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

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

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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

slide-1
SLIDE 1

Quinone electrochemistry in acidic and alkaline solutions

& its application in large scale energy storage Michael R. Gerhardt1, Kaixiang Lin2, Qing Chen1, Michael P. Marshak1,3, Liuchuan Tong2, Roy G. Gordon1,2, Michael J. Aziz1 1) Harvard School of Engineering and Applied Sciences, Cambridge, MA 02138 2) Department of Chemistry and Chemical Biology, Harvard University, Cambridge MA 02138 3) Department of Chemistry and Biochemistry, University of Colorado, Boulder CO 80309

1

slide-2
SLIDE 2

Energy Storage (kWh) Power Generation (kW)

Photo: Eliza Grinnell, SEAS Communications

2

slide-3
SLIDE 3

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). Nature, 505(7482), 195–198.

+ 2H+, 2e‐

OH OH O O

3

In aqueous acidic solution

3

slide-4
SLIDE 4

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). Nature, 505(7482), 195–198.

Chemistry Solution Cost ($/kWh) Quinone‐Bromide <$27 Vanadium Redox $50 – $180

+ 2H+, 2e‐

OH OH O O

4

“I wish I could get that price!” In aqueous acidic solution

4

slide-5
SLIDE 5

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). Nature, 505(7482), 195–198.

Chemistry Solution Cost ($/kWh) Quinone‐Bromide <$27 Vanadium Redox $50 – $180

+ 2H+, 2e‐

OH OH O O

5

“I wish I could get that price!” In aqueous acidic solution

5

slide-6
SLIDE 6

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). Nature, 505(7482), 195–198.

Chemistry Solution Cost ($/kWh) Quinone‐Bromide <$27 Vanadium Redox $50 – $180

+ 2H+, 2e‐

OH OH O O

6

“I wish I could get that price!” In aqueous acidic solution

6

slide-7
SLIDE 7
  • 0.3
  • 0.2
  • 0.1

0.0 0.1 0.2 0.3

  • 0.3
  • 0.2
  • 0.1

0.0 0.1 0.2

Current Density (mA/cm

2)

Overpotential (V)

AQDS

[1] K. B. Oldham, J. C. Myland, Electrochim. Acta. 56, 10612–10625 (2011). [2] B. Huskinson et al., Nature. 505, 195–198 (2014). 7 7

O O SO3H HO3S

Potentiostat Electrolyte Solution E0 = 0.210 V vs SHE

slide-8
SLIDE 8
  • 0.3
  • 0.2
  • 0.1

0.0 0.1 0.2 0.3

  • 0.3
  • 0.2
  • 0.1

0.0 0.1 0.2

Current Density (mA/cm

2)

Overpotential (V)

AQDS Model

[1] K. B. Oldham, J. C. Myland, Electrochim. Acta. 56, 10612–10625 (2011). [2] B. Huskinson et al., Nature. 505, 195–198 (2014). 8 8

Reversible 2‐electron model: assume AQDS concentration at electrode surface is dictated by Nernst equation [1]. Reaction rate is mass transport limited. Measured rate constant k0 = 7.2 × 10−3 cm/s [2]

O O SO3H HO3S

E0 = 0.210 V vs SHE

slide-9
SLIDE 9

9

Huskinson, B., Marshak, M. P., et al. (2014). Nature, 505(7482), 195–198.

