Sustainable, Safe and Scalable Stationary Energy Storage Dr. Olaf - - PowerPoint PPT Presentation

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Sustainable, Safe and Scalable Stationary Energy Storage Dr. Olaf - - PowerPoint PPT Presentation

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Organic Redox-Flow-Batteries Sustainable, Safe and Scalable Stationary Energy Storage Dr. Olaf Conrad, Managing Director 25.10.2017 1 About JenaBatteries GmbH (JB) Founded in 2012 , JB holds the global patent for

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Sustainable, Safe and Scalable Stationary Energy Storage

  • Dr. Olaf Conrad, Managing Director

Organic Redox-Flow-Batteries

25.10.2017 1

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SLIDE 2

About JenaBatteries GmbH (JB)

Founded in 2012, JB holds the global patent for Polymer-based-Redox-Flow-Batteries and filed further patents in the field of organic radical redox flow batteries. 2015 we won the IQ Innovationspreis 2015 (Mitteldeutschland). 2016, JB attracted two new investors with comprehensive expertise in R&D, engineering and business development. JenaBatteries is growing rapidly (5 employees in August 2016 to currently 16 employees) JenaBatteries ist focused on developing and producing stationary energy storage systems (with a capacity above 40 kWh). Currently delivering pilot installations in Germany and The Netherlands Actively building a global network of project development and technical support partners based

  • n a collaborative licensing business model

JB is supported by: Homepage: www.jenabatteries.com

2 25.10.2017

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SLIDE 3
  • Metal-free energy storage system based on patented
  • rganic, redox-active energy storage materials
  • Water based, near-neutral pH
  • No toxic heavy metals, no critical raw materials
  • Inexpensive raw materials and membranes
  • > 10.000 cycles
  • 10 kW to 2 MW and 40 kWh to 10 MWh
  • Targeted installation cost < 500 €/kWh

JenaBatteries – Cost effective organic based redox flow batteries

25.10.2017 3

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SLIDE 4

Management Team & Owners

Carsten Oder System & Electronics Tobias Janoschka Corporate Development

  • Dr. Norbert Martin

Electrolyte & Material Michael-Lothar Schmidt BD & Marketing

Ranft Gruppe Wirthwein AG

  • Dr. Olaf Conrad

Managing Director

www.jenabatteries.com Owners: Management Team:

4 25.10.2017

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Current material basis & challenges

25.10.2017 5

Cobalt (Lithium) Lead Rare earth elements (Ni-MeH) Vanadium (RFB) No sustainable raw material basis Important battery issues:

  • Safety
  • Sustainability
  • Scalability
  • Cycle Stability
  • …

Plus NiCd…

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SLIDE 6

Organic Active Materials and their Redox Potentials

25.10.2017 6

  • J. Winsberg et al. Angew. Chem. Int. Ed. ,2017, 56, 686-711

O2 evolution H2 evolution Water stability

0.0 V

  • Water based flow batteries desireable due to higher safety, higher conductivity and

price despite lower cell voltage

  • TEMPO / Viologen systems utilize a large portion of the potential available in water

Viologen TEMPO

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SLIDE 7

Conductive polymers & batteries

7

poly(pyrrole)

H N

n

poly(aniline)

H N H N

n Commercial button cells flopped

  • J. S. Miller, Adv. Mater. 1993, 5, 671-676; D. Naegele, R. Bittihn, Solid State Ionics 1988, 28-30, 983-989.

Bridgestone-Seiko

poly(aniline)/lithium (1987-1992)

VARTA/BASF

poly(pyrrole)/lithium (1987)

Discovered 1977, Nobel price in Chemistry 2000 (“for the discovery and development

  • f conductive polymers“)

poly(acetylene)

n

7 25.10.2017

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Polymer-based energy storage?

8

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

  • Adv. Mater. 2012, 24, 6397–6409.

conductive polymers

Capacity / % Cell voltage / a.u.

