Advanced Materials for Multi-Electron Redox Flow · PDF fileAdvanced Materials for...
Transcript of Advanced Materials for Multi-Electron Redox Flow · PDF fileAdvanced Materials for...
Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation,
for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-AC04-94AL85000
energy.sand ia .gov
Advanced Materials for Multi-Electron Redox Flow Batteries
Monday, September 26, 2016 Harry Pratt, Cy Fujimoto, Leo Small, Travis Anderson
Project Overview Problem: Cost competitive ionic liquids have high viscosities but are promising for higher energy density redox flow batteries due to higher metal concentrations and wider voltage windows.
Approach: Couple earth-abundant electrolytes with commercial and custom membranes and rapidly test and tune in an iterative fashion using laboratory-scale cell designs.
Energy DensityRFB ≈ ½nFVcellcactive EDAQ = ½1F1.5cell2active = 1.5F
EDIL = ½2F2cell3active = 6.0F Potential for four-fold improvement
2
Increased renewables penetration on the grid
+MetIL
MetIL–
Membrane Ion Content
Membranes contain a polyphenylene backbone with pendant ionic groups; ionic content was varied qualitatively high, medium, and low.
C
C
*m*
m
CCl
O
AlCl3
O
O
CH2Cl2
Br
Br
Br
NMe3
C
C
*m
O
O
Me3N
Me3N
Br
Br
3
Small, Pratt, Fujimoto, and Anderson, J. Electrochem. Soc., 2016, A5106.
Post Cycling Studies
4
Fc Fc+ + e–
Cu+ Cu2+ + e–
Catholyte
Anolyte
• The decreased electrochemical yield was
investigated by (1) cycling rate effects; (2) crossover measurements; (3) impedance; (4) membrane stability.
• The CV as well as the overlay of the static and cycled data show that crossover was responsible for the lowered yield.
Small, Pratt, Fujimoto, and Anderson, J. Electrochem. Soc., 2016, A5106.
Chemical Stability
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Small, Pratt, Fujimoto, and Anderson, J. Electrochem. Soc., 2016, A5106.
100 μm 100 μm
10 μm 10 μm
A B
C D
Before Cycling
After Cycling
• SEM and EDS data suggest that there was some decomposition of the ionic liquid.
• The increased resistance after cycling is attributed to the formation of a film on the surface of the membrane.
Membrane Before Cycling
Membrane After Cycling
Supporting Electrolyte
Infrared data shows membrane is stable.
Recently a number of groundbreaking solutions to higher energy density have appeared.
“Lightest Organic Radical Cation…” Huang, Wang, et. al, Science Reports, 2016
“Voltage Clustering in Redox-Active Ligands…” Zarkesh, Anstey, et. al, Dalton Trans., 2016
“Alkaline Quinone Flow Battery” Lin, Aziz, et. al, Science, 2016
25. N. H. Schlieben et al., J. Mol. Biol. 349, 801–813
(2005).
26. K. Tauber et al., Chemistry 19, 4030–4035 (2013).
27. See supplementary materials on Science Online.
28. A. C. Price, Y.-M. Zhang, C. O. Rock, S. W. White, Structure 12,
417–428 (2004).
29. The Ph-AmDHtolerates different buffers well (i.e., ammonium
chloride, formate, borate, citrate, acetate, oxalate). However, the
homotetrameric LBv-ADHs contains two Mg2+ centers; therefore,
strong chelators such as oxalate, citrate, and acetate must be
avoided as buffer salts. Removal of theseMg2+ ions inactivates the
enzyme (32).
30. B. R. Bommarius, M. Schürmann, A. S. Bommarius, Chem.
Commun. 50, 14953–14955 (2014).
31. R. Cannio, M. Rossi, S. Bartolucci, Eur. J. Biochem. 222,
345–352 (1994).