No catalyst required

O O SO3H HO3S

slide-10
SLIDE 10

10

Data: Qing Chen State of Charge 10% 30% 50% 70% 90%

  • 2
  • 1

1 2 3 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4

Voltage (V) Current Density (A cm

  • 2)

State of Charge 10% 30% 50% 70% 90% 0.0 0.5 1.0 1.5 2.0 2.5 3.0 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7

Power Density (W cm

  • 2)

Current Density (A cm

  • 2)
slide-11
SLIDE 11

O O SO3H HO3S Glassy carbon electrode, 3 mm dia, 25 mV/s scan rate, 25 °C. Ag/AgCl reference. Pt coil counter electrode. Supporting electrolyte 1 M H2SO4 Quinone concentration 1 mM

11

“AQDS”

11

  • 0.1

0.0 0.1 0.2 0.3 0.4 0.5

  • 0.3
  • 0.2
  • 0.1

0.0 0.1 0.2

Current Density (mA cm

–2)

Potential (V vs. SHE)

AQDS 9,10‐anthraquinone 2,7‐ disulfonic acid

slide-12
SLIDE 12

O O SO3H HO3S Glassy carbon electrode, 3 mm dia, 25 mV/s scan rate, 25 °C. Ag/AgCl reference. Pt coil counter electrode. Supporting electrolyte 1 M H2SO4 Quinone concentration 1 mM

“AQS”

12

“AQDS”

12

  • 0.1

0.0 0.1 0.2 0.3 0.4 0.5

  • 0.3
  • 0.2
  • 0.1

0.0 0.1 0.2

Current Density (mA/cm

2)

Potential (V vs. SHE)

AQDS AQS 9,10‐anthraquinone 2‐ sulfonic acid

slide-13
SLIDE 13

O O SO3H HO3S Glassy carbon electrode, 3 mm dia, 25 mV/s scan rate, 25 °C. Ag/AgCl reference. Pt coil counter electrode. Supporting electrolyte 1 M H2SO4 Quinone concentration 1 mM

“AQS” “DHAQDS”

13

“AQDS”

1,8‐dihydroxy 9,10‐anthraquinone 2,7‐disulfonic acid

13

  • 0.1

0.0 0.1 0.2 0.3 0.4 0.5

  • 0.3
  • 0.2
  • 0.1

0.0 0.1 0.2

Current Density (mA/cm

2)

Potential (V vs. SHE)

AQDS AQS DHAQDS

slide-14
SLIDE 14

Posolyte: 0.5 M Br2, 3 M HBr Negolyte: 1 M quinone, 1 to 2 M H2SO4 (3 M total proton concentration)

14

20 40 60 80 100 0.65 0.70 0.75 0.80 0.85 0.90 0.95 1.00 1.05 DHAQDS AQS AQDS

Open Circuit Potential (V) State of Charge (%)

14

O O SO3H HO3S

“AQS” “DHAQDS” “AQDS”

slide-15
SLIDE 15

Posolyte: 0.5 M Br2, 3 M HBr Negolyte: 1 M quinone, 1 to 2 M H2SO4 (3 M total proton concentration)

15

20 40 60 80 100 0.65 0.70 0.75 0.80 0.85 0.90 0.95 1.00 1.05 DHAQDS AQS AQDS

Open Circuit Potential (V) State of Charge (%)

15

O O SO3H HO3S

“AQS” “DHAQDS” “AQDS”

slide-16
SLIDE 16

16 16

Reversible 2‐electron model: assume AQS concentration at electrode surface is dictated by Nernst equation [1]. Reaction rate is mass transport limited.

Glassy carbon electrode, 3 mm dia, 25 mV/s scan rate, 25 °C. Ag/AgCl reference. Pt coil counter electrode. Supporting electrolyte 1 M H2SO4. Quinone concentration 1 mM [1] K. B. Oldham, J. C. Myland, Electrochim. Acta. 56, 10612–10625 (2011).

  • 0.3
  • 0.2
  • 0.1

0.0 0.1 0.2 0.3

  • 0.3
  • 0.2
  • 0.1

0.0 0.1 0.2

Current Density (mA/cm

2)

Overpotential (V)

AQS Model

slide-17
SLIDE 17

17 17

Quasireversible model: Assume Butler‐Volmer kinetics with a rate constant k0 = 2 × 10−3 cm/s [1].

