1. electrochemistry National Aeronautics and Space Administration www.nasa.gov Point of Contact: Tom Miller Email: thomas.b.miller@nasa.gov Phone: 216-433-6300 NASA Glenn Research Center – RPC Branch Introduction Saft America, Inc. is the Industrial Partner for the "Advanced Lithium-Based Chemistry Cell Development“ Battery Development Contract NNC09BA04B. Saft America, Inc. is responsible for the screening and scale-up of battery cell component materials developed via a combination of NASA in-house and NRA contracted efforts; the fabrication and delivery of evaluation cells; and the design, fabrication and delivery of advanced High-Energy (HE) and Ultra-High-Energy (UHE) flightweight Lithium-ion (Li-Ion) cells for Extra Vehicular Activity (EVA), Altair Ascent Module and Lunar Surface System customers. High Energy Cell Primary technology for Lunar Surface Systems Mobility Systems Back-up technology for EVA and Altair Deliver TRL 4 cells by 2012 and TRL 6 cells by September 2013 Approach The ETDP Team developed screening criteria and test plans for the evaluation of the following cell components: anodes, cathodes, separators, electrolyte, and safety functional components. NASA GRC, JSC, and JPL screen the various candidate component materials developed by various sources against the Key Performance Parameters to determine their suitability for the final flightweight cells. Those candidate materials that meet minimum performance requirements are then passed on to the industrial partner. Saft America evaluates the materials for manufacturability, compatibility with the production processing equipment, and scalability to quantities required to build the DD evaluation cells. Saft America scales-up the superior materials from the small laboratory batch sizes into sufficient production level quantities to accommodate the fabrication of the lithium-ion cells. Optimization Saft America performs electrochemical component optimization to enhance the overall safety and performance of the evaluation cells. Based upon modeling relationships and component test data, various component parameters undergo optimization such as electrode substrate, substrate porosity, electrode thickness, active material source, binder and diluent additives, manufacturing methods and material composition impacts, and other cell level design parameters. Ultra-High-Energy Cell Primary technology for EVA and Altair Deliver TRL 4 cells by 2013 and TRL 6 cells by Sept. 2014 Electroactive Anode Powder (Negative) Negative Anode Ink Mixing Activation / Formation Container Welding Assembly into Container Electrolyte Filling Characterization Testing Mission Life Testing Coating Drying Calendaring Slitting/ Cutting Negative Electrode Winding Stacking Separator Positive Cathode Ink Mixing Electroactive Cathode Powder (Positive) Coating Calendaring Slitting/ Cutting Drying Positive Electrode Exploration Technology Development Program Energy Storage Project Material Assessments and Manufacturing Approaches for Advanced Lithium-ion Cell Designs Basic (34 months) Option 1 Flightweight Cell Fabrication (18 months) High Energy Cell Component screening and evaluation for manufacturing suitability Component material scale- up Electrode optimization Fabrication and delivery of evaluation screening cells Flightweight Cell Design Fabrication and delivery of 12-48 (TBR) High Energy, ~35 Ah (TBR) flightweight cells that incorporate cell-level safety components. Ultra High Energy Cell Fabrication and delivery of 12-48 (TBR) Ultra High Energy, ~35 Ah (TBR) flightweight cells that incorporate cell-level safety components. TermDefinition High Energy Cell Expected cell-level specific energy: 180 Whr/kg specific energy at C/10 and 0 o C to 3.00 Volts/cell Expected components: NASA-defined Li(Li,NMC)O 2 cathode, electrolyte, separator and Contractor proposed carbonaceous anode, where NMC= Ni,Mn,Co Targeted Performance: 2,000 cycles at 100% DOD to 80% of original capacity at C/2 Ultra High Energy Cell Expected cell-level specific energy: 260 Wh/kg specific energy at C/10 and 0°C to 3.00 Volts/cell Expected components: NASA-defined Li(Li,NMC)O 2 cathode, electrolyte, separator, and silicon-composite anode, where NMC= Ni,Mn,Co Targeted Performance: 200 cycles at 100% DOD to 80% of original capacity at C/2 Flightweight Cell ~35 Ah (TBR) cell that meets the Key Performance Parameter requirements and passes environmental acceptance and qualification tests tailored by NASA per GLM-QE-8700.2 (SARG), and CxP-70036 (CEQATR) to meet TRL 6 MethodPurpose X-ray DiffractionEstablish crystalline pattern, unit cell and density of material Confirmation of Chemical Composition Wet chemical method, characterizing particle size distribution (PSD), BET surface area, EDAX and scanning electron microscope (SEM) images Tap DensityPractical consideration for manufacturing Preparation of Coated Electrode Preliminary evaluation of manufacturability and preparation for future testing Preparation of half-cells vs. Li metal Evaluation of cycling and irreversible capacity as function of cell potential at ambient and 0 o C Preparation of full cellsEvaluation of capacity, cycling and rate capability at ambient and 0 o C Coupon testing of coated charged cathode Evaluate metal contamination in a practical cell at ambient and 40 o C using atomic absorption (AA) MethodPurpose Confirmation of Chemical Composition Wet chemical method, characterizing particle size distribution (PSD), BET surface area, EDAX and scanning electron microscope (SEM) images Preparation of Coated Electrode Preliminary evaluation of manufacturability and preparation for future testing Preparation of half-cells vs. Li metal Evaluation of cycling and irreversible capacity as function of cell potential at ambient and 0 o C Preparation of full cellsEvaluation of capacity, cycling and rate capability at ambient and 0 o C MethodPurpose GC or HPLC confirmation of composition Establish analysis for esters Lithium analysisEvaluation of concentration Electrolyte conductivityEvaluate fundamentals of electrolyte as a function of temperature Open cup flash pointFundamental flash assessment Viscosity and Surface TensionFlow properties for filling and wetting electrodes Half cell performance versus graphite and silicon anodes Evaluation of anode performance in different electrolytes Full cell with Saft baseline chemistry Evaluate performance of novel electrolytes against Saft’s baseline chemistry design Cathode Material Screening Anode Material Screening Electrolyte Screening Battery Specific Energy Prediction Modelling Tools Spreadsheet-based battery prediction model Rapidly forecast effect of new materials and cell construction on specific energy Estimate the effects of porosity, electrode thickness, and irreversible capacity loss Provides target values for manufacturing lithium-ion components and cells Summary Significant material evaluations and screenings are necessary to select those candidates that exhibit superior performance and are likely to achieve the performance goals associated with the High Energy and Ultra-High Energy cell designs. Saft America’s evaluation of novel lithium-ion cell components provides insight associated with the manufacturing, electro-chemical compatibility, scale-up to production level quantities, and overall optimization of the lithium-ion cell design. A comparison between the modeling of selected key components (anode, cathode, and electrolyte) and the actual DD Evaluation cell performance provides confidence in determining the optimum cell attributes that lead to fabricating the TRL 6 Flightweight cells. Evaluation Cells DD Cell 10 Ah, 34 Wh 124mm L x 34 mm Ø 0.25 kg Hermitically sealed 140 Wh/kg, 325 Wh/L 34P Cell 48 Ah, 176 Wh 120mm H x 152mm L x 25mm W 0.98 kg Hermitically sealed 180 Wh/kg, 385 Wh/L