Battery research for smart mobility: Achievements and new directions. J.M. Tarascon

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1 Battery research for smart mobility: Achievements and new directions J.M. Tarascon

Electric mobility: an introduction Battery research is

30 th, 2015 100$ / kwh 650 Wh L 1 cell Energy density 300 Wh kg 1

the word of energy management but also in the way that research must

2 Electric mobility: an introduction Battery research is business-driven so are the basic research needs by 2020 Today April 30 th, $ / kwh 650 Wh L 1 cell Energy density 300 Wh kg 1 cell Specific energy 95 % capacity at 1C Power density Revolution in the word of energy management but also in the way that research must proceed Abundant Sustainability elements No cobalt Energy efficiency 98 % Cost 100 kwh pack 1

Improvements [150 mah/g] 2D via structure chemical substitutions: Replace Co by Replace CoOLi[Co]O Li[Co]O 2 6 2 Replace partially partially Li[Co]O 2 [150 mah/g] partially Co Replace by partially

3 Voltage (V vs. Li + /Li 0 ) The layered oxides and their evolution through the years Improvements LiCoO (1991) via chemical substitutions: Replace Li[Co]O 2 Improvements via chemical partially substitutions: Improvements [150 mah/g] 2D via structure chemical substitutions: Replace Co by Replace CoOLi[Co]O Li[Co]O Replace partially partially Li[Co]O 2 [150 mah/g] partially Co Replace by partially LiO[150 6 mah/g] Mn Co et by Ni Co by Mn et Co Niby Mn and Ni Mn et Ni Mn et Ni [150 mah/g] Capacité (mah/g) Capacité (mah/g) Li 0.5 CoO 2 Li 0.5 CoO Improvements via chemical substitutions: Chemically substituted samples Li[NiMnCo]O 2 Li[NiMnCo]O 2 [180 mah/g] [180 mah/g] NMC phases NMC phases Stellar "622" Li[NiMnCo]O 2 Li[NiMnCo]O [180 mah/g] 2 NMC [180 mah/g] phases ( mah/g) NMC phases mah/g 150 mah/g 150 mah/g x in in Li LixCoO 1-x x in in 22 Li LixCoO 1-x 22 Less than 1 Li + exchanged per metal T.Ozuku, Y. Makimura; Chem Lett. 642 (2001) 3

Increasing the capacity further via chemical substitution Dahn et al., Chemistry of materials 15, (2003),3214-3220 Voltage (V vs.

, 2013 + worldwide patent * The Li-rich NMC phases Co Ni Mn Li-excess Design model materials Li 2 Ru IV 0.75Sn IV 0.

4 Increasing the capacity further via chemical substitution Dahn et al., Chemistry of materials 15, (2003), Voltage (V vs. Li + / Li 0 ) Potentiel (Volts vs. Li + /Li ) Sathiya, Tarascon et al., Nature Mater., worldwide patent * The Li-rich NMC phases Co Ni Mn Li-excess Design model materials Li 2 Ru IV 0.75Sn IV 0.25O 3 : A single cationic redox center 3d 4d Li [Li 0.22 Ni II 0.11Mn IV 0.54Co III 0.13]O Capacité identique 250 mah/g 280mAh/g? mah/g Li 2 Ru 0.75 Sn 0.25 O x in Capacité Li x Ru 0.75 en SnmAh/g 0.25 O 3

5 E. McCalla, J.M. Tarascon et al., Science, 2015 Cell Voltage (V) d ''/db d ''/db M. Sathya, J.M. Tarascon et al. (Nature communications, Fevrier 2015) X-ray photoemission spectroscopy XPS XPS measurements (fully charged sample) Signal (O 2 ) n- 2 (H 2 O 2 ) (O 2 ) (H 2 O) Energiede Binding energy liaison (ev) Origin of the extra capacity in Li-rich materials? X-ray photoemission spectroscopy Electron paramagnetic resonance EPR RPE? (fully charged (fully sample) charged sample) XPS Li 2 Ru IV 0.75Sn IV 0.25O 3 (O 2 ) n- 2O -- Signal (O 2 ) n- 2O -- (O 2 ) n (O 2 ) n- 4.6 V Ru Ru Champs Magnetic magnétique field in [mt] [mt] Signal (O 2 ) n- 2 (H 2 O 2 ) (O 2 ) Energiede Binding energy liaison (ev) (H 2 O)? Electron paramagnetic resonance EPR measurements EPR RPE (fully charged sample) Signal (O 2 ) n 4.6 V Champs Magnetic magnétique field in [mt] [mt] Capacity in mah/g Direct evidence for an anionic redox process (2O -- (O 2 ) n- ) in Li-rich lamellar compounds