  • 0.3
  • 0.2
  • 0.1

0.0 0.1 0.2 0.3

  • 0.3
  • 0.2
  • 0.1

0.0 0.1 0.2

Current Density (mA/cm

2)

Overpotential (V)

AQS Model

Glassy carbon electrode, 3 mm dia, 25 mV/s scan rate, 25 °C. Ag/AgCl reference. Pt coil counter electrode. Supporting electrolyte 1 M H2SO4. Quinone concentration 1 mM [1] K. B. Oldham, J. C. Myland, Electrochim. Acta. 56, 10612–10625 (2011).

slide-18
SLIDE 18
  • 2
  • 1

1 2 3 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4

Voltage (V) Current Density (A/cm

2)

AQS AQDS

Posolyte: 0.5 M Br2, 3 M HBr

18 Discharge Charge 18

O O SO3H HO3S

AQS AQDS

slide-19
SLIDE 19

0.0 0.5 1.0 1.5 2.0 2.5 3.0 0.0 0.2 0.4 0.6 0.8

Power Density (W/cm

2)

Current Density (A/cm

2)

AQS AQDS Posolyte: 0.5 M Br2, 3 M HBr

19 19

O O SO3H HO3S

AQS AQDS 90% SoC 50% SoC

slide-20
SLIDE 20

20

slide-21
SLIDE 21

21

slide-22
SLIDE 22

22

slide-23
SLIDE 23

23

  • p

2 4 6 8 10 12 14

  • 300
  • 200
  • 100

100 200 300

E

0 (mV vs SHE)

pH

slide-24
SLIDE 24

2 4 6 8 10 12 14

  • 300
  • 200
  • 100

100 200 300

E

0 (mV vs SHE)

pH

24

2e−, 2H+ pKa1 = 7.70, pKa2 = 10.52 E0 = 0.229 V E0

dianion = −0.313 V

slide-25
SLIDE 25

25

2e−, 2H+ 2e−, 1H+ pKa1 = 7.70, pKa2 = 10.52 E0 = 0.229 V E0

dianion = −0.313 V

2 4 6 8 10 12 14

  • 300
  • 200
  • 100

100 200 300

E

0 (mV vs SHE)

pH

slide-26
SLIDE 26

26

2 4 6 8 10 12 14

  • 300
  • 200
  • 100

100 200 300

E

0 (mV vs SHE)

pH

2e− 2e−, 2H+ 2e−, 1H+ pKa1 = 7.70, pKa2 = 10.52 E0 = 0.229 V E0

dianion = −0.313 V

slide-27
SLIDE 27

O O SO3H HO3S

27

Glassy carbon electrode, 3 mm dia, 50 mV/s scan rate, 25 °C. Ag/AgCl reference. Pt coil counter electrode. Supporting electrolyte H2SO4 or KOH. Quinone concentration 1 mM

  • 0.3
  • 0.2
  • 0.1

0.0 0.1 0.2 0.3

  • 0.4
  • 0.3
  • 0.2
  • 0.1

0.0 0.1 0.2 0.3

Current Density (mA/cm

2)

Overpotential (V)

AQDS, pH 1

slide-28
SLIDE 28

O O SO3H HO3S

28

Glassy carbon electrode, 3 mm dia, 50 mV/s scan rate, 25 °C. Ag/AgCl reference. Pt coil counter electrode. Supporting electrolyte H2SO4 or KOH. Quinone concentration 1 mM

  • 0.3
  • 0.2
  • 0.1

0.0 0.1 0.2 0.3

  • 0.4
  • 0.3
  • 0.2
  • 0.1

0.0 0.1 0.2 0.3

Current Density (mA/cm

2)

Overpotential (V)

AQDS, pH 1 AQDS, pH 14

slide-29
SLIDE 29
  • 0.3
  • 0.2
  • 0.1

0.0 0.1 0.2 0.3

  • 0.4
  • 0.3
  • 0.2
  • 0.1

0.0 0.1 0.2 0.3

Current Density (mA/cm

2)

Overpotential (V)

