Aqueous Soluble Organic (ASO) Flow Battery Development · Vanadium Redox Flow Batteries (VRFB)...

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Aqueous Soluble Organic (ASO) Flow Battery Development

Aaron Hollas, Vijayakumar Murugesan, Bin Li, Zimin Nie, Wei Wang, David Reed, Vince Sprenkle

Pacific Northwest National Laboratory

Support from DOE Office of Electricity Delivery & Energy Reliability

Energy Storage Program

DOE OE Energy Storage Peer Review 2018

Santa Fe, NM

September 2018

Why Redox Flow Batteries (RFB)

2Zhenguo Yang, et. al. Chemical Reviews, 111, 2011, 3577

Wei Wang, et. al. Advanced Functional Materials , 23, 2013, 970

➢ High safety

Spatial separation of reactive materials

Major constituent is water

Easy thermal management.

Battery health monitoring

➢ Easy recycling after service life

Consumption vs. Investment

➢ Decoupling of Power and Capacity

Tailor system to application

➢ 7 confirmed lithium-ion ESS fires in

Korea this summer alone.

Vanadium Redox Flow Batteries (VRFB)



➢ Vanadium Redox Flow Battery (VRB)

Advantages

Current state-of-the-art, highly studied

High solubility

High cell voltage

MWh scale deployment

➢ …however…

High material cost

Capacity loss from crossover

Precipitation issues (temperature window)

Requires Nafion

V species -5°C 25°C 40°C

sulfate sulfate sulfate

V2+2M

(419 h)*

2M

(>30 d)

2M

(>30 d)

V3+2M

(634 h)

2M

(>30 d)

2M

(>30 d)

V4+ (VO2+)2M

(18 h)

2M

(95 h)

2M

(>30 d)

V5+ (VO2+)

2M

(>30 d)

2M

(>30 d)

2.2M

(95 h)

Vanadium Redox Flow Batteries (VRFB)



➢ …however…

High material cost



Requires Nafion

FY 2018 Milestone

➢ Evaluate new electrolyte composition on a pilot scale stack

capable of meeting $250/kWh cost target for a projected

1MW/4MWh system operating at 75 mA/cm2.

Aqueous-Soluble Organic (ASO) vs Vanadium



➢ …however…

High material cost



Requires Nafion

➢ Benefits of Organics vs Vanadium

Potentially lower cost

Vast library of candidates

Systems ranging from pH 0-14

Improved electrochemical kinetics

Candidates with 2e- redox events

J. Electrochem. Soc. 2016, 163 (7), A1442-A1449.

Nature Energy 1, Article number: 16102 (2016)Adv. Energy Mater. 2015, 1501449.Science 2015, 349 (6255), 1529.

Aqueous-Soluble Organic (ASO) RFB

6

➢ Benefits of Organics vs Vanadium

Potentially lower cost

Vast library of candidates

Systems ranging from pH 0-14

Improved electrochemical kinetics

Candidates with 2e- redox events

J. Electrochem. Soc. 2016, 163 (7), A1442-A1449.

Nature Energy 1, Article number: 16102 (2016)Adv. Energy Mater. 2015, 1501449.Science 2015, 349 (6255), 1529.

➢ System Challenges

Moderate Solubility

Low Potential

Chemical Instability

Membrane Crossover

Identifying Potential Redox-Active Species

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➢ Selection Strategy

Identify redox-active core structure

Flavin-based

Quinone-based

Phenazine-based

Nature-inspired

redox-actives


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Target solubilizing groups (pH dependent) and

appropriate redox-tuning groups

Phenazine-based

Control Solubility

-SO3−, -CO2

−, -PO32 −, -NH2, -NR3

+, -OH

Tune Redox Potential - Withdrawing

-SO3−, -CO2

−, -PO32 −, -NR3

+

Tune Redox Potential - Donating

-NH2, -OH


9





Substitute core structure based on readily available

reagents and scalable synthetic methods

Phenazine-based

Control Solubility

-SO3−, -CO2

−, -PO32 −, -NH2, -NR3

+, -OH

Tune Redox Potential - Withdrawing

-SO3−, -CO2

−, -PO32 −, -NR3

+

Tune Redox Potential - Donating

-NH2, -OH

?