6 NATURE MATERIALS, 2013, 12, NATURE MATERIALS VOL 14 FEBRUARY 2015, SCIENCE, 2015, 305 (6267) The anionic redox activity: a transformational change LIB has relied on cationic redox reactions This is no longer true since 2013 (2D Layered oxide) (2D Li-rich layered oxide) Cationic framework Anionic framework 150 mah/g 280 mah/g Li M O x in LiCoO 2

7 Structural dimensionality A. Perez, et al. Nature energy (2017) O M A new playground for designing high capacity electrodes 3-D 3D O Mn,Ti,Li Li 1.3 Nb 0.3 Me 0.4 O 2 (Me = Mn, Fe,) Cation-disordered Rock-salts Tridimensional ordered β-li 2 IrO 3 Li/M composition 2D 2-D Layered Li-rich NMC Li O Ni,Mn, Co,Li α-li 2 IrO 3 (isostructural with Li 2 MnO 3 or Li 2 RuO 3 ) Layered Li 3 IrO 4 Ir,Li 1-D 1D Ru chain-ordering in Li 3 RuO 4 0-D 0D Nb 4 O 16 clusters in Li 3 NbO 4 Isolated ReO 6 octahedra in Li 5 ReO 6

8 D. Larcher and J.M. Tarascon, Nature Chemistry (2015) Energy required (kwh per kwh produced) Layered LiMO 2 oxides have enabled today s boom in EV s Today s EV boom Life cycle analysis 1884 Ishihara, K. et al. Life Cycle Analysis Proc. 5 th Int. Conf. EcoBalance, (2009) (GM "Volt") Renault "Fluence" (Peugeot "ion ) (Bolloré "Bluecar ) 1960 (Nissan "Leaf ) Numerous Multitude de brands modèles Toyota "Prius" Is it the perfect solution with respect to sustainability? Tesla Assembly of a battery of 1kWh Energy needed 327 kwh CO 2 rejected 110 kg

9 D. Larcher and J.M. Tarascon, Nature Chemistry (2015) How to make more sustainable Li-ion batteries? A few trends Design electrode materials based on abundant chemical elements Ceramic Process T = x 100 C T ~ 100 C C / 24hr 3 T < 100 C Develop energy-saving synthesis routes 40 nm 1 25 C LiFePO 4 Use of renewable organic electrodes L io O O Explore chemistries beyond Li L io O Li 2 C 6 O 6 O

10 Sustainability thrust: diversification of the battery systems for enhanced performances Time to market long moderate soon Li/air batteries All solid-state (Li/Na) batteries Li/S batteries Li-ion batteries Multivalent cation (Mg 2+, Ca 2+ ) batteries Redox flow batteries None have reached the maturation stage

Cell potential (V) Name Earth abundance The Na-ion battery: an alternative to Li-ion for

98 Li 6.941 Lithium 0.006% Name Earth abundance Name Earth abundance 311 Lithium Sodium 1s 2s 1 0.

534 22.941 6.941 3 11 3 0.534 1s 2 2s 1 1s 2 2s 1 Lithium 0.

6% 2200 2s 2 2p 6 3s 1 separator NVPF Sodium 2.6% Sodium 2.

11 Cell potential (V) Name Earth abundance The Na-ion battery: an alternative to Li-ion for sustainability 3 Lithium 1s 2 2s Li Li 0.98 Li Lithium 0.006% Name Earth abundance Name Earth abundance 311 Lithium Sodium 1s 2s s 2 3s 2p Na Li s 2 2s 1 1s 2 2s 1 Lithium 0.006% Na 1s 2 2s 1 3 V 2 (PO 4 ) 2 F Lithium 3 Lithium Lithium 0.006% Lithium Sodium Sodium 2.6% s 2 2p 6 3s 1 separator NVPF Sodium 2.6% Sodium 2.6% Na 3 V 2 ((PO 4 )2F 3 NaPF 6 in PC/EC/DMC C 3.6 V Need of an extra Na source.. 25% of Na losses during the first cycle Oversodiated materials (Na 3+x V 2 (PO 4 ) 2 F 3 )??? Capacity in mah/g of NVPF

How to prepare a Na-rich phase via a sustainable approach?

