organic / polymer redox-flow-batteries for stationary ... · €/ kwh. pumped-storage...
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Organic / Polymer Redox-Flow-Batteries
for Stationary Energy Storage Applications
Ulrich S. Schubert
Laboratory of Organic and Macromolecular Chemistry (IOMC)
Center for Energy and Environmental Chemistry Jena (CEEC Jena)Friedrich-Schiller-University Jena, Germany
[email protected]; www.schubert-group.de
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Renewableenergy
Decentralenergystorage
Mobile devices
Biochips
Smart packaging
Need for energy storage systems
Selected reviews: Adv. Mater. 2012, 24, 6397; Adv. Energy Mater. 2015, 5, 1402034; Chem. Rev. 2016, 116, 9438.
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Cobalt(Lithium)
Lead
Rare earth
elements (Ni-MeH)
Vanadium(RFB)
No sustainable raw material basis and toxic
Current material basis of batteries
Important battery issues: • Higher capacity• Safety• Sustainability• Scalability, …
Plus NiCd…
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Nobel price in chemistry 2000: “For the discovery and development
of conductive polymers”
H. Shirakawa, E. J. Louis, A. G. MacDiarmid, C. K. Chang, A. J. Heeger, Chem. Commun. 1977, 578.
Polymers & energy: History
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OPVs
www.renewableenergyfocus.com; www.konarka.com; www.greentech.com; www.blogspot.com; www.mainova.com; www.samsung.com.
OLEDs/PLEDs/displays
OFETs
Organic/polymeric devices: Selection
Sensors Memory
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Energy storage & polymers?
Polymers are used for packaging, as separators, electrolytes, gels, …
- but not as active material
Selected reviews: Adv. Mater. 2012, 24, 6397; Adv. Energy Mater. 2015, 5, 1402034; Chem. Rev. 2016, 116, 9438.
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Historical perspective
poly(pyrrole)poly(aniline)poly(thiophene) PEDOT
conductive polymers
Commercial button cells flopped
J. S. Miller, Adv. Mater. 1993, 5, 671; D. Naegele, R. Bittihn, Solid State Ionics 1988, 28-30, 983.
Bridgestone-Seikopoly(aniline)/lithium
(1987-1992)
VARTA/BASFpoly(pyrrole)/lithium
(1987)
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Polymer-based energy storage?
❑ Sloping redox potential (redox potential gradually changes upon charging/discharging)
❑ Useless for numerous applications
❑ Polymers with distinct redox potential attributed to localized redox sites
❑ Stable cell voltage
Selected reviews: Adv. Mater. 2012, 24, 6397; Adv. Energy Mater. 2015, 5, 1402034; Chem. Rev. 2016, 116, 9438.
Conductivepolymers
Redoxpolymers
Charging state / %
Cell
voltage /
a.u
.
Desired discharging behavior
Conductive polymer battery
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Organic (radical) batteries
R●
R● -
-
-+
+
+
Charging
e-e-
p-type polymer
R+
R+
-
-
-
Discharging
e-e-
p-type Polymer
-
-
n-type polymer
R●
n-type Polymer
R-
+
+
+
+
+
Environmentally benign
• no heavy metals
• simple disposal with household garbage
• energetic recycling
Simple processing
• inkjet printing
• screen printing
• thin paper-like and flexible design
High power density
• rapid charging
• high charging and discharging rate performance
Excellent cycle life
• simple redox chemistry
• >1000 charging/discharging cycles
First reported: K. Nakahara, Chem. Phys. Lett. 2002, 359, 351; H. Nishide et al., Electrochim. Acta 2004, 50, 827.
→ Non-conjugated polymers!!
Voltage & capacity tuning
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From printable small scale batteries
to polymer redox flow batteryPhoto by Sumitomo.
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Renewable energies & off-the-grid
… needs new batteries, which are …
Cheap & scalable Sustainable High-volume & short-term
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A real big thing: Stationary batteries
“250-megawatt-hour installation”, Musk said, “without naming the utility. That's 2,500 Powerpack towers.”
