Theory-Based Development Of Safe High-Energy Batteries
Birger HorstmannTheory-Based Development ofSafe High-Energy Batteries
IntroductionWhy do we need (metal-air) batteries?G. A. Hoffman, Scientific American 215(4), 34-41 (1966). HIU 01.02.20182
IntroductionLithium Ion Battery Applications Standard energy storage device Stationary, mobile, and portable applications27 kWh5 MWh10 kWh1 Wh500 Wh5 Wh HIU 01.02.20183
IntroductionBattery Types and Energy Densities Examples of rechargeable batteries Lithium ion (standard) Metal sulfur Metal air Metal ionAdelhelm P. et al., Beilstein Journal ofNanotechnology 6(1), 1016–1055 (2015).Clark S., Latz A. Horstmann B., Batteries,4(1), 5 (2018). HIU 01.02.20184
IntroductionMacroscopic Modelsvalidation GDEaqueous Li-O2precipitationaqueous Li-O2inhomogeneous SEILi-ion batteriesprecipitationSi-O2blend electrodesLi-ion batteriesO2 concentration / mol/m3pore-cloggingaprotic Li-O21.61.41.21.00.80.60.40.20.0discharge0SOC 100%SOC 80%SOC 60%SOC 40%SOC 20%SOC0%150300450600Cathode thickness / m750CO2 absorptionalkaline Zn-O2complexes and pHneutral Zn-O2 HIU 28/2/20155
IntroductionMesoscopic Modelssurface growthLi2O2dissolutionLi dendriteelementary kineticsO2 reductiongrowthSEIdouble layerionic liquids HIU 01.02.20186
Aqueous Zinc-Air BatteriesContent1. Introduction2. Aqueous Zinc-Air Batteries Alkaline Electrolyte Near-Neutral Electrolyte3. Lithium-Ion Batteries Growth of Solid ElectrolyteInterphase4. Conclusion HIU 01.02.20187
Aqueous Zinc Air BatteriesOverview Primary zinc-air battery commercial High specific energy (1086 Wh kg-1) Low cost High operational safety Development of zinc-air batteries Goal: electrochemical rechargeability Application: stationary energy storage Electrolytes: Aqueous alkaline Aqueous neutral Ionic liquids HIU 01.02.20188
Aqueous Alkaline Zinc Air BatteriesAlkaline Electrolyte: OverviewKOH Zn 4OH Zn OH2 4 Oe2 Zn OHg O2 1 eO2 2COe22 4 2e ZnO 2OH H2 O H2 O 2e 2OH 2OH CO2 3 H2 OAdvantages High ionic conductivity Stable discharge voltage Reliable at low currentsChallenges Carbonation of electrolyte Dendritic/mossy Zn deposition Zn passivationJ. Stamm, A. Varzi, A. Latz, B. Horstmann,Journal of Power Sources, 360, 136-149 (2017). HIU 01.02.20189
Aqueous Alkaline Zinc Air BatteriesGalvanostatic Discharge21ExperimentSimulated ZAB dischargevalidated by experiment31. Nucleation of ZnO2. Conversion reaction3. Step due toinhomogeneous ZnOprecipitation4. Voltage loss due to zincpassivation421Simulation34J. Stamm, A. Varzi, A. Latz, B. Horstmann,Journal of Power Sources, 360, 136-149 (2017). HIU 01.02.201810
Aqueous Zinc Air BatteriesAlkaline Coin Cell: Volume FractionsJ. Stamm, A. Varzi, A. Latz, B. Horstmann,Journal of Power Sources, 360, 136-149 (2017). HIU 01.02.201811
Aqueous Alkaline Zinc Air BatteriesGalvanostatic Discharge Zn dissolution and ZnO precipitation is inhomogeneous ZnO does not nucleate at separatorZnO increasesreversible capacityJ. Stamm, A. Varzi, A. Latz, B. Horstmann,Journal of Power Sources, 360, 136-149 (2017). HIU 01.02.201812
