Innovative Materialien für Batterien der nächsten Generation

Transcription

1 Innovative Materialien für Batterien der nächsten Generation Dr. Andreas Fischer Vice President Battery Research and Electrochemistry BASF SE, Ludwigshafen 4. SEC 2012 Bad Dürkheim

2 Overview Batteries for Mobile Application Batteries for Stationary Application 2

3 Overview Batteries for Mobile Application Batteries for Stationary Application 3

4 Global Challenges require new concepts Growing population Urbanization Energy demand & climate protection MEGATRENDS New concepts for Mobility Globalization & Developing Markets Energy efficient Low emission Affordable Suited for daily use 4

5 CO 2 emission by propulsion concept Potentials for optimization Gramm CO 2 per Kilometer Electromobility ICE today ICE optimzed EV Electricity from hard coal EV Electricity German energy mix EV Electricity from renewables Assumption energy demand: 4,5 l/100 km ICE today, ICE optimized -20%, 18 kwh/100 km Source: Studien UBA, Agentur für Erneuerbare Energien, BMU, IES, Stand: 9/

6 The way to electromobility Measures Cheap renewable energy Development of efficient green technologies (wind, solar, etc.) Optimized grid integration Flexible energy storage New stationary storage systems (Batteries ) Utilization of car batteries for storage Smart and stable grids Grid expansion Grid management Low-loss transmission Competitive Electric Vehicles Development of affordable high-performance battery technologies Energy efficient comfort elements and materials 6

7 Improved Battery Technology Battery as key components in electric vehicles Materials Components Cells Batteries Electric Car The battery determines characteristics of an electric vehicle Range, Costs, Safety, The battery allows for differentiation and value creation Challenging technology and chance for chemistry / engineering / OEMs Materials are the heart of the battery cell Chemistry plays a central role as materials supplier 7

8 Improved Battery Technology Contributions of BASF Goals: higher energy density, safety, and life time at lower costs APPROACHES Improved materials for components and cells Continued improvement of the Li-ion technology and development of new battery concepts ONGOING ACTIVITIES International Research Network with renowned scientists and comprehensive industry consortia Building a production plant for cathode materials Work on new generations of cell chemistry 8

9 Comparing different battery technologies Power versus energy Specific Power (~Torque), W/kg Li-Ion Pb-Acid Ni-Cd Ni-MH Specific Energy (~Driving Range) Wh/kg 9

10 Lithium ion batteries Working principle charging Graphite Anode e - Metal oxide cathode 4.3 O V O O LiPF 6 Li + O O Li + containing Electrolyte O e - e - e - e - + e - e - e - e - 6 C + xe - + xli + Li x C 6 LiMO 2 Li (1-x) MO 2 + xe- + xli q 10

11 Lithium ion batteries Working principle discharging Graphite Anode A e - Metal oxide cathode e - e - e - e - e - e - e - e O V O O LiPF 6 Li + containing Electrolyte Li + O O O + Li x C 6 6 C + xe - + xli + Li (1-x) MO 2 + xe- + xli + LiMO q 11

12 Lithium ion batteries Cross section and schematic set up + Al current collector (18-25 µm) cathode ( µm) <0.5 mm separator (16-35µm) graphite anode ( µm) - Cu current collector (12-20 µm) 12

13 From raw material to lithium ion batteries Preparation steps Synthesis of cathode material Preparation of slurry Electrode coating Calendering Pouch cell preparation Electrochemical characterization NCM 20 µm 1000 : 1 13

14 Lithium ion batteries Cathode materials roadmap BASF has licensed a broad NCM Li 1+x (NiCoMn) 1-x O 2 patent portfolio from ANL. Standard NCM-111 will become first BASF product, standard voltage NCM-xyz will follow. High-Energy HE-NCM and High-Voltage HV-spinel materials as well as Li iron phosphates LFP are in the pipeline. 5 µm 5000 : 1 5 µm 5000 : 1 5 µm 5000 : 1 14

15 Metal Prices Historic Development Key Facts Metal prices dominate cathode cost Cobalt content drives total metal cost Metal prices are heavily fluctuating $/kg Cobalt Nickel Manganese

16 Chemical Composition NCM Cathodes Commercially Relevant Areas Manganese Cost Safety Lower-cost region High-stability region High-capacity region Nickel Energy Safety Cobalt Cost Lifetime 16

17 Lithium ion batteries Cathode materials with higher energy density Marked capacity increase at slightly lower voltage High Energy Discharge profiles BASF HE-NCM vs. BASF NCM-111 Voltage [V] HE-NCM Marked voltage increase at slightly lower capacity High Voltage Discharge profiles BASF HV spinel vs. BASF NCM-111 Voltage [V] HV spinel NCM NCM E = Q U E = Q U Capacity [Ah/kg] Capacity [Ah/kg] 17