AQDS, pH 1 AQDS, pH 14 Reversible model

O O SO3H HO3S

29

Glassy carbon electrode, 3 mm dia, 50 mV/s scan rate, 25 °C. Ag/AgCl reference. Pt coil counter electrode. Supporting electrolyte H2SO4 or KOH. Quinone concentration 1 mM

slide-30
SLIDE 30

3 3

30

slide-31
SLIDE 31
  • 1.0
  • 0.8
  • 0.6
  • 0.4
  • 0.2

0.0

  • 0.3
  • 0.2
  • 0.1

0.0 0.1 0.2

Current Density (mA/cm

2)

Potential (V vs SHE)

2,6-DHAQ AQDS

31

O O OH HO O O SO3H HO3S

“2,6‐DHAQ”

2,6‐dihydroxy 9,10‐ anthraquinone

pH 14

slide-32
SLIDE 32
  • 0.2
  • 0.1

0.0 0.1 0.2

  • 0.25
  • 0.20
  • 0.15
  • 0.10
  • 0.05

0.00 0.05 0.10 0.15 0.20

Current Density (mA/cm

2)

Overpotential (V)

2,6-DHAQ Model

k0 = 1 x 10‐2 cm/s

32 O O OH HO

slide-33
SLIDE 33
  • 0.2
  • 0.1

0.0 0.1 0.2

  • 0.25
  • 0.20
  • 0.15
  • 0.10
  • 0.05

0.00 0.05 0.10 0.15 0.20

Current Density (mA/cm

2)

Overpotential (V)

2,6-DHAQ Model

33 O O OH HO

k0 = 1 x 10‐3 cm/s

slide-34
SLIDE 34
  • 0.2
  • 0.1

0.0 0.1 0.2

  • 0.25
  • 0.20
  • 0.15
  • 0.10
  • 0.05

0.00 0.05 0.10 0.15 0.20

Current Density (mA/cm

2)

Overpotential (V)

2,6-DHAQ Model

34 O O OH HO

k0 = 1 x 10‐4 cm/s

slide-35
SLIDE 35
  • 0.2
  • 0.1

0.0 0.1 0.2

  • 0.25
  • 0.20
  • 0.15
  • 0.10
  • 0.05

0.00 0.05 0.10 0.15 0.20

Current Density (mA/cm

2)

Overpotential (V)

2,6-DHAQ

35 O O OH HO

slide-36
SLIDE 36
  • 0.2
  • 0.1

0.0 0.1 0.2

  • 0.25
  • 0.20
  • 0.15
  • 0.10
  • 0.05

0.00 0.05 0.10 0.15 0.20

Current Density (mA/cm

2)

Overpotential (V)

2,6-DHAQ Model i1

E0,1 = ‐0.657 vs SHE k0,1 = 7 * 10‐3 cm/s

36 O O OH HO

slide-37
SLIDE 37
  • 0.2
  • 0.1

0.0 0.1 0.2

  • 0.25
  • 0.20
  • 0.15
  • 0.10
  • 0.05

0.00 0.05 0.10 0.15 0.20

Current Density (mA/cm

2)

Overpotential (V)

2,6-DHAQ Model i1 Model i2

E0,1 = ‐0.657 vs SHE k0,1 = 7 * 10‐3 cm/s E0,2 = ‐0.717 vs SHE k0,2 = 7 * 10‐3 cm/s

37 O O OH HO

slide-38
SLIDE 38
  • 0.2
  • 0.1

0.0 0.1 0.2

  • 0.25
  • 0.20
  • 0.15
  • 0.10
  • 0.05

0.00 0.05 0.10 0.15 0.20

Current Density (mA/cm

2)

Overpotential (V)

2,6-DHAQ Model i1 Model i2 Model i1 + i2

E0,1 = ‐0.657 vs SHE k0,1 = 7 * 10‐3 cm/s E0,2 = ‐0.717 vs SHE k0,2 = 7 * 10‐3 cm/s

