Hochleistungskeramik für mobile und stationäre Batterien Alexander Michaelis Fraunhofer Institute for Ceramic Technologies and Systems, IKTS, Dresden

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1 Hochleistungskeramik für mobile und stationäre Batterien Alexander Michaelis Fraunhofer Institute for Ceramic Technologies and Systems, IKTS, Dresden Structural ceramics Functional ceramics Materials Sintering / Materials - Diagnostics and NDE (non destructive evaluation) Energy systems and life science TEG Processes and Components Additive Manufacturing 1 Fraunhofer Environmental Engineering Electronics / Smart Microsystems Industry 4.0

2 Energy and Environmental Technology at IKTS Fraunhofer IKTS

3 Take over of planar SOFC Technology from Siemens AG in 1998 Fraunhofer

4 Fuel Cell System Competence 1 W 10 W 100 W 1 kw 10 kw 1 MW portable portable portable stationary stationary hydrogen Ethanol PEFC Propane Tubular SOFC LPG Ethanol SOFC NG SOFC Biogas + NG SOFC Elektrolyse Biogas + NG MCFC Fraunhofer

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6 Erweitertes Ceragen KWK Produkt Bürgerkraftwerk Stromerzeugender Wasserspeicher mit Grundlastspeicherbatterie Optionale PV Einbindung (1 2 kw p ) Standard Gaskessel / Therme Rücklauf Heizungsvorlauf PV Strom Spitzenlastbeheizung 70 90% (Winter/Sommer) Eigenstromerzeugung -6- Grundlaststrom Warmwasser Mikro Batteriespeicher (Li Ion) inkl. Wechselrichter Ceragen Gerät mit Brauchwasserspeicher Kaltwasser business confidential

7 Technische Vorteile höherer Wirkungsgrad durch Umgehung des Motor/Generator-Prinzips => el bis zu 40 % Flexibilität hinsichtl. Brennstoffeinsatz => neben Diesel & Benzin auch LPG, CNG und EtOH möglich Technische Nachteile limitierte Leistungsdichte, begrenzte Systemdynamik Zusätzliche Produkt-Features Abwärmenutzung zur Fahrzeugbeheizung => Strom erzeugende Standheizung Haushaltsstromversorgung / Netzeinspeisung mit Elektrofahrzeug in der Garage => Reversed Plug-In Hybrid Fraunhofer IKTS - 7 -

8 Li-Ion Battery value chain Powder synthesis Slurry Mixing Electrode manufacturing Cell assembly & packaging Cell testing Powder synthesis and modification Methods for analysis and optimization of thermal process Methods for characterization of powders (FESEM, XRD; Raman; thermal properties; particle size ) Development of an adapted slip compositions for the coating process Sophisticated methods of slurry characterization and optimization Efficient methods for slurry mixing Development of technologies for coating of electrode films Material and electrode characterization Sophisticated spectroelectrochemical characterization (impedance, Raman, ) Electrical and thermal characterization of commercial cells Stationary and dynamic modeling of battery cell performance Fraunhofer IKTS

9 Ceramic technology determines performance of batteries g kg Tap density Capacity Processing Discharge current Cycle stabilty Power density Life time Safety 9 Fraunhofer IKTS

10 Electrochemical characterization of materials and films Electrochemical tests of cathode materials (capacity, cycling capability, cell voltage, impedance, ) Vibrational spectroscopic measurement methods for electrolyte systems and electrodes (IR, Raman spectroscopy) IR spectrometer with ATR setup i / macm Redox couple of LiCoO 2 E Redox = 3,95 V vs. Li/Li + micro capillary CE RE particle -1 3,0 3,5 4,0 4,5 potential E Li/Li + / V i-raman WE substrate Fraunhofer IKTS

11 Fraunhofer

12 Heat generation in LIBs Isolation Anode Separator Kathode Measurement setup for microscopic in-operando Thermography Isolation In-operando cell build at IKTS Specifications: - T resolution: 0.025K - x resolution: 0.005mm Local heat generation rates Heat evolution mechanisms C Heubner, C Lämmel, N Junker, M Schneider, A Michaelis, Electrochemistry Communications 48 (2014) C Heubner, M Schneider, C Lämmel, A Michaelis, Electrochimica Acta 186, Fraunhofer

13 3D nanostructured high-energy electrodes Anodizing Preparation Deposition Removal Al Al Al 1.0 i = 150 ma g -1 Li 7 Sn 3 LiSn E [ V ] 0.5 Li 7 Sn 2 Li 22 Sn 5 Al-oxide Ti-oxide graphite 3D Sn Capacity [ mah g -1 ] Fraunhofer

14 Efficient manufacturing methods for high-performance lithium ion batteries: From Lab. to Fab. Pilot scale production of Li-Ion-Batteries since 2012 Development of optimized manufacturing methods along the entire value chain of lithium ion cell production Slurry mixing Electrode manufacturing Cell assembly + packaging Cell testing Battery assembly IKTS TKSY 14 Fraunhofer

15 Example: Electromobility Tesla Model S Ca. 500 km Reichweite 96 Zellen je 60 Ah ~ 8000 Zellen je 3,4 Ah BMW i3 150 km Reichweite Fraunhofer IKTS -15-