18 BASF s HED TM HE-NCM vs. graphite Cycling stability in Swagelok cells Specific capacity [Ah/kg] HE-NCM NCM C, 0,5 C Cycle No. 18

19 BASF s HED TM HV-spinel vs. graphite Cycling stability in pouch cells Specific capacity [Ah/kg] Cell chemistry 2 ( modification ) Cell chemistry 1 ( additives ) Standard cell chemistry 25 C, 1.0 C 4.25V 4.80V Cycle No. 19

20 Requirements for next generation electrolytes Performance Improved energy and power density Conductivity / Rate capability Higher voltage window Low temperature behavior Long-term stability Cycle life Self discharge Safety Flammability Overcharge protection Thermal runaway Unfortunately improving one characteristic often leads to worsening another 20

21 Lithium ion batteries Cathode material and electrolyte from BASF used High cycle stability successfully demonstrated Capacity [mah/g] Efficiency [%] Cycle No Cell type: Pouch cell Cathode: NCM523 (BASF) Anode: Graphite Electrolyte: Carbonates (BASF) Charge: 4.2V, CCCV, 0.5C Discharge: 3.2V, CC, 0.5C Formation: 0.1C at 1 st & 2 nd Cycle Temperature: Room temperature 21

22 From Li-Ion to Li/S and Li/Air: The next Generation of Batteries Specific Power / W/kg Li-Ion Li-S Li-Air Specific Energy / Wh/kg BASF battery research focuses on advanced Li-Ion and next Generation systems 22

23 Lithium/Sulfur batteries Working principle Discharge e Sulfur-cathode Li + S 2- Li-anode + S 2- -ions Li + -ions e - 23

24 Lithium/Sulfur batteries Advantages and Challenges Advantages High gravimetric energy density Low cost and abundant raw materials Operability at low temperatures Challenges Cycle life yet too low Self discharge yet too high Safety must be guaranteed Fast charging capabilities are essential High potential but challenges to be solved 24

25 Lithium/Sulfur batteries Joint Development with Sion Power Corporation Sion Power is a global leader in the development of a new generation of high-energy, rechargeable lithium sulfur batteries and is located in Tuscon, Arizona. In 2009 BASF and Sion Power agreed on a joint development program on Li/S battery materials The collaboration targets the development of materials to improve Li/S batteries life and energy density 25

26 Field of work Several parts and components need further optimization and improvement 26

27 Lithium/Sulfur batteries Cathode development Evaluation of special cathode preparation techniques as spraying, doctor blading, screen printing Smoother sprayed BASF cathode Mud cracks on standard cathode New cathode additives (e.g. expanded graphites, graphenes) Graphite Expanded Graphite Micropockets for sulfur uptake 5000 : 1 5 µm Improved sulfur utilization and structural stability 27

28 Lithium/Sulfur batteries Cathode development State of the art Li/S battery with PTFE binder Capacity [mah/g] 1400 Li/S batteries with advanced BASF binder Capacity [mah/g] capacity drop ~ 20% 800 capacity drop ~ 50% Cycle No Cycle No. Higher structural stability results in better cycle life 28

29 Lithium/Sulfur batteries Electrolyte development C a p a c it y / m A h Advanced electrolyte based on BASF materials Standard electrolyte based on DME, DOL, LiTFSI Cycle no. New electrolytes and additives for improved Li re-plating Inhomogenous Li re-plating 29

30 Lithium/Sulfur batteries Safety Safety issues At 180 C lithium and sulfur are liquid fast reaction Special protection needed Li/S batteries with BASF polymer layer Tcell-Theater [ C] Conventional design Sulfur melting Li melting Advanced design Sion-BASF Protective Layer Temperature [ C] BASF protective polymer layer enhances safety of Li/S cells 30

31 Energy efficient comfort elements and materials Examples Special requirements in EVs because of limited energy availability 1 Light weight construction e.g. fibre-reinforced composites 2 Heat management reflecting paints/shields, high performance insulating materials Energy by sun light Organic Photovoltaics 4 New lighting systems LEDs Innovative cooling systems Magneto caloric 31

32 Energy efficient comfort elements and materials light weight construction Contributions of BASF Goals: Energy saving and increased range APPROACHES Use of polymer based light weight materials Saving potential of 150 kg per car Use in several construction elements largest impact in load bearing elements like chassis ONGOING ACTIVITIES Evaluation of new material concepts and technologies Sandwichstructures, fibre-reinforced composites Use of high-performance polymers Polyamides, Polyurethanes 32

33 Energy efficient comfort elements and materials heat management Contributions of BASF Goals: Energy saving and increased comfort APPROACHES New heat relecting pigments for shields, paints and interior Use of high performance insulating materials Isolation of cabin and engine compartment EVs today up to 35% of energy demand for operation of air condition ONGOING ACTIVITIES Intense research and development on innovative pigments and new insulating materials Insulating materials Polymer foams In-cabin temperature today up to 60 C in the future C 33

