Current and long term vision of battery research at NIC

Current and long term vision of battery research at NIC Prof. dr. Robert Dominko Head of the laboratory for modern battery systems Deputy director of Alistore-ERI Scientific coordinator of EU project HELIS

Battery research at NIC in Ljubljana Strong battery research center in the southeast of Europe Well equipped laboratory designed for battery research up to TRL3, TRL4 Ljubljana Robert Dominko 13 th november 2018 2

Who are we o Well established research group worldwide o LEADING RESEARCH GROUP IN ALISTORE-ERI (25 laboratories and 6 companies from EU) o LEADING RESEARCH GROUP ON EU LEVEL (EU projects and Flagship initiative) o INDUSTRIAL COLLABORATION (SAFT, OEM s, Slovenian companies,...) WHY BLED Ljubljana Robert Dominko 13 th november 2018 3

Coorperation Alistore ERI Deputy director of ALISTORE ERI network ALISTORE Academic partner ALISTORE Industry Club Partners ALISTORE Patent manager Research 25 European Laboratories (2 more to come) 110 researchers, >150 publications, 22 White Papers 42 joint PhD/Post-Doc projects financed within ALISTORE Innovation 20 active patents 6 Industry Club partners (2 more to come) ALISTORE ERI was created in 2004 as an EC funded FP6 Network of Excellence Ljubljana Robert Dominko 13 th november 2018 4

Education partner in European joint master degree ERASMUS MUNDUS 1 (2005-2010) ERASMUS MUNDUS 2 (2010-2015) ERASMUS MUNDUS EMJMD (2018-2024) https://www.u-picardie.fr/mundus-mesc/ 2-years program in English (3 semesters of Class, 1 6-months thesis) Inorganic chemistry Characterisation techniques: XRD, Microscopy, Thermal analysis,... Electrochemistry Thermodynamics Crystallography Energy/hydrogen storage Nanomaterials Intellectual Property 7 Universities as partners Amiens, Toulouse(FRANCE) Bilbao Pais Vasco (SPAIN) Warsaw (POLAND) Ljubljana (SLOVENIA) DEAKIN (AUSTRALIA), DREXEL (USA) Strong connections with all ALISTORE members MSc theses/phds at ALISTORE Labs or in the facilities of our Ljubljana Robert Dominko 13 th november 2018 5

D10 batteries Li-S batteries modelling Mg batteries Li-ion batteries A. Vizintin, J. Bitenc,..., R. Dominko, Probing electrochemical reactions in organic cathode materials via in operando infrared spectroscopy, Nature Commun. 9, Article number: 661 (2018) doi:10.1038/s41467-018-03114-1 Ljubljana Robert Dominko 13 th november 2018 6

Energy density of different battery systems 1200 Energy Density / Wh L -1 1000 Battery 800 * LIB (state of the art) Li/S Li/O 2 600 Battery Battery Battery System 400 System 200 System System *metallic Li 0 0 100 200 300 400 500 600 700 800 Specific Energy / Wh kg -1 Wh/L = Wh/kg Ljubljana Robert Dominko 13 th november 2018 7

Lithium sulfur batteries - Project: HELIS (Horizon2020) COORDINATOR COORDINATOR 14 PARTNERS 7,97 mio EUR Ljubljana Robert Dominko 13 th november 2018 8

Li-S batteries Region I: S 8 S 2- x ; x ~ 6-8 Region II: S 2- x S 2- x ; x ~ 3-4 Region III: polysulphides equilibrium, Li 2 S formation R. Dominko, et al., J. Phys. Chem. C, 2015, 119, 19001-19010 Ljubljana Robert Dominko 13 th november 2018 9

HELIS - European Li-S battery value chain materials Recycling production Safety Cell manufacturing Cell testing 3,2 50 3,0 2,8 0 Voltage / V 2,6 2,4 2,2 2,0 1,8 1,6 Voltage / V 3,0 2,8 2,6 2,4 2,2 2,0 current / ma -50-100 -150 current / ma Ljubljana Robert Dominko 13 th november 2018 1,4 1,8 1,6 time -200 220000 240000 260000 time 10

Use of microporous carbon Use of ultra microporous carbon (pore size < 1nm) and FEC:DEC based electrolyte enables long term cycling and high energy high power cells C / ma h g -1 1600 1400 1200 1000 800 600 400 200 0 0 10 20 30 40 50 60 Cycle 105 100 95 Coulombic Efficiency / % Li metal degradation is much slower compared to other electrolytes Ljubljana Robert Dominko 13 th november 2018 11

Stabilization of metallic lithium surface Use of nano cellulose it can act as lithium protection (due to anisotropy) and separator (porosity and tortuosity) Ljubljana Robert Dominko 13 th november 2018 12

Energy density of different battery systems 1200 Energy Density / Wh L -1 1000 Battery 800 * LIB (state of the art) Li/S Li/O 2 600 Battery Battery Battery System 400 System 200 System System *metallic Li 0 0 100 200 300 400 500 600 700 800 Specific Energy / Wh kg -1 Wh/L = Wh/kg Ljubljana Robert Dominko 13 th november 2018 13