Current approaches / products:• Tesla• Sonnenbatterie• Daimler (Accumotive)• Solarwatt• Samsung• Varta Storage• LG• …
www.tesla.com; www.samsung.com; www.bloomberg.com; www.pv-magazin.de; www.manager-magazin.de
All based on lithium (and cobalt…)!!!Cell fabrication nearly exclusively in Asia (in the future also in Nevada)
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Stationary storage technologies
MVV Energie AG: Technology and Innovation, Frankfurt/February 28, 2013; Jenabatteries GmbH, Jena October, 2015.
* Capex - Capital expenditure
AccumulatorType
Efficiency Self-discharge Cycle times Reaction timeCapex* in
€/ kWh
Pumped-storagehydrolectricity
70-80% 0-0.5% per day 100,000 90-120 s 1,000
Fly wheel90-95%
Up to 20% per hour
>100,000 <1 s 1,000
Lithium batteries
>95% 2% per month 10,000<1 s
1,100-1,800
Lead-acid batteries
80-90% 5% per month 300-2,000<1 s
200
Sodium-sulfur batteries
≈87% Negligible 2,500<1 s
300
Vanadium redox flow batteries
≈80% Negligible >10,000<1 s
1,000-1,600
Hydrogen storage
20-40% Up to 1% per day n.a. Several minutes 1,000
RFB: Only technology able to scale energy and power independently!
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The solution: Redox flow battery
EnerVault
RFB: Only technology to scale energy and power independently!
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Vanadium redox flow batteries
Status Quo
• Energy density limited
• 20-40 Wh/L
• Active material: vanadium with sulfuric acid
Disadvantages
• Tight temperature range (vanadium salt precipitation)
• Risk of hydrogen generation (operation at > 40/45 °C)
• Expensive core material(metal based!)
• Expensive special membranes (e.g. NafionTM)
http://buychemicalelement.blogspot.de/2015/04/vanadium.html
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A brand-new direction: Organic RFB’s
Angew. Chem. Int. Ed. 2017, 56, 686 (open access).
HBr+H2SO4/watercharging: 1.0 V/discharging: 0.6 V200-500 mA/cm2; 16 Wh/L; 20 cyclesNature 2014, 505, 195-198.
LiPF6/mixture of org. carbonatescharging: 3.5-4.0 V/discharging: 3.4-2.7 V1-10 mA/cm2; 70-130 Wh/L; 100 cyclesAdv. Mater. 2014, 26, 7649-7653.
In addition, see e.g.: Science 2015, 349, 1529; Adv. Energy Mater. 2016, 6, 10.1002/aenm.201501449.
Organic electrolyte: → Low current density & ion mobilityAqueous electrolyte: → Higher current density & ion
mobility; often corrosive H2SO4
Semi-organic RFB: → Higher capacity, good solubility,
toxic & corrosive materialsMembranes → Often Nafion
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Novel polymer-RFB
size-exclusionmembrane
polymeraqueous
electrolyte
electrode
anolyte tankcatholyte tank
P2P1
The Jena invention
Germ. Pat. Appl. 2014 DE 102012016317 A1, Eur. Pat. Appl. 2014, EP 2785442 A1, PCT Int. Appl. 2014, WO 2014026728 A1 20140220.
Sustainable and easy-to-handle: A salt water-based polymer electrolyte replaces vanadium-based concentrated acid electrolytes and enables the utilization of cheap membranes
Nature 2015, 527, 78.
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Novel polymer-RFB
Nature 2015, 527, 78.
20 mA cm-², unpumped test cell; material utilization 41%; Inset: Open-circuit voltage (OCV) as a function of the state of charge (SOC) provides a sigmoid function, determination of the remaining battery capacity at any time (static 5 cm² test cell, P1 (2 Ah L-1) and P2 (4 Ah L-
1) in aqueous NaCl solution (2 mol L-1), 25 °C).