Aqueous Alkaline Zinc Air BatteriesLifetime Limitation Exposure to CO2 limitsalkaline ZAB lifetimeCOe2 2OH CO2 3 H2 O Lowers electrolyte conductivity Slows reaction kineticsJ. Stamm, A. Varzi, A. Latz, B. Horstmann,Journal of Power Sources, 360, 136-149 (2017). HIU 01.02.201813
Aqueous Neutral Zinc Air BatteriesNear-Neutral Aqueous Electrolyte: OverviewZnCl2 – NH4Cl – NH4OH Zn Zn2 2e Zn2 𝑥𝑋 Zn 𝑋𝑦𝑦𝑥 Zn 𝑋 𝑥 H2 O Zn 𝑋 NH4 NH3 H 𝑥s 𝑦H g O2 Oe2 1 eO2 2 2H 2e H2 OAdvantages No carbonation of the electrolyte More homogeneous zinc deposition Improved cycling stabilityChallenges pH stability Solid discharge product Stable air electrodeS. Clark, A. Latz, B. Horstmann,Rational Development of Neutral Aqueous Electrolytes for Zinc-Air Batteries.ChemSusChem 10, 4735–4747 (2017). HIU 01.02.201814
Aqueous Neutral Zinc Air BatteriesExperimental Validation A*STAR-IMRE, Singapore(Prof. Yun Zong) Experiments proof cyclingstabilityGoh, et al., J. Electrochem. Soc. 161 (14) A2080-2086, (2014).Sumboja et al., Power Sources 332, 330–336 (2016).S. Clark, A. Latz, B. Horstmann, ChemSusChem 10, 4735–4747 (2017). HIU 01.02.201815
Aqueous Neutral Zinc Air BatteriesThermodynamics ofNeutral Electrolyte Quasiparticle model forzinc complexes Various zinc precipitates[Cl]T 3.36M[Cl]T 5.54MS. Clark, A. Latz, B. Horstmann,Rational Development of Neutral Aqueous Electrolytes for Zinc-Air Batteries.ChemSusChem 10, 4735–4747 (2017). HIU 01.02.201816
Aqueous Neutral Zinc Air BatteriesElectrolyte Dynamics Electrolyte composition strongly coupled with pH, Zn2 ZnBAEZnBAENH4 NH3 H Zn2 nNH3 Zn(NH3)n2 Buffer reactionsstabilize pH Limited by slow NH3transport pH in BAE can becomeacidic during chargingS. Clark, A. Latz, B. Horstmann,Rational Development of Neutral Aqueous Electrolytes for Zinc-Air Batteries.ChemSusChem 10, 4735–4747 (2017). HIU 01.02.201817
Aqueous Neutral Zinc Air BatteriesOptimization of Electrolyte Composition Electrolyte composition strongly affects cell performance. pH 6 - 7, high chloride content precipitation of unwanted solids pH 8, lower chloride content stable operationS. Clark, A. Latz, B. Horstmann,Rational Development of Neutral Aqueous Electrolytes for Zinc-Air Batteries.ChemSusChem 10, 4735–4747 (2017). HIU 01.02.201818
Aqueous Neutral Zinc Air BatteriesDischarge Product and Energy Density Unwanted discharge product consumes electrolyte andpassivates Zn electrode.S. Clark, A. Latz, B. Horstmann,Rational Development of Neutral Aqueous Electrolytes for Zinc-Air Batteries.ChemSusChem 10, 4735–4747 (2017). HIU 01.02.201819
Aqueous Neutral Zinc Air BatteriesConclusion Metal air batteries: High risk / high gain Applications: Stationary, mobile, portable Various metal ions Lithium air batteries: lightweight Zinc air batteries: commercial Various electrolytes New aqueous electrolytes Ionic liquids HIU 01.02.201820
Lithium-Ion BatteriesContent1. Introduction2. Aqueous Zinc-Air Batteries Alkaline Electrolyte Near-Neutral Electrolyte3. Lithium-Ion Batteries Growth of SolidElectrolyte Interphase4. Conlusion HIU 01.02.201821
Lithium-Ion BatteriesLithium-Ion Batteries: Electrochemical Cellnegative electrodedischarge: anodeseparatorpostive electrodedischarge: cathodeSEIScrosati, B. & Garche, J., Journal of Power Sources,195(9), 2419. (2010). HIU 01.02.201822
