EERA EXPERT WORKSHOP OPPERTUNITIES AND CHALLENGES OF BATTERIES FOR ENERGY STORAGE IN THE EU

Brussels, 19th October 2016

Novel Materials for Electrochemical Storage

Prof. Maximilian Fichtner – HIU

Dr. Edel Sheridan – Research Scientist SINTEF

EERA ES Research Topics Recent Survey of EERA ES members – 11 responces of largest research institutes

What types of battery technology research outside of Li ion are you engaged in?

Na ion / Mg ion

Redox flow

Zn air / Al air / Li air / Na air

High temp battery systems

Who is funding the described projects?

Most nationally funded ; Germany and Spain funding the greatest variety of projects

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TESLA Gigafactory 5.000 t/a Li for car batteries

8.000 t/a Li for PowerWall batteries

Li resources / Cost: ~13.000 t/a Li are currently produced for world market of Li ion batteries

Why alternatives to Li?

Cobalt supply chain: Co production is falling in 2016 and may be declining further

Co is heavily associated with children labour

Estimated 10 more gigafactories are under consideration worldwide

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Estimated capacity of new mega-/gigafactories for Li ion batteries worldwide, with $20bn committed to creating new factories (from: http://benchmarkminerals.com).

Where is the future Li battery production?

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Systems Beyond Li

Fluoride Ion Battery

Chloride Ion Battery

Magnesium Battery

Sodium Ion Battery

Anionic Shuttles

Cationic Shuttles

Zinc battery

Calcium Battery

Aluminum Battery

„multivalent shuttles“

Partly great promises for improving sustainability, cost, safety, energy density

but no system commercialized, yet, due to novelty and scientific/technical obstacles

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Theoret. storage capacities of electrochemical couples of Li Ion- and post-Li batteries (materials basis)

Gravimetric energy density (Wh/kg)

Li-ion

Ca/CoF3

Chlorides

Mg/CuCl2

Ca/CuCl2

Li/CuCl2

Fluorides

La/CoF3

Ca/CoF3

Li/FeF3

Li/CuF2

LiC6 / NMC

Volu

met

ric e

nerg

y de

nsity

(Wh/

l) Mg

batteries Metal

Sulphur

Li/S

Mg/S

Metal-Air

Li/O2

Mg/O2

Na/O2

Zn/O2

Na-ion

Hard-C / NaNMC

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Element Charge

of ion

crystal ionic radii /pm

Earth crustal abundance/ppm by weight

Price (pure)4 US$ per

100g

specific capacity Potential vs. NHE/V

mA·h·g-1 mA·h·cm-3

Li 1 90 20 27 3862 2047 -3.04

Na 1 116 24000 + 10.8 g/L in seawater 25 1166 1130 -2.71

Mg 2 86 23300 3.7 2206 3840 -2.37

Ca 2 114 41500 20 1338 2006 -2.87

Zn 2 88 70 5.3 820 6845 -0.76

Al 3 68 82300 15.7 2980 8050 -1.66

Cl -1 167 145 + 19.4g/L in seawater 0.15 - - used only as

shuttle

[1] For coordination number 6, from R. D. Shannon "Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides". Acta Crystallogr A. 32 (1976) 751–767. [2] David R. Lide, ed., CRC Handbook of Chemistry and Physics, 89th Edition (Internet Version 2009),

Facts about post Li systems

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Take home message

• As Li costs increase there will be greater demand for batteries based on alternative materials.

• Will the EU be a leader or follower ?

• To lead we need

• Greater engagement from Industry in R & D

• Investment and commitment from the EU to promote non Li ion battery development over a long period (> 20 years)

• Incentivise research institutes and universities to Patent before Publishing

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A few examples of recent developments

Titel der Präsentation

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Mg2+

e-

e-

Anode Cathode

discharge

charge

Mg

Mg offers good handling and operational safety.

No dendrite formation with Mg metal as anode major safety issue with Li metal batteries.

Mg is naturally 1000x more abundant on earth than Li.

Mg/S offers theoretical 3200 Wh/L compared to theoretical 2800 Wh/L for Li/S

But: Sulfur cathode needs non-nucleophilic electrolyte for Mg!

Properties of Magnesium and Lithium

Li Mg Atomic weight 6.9 24.3

Ionic radius 90 pm 86 pm

Ionic charge + 1 + 2

Reduction potential - 3.04 V - 2.37 V

Density 0.53 g/cm3 1.74 g/cm3

Gravimetric capacity 3861 mAh/g (Li) 372 mAh/g (LiC6)

2205 mAh/g

Volumetric capacity 2061 mAh/cm3 3832 mAh/cm3

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M. Fichtner et al., EP 2824751A1 (2013) Zh. Zhao-Karger et al., RSC Advances 3 (2013) Zh. Zhao-Karger et al., RSC Advances 4 (2014) Zh. Zhao-Karger et al., Adv. Energy Mater. 5

(2015) 1401155 B.P. Vinayan et al., Nanoscale 8 (2016) 3295

New non-nucleophilic and powerful electrolyte. Simple to make from standard materials in various solvents. Stable up to 3.9 V

First reversible Mg-S cells

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Na-Ion Batteries

Na-ion cell with hard carbon anode made of apple biowaste

L. Wu et al., ChemElectroChem (2015) doi: 10.1002/celc.201500437 http://www.swr.de, Landesschau aktuell: „Forschung am Ulmer Helmholtz-Institut: Batterien aus Apfelresten“