32. K. Niefind, J. Müller, B. Riebel, W. Hummel, D. Schomburg,
J. Mol. Biol. 327, 317–328 (2003).
ACK N OWLEDGM EN TS
The research leading to these results received funding from the
European Union’s Seventh Framework Programme FP7/ 2007-2013
under grant agreement 266025 (BIONEXGEN). The project leading
to this application has received funding from the European
Research Council under the European Union’s Horizon 2020
research and innovation program (grant agreement no. 638271,
BioSusAmin). T.K. and N.S.S. received funding from UK
Biotechnology and Biological Sciences Research Council (BBSRC;
BB/ K0017802/ 1). N.J.T. is grateful to the Royal Society for a
Wolfson Research Merit Award. Some aspects of the results
reported here are the subject of a provisional patent application.
Author contributions: F.G.M. and N.J.T. conceived the project and
wrote the manuscript; F.G.M. planned the experiments, expressed
and purified the AmDHs, performed the biocatalytic reactions, and
analyzed the data; T.K. performed the gene cloning of all AmDHs
and purified the ADHs; N.S.S. and M.B. provided intellectual and
technical support; and M.B. and BASF provided the ADHs. We
thank R. Heath for a preliminary kinetic assay of the Ph-AmDH.
SUPPLEMENTARY MATERIALS
www.sciencemag.org/ content/ 349/ 6255/ 1525/ suppl/ DC1
Materials and Methods
Figs. S1 to S12
Tables S1to S20
References (33–36)
30 June 2015; accepted 14 August 2015
10.1126/ science.aac9283
BATTERIES
Alkaline quinone flow batteryK aixiang Lin,1 Qing Chen,2 M ichael R. Gerhardt,2 Liuchuan Tong,1 Sang Bok K im,1
Louise Eisenach,3 Alvaro W . Val le,3 David H ardee,1 Roy G. Gordon,1,2*
M ichael J. Aziz,2* M ichael P. M arshak1,2*
Storage of photovoltaic and wind electricity in batteries could solve the mismatch problem
between the intermittent supply of these renewable resources and variable demand. Flow
batteries permit more economical long-durat ion discharge than solid-electrode batteries by
using liquid electrolytes stored outside of the battery. We report an alkaline flow battery based
on redox-act ive organic molecules that are composed ent irely of Earth-abundant elements
and are nontoxic, nonflammable, and safe for use in residential and commercial environments.
The battery operates efficiently with high power density near room temperature.These results
demonstrate the stability and performance of redox-active organic molecules in alkaline
flow batteries, potentially enabling cost-effect ive stationary storage of renewable energy.
The cost of photovoltaic (PV) and wind elec-
tricity hasdropped so much that oneof the
largest barriers to getting most of our elec-
tricity from theserenewablesources is their
intermittency(1–3).Batteriesprovideameans
to storeelectrical energy; however, traditional, en-
closed batteriesmaintain dischargeat peak power
for far too short a duration to adequately regulate
wind or solar power output (1,2). In contrast, flow
batteries can independently scale the power and
energy components of the system by storing the
electro-activespeciesoutsidethebatterycontainer
itself (3–5). In a flow battery, the power is gen-
erated in a device resembling a fuel cell, which
containselectrodesseparated byan ion-permeable
membrane. Liquid solutions of redox-active spe-
cies are pumped into the cell, where they can be
charged and discharged, beforebeing returned to
storage in an external storage tank. Scaling the
amount of energy to be stored thus involves sim-
ply making larger tanks (Fig. 1A). Existing flow
batteries are based on metal ions in acidic solu-
tion, but challengeswith corrosivity,hydrogen evo-
lution, kinetics, materialscost and abundance, and
efficiency thusfar haveprevented large-scalecom-
mercialization. The use of anthraquinones in an
acidic aqueous flow battery can dramatically
SCI EN CE sciencemag.org 25 SEPTEMBER 2015 • VOL 349 I SSUE 6255 152 9
Fig. 1. Cyclic voltammetry of elect rolyte and cell schemat ic. (A) Schematic
of cell in charge mode. Cartoon on top of the cell represents sources of
electrical energy from wind and solar. Curved arrows indicate direction of
electron flow, and white arrows indicate electrolyte solution flow. Blue ar-
row indicates migration of cations across the membrane. Essential com-
ponents of electrochemical cells are labeled with color-coded lines and
text. The molecular structures of oxidized and reduced species are shown
on corresponding reservoirs. (B) Cyclic voltammogram of 2 mM 2,6-DHAQ
(dark cyan curve) and ferrocyanide (gold curve) scanned at 100 mV/ s on
glassy carbon electrode; arrows indicate scan direction. Dotted line rep-
resents CV of 1 M KOH background scanned at 100 mV/ s on graphite foil
electrode.