38 O O OH HO

slide-39
SLIDE 39

39

Figure by Kaixiang Lin, manuscript under review

slide-40
SLIDE 40

40

Cyclic voltammogram of 4 mM 2,6‐DHAQ (dark cyan curve) and ferrocyanide (gold curve) scanned at 100 mV/s Work performed by Kaixiang Lin, manuscript under review

slide-41
SLIDE 41

41

O O SO3H HO3S

Use functional groups to create more reducing quinones

  • 0.1

0.0 0.1 0.2 0.3 0.4 0.5

  • 0.3
  • 0.2
  • 0.1

0.0 0.1 0.2

Current Density (mA cm

–2)

Potential (V vs. SHE)

AQDS AQS DHAQDS

slide-42
SLIDE 42

42

O O OH HO

Use functional groups to create more reducing quinones Use quinones in alkaline environment

2 4 6 8 10 12 14

  • 300
  • 200
  • 100

100 200 300

E

0 (mV vs SHE)

pH

  • 0.1

0.0 0.1 0.2 0.3 0.4 0.5

  • 0.3
  • 0.2
  • 0.1

0.0 0.1 0.2

Current Density (mA cm

–2)

Potential (V vs. SHE)

AQDS AQS DHAQDS

O O SO3H HO3S O O SO3H HO3S

slide-43
SLIDE 43

43

Use functional groups to create more reducing quinones Use quinones in alkaline environment

2 4 6 8 10 12 14

  • 300
  • 200
  • 100

100 200 300

E

0 (mV vs SHE)

pH

  • 0.1

0.0 0.1 0.2 0.3 0.4 0.5

  • 0.3
  • 0.2
  • 0.1

0.0 0.1 0.2

Current Density (mA cm

–2)

Potential (V vs. SHE)

AQDS AQS DHAQDS

ENFL 403: Organic Aqueous Redox Flow Batteries

  • Prof. Michael J. Aziz

Thursday, August 20, 1:35 pm Room 258B

slide-44
SLIDE 44

This work was partially funded through the US Department of Energy ARPA-E Award DE-AR0000348 and partially funded through the Harvard School of Engineering and Applied Sciences. Top to bottom, left to right: Drew Wong, Prof. Mauricio Salles, Alvaro Valle, Dr. Junling Huang Dhruv Pillai, Prof. Michael Marshak, Dr. Rafa Gómez-Bombarelli, Liuchuan Tong Lauren Hartle, Dr. Sungjin “James” Kim, Dr. Changwon Suh, Kaixiang Lin, Michael Gerhardt, Dr. Eugene Beh

  • Dr. Qing Chen, Louise Eisenach, Jennifer Wei
  • Prof. Michael Aziz, Prof. Roy Gordon, Prof. Alán Aspuru-Guzik
slide-45
SLIDE 45

45

slide-46
SLIDE 46
  • Linear, planar diffusion

–

,

  • ,
  • Initial conditions:

– , 0

∗, , 0 0

  • Boundary conditions:

– → ∞,

∗

  • All current is diffusion controlled

–

,

  • Reversible reaction. Nernst equation applies:

–

, , /

Notation follows Bard and Faulkner for the reaction O + ne  R.

slide-47
SLIDE 47
  • New boundary condition:
  • ,
  • Define a new variable:
  • Nicholson, R. (1965). Theory and Application of Cyclic Voltammetry for Measurement of Electrode Reaction Kinetics. Analytical Chemistry, (21), 1351–1355.

