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1558 www.schubert-group.de 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

Organic / Polymer Redox-Flow-Batteries for Stationary ... · €/ kWh. Pumped-storage hydrolectricity. ... 1600 square meter labs/office, EUR 14 Mio. (funding from two foundations)

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Page 1: Organic / Polymer Redox-Flow-Batteries for Stationary ... · €/ kWh. Pumped-storage hydrolectricity. ... 1600 square meter labs/office, EUR 14 Mio. (funding from two foundations)

1558 www.schubert-group.de

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

Page 2: Organic / Polymer Redox-Flow-Batteries for Stationary ... · €/ kWh. Pumped-storage hydrolectricity. ... 1600 square meter labs/office, EUR 14 Mio. (funding from two foundations)

1558 www.schubert-group.de

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.

Page 3: Organic / Polymer Redox-Flow-Batteries for Stationary ... · €/ kWh. Pumped-storage hydrolectricity. ... 1600 square meter labs/office, EUR 14 Mio. (funding from two foundations)

1558 www.schubert-group.de

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…

Page 4: Organic / Polymer Redox-Flow-Batteries for Stationary ... · €/ kWh. Pumped-storage hydrolectricity. ... 1600 square meter labs/office, EUR 14 Mio. (funding from two foundations)

1558 www.schubert-group.de

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

Page 5: Organic / Polymer Redox-Flow-Batteries for Stationary ... · €/ kWh. Pumped-storage hydrolectricity. ... 1600 square meter labs/office, EUR 14 Mio. (funding from two foundations)

1558 www.schubert-group.de

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

Page 6: Organic / Polymer Redox-Flow-Batteries for Stationary ... · €/ kWh. Pumped-storage hydrolectricity. ... 1600 square meter labs/office, EUR 14 Mio. (funding from two foundations)

1558 www.schubert-group.de

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.

Page 7: Organic / Polymer Redox-Flow-Batteries for Stationary ... · €/ kWh. Pumped-storage hydrolectricity. ... 1600 square meter labs/office, EUR 14 Mio. (funding from two foundations)

1558 www.schubert-group.de

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)

Page 8: Organic / Polymer Redox-Flow-Batteries for Stationary ... · €/ kWh. Pumped-storage hydrolectricity. ... 1600 square meter labs/office, EUR 14 Mio. (funding from two foundations)

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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

Page 9: Organic / Polymer Redox-Flow-Batteries for Stationary ... · €/ kWh. Pumped-storage hydrolectricity. ... 1600 square meter labs/office, EUR 14 Mio. (funding from two foundations)

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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

Page 10: Organic / Polymer Redox-Flow-Batteries for Stationary ... · €/ kWh. Pumped-storage hydrolectricity. ... 1600 square meter labs/office, EUR 14 Mio. (funding from two foundations)

1558 www.schubert-group.de

From printable small scale batteries

to polymer redox flow batteryPhoto by Sumitomo.

Page 11: Organic / Polymer Redox-Flow-Batteries for Stationary ... · €/ kWh. Pumped-storage hydrolectricity. ... 1600 square meter labs/office, EUR 14 Mio. (funding from two foundations)

1558 www.schubert-group.de

Renewable energies & off-the-grid

… needs new batteries, which are …

Cheap & scalable Sustainable High-volume & short-term

Page 12: Organic / Polymer Redox-Flow-Batteries for Stationary ... · €/ kWh. Pumped-storage hydrolectricity. ... 1600 square meter labs/office, EUR 14 Mio. (funding from two foundations)

1558 www.schubert-group.de

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)

Page 13: Organic / Polymer Redox-Flow-Batteries for Stationary ... · €/ kWh. Pumped-storage hydrolectricity. ... 1600 square meter labs/office, EUR 14 Mio. (funding from two foundations)

1558 www.schubert-group.de

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!

Page 14: Organic / Polymer Redox-Flow-Batteries for Stationary ... · €/ kWh. Pumped-storage hydrolectricity. ... 1600 square meter labs/office, EUR 14 Mio. (funding from two foundations)

1558 www.schubert-group.de

The solution: Redox flow battery

EnerVault

RFB: Only technology to scale energy and power independently!