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Advantages of the polymer-RFB
Environmentally benign
• no heavy metals
• no hazardous substances like bromine
• Water-based
Simple membrane design
• no ion-selective membranes needed
• cheap industrial membranes
Scalable capacity
• capacity is “unlimited”
• raw material costs
Rechargeability
• superior to “one-way”, non rechargeable fuel cells
Peak shaving
Load balancing
Distributed energy storage
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pRFB: Development overview & future
2012
2014
20172019
2020-
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The world‘s largest battery?
https://www.ewe-gasspeicher.de/en/home/b4p
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Brind4power storage I
Caverns with saline solutions containing polymers
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700-900 MWh
120-200 MW power plant
The electrical capacity of 700 MWh is sufficient to supply over 75,000 households with electricity for one day.
Brind4power storage II
The challenge:
6 M Salt solution (brine)KCl, NaCl, Fe, Br, …
40 to 70 °C
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Spiegel (23.11.2017), Wirtschaftswoche (22.11.2017), FAZ (09.07.2017), FAZ (22.06.2017), ...
Publicity & outreach b4p storage
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Angew. Chem. Int. Ed. 2016, 55, 4427.
PCT/EP2016/001338, DE102016009904
Aqueous organic RFB
(At date of publication) Highest demonstrated
capacity of any aqueous organic RFB: 54 Ah L-1
(energy density: 38 Wh L-1),
1.4 V; peak current densities up to 200 mA cm-2
Other PRFB, ORFB & Hybrid RFB I
Aqueous polymer RFB
Nature 2015, 527, 78.
WO2014026728, EP2785442, SG11201500701SEP15705198
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Other PRFB, ORFB & Hybrid RFB II
Aqueous hybrid polymer RFB
Adv. Mater. 2016, 28, 2238; Polym. Chem. 2016, 7, 1711.
WO2017084749A1
Aqueous hybrid organic RFB
0 200 400 600 800 10000.0
0.5
1.0
1.5
2.0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
1.2
1.3
1.4
1.5
1.6
1.7
1.8
1.9
Voltage / V
Capacity / mAh
1st
500th
1000th
Charging cap.
Discharging cap.
Coulombic eff.
Energy eff.
Voltage eff.
Capacity / m
Ah
Cycle
c)
0.0
0.2
0.4
0.6
0.8
1.0
Effic
iency
ACS Energy Lett. 2017, 2, 411.
DE102015014828A1
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Polymer-Redox-Flow-Battery NaS-Battery
Printable batteries
Availabe materials (C, Na, S)
No usage of Co, V and other heavy metals and rare earths“Alternatives to current Lithium Batteries”
The center: CEEC Jena – Research
27
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11/2015 (incl. lab2fab, transfer to industry)1600 square meter labs/office, EUR 14 Mio. (funding from two foundations) Battery test labs (100 channels), ESR, electrochemistry/spectroelectro-chemistry, upscaling, MAS-NMR, redox-flow-cell prototypes & solar cell panels, gloveboxes, …Top floor: Start-up offices (200 square meter)
Development CEEC Jena
Starting winter semester 2015/16 new master program Chemisty– energy – environment
New professorships & research groups (since 2012):Carbon Nanomaterials (Prof. Adelhelm), Applied Electrochemistry (Prof. Balducci), Printable Organic Solar Cells (PD Dr. Hoppe), Polymer Nanomaterials (Prof. Schacher), Molecular Nanotechnology (Prof. Turchanin), Glass Chemistry (Prof. Wondraczek), Molecular Photonics (Prof. Dietzek), Conjugated Polymer (Dr. Hager), …
