Progress and Challenges: Generation 3b Tobias Placke

Transcription

1 Progress and Challenges: Generation 3b Tobias Placke Division Manager, Materials Division, MEET Battery Research Center (University of Münster)

2 Progress and Challenges: Generation 3b Dr. Tobias Placke MEET Battery Research Center Prof. Dr. Martin Winter Helmholtz Institute Münster European Union, 2017

3 Outline Introduction and Motivation Definition of LIB Generations and State-Of-The-Art Cell Chemistry Advanced Lithium Ion Technologies ( Generation 3b ) Promises and Challenges of Advanced Materials Research Gaps and Need for R&I Activities Conclusions 2

4 Motivation for Battery Research 2018: 1991: The demand as well as the economic and social importance of rechargeable batteries increases rapidly (electronics, mobility, home storage, etc.) Versatile requirements: Significant diversification of battery technologies in the past 25 years [1] Placke, T.; Kloepsch, R.; Dühnen, S.; Winter, M., J. Solid State Electrochem. 2017, 21, (7),

5 Lithium ion battery sales / MWh Worldwide Rechargeable Battery Market Others Industrial Automotive worldwide Electronic devices others: power tools, gardening tools, e-bikes, medical devices, etc. cell level Global market for LIBs in xevs and energy storage applications is huge xev market will be the largest in the near future Year [1] Pillot, C., The Rechargeable Battery Market and Main Trends Talk at the Advanced Automotive Battery Conference (AABC) Europe, Mainz

6 Technological Roadmap of Battery Cell Chemistries Generation 5 Generation 4 Generation 3b Generation 3a Generation 2b Generation 2a Generation 1 Li/O 2 (lithium-air) All-solid-state with Li metal anode; Conversion materials (Li/S) Cathode: HE-NCM, HVS Anode: Silicon/carbon Cathode: NMC622 to NMC811 Anode: Carbon + Si (5-10%) Cathode: NCM523 to NCM622 Anode: 100% Carbon Cathode: NCM111 Anode: 100% Carbon Cathode: LFP, NCA Anode: 100% Carbon Evolutionary development New cell chemistry: Li metal Technology Different battery technologies will be transition available at the market in parallel Application-specific usage of different battery systems (e.g. high energy vs. high power) Evolutionary development of each specific battery technology Classification of battery technologies: Lithium ion systems Lithium metal systems Other/alternative battery systems (Na, Mg, Ca, Al, etc.) Advanced lithium ion cells Lithium ion cells First application date in EV [1] Adapted from: Nationale Plattform Elektromobilität (NPE), Roadmap integrierte Zell- und Batterieproduktion Deutschland, ) Risk of earlier market entrance 5

7 Energy density (Wh L -1 ) Specific energy (Wh kg -1 ) Performance Targets: Energy Density * * [1] [2, 3] Physicochemical limit: 400 Wh/kg, 800 Wh/L energy density specific energy *: pack level 100 Cylindrical lithium ion cells Year 50 0 [1] Andre, D.; Kim, S.-J.; Lamp, P.; Lux, S. F.; et al., J. Mater. Chem. A 2015, 3, [2] Placke, T.; Kloepsch, R.; Dühnen, S.; Winter, M., J. Solid State Electrochem. 2017, 21, (7), [3] Janek, J.; Zeier, W. G., Nature Energy 2016, 1,

8 Performance Targets: Energy Density Volume-critical applications cell level Wh/L [1] [2] Wh/L = Wh/kg Weight-critical applications [1] Placke, T.; Kloepsch, R.; Dühnen, S.; Winter, M., J. Solid State Electrochem. 2017, 21, (7), [2] Fraunhofer-Allianz Batterien, Entwicklungsperspektiven für Zellformate von Lithium-Ionen-Batterien in der Elektromobilität,

9 Cost Targets Costs of lithium ion batteries decrease continuously (on cell and pack level) and will reach soon the target value of 100 /kwh at pack level to achieve cost competitiveness with internal combustion engine-driven vehicles /kwh cell level [1] Current battery costs: /kwh at cell level and /kwh at pack level (which strongly depends on the cell chemistry used) Main cost reduction drivers: Manufacturing and production improvements (increasing yield, higher throughput rate, decreasing material cost per kwh, etc.) /kwh module level [1] Fraunhofer-Allianz Batterien, Entwicklungsperspektiven für Zellformate von Lithium-Ionen-Batterien in der Elektromobilität,