34 Smart Forvision in Cooperation with BASF Technologies for the Car of Tomorrow Goals: maximum energy efficiency, longer driving range and more comfort Electrical energy efficiency Solar roof with transparent organic solar cells Transparent organic OLEDs Holistic temperature management IR-reflecting films/pigments High performance foams for insulation Multifunctional lightweight construction Lightweight ergonomically designed seats Thermoplastic polyamide wheel Go online at 34

35 Overview Batteries for Mobile Application Batteries for Stationary Application 35

36 Energy Production Worldwide Energy Mix 2007 Hydro 15.9% Solar PV 0.02% Geothermal 0.31% Wind 0.87% Nuclear 13.7% Waste 0.34% Biomass 0.96% Gas 20.8% 19,855 TWh Coal 41.4% Oil 5.6% Source: IEA Energie Statistics 36

37 Energy Production Changing the Energy Mix Bruttoleistung [GW] 200 Today: 1 / 6 fluctuating / adjustable Year 2050: 2 / 1 fluctuating / adjustable EU -Verbund EE fossil regenerativ Photovoltaik Wind an Land Wind Offshore Laufwasser Biomasse, Biogase Geothermie KWk, fossil Gas Kond. Kohle Kond. kontinuierlich fluctuating fluktuierend Adjustable regelbar Germany Kernenergie Quelle: Grafik Fraunhofer, Daten BMU Leitstudie

38 Energy production Renewables need storage Wind and solar are fluctuating and so does the energy harvest. Consumption is fluctuating as well but not accordingly. Buffer Demand Power generation Buffer Time What are alternatives to buffers: Gas peaker plants as back-up Grid expansion and distribution Steering demand by smart metering 38

39 Energy storage Options Mechanical Energy Thermal Energy Chemical Energy Electrochemical Energy Pumped Hydro Fly Wheels Compressed Air Hot Water Storage Salt Melts Phase-Change Materials Hydrogen, Methanol, Methane etc. Lithium-Ionen- Battery NaS-Battery Redox-Flow- Battery Fuel Cells

40 Energy storage Applying chemical industry technologies Advantages Efficient energy storage Low costs BASF expertise Electrochemistry Chemicals Operation of large chemical plants

41 Redox-Flow Battery Membrane Electrode + VO 2+ + H 2 O VO H + +e - V 3+ + e - V 2+ Electrolyte I Electrolyte II Pump Pump charge/discharge 1.3 Volt 3.02 kg V / kwh Source: Prof. Dr. Dirk Uwe Sauer RWTH Aachen 41

42 Sodium-Sulfur Battery Load Discharge 2Na 2Na + + 2e - Source / + Charge + 2Na + + xs + 2e - Na 2 S x Na Na + S Na 2 S x e Terminal(-) Na-Electrode Solid Electrolyte β -Alumina S Electrode Terminal(+) 2.06 Volt kg Na / kwh Source: NGK Insulators Ltd. 42

43 Sodium-Sulfur Battery High temperature battery: C, ~ 100 Wh/kg Source: NGK 43

44 Sodium/Sulfur Battery - Research Topic at BASF + Sodium e - Sulfur 2Na 2Na + + 2e - Sodiumpolysulfide 2Na + + xs + 2e - Na 2 S x Separation of power and energy Modular approach, aiming at GW range 44

45 Scientific Network on Batteries Joining forces with academia Task academic partners in the network Fundamental evaluation of system and components Development of a mechanistic understanding of the interaction of components and materials Syntheses of materials Specific analytics for batteries Task BASF in the network Coordination of all work-packages in the network Extending the network into BASF Benchmarking Adoption of respective materials to the system Extensive testing options for cells and components Scale-up 45

46 Scientific Network on Batteries Partner Prof. Jürgen Janek, University of Gießen, GER Prof. Hubert Gasteiger, Technical University of Munich, GER Prof. Petr Novák, PSI Villigen, CH Prof. Doron Aurbach, Bar-Ilan University, ISR Prof. Brett Lucht, University of Rhode Island, USA Prof. Linda Nazar, University of Waterloo, CAN Further partners about to be identified 46

47 Joint Lab BASF / KIT Batteries and Electrochemistry Laboratory Ten scientists working jointly on the development of materials and components for next generation of batteries First projects related to ceramic ion conductors as electrolytes and protecting layers for advanced battery systems Scientific supervisors are Prof. J. Janek and Dr. A. Fischer The Joint Lab is having 361 m² lab and office space located at KIT Campus North All costs of about 12 million Euro over 5 years are shared equally by BASF and KIT The Joint Lab is part of the scientific network on batteries of BASF 47

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