Desired discharging behavior Conductive polymer battery

redox polymers

N H H N N H

N O O O N O O O N O O O

8 25.10.2017

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SLIDE 9

Bi-Polar Polymers - Poly(BODIPY) – Organic Solvents

25.10.2017 9

  • J. Winsberg. et al. Chem. Mater., 2016, 28 (10), pp 3401–3405
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Polymer design for aqueous systems

25.10.2017

TEMPO- and viologen-polymers for water-based redox-flow batteries

A + A + A + + A

m N H O O N H O O R O R O n m N O O R O n O H2O2 Na2WO4 R= a -O(CH

2CH2O)nCH3

@ 450 g mol-1 R= b -O(CH

2CH2O)nCH3

@ 950 g mol-1 R= c -O(CH

2CH2O)2CH3

R= d -NH

2

R= e -O(CH

2)2N(CH3)3 + Cl-

+

10

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Design criteria for TEMPO and Viologen Polymers

25.10.2017

0.1 1 10 100 P1 P2

Intensity / a.u. <Rh>n,app / nm

Energy Storage Monomer (EM) Solubilizing Monomer (SM)

N O O X O Polar group

n m

O

n

N N Cl Cl Polar group

m

Energy Storage Monomer (EM)

11

  • T. Janoschka, N. Martin, U. Martin, C. Friebe, S. Morgenstern, H. Hiller, M. D. Hager, U. S. Schubert, Nature 2015, 527, 78-81.
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SLIDE 12
  • T. Janoschka, N. Martin, U. Martin, C. Friebe, S. Morgenstern, H. Hiller, M. D. Hager, U. S. Schubert, Nature 2015, 527, 78-81.

N H O O O O N H O O O O N +

n m

Na2WO4/H2O2 N Cl

  • 1. HCl/H2O
  • 2. ABCVA/HSC2H4OH
  • 3. NaOH/H2O

N O O O O N

n m

Cl Cl N N DMSO AIBN + N N N ion exchange N N I Cl Cl Cl Cl Cl 1 2 P1 O 4 P2

n m n m

Cl Cl 3

Co-Polymer for TEMPO and Viologen Polymers

25.10.2017 12

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Rheological Data and Charge / Discharge Behavior in Flow Cells

25.10.2017 5,000 10,000 15,000 0.0 0.3 0.6 0.9 1.2 1.5

Cell voltage / V Time / s

TEMPO TEMPO+ N R O N R O

  • e
  • + e
  • N

N R R N N R R + e

  • e
  • Viol++

Viol+· P1: P2:

10

  • 2

10

  • 1

10 10

1

10

2

10

3

10

  • 2

10

  • 1

P1 P2

Viscosity / Pa s Shear rate / s

  • 1
  • Viscosity in flow range (shear rate > 1 s-1 between 5 and 20 mPas
  • Stable redox cycling in water based solutions confirmed
  • T. Janoschka, N. Martin, U. Martin, C. Friebe, S. Morgenstern, H. Hiller, M. D. Hager, U. S. Schubert, Nature 2015, 527, 78-81.

13

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“Small molecules”-based RFB

25.10.2017 14 ion-selective membrane active material aqueous electrolyte electrode

R N N R Cl Cl N R O

anolyte tank catholyte tank

low viscosity and good solubility will lead to higher capacity, ion mobility, current density

more expensive ion-selective membrane

simplified synthetic access allows for lower-cost electrolyte

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Cathode

  • commercially

available

  • low-cost
  • low retention by

membrane

  • expensive
  • anionic species
  • low retention by

membrane

  • expensive
  • low retention by

membrane

  • not commercially

available

  • high retention by

membrane

O

  • N

R R OH R COOH R NH2 R N R N R OH

  • T. Liu, X. Wei, Z. Nie, V. Sprenkle, W. Wang, Adv. Energ. Mat. 2015, DOI: 10.1002/aenm.201501449.
  • low solubility of TEMPOL of only 0.5 mol/L in 1.5

mol/L NaClaq → 13 Ah/L

  • high solublity of MV, but only 0.5 mol/L

demonstrated

  • high amount of supporting electrolyte (1.5

mol/L NaClaq)

25.10.2017 15

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Improved synthesis route

N H O N H N N H N Me2NH (gas), H2, Pd/C, MeOH Cl CH3Cl MeCN/toluene O

  • N

N Cl H2O2/MgSO4 

up-scaling to kg-scale by …

… substitution of dimethylammonium hydrochloride (difficult purification

procedure) with dimethylamine gas

… substitution of expensive, B-based reduction agent with hydrogen … direct methylation with chloromethane and substitution of CH3I … low-cost oxidation catalyst … simple purification procedures