10 State-of-the-Art LIB Materials: Cathodes NCM111 (Gen2a) NCM523 (Gen2b) NCM622 (Gen2b-3a) Increasing nickel content Increasing capacity NCM811 (Gen3a) NCM910 (Gen3a/b) Ni: 33% Co: 33% Mn: 33% Ni: 50% Co: 20% Mn: 30% Ni: 60% Co: 20% Mn: 20% Ni: 80% Co: 10% Mn: 10% Ni: 90% Co: 10% Mn: 0% NCM523 and NMC622 can be considered as state-of-the-art materials for xev applications NCM811: short/medium-term goal for EV applications [1] Noh, H.-J.; Youn, S.; Yoon, C. S.; Sun, Y.-K., J. Power Sources 2013, 233,

11 State-of-the-Art LIB Materials: Anodes Carbonaceous materials: Synthetic (SGs) and natural graphites (NGs) as well as amorphous carbons Cost: 8 $/kg for NG and 13 $/kg for SG (2016) EV applications: SGs show - compared to NGs - outstandingly high levels of purity and less fluctuating quality Often, mixtures of amorphous and graphitic carbons are used to optimize the P/E-ratio Currently, only some commercial cells (e.g. Panasonic) use silicon (SiO x ) in small amounts (few wt.%) [1] Pillot, C., The Rechargeable Battery Market and Main Trends Talk at the Advanced Automotive Battery Conference (AABC) Europe, Mainz

12 Potential vs. Li/Li + [V] Promises of Generation 3b Cathode Materials Motivation: Energy density [Wh/L] L F P L N M O N M C N C A L R N M C Li 2 S Si/C Si LiC 6 Li LNMO: High-voltage spinel (HVS; LiNi Mn 1.5 O 4 ) LRNMC: Li-rich NMC Volumetric Capacity[mAh/cm 3 ] (HE-NMC; x LiMO. 2 1-x Li 2 MnO 3 v Volumetric energy density [Wh/L] is of higher importance for mobile applications than specific energy [Wh/kg] With respect to cathodes: - High capacity - High redox potential - High material density [1] Placke, T.; Kloepsch, R.; Dühnen, S.; Winter, M., J. Solid State Electrochem. 2017, 21, (7),

13 Promises and Challenges of HE-NCM Cathodes Two-phase composite material: x LiMO 2. 1-x Li 2 MnO 3 cationic and anionic (O 2- / O 2- ) redox contribution Advantages High capacity and energy Good thermal stability Low cost material LiMO 2 M = Mn, Ni, Co >300 mah/g (!) Disadvantages/Challenges Limited cycle life Voltage decay (gradual phase transformation to spinel) Lower material density Low initial Coulombic efficiency (electrochemical activation) Li 2 MnO 3 [1] Li, J.; Kloepsch, R.; Stan, M. C.; Nowak, S.; et al. J. Power Sources 2011, 196, (10),

14 Promises and Challenges of High-Voltage Spinel (HVS) High-voltage spinel LiNi 0.5 Mn 1.5 O 4 (LNMO ) Ni 2+/4+ redox plateau at 4.7 V Mn exists almost exclusively as Mn 4+ LiO 4 NiO 6 MnO 6 [1] Advantages High operating voltage Fast lithium diffusion Low cost material Over-lithiated spinel might be used as pre-lithiation agent Disadvantages/Challenges Low practical capacity (140 mah/g) Capacity fading at elevated temperatures (60 C) Need for high voltage electrolytes and stabilization of electrode/electrolyte interface [1] Patoux, S.; Daniel, L.; Bourbon, C.; Lignier, H.; et al. J. Power Sources 2009, 189, (1),