Lithium-Ion BatteriesSolid Electrolyte Interphase (SEI)SEI is complicated Inorganic and organic components StructureYES, but universal stry/research/hardwick-group/research Long-term growth law 𝑳 𝒕 𝒕 SEI works in various systemsOur goal Develop simple mechanistic model Predict new observable properties fromfundamental assumptionsNie et. Al, JECS, 162 A7008-A7014 (2015) HIU 01.02.201823
Lithium-Ion BatteriesSolid Electrolyte Interphase (SEI)Formation Reduction of electrolyte on graphite,e.g. Ethylene Carbonate (EC)2EC 2Li 2e CH2 OCO2 Li 2 RSEI advantages Almost no further electrolyte reduction Protection of graphite from exfoliation Increase in mechanical stability ofgraphiteSEI disadvantages Li-ion consumptioncapacity fade Continuous growth Increase in impedancegraphiteLi SEI electrolyteECY Reviews & Papers on SEI composition:- Agubra, V. a., & Fergus, J. W. Journal of Power Sources268, 153–162 (2014).- Verma, P., Maire, P., & Novák, P. Electrochimica Acta55(22), 6332–6341 (2010).- Seo, D. M., Chalasani, D., Parimalam, B. S., Kadam, R.,Nie, M., & Lucht, B. L. (2014). ECS ElectrochemistryLetters , 3 (9), A91. HIU 01.02.201824
Lithium-Ion BatteriesContinuum Models in LiteratureDifferent rate-limiting transport mechanisms (RLTM) inliterature:Long-term SEI growth Homogeneous composition Single transport mechanism Fast reaction kineticstransportlimited growth𝑳 𝒕 𝒕 Single reaction interfaceSolvent/anion diffusion:- Pinson, M.B. & Bazant, M.Z. Journal of theElectrochemical Society 160, A243-A250 (2012).- Ploehn, H.J., Ramadass, P. & White,R.E. Journal of The ElectrochemicalSociety 151, A456 (2004).Electron conduction:- Christensen, J. & Newman, J. Journal of TheElectrochemical Society 151, A1977 (2004).Both:- Tang, M., Lu, S., & Newman, J. (2012). Journalof The Electrochemical Society, 159(11), A1775Tunneling:. Li et. al (2015). Journal of the ElectrochemicalSociety, 162(6), A858–A869.vs.Li Y ECe graphiteSEIelectrolyte HIU 01.02.201825
Lithium-Ion BatteriesModel Overview - Concept1D model for long-term growthTransport of all SEI precursors 𝑒 restricted to SEI Solvent restricted to poresNano porous SEIBinary solvent mixture EC/DMC Neglect Li and salt anionUp to two SEI compoundsF. Single, B. Horstmann, A. Latz, Journal of The Elec. Society, 164(11), E3132 (2017). HIU 01.02.2018F. Single, B. Horstmann, A. Latz, Phys. Chem. Chem. Phys., 18, 178101, (2016).26
Lithium-Ion BatteriesModel Overview – Transport & ReactionsElectronic current Ohm‘s law𝒋𝑬 𝝈 𝚽Solvent Fick s law Convection𝒋𝑬𝒋𝑫 𝑫 𝒄𝒋𝑪 c𝒗𝒋𝑫 𝒋𝑪Bruggeman Relation 𝝈 (𝟏 𝜺)𝟏.𝟓 𝝈𝐁𝐮𝐥𝐤 𝑫 𝜺𝜷 𝑫𝐁𝐮𝐥𝐤B.V. Reaction Rate, 𝒔 𝑨 sinh 𝜼𝟎 𝜼 𝚽 𝚽𝐄𝐂 ln 𝒄 𝑨 6𝜺𝑎01 𝜺 𝑎02 ′′𝜺6Primary Variables𝜺 𝜺𝟏 𝜺𝟐 ,𝒄,𝚽,𝒗Parameters𝟎𝜷, 𝝈𝐁𝐮𝐥𝐤 , 𝑫𝐁𝐮𝐥𝐤 , 𝒂𝟎 , 𝚽𝐄𝐂F. Single, B. Horstmann, A. Latz, Journal of The Elec. Society, 164(11), E3132 (2017). HIU 01.02.2018F. Single, B. Horstmann, A. Latz, Phys. Chem. Chem. Phys., 18, 178101, (2016).27
Lithium-Ion BatteriesSimulation: Single SEI CompoundPorous SEI HomogeneousSEI growth Transport limited 𝒕 - growth Governed / limited byelectron conduction𝝈 2𝑅𝑇 1 𝜷𝜺 𝐒𝐄𝐈 𝑫 𝑐𝐹 2 2𝜺𝑳 𝒕 𝑉1 𝝈 𝚫𝚽/𝜀SEI𝐹 𝒕F. Single, B. Horstmann, A. Latz, Journal of The Elec. Society, 164(11), E3132 (2017). HIU 01.02.2018F. Single, B. Horstmann, A. Latz, Phys. Chem. Chem. Phys., 18, 178101, (2016).28
