STABLE Description WP3 LEITAT– January,2013 Synthesis and optimization of electrolyte of Li-air cells David Amantia Christophe Aucher LEITAT STABLE WP3 organization January, 2013

STABLE Description WP3 LEITAT– January,2013 Overview Information available from page 6 to 51 of Annex I Work package numberWP 3Start date or starting event: M32 Work package titleSynthesis and optimization of electrolyte of Li-air cells Activity TypeRTD Participant id POLITO LEITAT LUREDERRA IVF UCC SAU CEGASA ELAPHE Person-months per beneficiary: Start date or starting event: M1 End date: M32

STABLE Description WP3 LEITAT– January,2013 Overall goals Information available from page 6 to 51 of Annex I Objectives  - Synthesis and characterization of stable electrolyte with low viscosity and high oxygen solubility to increase the discharge current density.  - Synthesis, characterization and evaluation of the performance of the electrolyte with different additives in terms of their effect to volatility, viscosity and conductivity of electrolyte.  - Determination of the most suitable lithium air battery materials and technology for the use in EVs.

STABLE Description WP3 LEITAT– January,2013 Objective Work will be focused on: - the preparation/characterization of IL/solvent/additives/salt melts - studies on SEI - Optimization of PC/EC/DEC/DMC melts - Build new ILs by ions exchange from conventional RTILs or other precursors. - Additives for by-products and oxygen solubility Challenge = reach the best ratio between: Conductivity (& viscosity, temperature) ↑ Solvent evaporation ↓ Electrolyte quantity Oxygen & by-product solubility ↑ Water content ↓, Hydrophobicity ↑ Electrochemical windows ↑ Stability (cycling) ↑ Safety ↑

STABLE Description WP3 LEITAT– January,2013 Filling amount Objective Commercial solution Price Water content Conduc tivity Viscosity Oxygen solubility Stability By- product solubility Solvent Evapor ation EE Safety New Electrolyte Bibliographic survey Most of these parameters could be evaluated by a simple survey of the previous works or by comparison of the technical data sheets for the commercial products. Will we be able to upscale the quantity? Candidates Physical and chemical characterization There is an interest to not use a commercial solution ? Candidates Electrochemical characterization Final confrontation between commercial and innovative solution (performances) yes No

STABLE Description WP3 LEITAT– January,2013 Workplan Information available from page 6 to 51 of Annex I  Task 3.1: Synthesis and optimization of room temperature ionic liquids (RTILs) or combinations solvents properties for the aim of obtaining good performance electrolyte solvents (Month 1- Month 32, POLITO (14 MM), LEITAT (12 MM) and CEG (6 MM)).  Task 3.2: Investigation on influence of aprotic additives to RTILs on properties and oxygen solubility etc. (Month1- Month 32, 8MM, SAU).  Task 3.3: Investigation and evaluation of physical properties of RTILs and the optimum filling amount of electrolyte. Material and production techniques analysis including LCA (Month 1- Month 32, LEITAT (8MM), LUREDERRA (6MM), Elaphe (2MM)) Milestones (M7, M8, M9) Deliverables (D3.1, D3.2, D3.3)

STABLE Description WP3 LEITAT– January,2013 Organization (proposition) Task 3.3 Task 3.2 Task 3.1 PC/DEC/EC RTILs (melts preparation) Additives 1) electrolyte 2) LISICON modification Additives RTILs (characterization) Database Repport (template proposed: (1) State of the art SoA, (2) Beyond SoA, (3) Table comparative) All technical data (numbers), Price, Safety, Other… Synthese & Physical/Chemical Characterizations Battery Samples water content, purity (ions contents), conductivity, thermal properties (volatility, degradation, Mp, Bp…), O 2 solubility, viscosity, Other… SamplesUp scaling Electrochemical windows, Capacity, EIS, rate of charge/discharge, energy & power density, Stability (cycling), By-product solubility, Filling amount, gas (nature, flow), Price, SEI, Other… Melts Preparation. To complete a database by studying always the same parameters. Exchange between partners to lead to the complete evaluation of the samples depending of the skill/equipment availabilities. (dry/glove box, potentiostat, karl fisher, ionic chromatography, reference cell, cell pack…) Lab scale Cegasa, Polito, Leitat ? Input (Material, production, Power&Energy needs…) M24 M7 M12 M7 EV Lab scale M24 Samples transfert Feedback ?