DFT-Directed Synthesis





Substitute core structure based on readily available

reagents and scalable synthetic methods

Vijayakumar Murugesan10

Synthetic Methods for Phenazine Derivatives

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➢ Synthetic Strategy

Readily available precursors – Low cost

Straightforward synthetic procedures – Scalability

Modular syntheses – Readily access diverse derivatives

Synthetic Methods for Phenazine Derivatives

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➢ Synthetic Strategy

Readily available precursors – Low cost

Straightforward synthetic procedures – Scalability

Modular syntheses – Readily access diverse derivatives

➢ Yields >90%

➢ Reactions performed in water

➢ Simple product isolation

Down-Selected Candidates

131 M NaOH, 100 mV/s,GC electrode, saturated anolyte

-1.6 -1.4 -1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0.0

Potential (V vs Ag/AgCl)

phenazine

Solubility (M)

1M NaOH

E°’1/2 (V vs Ag/AgCl)

phenazine trace -0.56


141 M NaOH, 100 mV/s,GC electrode, 8.5 mM anolyte

-1.6 -1.4 -1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0.0


phenazine

R = CO2H

Solubility (M)

1M NaOH



R = CO2H 0.95 -1.08



-1.6 -1.4 -1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0.0


phenazine

R = CO2H

R = SO3H

Solubility (M)

1M NaOH



R = CO2H 0.95 -1.08

R = SO3H 1.45 -1.06



-1.6 -1.4 -1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0.0


phenazine

R = CO2H

R = SO3H

R = H

Solubility (M)

1M NaOH



R = CO2H 0.95 -1.08

R = SO3H 1.45 -1.06

R = H 1.6 -0.98


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Solubility (M)

1M NaOH



R = CO2H 0.95 -1.08

R = SO3H 1.45 -1.06

R = H 1.6 -0.98

Fe(CN)6x- ----- 0.34


-1.6 -1.2 -0.8 -0.4 0.0 0.4 0.8


phenazine

R = CO2H

R = SO3H

R = H

Fe(CN)6

x-

Down-Selected Candidate - DHPS

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Solubility (M)

1M NaOH

E°’1/2 (V vs Ag/AgCl) Solubility (M)

Charged State

phenazine trace -0.56 -----

R = CO2H 0.95 -1.08 -----

R = SO3H 1.45 -1.06 ≥1.4

R = H 1.6 -0.98 <0.1

Fe(CN)6x- ----- 0.34 -----


-1.6 -1.2 -0.8 -0.4 0.0 0.4 0.8


R = SO3H (DHPS)

Fe(CN)6

x-

1.4 V Theoretical Potential

DHPS: 1.4 M Concentration, 10 cm2 Cell

191.4 M 5 + 3 equiv. NaOH in 5mL of 1M NaOH2 equiv. K4Fe(CN)6/2 equiv K3Fe(CN)6 in 45 mL 2M NaOHInterdigitated cell, 100 mL/min, ELAT/CP-ESA, N212, 100 mA/cm2

1.4 M DHPS → 2.8 M e−

90% capacity retention after 500 cycles

Scale-Up: 57 cm2 Cell

201M DHPS3- in 60 mL of 1M NaOH0.5M K4Fe(CN)6 and 0.125M K3Fe(CN)6 in 225 mL of 1M NaOHN212, ELAT/ESA, 100 mL/min

57 cm2 interdigitated cell design

1 M DHPS

70% EE at 75 mA/cm2

0.0 0.5 1.0 1.5 2.0 2.5 3.0

0.8

0.9

1.0

1.1

1.2

1.3

1.4

1.5

1.6

1.7

1.8

Voltage (

V)

Capacity (Ah)

75 mA/cm2

100 mA/cm2

125 mA/cm2

Summary & Acknowledgements

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Financial support from US DOE Office of Electricity Delivery & Energy Reliability

Pacific Northwest National Laboratory is a multi-program national laboratory

operated by Battelle Memorial Institute for the U.S. Department of Energy under

Contract DE-AC05-76RL01830.

Developed high energy anolyte: 1.4 M solubility, -1.06 V vs Ag/AgCl

Demonstrated promising performance at 10 cm2 cell: >80% EE and >1.2V at 100 mA/cm2

Initiated scale-up to 57 cm2 cell design: 70% EE at 75 mA/cm2 (early-stage)

➢ Improve cell performance at 57 cm2 cell and continue scale-up

➢ Develop full understanding of capacity loss mechanisms and address through

electrolyte composition, molecular design, and membrane/electrode choice.

Summary

FutureDirection

Support

Supplementary –DHPS Electrochemical Kinetics

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-1.4 -1.2 -1.0 -0.8 -0.6


Ketjen black on glassy carbon

-1.4 -1.2 -1.0 -0.8 -0.6

Glassy Carbon


Poor electrochemical kinetics at pristine glassy carbon

Facile kinetics with ketjen black deposit

Carbon paper electrodes in cell

Supplementary –Stability of DHPS in 1M NaOH

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* Diminished intensity a result of H/D exchange1.4 M in 1 M NaOH/D2O

Discharged State Charged State

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Aqueous Soluble Organic (ASO) Flow Battery Development · Vanadium Redox Flow Batteries (VRFB)...

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