 M HBr 15 15 Negolyte: 1 M quinone, 1 to 2 M H 2 SO 4 (3 M total proton concentration)

0.2 AQS Model 2 ) Current Density (mA/cm Reversible 2 ‐ electron model: 0.1 assume AQS concentration at electrode surface is dictated 0.0 by Nernst equation [1]. Reaction rate is mass transport limited. -0.1 -0.2 -0.3 -0.3 -0.2 -0.1 0.0 0.1 0.2 0.3 Overpotential (V) Glassy carbon electrode, 3 mm dia, 25 mV/s scan rate, 25 °C. Ag/AgCl reference. Pt coil counter electrode. Supporting electrolyte 1 M H 2 SO 4 . Quinone concentration 1 mM 16 16 [1] K. B. Oldham, J. C. Myland, Electrochim. Acta . 56 , 10612–10625 (2011).

0.2 AQS Model 2 ) Current Density (mA/cm Quasireversible model: Assume 0.1 Butler ‐ Volmer kinetics with a rate constant k 0 = 2 × 10 − 3 cm/s 0.0 [1]. -0.1 -0.2 -0.3 -0.3 -0.2 -0.1 0.0 0.1 0.2 0.3 Overpotential (V) Glassy carbon electrode, 3 mm dia, 25 mV/s scan rate, 25 °C. Ag/AgCl reference. Pt coil counter electrode. Supporting electrolyte 1 M H 2 SO 4 . Quinone concentration 1 mM 17 17 [1] K. B. Oldham, J. C. Myland, Electrochim. Acta . 56 , 10612–10625 (2011).

1.4 1.2 AQS 1.0 AQDS Voltage (V) 0.8 0.6 0.4 0.2 Charge Discharge 0.0 -2 -1 0 1 2 3 2 ) Current Density (A/cm O HO 3 S SO 3 H O AQS AQDS 18 18 Posolyte: 0.5 M Br 2 , 3 M HBr

0.8 90% SoC 2 ) 0.6 Power Density (W/cm 50% SoC 0.4 AQS AQDS 0.2 0.0 0.0 0.5 1.0 1.5 2.0 2.5 3.0 2 ) Current Density (A/cm O HO 3 S SO 3 H O AQS AQDS 19 19 Posolyte: 0.5 M Br 2 , 3 M HBr

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300 200 100 0 (mV vs SHE) 0 -100 E -200 -300 0 2 4 6 8 10 12 14 pH � � � � � � �� � � � p� � � � � � � 23

300 200 2e − , 2H + 100 0 (mV vs SHE) pKa 1 = 7.70, 0 pKa 2 = 10.52 E 0 = 0.229 V -100 E 0 dianion = − 0.313 V E -200 -300 0 2 4 6 8 10 12 14 pH 24

300 200 2e − , 2H + 100 0 (mV vs SHE) pKa 1 = 7.70, 0 pKa 2 = 10.52 E 0 = 0.229 V -100 E 0 dianion = − 0.313 V 2e − , 1H + E -200 -300 0 2 4 6 8 10 12 14 pH 25

300 200 2e − , 2H + 100 0 (mV vs SHE) pKa 1 = 7.70, 0 pKa 2 = 10.52 E 0 = 0.229 V -100 E 0 dianion = − 0.313 V 2e − , 1H + E -200 2e − -300 0 2 4 6 8 10 12 14 pH 26

0.3 AQDS, pH 1 0.2 2 ) Current Density (mA/cm 0.1 0.0 -0.1 -0.2 O HO 3 S SO 3 H -0.3 O -0.4 -0.3 -0.2 -0.1 0.0 0.1 0.2 0.3 Overpotential (V) Glassy carbon electrode, 3 mm dia, 50 mV/s scan rate, 25 °C. Ag/AgCl reference. 27 Pt coil counter electrode. Supporting electrolyte H 2 SO 4 or KOH. Quinone concentration 1 mM

0.3 AQDS, pH 1 0.2 AQDS, pH 14 2 ) Current Density (mA/cm 0.1 0.0 -0.1 -0.2 O HO 3 S SO 3 H -0.3 O -0.4 -0.3 -0.2 -0.1 0.0 0.1 0.2 0.3 Overpotential (V) Glassy carbon electrode, 3 mm dia, 50 mV/s scan rate, 25 °C. Ag/AgCl reference. 28 Pt coil counter electrode. Supporting electrolyte H 2 SO 4 or KOH. Quinone concentration 1 mM

0.3 AQDS, pH 1 0.2 AQDS, pH 14 Reversible model 2 ) Current Density (mA/cm 0.1 0.0 -0.1 -0.2 O HO 3 S SO 3 H -0.3 O -0.4 -0.3 -0.2 -0.1 0.0 0.1 0.2 0.3 Overpotential (V) Glassy carbon electrode, 3 mm dia, 50 mV/s scan rate, 25 °C. Ag/AgCl reference. 29 Pt coil counter electrode. Supporting electrolyte H 2 SO 4 or KOH. Quinone concentration 1 mM

3 3 30

O 2,6-DHAQ OH 0.2 AQDS 2 ) HO Current Density (mA/cm 0.1 O “2,6 ‐ DHAQ” 2,6 ‐ dihydroxy 9,10 ‐ 0.0 anthraquinone -0.1 O -0.2 HO 3 S SO 3 H pH 14 -0.3 O -1.0 -0.8 -0.6 -0.4 -0.2 0.0 Potential (V vs SHE) 31

0.20 0.15 2,6-DHAQ Model 2 ) 0.10 Current Density (mA/cm 0.05 0.00 -0.05 -0.10 -0.15 -0.20 -0.25 -0.2 -0.1 0.0 0.1 0.2 O Overpotential (V) OH k 0 = 1 x 10 ‐ 2 cm/s HO 32 O

0.20 0.15 2,6-DHAQ Model 2 ) 0.10 Current Density (mA/cm 0.05 0.00 -0.05 -0.10 -0.15 -0.20 -0.25 -0.2 -0.1 0.0 0.1 0.2 O Overpotential (V) OH k 0 = 1 x 10 ‐ 3 cm/s HO 33 O

0.20 0.15 2,6-DHAQ Model 2 ) 0.10 Current Density (mA/cm 0.05 0.00 -0.05 -0.10 -0.15 -0.20 -0.25 -0.2 -0.1 0.0 0.1 0.2 O Overpotential (V) OH k 0 = 1 x 10 ‐ 4 cm/s HO 34 O