Development of high energy density cathodes FET Open project LiRichFCC O: 66% F: 33% High volumetric energy density of Li 2 MO 2 F materials M: 33% Li: 66% R. Chen, S. Ren, M. Knapp, D. Wang, R. Witter, M. Fichtner, and H. Hahn, Adv. Energy Mater., vol. 5, no. 9, 2015. Ljubljana Robert Dominko 13 th november 2018 14

Characterization HRTEM images O / F HAADF Li 1.25 FeO 2 F 0.25 cs-bm 70a ABF HAADF Li 2 FeO 2 F bm 88b ABF Fe / Li <001> HAADF Fe HAADF Inhomogeneous site occupancy Clustering of defects higher crystallinity partially amorphous Ljubljana Robert Dominko 13 th november 2018 15

Electrochemistry Discharge capacity (mah/g) Fe based oxyfluorides 120 90 Li 1.25 FeO 2 F 0.25 60 Li 2 FeO 2 F 30 LiFeO 2 Li 2 FeO 2 F 0 0 10 20 30 40 50 Cycle number Discharge capacity (mah.g -1 ) 500 400 300 200 100 Ti based oxyfluorides Li 1.25 TiO 2 F 0.25 Li 2 TiO 2 F (ball-milling) Li 2 TiO 2 F (ceramic synthesis) 0-5 0 5 10 15 20 25 30 35 40 Cycle numbers Other combinations, like Mn, V or other TM offers interesting energy densities (capacity and voltage) Ljubljana Robert Dominko 13 th november 2018 16

Alternative battery technology Why we need alternative battery technologies Mg, Na, Ca are geopolitically neutral South America Ljubljana Robert Dominko 13 th november 2018 17

Mg redox active polymers battery Cathode (redox active polymer) 250 Mg/Mg(TFSI) 2-2MgCl 2 DME/K238_sox_NaCl 1,1 3,0 Mg/Mg(TFSI) 2-2MgCl 2 DME/PFQ 200 Col. efficiency 1,0 2,5 Capacity (mah/g) 150 100 Capacity 0,9 0,8 0,7 Col. efficiency E (V) 2,0 1,5 cycle 10 cycle 50 cycle 100 cycle 200 cycle 300 cycle 400 50 0,6 1,0 0 0,5 0 100 200 300 400 500 Cycle number 0,5 0 50 100 150 200 Capacity (mah/g) Anode (Mg particles) Comparison between Mg foil and electrodes made with carbon black and carbon nanotubes in 0,6 M Mg(TFSI) 2, 1,2 M MgCl 2 in DME electrolyte 1,00 0,95 Coulombic efficiency 0,90 0,85 0,80 0,75 0,70 CNT_WBM2 SC45_WBM2 Mg foil 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 Cycle number Ljubljana Robert Dominko 13 th november 2018 18

Al/organic battery Theoretical energy density of Al battery can be as high as 700 Wh/kg Proof of concept Al//AlCl 3 :EMIMCl//AQ J. Bitenc, et all, in review Ljubljana Robert Dominko 13 th november 2018 19

Ca batteries Incompatibility with classical electrolytes Need of elevated temperature Surface- film controlled Lack of Positive Electrode Materials Ponrouch, Elsevier (2018) Ljubljana Robert Dominko 13 th november 2018 20

Ca battery proof of concept Electrolyte: Ca(BH4)2 2THF in THF (1,5 M) Scan rate: 25 mv/s Potential voltage: -1,5/+2,5 V Room temperature working! Cathode: PAQS Anode: Ca shot (99,5%) Electrolyte: Ca(BH 4 ) 2 2THF in THF (1,5 M) Current density: C/50 Potential range tuning Both electrodes supported on graphite disc Ljubljana Robert Dominko 13 th november 2018 21

Future plans BATTERY 2030+ Excellence in research FET Flagship initiative, collaboration with industry Ljubljana Robert Dominko 13 th november 2018 22

Why we need long term research Ljubljana Robert Dominko 13 th november 2018 23

BIG MAP Materials Acceleration Platform (MAP) Battery Interface Genome (BIG) Ljubljana Robert Dominko 13 th november 2018 24

Sensors and self healing 4000 5 Optimum (China) - elektricni avtobusi na OI Peking 2008 Kapaciteta /mah 3500 3000 2500 2000 1500 1000 kontinuirno polnjenje praznjenje s tokom 4A polnjenje praznjenje Kapaciteta / Ah 4 3 2 1 26650 celica s kapaciteto 5Ah in 3.2V polnjenje 1A praznjenje 10A potencialno obmocje 2.7-3.6V 0.76Ah (16%) 500 0 22-28 C 0 0 50 100 150 200 250 Cycle No. 0 200 400 600 800 1000 število ciklov Ljubljana Robert Dominko 13 th november 2018 25

Future battery research Ljubljana Robert Dominko 13 th november 2018 26

Acknowledgement Ljubljana Robert Dominko 13 th november 2018 27

Acknowledgement European Commission under grant agreement No. 666221 European Commission under grant agreement No. 711792 Lon term collaboration on Mg batteries research program and projects Ljubljana Robert Dominko 13 th november 2018 28

INTERNATIONAL BATTERY ASSOCIATION CONFERENCE 8-13. march 2020 IN BLED, SLOVENIA Ljubljana Robert Dominko 13 th november 2018 29