NaNMC – Apple Hard Carbon

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Na-Ion Battery with sustainable cathode

M. Keller et al., Adv. Energy Mater. (2015), doi: 10.1002/aenm.201501555 (selected as Frontispiece) B. Oschmann et al., Adv. Energy Mater. (2015) doi: 10.1002/aenm.201501489

Extraordinary Performance 600 cycles (90% cap. retention), 3.4 V

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Na-Ion Batteries

M. Keller et al. (in preparation)

High Energy (175-150 Wh kg-1) High Voltage Efficiency (93-90%) High Energy Efficiency (94-91%) Stable Discharge Voltage (3.4 V)

Good Battery Lifetime (600 cycles, 83%)

Na-Ion Cell: Mixed Layered Oxide – Starch Hard Carbon

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Zinc-Air Batteries

• Chemical Reactions I. Zn + 4OH−⇌ Zn OH 4

2− + 2e− II. Zn OH 4

2−⇌ ZnO + 2OH− + H2O III. O2

g ⇌ O2e

IV. 12

O2e + H2O + 2e− ⇌ 2OH−

• Specific energy: 1086 Wh∙kg-1 Energy density: 6090 Wh∙l-1 Low cost and safe

• Challenges include: Zn dendrites, electrolyte carbonation, Zn passivation

ZAS PROJECT – TECHNO ECONOMIC EVALUATION

• Possible Hybridization according to current capabilities of ZAS battery

Definition of specifications and test procedure of module and operating conditions

Parameter / OM OM 4 (Load Shifting) OM 3 (Backup) Chemistry mix Li-Ion Li-Ion + ZAS Li-Ion Li-Ion + ZAS

BESS Total Power 250 250 500 500 BESS Total Energy 1.000 1.000 1.000 1.000

% of Li-Ion (energy) 100% 30% 100% 40% % of ZAS (energy) 0% 70% 0% 60% Ultracaps added? No No No Yes*

Cost Ratio (€/kWh) 443 227 473 332 Nº of 20 ft containers 2 1 2 2

*: Configuration Li-Ion + ZAS in OM 3 has a 200 kW / 20 s ultracaps system to compensate the low power capability of ZAS batteries

Estimation of cost ratio provided includes the cost of the following equipment: • Batteries • Power Converter • Housing (20 ft containers) • Auxiliary equipment (FFS, HVAC, LV

switchgear, etc)

Estimation of cost ratio provided excludes the following: • Permitting • Workforce (engineering, assembly, etc) • Transport to site • Installation • Commissioning & Start-Up • Others

CONFIDENTIAL

ZAS PROJECT – TECHNO ECONOMIC EVALUATION

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• Possible Hybridization according to current capabilities of ZAS battery

Definition of specifications and test procedure of module and operating conditions

21 CONFIDENTIAL

Results obtained

Hybridization of Li-Ion with Zinc-Air produces a significant cost reduction The cost reduction is more relevant in OM 4 as ultracaps are not considered in that case

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The Chloride Ion Battery

MCln + M0´ M0 + M´Cln

Using Cl- as charge transfer ion

Reversible chlorination and de-chlorination

Cl-

Cl- MClx

X. Zhao, Zh. Zhao-Karger, D. Wang, and M. Fichtner, Angew. Chemie Int. Ed. 52 (2013) X. Zhao, Sh. Ren, M. Bruns, and M. Fichtner, J. Power Sources 245 (2014) M. Fichtner, X. Zhao, H. Hahn, (2012) EP Application (Nov. 2012)

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Chloride-Ion Batteries

VOCl as cathode for Chloride Ion Batteries

P. Gao, M. Fichtner et al., Angew. Chemie Int. Ed. (2016)

0 30 60 90 120 150 180

1,2

1,6

2,0

2,4

2,8

1st10th

Volta

ge /

V

Capacity (mAh/g)

@ 0.5 C rate

0 10 20 30 40 50

30

60

90

120

150

180

2 C 0.5 C1 C1 C0.5 C

Capa

city

(mAh

/g)

Cycle number

The theoretical capacity is 261 mAh g-1 based on 1 mol e- transfer; < 0.7 e- should be kept in practice to avoid structural collapse

Rate performance

0.5 mol PP14Cl in PC as electrolyte

Mixed intercalation and conversion mechanism

stable in air

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A new class of highly conjugated porphyrin complex enabling high performance of rechargeable batteries

Organic batteries based on natural resources

Hemocyanin-derived (Molluscs, Arthropoda) 4 electron transfer from 16 to 20 𝜋𝜋 electrons; OCV vs. Li: 3.0 V TDec: 300 °C

N

N N

N

Cu

1

R R

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Performance

Cycling performance of Li / LiPF6 / Organic cell in voltage ranges of 4.5 - 1.8V

Li / LiPF6 / Cu-DEPP no carbon, no binder

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Ragone Plot

Power density measured up to 30 kW/kg

M. Fichtner, P. Gao, Zh. Zhao-Karger, Z. Chen, M. Ruben, WO Application (2016)

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• Liquid metal molten salt battery

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• Cheap (€/kWh) • Built from abundant materials

• For stationary storage • Weight and size not critical

• High throughput • No crystalline growth • No solid phases

• Grid balancing • Increases value of wind and solar

power

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Thank You!