Page 15: Organic / Polymer Redox-Flow-Batteries for Stationary ... · €/ kWh. Pumped-storage hydrolectricity. ... 1600 square meter labs/office, EUR 14 Mio. (funding from two foundations)

1558 www.schubert-group.de

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

Page 16: Organic / Polymer Redox-Flow-Batteries for Stationary ... · €/ kWh. Pumped-storage hydrolectricity. ... 1600 square meter labs/office, EUR 14 Mio. (funding from two foundations)

1558 www.schubert-group.de

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

Page 17: Organic / Polymer Redox-Flow-Batteries for Stationary ... · €/ kWh. Pumped-storage hydrolectricity. ... 1600 square meter labs/office, EUR 14 Mio. (funding from two foundations)

1558 www.schubert-group.de

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.

Page 18: Organic / Polymer Redox-Flow-Batteries for Stationary ... · €/ kWh. Pumped-storage hydrolectricity. ... 1600 square meter labs/office, EUR 14 Mio. (funding from two foundations)

1558 www.schubert-group.de

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).

Page 19: Organic / Polymer Redox-Flow-Batteries for Stationary ... · €/ kWh. Pumped-storage hydrolectricity. ... 1600 square meter labs/office, EUR 14 Mio. (funding from two foundations)

1558 www.schubert-group.de

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

Page 20: Organic / Polymer Redox-Flow-Batteries for Stationary ... · €/ kWh. Pumped-storage hydrolectricity. ... 1600 square meter labs/office, EUR 14 Mio. (funding from two foundations)

1558 www.schubert-group.de

pRFB: Development overview & future

2012

2014

20172019

2020-

Page 21: Organic / Polymer Redox-Flow-Batteries for Stationary ... · €/ kWh. Pumped-storage hydrolectricity. ... 1600 square meter labs/office, EUR 14 Mio. (funding from two foundations)

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The world‘s largest battery?

https://www.ewe-gasspeicher.de/en/home/b4p

Page 22: Organic / Polymer Redox-Flow-Batteries for Stationary ... · €/ kWh. Pumped-storage hydrolectricity. ... 1600 square meter labs/office, EUR 14 Mio. (funding from two foundations)

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Brind4power storage I

Caverns with saline solutions containing polymers

Page 23: Organic / Polymer Redox-Flow-Batteries for Stationary ... · €/ kWh. Pumped-storage hydrolectricity. ... 1600 square meter labs/office, EUR 14 Mio. (funding from two foundations)

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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

Page 24: Organic / Polymer Redox-Flow-Batteries for Stationary ... · €/ kWh. Pumped-storage hydrolectricity. ... 1600 square meter labs/office, EUR 14 Mio. (funding from two foundations)

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Spiegel (23.11.2017), Wirtschaftswoche (22.11.2017), FAZ (09.07.2017), FAZ (22.06.2017), ...

Publicity & outreach b4p storage

Page 25: Organic / Polymer Redox-Flow-Batteries for Stationary ... · €/ kWh. Pumped-storage hydrolectricity. ... 1600 square meter labs/office, EUR 14 Mio. (funding from two foundations)

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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

Page 26: Organic / Polymer Redox-Flow-Batteries for Stationary ... · €/ kWh. Pumped-storage hydrolectricity. ... 1600 square meter labs/office, EUR 14 Mio. (funding from two foundations)

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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

Page 27: Organic / Polymer Redox-Flow-Batteries for Stationary ... · €/ kWh. Pumped-storage hydrolectricity. ... 1600 square meter labs/office, EUR 14 Mio. (funding from two foundations)

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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

Page 28: Organic / Polymer Redox-Flow-Batteries for Stationary ... · €/ kWh. Pumped-storage hydrolectricity. ... 1600 square meter labs/office, EUR 14 Mio. (funding from two foundations)

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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), …

Page 29: Organic / Polymer Redox-Flow-Batteries for Stationary ... · €/ kWh. Pumped-storage hydrolectricity. ... 1600 square meter labs/office, EUR 14 Mio. (funding from two foundations)

1558 www.schubert-group.de

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

Page 30: Organic / Polymer Redox-Flow-Batteries for Stationary ... · €/ kWh. Pumped-storage hydrolectricity. ... 1600 square meter labs/office, EUR 14 Mio. (funding from two foundations)

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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.

Page 31: Organic / Polymer Redox-Flow-Batteries for Stationary ... · €/ kWh. Pumped-storage hydrolectricity. ... 1600 square meter labs/office, EUR 14 Mio. (funding from two foundations)

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Page 32: Organic / Polymer Redox-Flow-Batteries for Stationary ... · €/ kWh. Pumped-storage hydrolectricity. ... 1600 square meter labs/office, EUR 14 Mio. (funding from two foundations)

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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 €