25.10.2017 16

  • T. Janoschka, N. Martin, M. D. Hager, U. S. Schubert, Angew. Chem. Int. Ed. 2016 Nov 7;55(46):14427-14430
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20 40 60 80 100 100 200 300 400 500 Capacity / mAh Cycle number 90 92 94 96 98 100 Coulombic efficiency / %

High cyclability of the storage material

25.10.2017

Facile one-electron transfer reactions without ion insertion/intercalation on charge and discharge  no mechanical stress, no volume change  high cycle stability Molecular structure unchanged during charging/discharging  no degradation from conformational changes Excellent cross-over characteristics due to size and charge of storage material

N R O N R O

  • e
  • +e
  • 2000

4000 6000 8000 10000 20 40 60 80 100

Residual Capacity [%] Zyklus

  • T. Janoschka et al. Angew. Chem., Int. Ed.2016, 55, 14427−14430

17

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Practical energy density > 20 Wh/l

25.10.2017

20 40 60 80 100 1,10 1,15 1,20 1,25 1,30 1,35 1,40

Leerlaufspannung [V] Ladezustand [%]

Resting voltage at SOC = 50% is 1.25 V, compare to NiMH-battery 1.2 V Solubility of organic storage material is > 50 wt-% Optimization with NaCl concentration – viscosity <-> conductivity <-> energy density Design point for product at 20 Wh/l, lab scale demonstration of up to 35 Wh/l

  • T. Janoschka et al. Angew. Chem., Int. Ed.2016, 55, 14427−14430

50 90 Organic storage material [wt-%] 10 17 Supporting electrolyte [wt-%] State of Charge [%] Resting Voltage [V] 18

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Rheological behaviour allows for wide operating window

25.10.2017

Viscosity is impacting the pumping losses  low viscosity results in low pumping losses Viscosity at design point (20 Wh/l) is 3 mPas (anolyte) and 6 mPas (catholyte) at 25 °C, respectively

  • Compare water: 1 mPas, grape juice 2 .. 5 mPas, syrup approx. 10.000 mPas

At 5 °C viscosity remains suitably low at 5 mPas (anolyte) and 12 mPas (catholyte), respectively

19 19

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Stack efficiency > 85% at rated stack power of 5 kW

25.10.2017

Ladegrad (SoC): 10 … 90 % Results from laboratory installation 0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0 16.0 2 4 6 8 10 12 14 Verlustanteil (%) Leistung Stack (kW)

Leistung Entladen (kW) Leistung Laden (kW)

10 20 30 40 50 60 2 4 6 8 10

Widerstand [Ohm*cm²] Temperatur [°C]

Stack design allows high efficiency at rated power with ability to deliver 2x peak power Operation at higher temperatures improves stack efficiency and overall system efficiency

  • Elevated temperature reduces ohmic stack losses and pumping losses

20

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Pilot Installation I – 10 kW / 40 kWh Project targets Development of new organic storage materials Mass production ready stack design Development of a battery management system Extended operation data Containerised solution Coupling to a PV-installation in Thuringia/Germany Status Final assembly and initial tests at the end of 2017 Installation in the field in Q1/2018 Collaboration with regional development and production partners

Dieses Projekt wird von der Europäischen Union (EFRE) und dem Freistaat Thüringen (Thüringer Ministerium für Wirtschaft, Wissenschaft und Digitale Gesellschaft) kofinanziert. 25.10.2017 21

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Pilot Installation II – 100 kW / 350 kWh Scale up of pilot installation I by factor of 10 Coupling of an organic RFB with a Smart Grid Wind, PV, biomass BEV-Charging station, residential building, agricultural enterprise Development of business models Development of an energy management system Battery introduced via Plug & Play-capability Status Hardware and software engineering nearing completion Setup and operation planned for Q3/2018 10 partners from 5 EU-countries + Israel

This project has received funding from the European Union’s Horizon 2020 research and innovation program under grant agreement No 731239.

25.10.2017 22

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Thank you for your attention!

25.10.2017 23