16 LiNi 0,5 Mn 1,5 O 4 /Li 4 Ti 5 O 12 Bipolar battery Fraunhofer IKTS -16-

17 IKTS competences electrolyte/separator Overview Liquid electrolyte Polymer electrolyte Ceramic all solid state electrolyte non ion conducting polymer separator non ion conducting ceramic separator gel electrolyte (liquid electrolyte in polymer matrix) ion conducting polymer electrolyte polymer electrolyte + non ion conducting ceramic components non ion conducting polymer + ceramic electrolyte particles all ceramic electrolyte Celgard 2500 Litarion 1 µm 1 µm 1 µm Investigation of wetting properties Al 2 O 3 Polymer electrolyte infiltrated LTO-electrode Free standing polymer electrolyte with ceramic nanoparticles Tape of polymer filled with Li conductive particles Tapes of sintered ceramic made of Li conductive powder LiFe PO 4 Development of ceramic separator coatings on top of the electrode; Free standing separator foils Characterization Hebb- Wagner- Polarization Impedance spectra, ionic conductivity Electrical conductivity - strictly confidential - Fraunhofer

18 Solide state electrolytes Li ion conductive separator and solid slectrolyte Ceramic all solid state electrolyte Polymers Sulfides Oxides PEO polymer chain Li + Li + Li + T. Niitani, et al., Electrochemical and Solid- State Letters 8 [8] A385-A388 (2005). + Good processibility and flexibility - low ionic conductivity ( S/cm) - low mechanical stability A. Sakuda, et al., Scientific Reports 3, 2261 (2013). + high ionic conductivity ( S/cm at RT) - high hygroscopicity - low mechanical stability Y. Ren et al., J. Am. Ceram. Soc. 98 [12] (2015). + good ionic conductivity (< 10-3 S/cm at RT) + stable against air and high temperatures Fraunhofer - strictly confidential -

19 Ceramic composite electrolytes Ceramic all solid state electrolyte From synthesis of Li conductive particles to composite electrolytes Powder preparation Sol-Gel Synthesis Melting and Quenching Powder processing Powder characterization Particle Size Morphology Phase Analysis Powder processing Dispersing in Polymer Tape Casting Fraunhofer - strictly confidential -

20 ZEBRA Hochtemperaturbatterien - Historie NaNiCl: 1987 NaNiCl: 1991 NaNiCl: Fraunhofer IKTS - confidential -

21 Na/NiCl 2 solid state electrolyte batteries for stationary applications Operation principle (Zebra) NiCl 2 + 2Na Ni + 2NaCl, E 0 = 2,58 V Electrolyte Na-ß -aluminate (ceramics) Cathode: Ni, common salt (NaCl), NiCl 2, NaAlCl 4 Anode: Na (melt) Operation temperature: C - + lid (Al2O3) case electrode Na + Ni NaCl NaAlCl 4 NiCl 2 Na-ß -aluminate Na 21 Fraunhofer IKTS - confidential -

22 Material costs: NaNiCl (long run marginal costs) source: Fiamm 52 $ Ni-prize $ 22 Fraunhofer IKTS - confidential -

23 reduction of production cost by factor 10 Isostatic pressing (conventional technology) costreduction: factor 10 Extrusion System development 23 Fraunhofer IKTS

24 Stationäre Speicherung: Es gibt nicht DEN einen Speicher Leistungsspeicher Sekunden bis Minuten Netzdienstleistungen Regelleistung Einsatz mehrmals pro Tag Batterien, Kondensatoren Verschiebespeicher Minuten bis Stunden Ausgleich innerhalb eines Tages EE-Eigenverbrauch ein bis zwei Zyklen pro Tag Batterien, Druckluftspeicher, PSW 24 Fraunhofer IKTS - confidential -

25 Batterie - Technologie-Roadmap IKTS RCC-40; 40 Ah Keramische Natrium-Batterie CERES / cerenergy große, vollkeramische Na-NiCl-Batterien (stationär) TRL 5 TRL 7 TRL 8 QuantumScape (VW) Innovationsgrad / Disruption Keramischer Festelektrolyt Polymerer Festelektrolyt Flüssiger Elektrolyt TRL 5 EMBATT1.0 großflächige Bipolarbatterie basierend auf konv. Lithium-Batterietechnik TRL7 Keramische Festkörperbatterie Lithium-Batterietechnik basierend auf vollständig anorganischen Komponenten TRL 1 TRL3 TRL5 TRL7 EMBATT2.0 großflächige Bipolarbatterie basierend auf polymeren Elektrolyten in Lithium-Batterietechnik TRL 2 TRL3 TRL5 TRL7 Konventionelle Lithium-Ionen-Technik Seeo (Bosch) Fraunhofer - Vertraulich -

26 Advanced Ceramics for product innovations at IKTS MATERIALS AND PROCESSES ENVIRONMENTAL ENGINEERING MECHANICAL AND VEHICLE ENGINEERING NDE BIO- AND MEDICAL TECHNOLOGIES ELECTRONICS AND MICRO SYSTEMS OPTICS ENERGY MATERIAL- AND PROCESS ANALYSIS 26 Fraunhofer