Lithium-Ion BatteriesDual-layer SEI 𝑳 total SEI thickness 𝑳𝐈 thickness of the inner layerConversionDifferent reduction potentials𝟎 𝚽𝐄𝐂 𝟎. 𝟖 𝐕𝟎 𝚽𝐃𝐌𝐂 𝟎. 𝟑 𝐕ConversionSecond SEI species Co-solvent reduction Reduction of Li2EDCCo-solventreductionSimulation: Dual-Layer SEIBorodin, O., et al. (2015). Nanotechnology, 26(35), 354003.Lu, P., Li, C., Schneider, E. W., & Harris, S. J. (2014). Journal of PhysicalChemistry C, 118(2), 896. HIU 01.02.201829
Lithium-Ion BatteriesIdentifying RLTM HIU 01.02.201830
Lithium-Ion BatteriesIdentifying the RLTMCompare four differentRLT mechanisms1. Electron conduction2. Electron tunnelin3. Li-interstitial diffusion4. Solvent diffusionRelative capacity fade 𝚫𝐂after 9.3 months storage(open circuit) vs. the SOCduring storage.Experimental data:Keil, P., et al., (2016). Journal of TheElectrochemical Society, 163(9), A1872–A1880. HIU 01.02.201831
Lithium-Ion BatteriesIdentifying the RLTMCompare four differentRLT mechanisms 𝐂 𝟎𝚽𝐄𝐂 𝐎𝐂𝐕(𝐒𝐎𝐂) 𝐂 𝜶 𝐒𝐎𝐂 ln 𝟏 𝜷 𝐒𝐎𝐂𝟏 𝑭 𝐂 𝐞𝐱𝐩𝐎𝐂𝐕 𝐒𝐎𝐂𝟐 𝑹𝑻 𝐂 𝐜𝐨𝐧𝐬𝐭.Experimental data:Keil, P., et al., (2016). Journal of TheElectrochemical Society, 163(9), A1872–A1880. HIU 01.02.201832
OutlookConclusionExtended SEI modeling approach, predictions: Thickness evolution Dual-layer SEI (several scenarios) Porosity SOC dependence of cap. fadeComparison of different RLTMs: SEI thickness fluctuations (solvent diffusion) SOC dependence of cap. Fade RLTM: Interstitial DiffusionF. Single, B. Horstmann B., A. Latz, Phys.Chem. Chem. Phys., 18, 178101 (2016). Impedance spectroscopyF. Single, B. Horstmann B., A. Latz, Journal ofThe Elec. Society, 164(11), E3132 (2017).F. Single, A. Latz, B. Horstmann,submitted to ChemSusChem (2018). HIU 01.02.201833
ConclusionContent1. Introduction2. Aqueous Zinc-Air Batteries Alkaline Electrolyte Near-Neutral Electrolyte3. Lithium-Ion Batteries Growth of SolidElectrolyte Interphase4. Conclusion HIU 01.02.201834
ConlusionOutlook Understanding electrochemical surfaces (in-situ experiments?) Electrochemical surface layers, e.g., ionic liquids Interfacial stability, e.g., SEI, plating Electrodeposition and –dissolution, e.g., lithium metal Designing next-generation batteries Metal-air batteries Multi-valent ions Experimental designs Probabilistic/stochastic modeling of lithium-ion batteries State estimation Uncertainty propagation Stochastic scale coupling HIU 01.02.201835
ConclusionFunding Sources & Institutions BMBF: LuLi, LuZi, Li-EcoSafe EU-Horizon 2020: ZAS! Eureka-Eurostars: Simba DAAD: PostDoc Scholarship Helmholtz Association: HIU, GigaStore HIU 01.02.201836
ConclusionCo-Supervised StudentsPhD Students Timo Danner Fabian Single Simon Clark Tobias Schmitt Max Schammer Linda BolayMaster Students Daniel Eberle Emre Durmus Erkmen Karaca Johannes StammUniversity StuttgartInstitute for Thermodynamicsand Thermal EngineeringThank You! HIU 01.02.201837
HIU 2 Why do we need (metal-air) batteries? Introduction G. A. Hoff
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