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.sandia.gov Advanced Membranes for Vanadium Redox Flow Batteries (VRFB) Cy Fujimoto Travis Anderson and Harry Pratt @ SNL; Tom Zawodzinski and Zhijang Tang @ ORNL; Vince Sprenkle and Wei Wang @ PNNL; Michael Aziz and Eugene Beh @ Harvard
Transcript
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 Membranes for Vanadium Redox Flow Batteries (VRFB)
Cy Fujimoto
Travis Anderson and Harry Pratt @ SNL; Tom Zawodzinski and Zhijang Tang @ ORNL; Vince Sprenkle and Wei Wang @ PNNL; Michael Aziz and Eugene Beh @ Harvard
Membrane Commercialization
2
DOE has vested interest
into….
1. Largest potential customer in energy storage space is vanadium redox flow batteries (VRFB).
2. VRFB is most common type of flow battery installed and demonstration in US.
3. Li ion batteries have the highest installation rates of all large electrochemical storage in 2017
4. Next challenge comparing performance between the LARGE scale storage (largest Li ion Australia 100MW/129MWh vs largest VRFB in China 200MW/800MWh)
Cost is issue with VRFBMembranes are approximately 1/3 the cost of materials
Membrane CommercializationProceeding through a start up incubator
within Albuquerque company
• SolAero is a leader in solar cells and panels in the aerospace industry
($100M) is looking to expand their business space
• Energy related technology market extremely large
• SolAero offers lab/office space at discounted price
• Current name of membrane start up is Energy Enablers (E2)
Energy Enablers negotiating licenses of two membrane products, an cation and anion exchange membranes
4
Types of ion exchange membranes
Nafion (has fixed SO3-)
State of the art
1. Cation exchange
membrane strong
incumbent: Nafion
2. Cation market > Anion
market
3. Weakness: High Cost
1. Anion exchange
membrane no strong
incumbent
2. Anion market small, but
growth in alkaline stable
3. Weakness: Most
commercial anion
membranes are not
alkaline stable.
Asahi Selemion
Potentially Market Ready• Alkaline environment attractive since non precious
metal catalyst can be employed• Several start up developing alkaline stable anion
exchange membranes1. Ecolectro in NY2. Dioxide Materials in Fl3. Ionomer Innovations in BC (H3C)3N
N(CH3)3
**
(H3C)3N
m
OH
OH OH
US 8,809,483
Michael Aziz and Eugene Beh @ Harvard
Resistance data of various membranes in NaClAlkaline fuel cell performance
Yu Seung Kim @ LANL
R&D Focus
R&D Focus: Cation exchange membrane
• Largest market (chloro-alkali industry) and new emerging markets (fuel cell, flow battery, electrolyzers).
• The incumbent technology is Nafion™ and “Nafion ™ like” materials. • Great performance/durability, but cost issue ($200-500/m2).• Our goal to functionalize the poly(phenylene) backbone to improve performance
and approach Nafion like durability at lower cost.
SNL acid membrane
Can we approach Nafionperformance and durability?
7
PEM Fuel Cell work with
• Will need large OEM, like General Motors, get behind materials
• Sandia membrane almost equivalent to Nafion
• Demonstrated SNL membrane equivalent at low RH [32% RH and 80 oC]
• Under hotter (95 oC) and drier (26% RH) conditions performance difference more
pronounced
GM large OEM interested in SNL acid membrane
Craig Gittleman at GM
VRFB Membranes
Shown that the SNL membrane can perform better than Nafion in VRFBs, but durability concerns
Gen 4
2 months
Potential segment that is oxidized
VRFB Membranes - Durability
Incorporate fluorine groups- High stability over oxidation
- Lower water and vanadium uptake
Gen5 no apparent signs of degradation
4 months
Added fluorine groups to improve oxidization stability
Wei Wang @ PNNL
Industry Durability Testing of Gen 5
Founded in 2012 in Devens, MATest conditions:
• Test cell: 25-cm2 cell
• Temperature: 45°C in constant-temperature oven with air atmosphere
• Cycling current: 7.5 A charge and discharge (300 mA/cm2)
ASR of Gen 5: 0.43Ω-cm2 PFSA: 0.505 Ω-cm2
Under aggressive indusial testing, Gen 5 did fail
VRFB Membranes - Durability
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Gen 5HO3S
SO3H
HO3S
SO3H SO3H
SO3HSO3H
SO3H
SO3H
HO3SHO3S
HO3S
O OS
O
O
FF
FFFF
F F
O
FF
FFFF
F F
nSO3Hm
*
Believe segment is still being attackedCannot have ether containing groups
Small molecule conformation that poly(phenylene) is not degrading• Use Fenton’s reagent to test stability of unit representing poly(phenylene)• Fenton’s reagent (2.8 V) more oxidative than V+5 (1.0 V)
Benzene sulfonic acid is stable under Fenton’s
reagent, therefore stable in V+5
SO3Ha
b
c
d
VRFB Membranes – Membrane Development
SO3H
SO3HSO3H
**
R R
R
• Have shown benzene sulfonic
acid stable under Fenton’s
reagent = V+5
• Recently developed new
chemistry that allows to
attach other electron
withdrawing groups on non
sulfonic acid containing rings
• Beginning initial testing of
new polymers in FY18
Summary/Conclusions▪ SNL membranes can be functionalized for a multitude of
electrochemical applications
▪ Interest from large OEM
▪ Gen5 membranes did not survive industrial testing
▪ Showed poly(phenylene) components are stable in
oxidative environments
▪ Development of new stable polymer architecture
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Future Tasks▪ Membrane commercialization
▪ Begin VRFB testing of new polymer architecture and
probe durability
Thank You to the DOE OE and especially Dr. Gyuk for his dedication and support to the ES