1Department of Chemistry and Chemical Biology, Harvard
University, 12 Oxford Street, Cambridge, MA 02138, USA.2Harvard John A. Paulson School of Engineering and Applied
Sciences, 29 Oxford Street, Cambridge, MA 02138, USA.3Harvard College, Cambridge, MA 02138, USA.
*Corresponding author. E-mail: [email protected] (M.J.A.);
[email protected] (R.G.G.); michael.marshak@colorado.
edu (M.P.M.)
RESEARCH | REPORTS
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“High-energy density non-aqueous …” Jia et. al, Science Adv., 2016
Hybrid Nafion-PVDF Li-conducting membrane
Increasing Energy Density
6
Can we make the solvent and supporting electrolyte “filler” electrochemically active?
Start with Sandia’s MetILs and replace increasing amounts of “filler” with redox active compounds (I-, Fc) until it becomes impractical.
Replace 1st OTf-
with redox-active I- Single liquid
phase at 25 °C
Replace 2nd OTf-
with redox-active I- Phase
separation
Couple FcCOOH to 1st ligand
Tmelt ~70 °C
Couple FcCOOH to 2nd ligand
Tmelt >100 °C
Tmelt ~60 °C Single liquid
phase
Increasing Energy Density–Strategy
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Fe-MetIL Fe-MetIL3
Redox activity added to the ligands and anions
2.8 M redox-active e-
7.4 M redox-active e-
Fe2+ Fe3+ + e- Fe2+ Fe3+ + e-
Fc Fc+ + e- 3I- I3
- + 2e-
MetILs3
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Fe2+ and Fc-ligand shift to lower potentials when MetIL forms
Square Wave Voltammetry
Ethanolamine Peak
3354 (N-H) 2860 (O-H)
Fe-MetIL 7 20
Fe-MetIL3 8 15
Ethanolamine O-H and N-H IR peaks shift upon complexation
Infrared Spectroscopy
O-H N-H
MetILs3 Characterization
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MetIL3
Membrane: Fumasep FAP-PK (anion exchange)
cobaltocene
200 mM 0.5 M LiNTf2 in PC 5 mA/cm2
Cc Cc+ + e- Fe3+ + e-
Fe3+
Fc+ + e- Fc
I3- + 2e-
3I-
100 mM 0.5 M LiNTf2 in PC 5 mA/cm2
Cell shows good cyclability after initial capacity loss.
MetILs3 Initial Flow Cell Studies
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Polyoxometalate (POM) cathode: Na3PW12O40 PW12O40
3- + 24e- PW12O40
27-
POM
Potential
Cu
rre
nt
POM +mediator -mediator
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Mediated Flow Batteries
• energy stored in easily exchangeable canisters of material
• mediators serve as redox shuttles between electrodes and canisters
• polyoxometalates may be substituted with traditional lithium intercalation materials
Sandia Laboratory Directed Research and Development
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Summary and Acknowledgements
• Diels Alder polyphenylene membranes with tunable ion content provide an alternative to commercial systems.
• MetILs3 utilizes electrolyte “filler” to increase theoretical energy density 3X from 190 to 620 Wh/L over MetILs.
• In 2016 the team published two new papers including one featured on the cover of Journal of Materials Chemistry A and was granted one new patent.
The authors acknowledge the Department of Energy, Office of Electricity Delivery and Energy Reliability for funding and in particular Dr. Imre Gyuk, Energy Storage Program Manger, for his dedication and support to the entire energy storage industry.
OFFICE OF ELECTRICITY DELIVERY & ENERGY RELIABILITY