4 V Na 2 (PO 3+x V 2 (PO 4 ) 2 F 2 F 3 (New phase) 3

Assembly of 18650 Na-ion cells for benchmarking against

12 How to prepare a Na-rich phase via a sustainable approach? Synthesis via ball milling Na 3 V 2 (PO 4 ) 2 F 3 + Na Na 4 V Na 2 (PO 3+x V 2 (PO 4 ) 2 F 2 F 3 (New phase) 3 Electrochemical performance Milling time = 2hours separator NVPF % "Na 3+x V 2 (PO 4 ) 2 F 3 composite s (3<x<4) Assembly of Na-ion cells for benchmarking against Li-ion B. Zhang et al. Nature communications Volume: 7, ( 2016) Patent: B. Zhang et al. N de dépôt : EP

Discharge capacity (Ah) Disharge capacity

cells at 1 C Power rate of C/NVPF Na-ion

restituted at 100C 0 0 500 1000 1500 2000

13 Discharge capacity (Ah) Disharge capacity in % The Na 3 V 2 (PO 4 ) 2 F 3 /C technology: First prototypes (105Wh/kg) Cycle life of C/NVPF Na-ion cells at 1 C Power rate of C/NVPF Na-ion cells Cycle life of Na-ion cells at 1C rate 4000 cycles 75% of the capacity restituted at 100C Cycle number C rate Poor 55 C cycling and self-discharge performances

life & One week self-discharge of NVPF/C at 55 C 4.5 New electrolyte formulation 4.0 3.5 11th 15th 20th 3.0 2.5 2.

14 Cell voltage (V) G. Yan and J.M. Tarascon : Patent W3016-GPS2017 Capacity retention (%) The Na 3 V 2 (PO 4 ) 2 F 3 /C technology: 55 C cycling & self discharge Cycle life & One week self-discharge of NVPF/C at 55 C 4.5 New electrolyte formulation th 15th 20th Capacity (mah g -1 based on NVPF mass) Cycle number 55 C at C/10 One week at 55 C Capacity (mah g -1 ) Wh/kg ~ 3000 cycles 80 % at 10C 55 C storage

15 What could be tomorrow s battery research Basic problems emerging from concrete technological challenges

C. Grey and J.M. Tarascon, Nat. Mater. 2016, 16, 45 56.

16 C. Grey and J.M. Tarascon, Nat. Mater. 2016, 16, Looking ahead: New research challenges Business players change today s traditions Cost per kwh = [ Chemistry/ Battery Material performance+ Volume ] of stored energy production+ second life Better traceability E. Musk: (100 $ kwh in 2025) Establish the state of health record of the battery just like for humans Efforts towards instrumental miniaturization for real time monitoring of the batteries in the field

17 C. Grey and J.M. Tarascon, Nat. Mater. 2016, 16, Looking ahead: New research challenges Establish the state of health record of the battery just like for humans Develop self-healing processes Electrode recovered by an SEI (Prevents the crossing of Li + ) Libération Build self-healing contrôlée d auto-réparants processes pour into limiter the original l usure des battery tissus design d électrodes au sein (vectorization) des batteries (vectorisation) Clogged artera by cholesterol (Prevents blood circulation) Réciproquement: utiliser l énergie «humaine» (=marche) pour déclencher «à la demande» la libération d un médicament Interdisciplinary research which is still in its embryonic state

External or internal stimulation Encapsulated self-healing molecules

18 Multilayers How to tackle this issue? Innovative chemistry on the battery separator Surfacefunctionalization External or internal stimulation Encapsulated self-healing molecules Functionalization with SO 3- Nafion groups Fluorinated graphene oxide Functionalization to trap species released from side reactions

Electric mobility: Conclusions Anionic redox as a new paradigm to design electrodes with double

electrolytes innovations 150 mah/g 280 mah/g x in LiCoO 2 Li-ion batteries with ~ 20% energy

dealing with SOH batteries Development of sensing and self-healing processes via innovative

19 Electric mobility: Conclusions Anionic redox as a new paradigm to design electrodes with double capacities Development of a C/Na 3 V 2 (PO 4 ) 2 F 3 Na-ion technology via materials and electrolytes innovations 150 mah/g 280 mah/g x in LiCoO 2 Li-ion batteries with ~ 20% energy density improvements Foreseen EV future Hardware Software + services Future research challenges dealing with SOH batteries Development of sensing and self-healing processes via innovative chemistry Na-ion batteries with attractive power rate performances Foreseen battery future Materials Sensing + monitoring)

20 Acknowledgments 20

The anionic redox activity: From fundamental understanding to practical challenges

1st International Conference of Young Scientists TOPICAL PROBLEMS OF MODERN ELECTROCHEMISTRY AND ELECTROCHEMICAL MATERIALS SCIENCE September 17 th, 2017 The anionic redox activity: From fundamental understanding