STABLE Description WP3 LEITAT– January,2013 Deliverables Information available from page 6 to 51 of Annex I D3.1) Electrolyte solvent synthesis and optimization (I): Report on description of preparation and characterization of lithium air battery electrolytes: 1) Preparation and characterization of salt and different compositions of ionic liquids with physical and chemical specifications; 2) Preparation and characterization of suitable additives or fillers to RTILs; 3) Investigation of suitable conditions for electrolyte such as filling amount and environment impact specifications such as temperature and pressure etc. [month 12] D3.2) Electrolyte solvent synthesis and optimization (II): Report on description of improvement on performance of produced lithium air battery electrolytes: 1) Optimization of the physical properties and electrochemical performance of the produced electrolytes such as viscosity and ion conductivity through adding suitable additives. Electrolyte will be analyzed by Raman spectroscopy after subjecting the anode to the electrolyte with different times, oxygen solubility will also be tested; 2) Optimization of the salt and different compositions for ionic liquids; 3) Determination of suitable conditions for electrolyte such as filling amount and environment impact specifications such as temperature and pressure etc. [month 24] D3.3) Conclusion on electrolyte solvent synthesis and optimization: Report on description of assessment on the prepared electrolytes in terms of physical and electrochemical performances: 1) Selection of optimum additives for electrolyte; 2) Selection of optimum electrolyte compositions with good physical specification (i.e. conductivity versus temperature, electrochemical windows, viscosity versus temperature); 3) Obtaining the optimum physical conditions for electrolyte. [month 32]

STABLE Description WP3 LEITAT– January,2013 Deliverables Information available from page 6 to 51 of Annex I TitleDescriptionDate D1.1Electrolyte solvent synthesis and optimization (I): Report on description of preparation and characterization of lithium air battery electrolytes: 1) Preparation and characterization of salt and different compositions of ionic liquids with physical and chemical specifications 2) Preparation and characterization of suitable additives or fillers to RTILs 3) Investigation of suitable conditions for electrolyte such as filling amount and environment impact specifications such as temperature and pressure etc. M12

STABLE Description WP3 LEITAT– January,2013 Proposed deadlines M7 – April 2013: Reports (SaO, specifications, parameters...) First synthesis or melts preparation First characterizations (chemical, physical) M24 – septembre 2014: First pack cells M12 – September 2013: First complete experimental specifications (e.g. All: chemical, physical and electrochemical tests)

STABLE Description WP3 LEITAT– January,2013 Thank you for your attention

STABLE Description WP3 LEITAT– January,2013 Synthesis and optimization of electrolyte of Li-air cells  Leitat Toolbox DesignationUtilityEquipment Glove boxRate of O 2 and H 2 O > 0.1 ppm 1) Preparation of the electrolyte (i.e. salt of lithium+ solvent.) 2) Assembly of the electrochemical cell 3) Electrochemical test inside the glove box (Electrolyte electrochemical Windows) Glove Box UNILAB (4 gloves) ICIonic Chromatography Cl -, BF 4 -, TFSI -, TFO -, PF 6 -, NO 3 -, CH 3 COO -, NH 3 - … (detection limit = 0,1 ppm – 10 ppm) Dionnex ics 300 Sample charger As-DV Karl FisherHigh precision for the determination of the water content. 10 – 1000 µg, ± 3 µg Coulometer KF 831 Potentiostat / Galvanostat 2 potentiostat / galvanostat are available for testing, (1) electrolyte (conductivity, O 2 reduction, potentials windows) and (2) complete cell in a Swagelok system where the purity and gas pressure could be controlled. VMP3 Autolab TGAThermal Gravimetric Analyze Conventional method for determining the temperature of the degradation of the solvent and the water content. TGA Q500 DSCDifferential Scanning Calorimeter Conventional method for determining the physical properties of the solvent (melting, freezing points…) DSC Q20 FTIRFourier Transform InfraRed spectrophotometer Conventional method for determining the nature of the different bonds. IRAffinity-1 ConductimeterConventional method for determining the conductivity of the solvent and electrolyte. Possibility for checking the conductivity at different temperature. Ec-Meter Basic 30+ Titanium cell for viscous liquid and Platinum cell for conventional liquid. ViscosimeterConventional method for determining the viscosity of the solvent and electrolyte. Possibility for checking the viscosity at different temperature. Brookfield LV DV-E Vicometer LV spindle set (from 61 to 64)