15 Amount of elements on earth's crust (wt.%) Costs of raw materials (USD lb -1 ) Capacity (mah g -1 ) Capacity (mah cm -3 ) Promises of Generation 3b Anodes: Silicon/Carbon ,5 26,0 25,5 25,0 4,75 4,50 4,25 4,00 0,020 0,015 0,010 0,005 0,000 (a) (c) Gravimetric Capacity C Sn Ge Si ZnFe 2 O 4 Abundance C Sn Ge Si Zn Fe Why Silicon? (b) (d) Volumetric Capacity C Sn Ge Si ZnFe 2 O 4 Costs 5 year price range Lowest price Highest price C Sn Ge Si Zn Fe Gravimetric and volumetric energy densities of LIB electrode stacks: [1] [1] Placke, T.; Kloepsch, R.; Dühnen, S.; Winter, M., J. Solid State Electrochem. 2017, 21, (7),

16 Challenges and Strategies for Si-Based Anodes High volume changes during lithiation/de-lithiation Pulverization/ cracking of Si particles Contact loss of particles from electronically conductive network or current collector Instability of solid electrolyte interphase (SEI): Breakage and re-formation High active lithium losses by continuous electrolyte decomposition (low Coulombic efficiency) Strategies Active/inactive matrix concept (nano-si in inactive matrix) - Si/Carbon composite materials - Si/intermetallics/carbon composite materials 3M approach: [1] [1] ] Kaiser J., 3M, Talk at the Batterieforum Deutschland, Berlin,

17 Need for R&I Activity: Advanced Materials Development of advanced Gen3b cathode materials (Ni-rich NCM and HE- NCM, HVS, protective coatings for safety improvements, gradient materials, etc.) Development of Si/C anode materials (Si 5 wt%) and strategies for stabilization, e.g. concepts for pre-lithiation Development of high voltage electrolytes and electrolyte additives for interphase stabilization (SEI, CEI) at the electrode/electrolyte interfaces and safety improvements Development of suitable inactive materials (binders, conductive carbons, current collectors, separators e.g. ceramic coated membranes) for high capacity and high voltage ( 4.5 V) systems Development of advanced processing technologies for the above 16

18 R&I Actions along the Battery Value Chain Development of advanced electrode and cell/module designs and formats to maximize the energy content while ensuring a high power density and safety Development of advanced processing/production routes for novel materials (e.g. aqueous processing, solvent-free processing, conductive binders, etc.) Strategies for recycling and/or 2 nd life of batteries Focus on sustainability (materials, etc.), CO 2 -footprint (energy-efficient processes, etc.) and smart batteries (sensing technologies, etc.) [1] ] Schmuch, R.; Wagner, R.; Hörpel, G.; Placke, T.; Winter, M., Nature Energy 2018, submitted. 17

19 Conclusions (European View) Roadmaps have identified the dominant technology for the next decade(s): LIB (with or w/o solid electrolyte). Sustained and/or increased R&I efforts are needed to underline competitive manufacturing. There is a lack of know-how in large scale manufacturing, not in proposing alternative ( beyond ) cell technologies. A closed value chain on the large scale is needed and has to be verified with LIB first. Development of advanced active and inactive materials, manufacturing processes and cell concepts in terms of improved performance, costs, safety and sustainability would pave the way for competitive and resilient manufacturing capabilities. Against common believe in the past, there is enormous room for more LIB cell manufacturing, as the demand will be tremendous see: Eastern Europe, where at the moment large cell production facilities are set-up. Against common believe in the past, there is still room for internationally competitive large scale cell-makers see: China, who is in the stage of becoming the 3 rd large cellmanufacturing country after Japan and Korea. 18

20 Contact: Thank you for your attention! MEET Battery Research Center University of Münster & Helmholtz-Institute Münster FZ Jülich GmbH Corrensstr Münster, Germany Prof. Dr. Martin Winter Dr. Tobias Placke Nothing great was ever achieved without enthusiasm. Ralph Waldo Emerson, American Philosopher 19

21 Break-out Sessions Session 1 ( ; 09:00-11:00 & 11:30-12:30, Room 0B): Advanced Lithium-Ion Technologies (Generation 3b) Chaired by Josef AFFENZELLER (AVL) Maximilian FICHTNER (Helmholtz-Institute Ulm) 20