Retrieved from http://pubs.acs.org/doi/abs/10.1021/ac60230a016

∗ ∗

⁄

  • 1
  • ∗

∗

⁄

  • → ∞: Reversible

→ 0: Irreversible

slide-48
SLIDE 48

48

slide-49
SLIDE 49

49

slide-50
SLIDE 50

50

slide-51
SLIDE 51

51

slide-52
SLIDE 52

52

slide-53
SLIDE 53

53

slide-54
SLIDE 54

54

slide-55
SLIDE 55

Aqueous quinone/hydroquinone couples exhibit rapid redox kinetics, require no electrocatalyst, and are inexpensive, making them attractive candidates for large-scale energy storage devices such as flow batteries 1–3. In acidic solutions, quinones undergo a rapid two-proton, two-electron reduction; however, in alkaline aqueous solutions, the picture is less clear4. Under the right conditions, a two-electron reduction can occur as successive one-electron steps separated by a small difference in the reduction potential of each step. The underlying mechanism for the reduction of various quinones is explored as a function of pH and reduction potential. Using substituted anthraquinones and the bromine/hydrobromic acid couple, a flow battery exhibiting an open circuit voltage above 1.0 V and a peak galvanic power density above 0.7 W cm−2 is

  • demonstrated. Furthermore, by employing soluble metal coordination

complexes, a flow battery with an open circuit voltage exceeding 1.3 V is

  • demonstrated. Mechanisms of capacity loss during cell cycling are discussed.

(1) Huskinson, B.; Marshak, M. P.; Suh, C.; Er, S.; Gerhardt, M. R.; Galvin, C. J.; Chen, X.; Aspuru- Guzik, A.; Gordon, R. G.; Aziz, M. J. Nature 2014, 505 (7482), 195. (2) Huskinson, B.; Marshak, M.; Gerhardt, M.; Aziz, M. ECS Trans. 2014, 61 (37), 27. (3) Yang, B.; Hoober-Burkhardt, L.; Wang, F.; Surya Prakash, G. K.; Narayanan, S. R. J. Electrochem. Soc.2014, 161 (9), A1371. (4) Quan, M.; Sanchez, D.; Wasylkiw, M. F.; Smith, D. K. J. Am. Chem. Soc. 2007, 129 (42), 12847.

55

slide-56
SLIDE 56
  • 1.0
  • 0.5

0.0 0.5

  • 0.3

0.0 0.3

Current Density (mA/cm^2) Volts (V) Current Density

Check out 2013‐04‐xx thru 2013‐06‐xx In Half Cell Electrochemistry Also the Pourbaix diagram origin file

  • 1. Is concentration constant?

I think it’s a fair assumption to make. I don’t explicitly say it is anywhere and I don’t have a good record of it in my lab notebook. But my slide deck from 2013‐05‐23 says I was adding KOH and H2SO4 to adjust pH. Likely the volume didn’t change much so conc shouldn’t change much. From Bard: A case of particular interest

  • ccurs when deltaE0 = ‐2RT/F

ln 2 ~ ‐35.6 mV. This occurs when there is no interaction between the reducible groups

  • n O, and the additional

difficulty adding the extra electron arises purely from statistical (entropic) factors.

56

slide-57
SLIDE 57

Reversible model doesn’t quite fit

57

slide-58
SLIDE 58

Plugging in measured k0 value helps a little

58

slide-59
SLIDE 59

Assuming a higher bulk DHAQDS concentration explains the height of the reduction peak

59

slide-60
SLIDE 60

Assuming more sluggish kinetics on top of concentration error doesn’t explain it

60

slide-61
SLIDE 61

61

  • 0.9
  • 0.8
  • 0.7
  • 0.6
  • 0.5
  • 0.2
  • 0.1

0.0 0.1 0.2

Current Density (mA/cm

2)

Potential (V vs SHE)

Experiment First reduction Second reduction Total current E0,1 = ‐0.657 vs SHE k0,1 = 7 * 10‐4 cm/s E0,2 = ‐0.717 vs SHE k0,2 = 7 * 10‐4 cm/s

slide-62
SLIDE 62
  • 0.2
  • 0.1

0.0 0.1 0.2

  • 0.25
  • 0.20
  • 0.15
  • 0.10
  • 0.05

0.00 0.05 0.10 0.15 0.20

Current Density (mA/cm

2)

Overpotential (V)

2,6-DHAQ Model i1 Model i2 Model i1 + i2

62