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Development CEEC Jena: Masterplan
CEEC Jena new Building II(2500 square meter labs/office), EUR 28 Mio.Evaluation and granted (“Wissenschaftsrat”)
Planned application center (AWZ CEEC Jena)(EUR 12 Mio., 1500 square meter labs/office)
CEEC ICEEC IIAWZPlanned start-up center
Start-up(incuba-tor)
JCSM
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Selected publications, spin-off, IP, people
Adv. Mater. 2012, 24, 6397J. Polym. Sci., Part A: Polym. Chem. 2012, 50, 1394 Adv. Energy Mater. 2013, 3, 1025Macromol. Rapid Commun. 2014, 25, 882 J. Mater. Chem. A 2014, 2, 8999; J. Mater. Chem. A 2014, 2, 15345 Macromol. Rapid Commun. 2014, 35, 1367 Adv. Energy Mater. 2015, 5, 1402034, 34J. Mater. Chem. A 2015, 3, 19575; Polymer 2015, 68, 328 Nature 2015, 527, 78; Polym. Chem. 2015, 6, 7801Adv. Energy Mater. 2016, 6, 1500369Polym. Chem. 2016, 7, 1711; Nature 2016, 534, 1 (summary)
Macromol. Rapid Commun. 2016, 37, 725Adv. Mater. 2016, 28, 2238; Chem. Mater. 2016, 28, 3401NPG Asia Mater. 2016, 8, e283; Chem. Rev. 2016, 116, 9438ACS Energy Lett. 2016, 1, 976Angew. Chem. Int. Ed. 2016, 55, 14427 J. Power Sour. 2016, 335, 155; NPG Asia Mater. 2017, 9, e340 Angew. Chem. Int. Ed. 2017, 56, 686 Energy Techn. 2017, 5, 225; ChemistryOpen 2017, 6, 216Adv. Energy Mater. 2017, 7, 1601415 Top. Curr. Chem. 2017, 373, 19; ACS Energy Lett. 2017, 2, 411Electrochim. Acta 2017, 228, 494; J. Power Sour. 2018, 378, 546; Macromol. Chem. Phys. 2018, 219, 1700267. ...PCT/EP2013/002206; WO 2015003725, WO 2014026728, PCT/EP2015/056497; PCT/EP2015/048937 ...In blue color: Redox-flow-battery publications.
Spin-off (IQ Innovationspreis 2015):Positions for PhD students, Postdocs, visiting scientists, exchange master students are available
The Schubert-group Battery Team:Tobias Janoschka, Dr. Bernhard Häupler,Dr. Daniel Schmidt, Dr. Andreas Wild,Dr. Jan Winsberg, Tino Hagemann, Christian Stolze, Simon Münch, Philip Rohland, Kristin Schreyer, Maria Strumpf, René Burges,Dr. Christian Friebe, Dr. Alexandra Lex-Balducci, Dr. Martin HagerItalic: Left to industry.
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1558 www.schubert-group.de
CEEC Jena
Energy storage
Batteries(Li-Ion-, Li-Hybride-, Polymer-,
Redox Flow- and NaS-Batteries; stationary, mobile, printable; combined with photovoltaics;
separators)
Supercaps
Energy generation
Photovoltaics(inorganic & polymer solar-
cells, printable photovoltaics)
Fuel cells
H2-Generation
Cleantech
Membrane technology(Ceramic- & polymer-based
materials)
Green Engineering
Certification
Education: Environmental chemistry, material science, physics & chemistry
High performace ceramics, electrochemistry, glass chemistry, material science, solidphase physics, technical chemistry & organic chemistry, polymer scienceDesign, synthesis, up-scaling, characterisation & modelling/simulation
From fundamental research to demonstrators; from invention to products
Autumn 2015New building CEEC Jena Phase I
2016: Proposal submitted 91b CEEC Jena Phase II
2010 Concept CEEC Jena
2011 Fukushima
Starting 2011: Two Research Units (TAB), Jun.-Prof. Electrochemistry (CZ), equipment infrastr. (TMBWK/TMWAT) “Proexzellenz” professorship, GreenTech-Campus Hermsdorf (TMWAT)
Starting winter semester2015/16 master coursechemisty– energy – environment
Planned 2017: Proposalapplications laboratory
Total funding of CEEC Jena already >20 Mio €