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Scherson, Daniel

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Case Western Reserve University Scholarly Commons @ Case Western Reserve University Great Lakes Energy Institute: Presentations & Events Case School of Engineering 6-1-2009 Microbatteries and Advanced Battery Design Daniel Scherson Follow this and additional works at: https://commons.case.edu/glei-events Recommended Citation Scherson, Daniel, "Microbatteries and Advanced Battery Design" (2009). Great Lakes Energy Institute: Presentations & Events. 26. https://commons.case.edu/glei-events/26 This Book is brought to you for free and open access by the Case School of Engineering at Scholarly Commons @ Case Western Reserve University. It has been accepted for inclusion in Great Lakes Energy Institute: Presentations & Events by an authorized administrator of Scholarly Commons @ Case Western Reserve University. For more information, please contact digitalcommons@case.edu. Mi b tt i d Ad dcro a er es an  vance  Battery DesignDaniel Scherson Department of Chemistry  Case Western Reserve UniversityEnergy Storage: Technological Innovation & Collaborative Opportunities Great Lakes Energy Institute WEBCAST    June 1, 2009Batteries: General OverviewBattery electrodes composed in general of particles μm in size:Zn in Zn/MnO2Ni(OH) in Ni Metal Hydride2    Graphite and transitions metal oxides in lithium ion batteriesP V l Cower = o tage x    urrentChemistry DesignMajor factors that limit performance of Li-ion batteries: •Small rates of ion-transport within crystal lattice – Low rates of charge and discharge. •Chemical Stability - Long term performance.•Lower than expected Li-ion storage capabilities - Reduced energy density.Strategies to Overcome Performance LimitationsfRational Design o  Materials Based on Theoretical Understanding of Phenomenological Observations Decrease diffusion length by decreasing particle      size – nano represents a true advantage.S f f i li i i i i d/ur ace unct ona zat on us ng norgan c an or organic coatings Mission of Basic Science:    To show what is possibleDevelop Predictive ToolsMission of Technology:To exploit what is possible to d t i l d d ipro uce ma er a s an  ev ces displaying optimum performance   characteristics in the most efficient and economical way.MW-ST SYNTHESIS OF LiMPO4 (M = Mn, Fe, Co AND Ni)N t ianome r c Materials• Microwave solvothermal (MW ST) processA. Vadivel Murugan, T. Muraliganth and A. Manthiram, Inorg. Chem. (in press)-  -  produces LiMPO4 (M = Mn, Fe, Co, and Ni) within 5 -15 min at 300 oCTEM IMAGES OF LiMPO4 (M = Mn, Fe, Co AND Ni)TEM indicate that the nanorods are single crystalline in all the four phospho-olivines (M= Mn, Fe, Co, Ni)REVERSIBLE CAPACITY LIMITS OF LAYERED CATHODESMO2LiMO2 [Li+][M3+]O2Li MO2Li Li+ and M3+ occupy alternate (111) planes of NaCl structureCathode Reversible % of Intercalation MO2Capacity (mAh/gTheoretical CapacityRange in Li1-xMO2Li CoO 140 50 0 5 ≤ (1 x) ≤ 1 01-x 2 .  -  .Li1-xNi0.85Co0.15O2 180 65 0.35 ≤ (1-x) ≤ 1.0Li Ni Mn Co O 180 65 0 35 ≤ (1-x) ≤ 1 01-x 1/3 1/3 1/3 2 .   .Li1-xNi1-y-zMnyLizO2 250 80 0.20 ≤ (1-x) ≤ 1.0Why do materials with same overall structure show such different capacities?ORIGIN OF CHEMICAL INSTABILITYLiCoO2 LiNiO2 LiMnO2Co3+/4+ : eCo3+/4+ : t2 gNi3+/4+ : egMn3+/4+ : eg gO2- : 2pO2- : 2pO2- : 2pNi3+/4+ : t2gMn3+/4+- : t2gC 3+ (LS) t 6 0 Ni3+ (LS) t 6 1 M 3+ (HS) t 3 1As overlap between the M3+/4+:3d band with the top of the O2-:2p band o : 2 e                  : 2 e                   n : 2 e  increases, the lithium content at which chemical instability sets in during charge increases. Factor limits the reversible capacityOLIVINE LiFePO4caView down b - axisAdvantages:• Fe is inexpensive and environmentally benign         • Offers high rate capability and excellent safety due to- good structural stability (covalently bonded PO4 groups)good chemical stability (Fe2+/3+:e band lying well above the O2-:2p band)-    g       Problem:• Poor electronic and lithium ion conductor (one-dimensional Li+ diffusion)       • Needs to be made as small particle and decorated with conductive carbonCARBON COATING ON MW-ST LiFePO4MICROWAVE-SOLVOTHERMALEx situ carbon coatingMixed with sucrose and heated at 700 oC,LiFePO4 nanorods      1 h, H2/Ar atm LiFePO4/CnanocompositeTEM MICROGRAPHSS  -EMA. Vadivel Murugan, T. Muraliganth and A. Manthiram, J. Phys. Chem. C 112, 14665 (2008)MICROWAVE-SOLVOTHERMAL SYNTHESIS OF LiFePO4SOOSOOSOOSOOn SO3- SO3-++CH3 CH3Microwave irradiation Polymer coating5 min, 300oC LiFePO4 nanorodsQuartz vessel containing       gel of  Fe(CH3COO)2,  LiOH, & H3PO4dissolved inQuartz vessel containing LiFePO4 nanorods after microwave-solvothermal reactionLiFePO4 / PEDOT nanocomposite• Microwave assisted solvothermal process to produce LiFePO4- within 5 min at 300 oC   tetraethylene glycol  - without requiring any reducing gas atmospheres - subsequent coating with doped PEDOT at ambient temperature(p-toluene sulphonic acid (p-TSA) doped poly(3 4-ethylenedioxythiophene)     ,A. Vadivel Murugan, T. Muraliganth, and A. Manthiram, Electrochem. Comm. 10, 903 (2008)SEM, TEM & STEM IMAGES OF LiFePO4FeP• MW ST method offers nanorods and the size depends on synthesis conditions:-           (a) 40 nm width, 1 μm length    (b) 25 nm width, 100 nm length• No agglomeration of the PEDOT polymer• HRTEM: crystalline fringe region of LiFePO and amorphous region of polymer    4     • Easy lithium diffusion direction (b axis) perpendicular to the long nanorod axisAlPO4-MODIFIED HIGH CAPACITY LAYERED OXIDE(a) (b)AlP5 nmY. Wu, A. Vadivel Murugan, and A. Manthiram, J. Electrochem. Soc. 155, A635 (2008).• A smooth, porous layer with a thickness of ~ 5 nm exists on the surface• EDS analysis indicates aluminum and phosphorous on the surfaceCross-Cutting Science:Basic Science Challenges OpportunitiesMonitor with temporal resolution down to fs elementary  , , and Needs♣,      ,  interfacial events (concerted electron and ion transfer) and bulk events (ion transport within lattice)     Image, in real time and with nm spatial resolution, charge transport in electrodes and devices, including front evolution and moving boundaries in single particlesMonitor, in situ, during charge, discharge and cycling: structure, morphology and composition of the SEI (solid electrolyte interface)electrolyte compositionBasic Research Needs Workshop: Electrical Energy Storage, DOE, 2007Model Systems: Single Particle BatteriesW spearZn particleMnO2 particleAPrimary: Zn|MnO2Measurement Circuitseparator100μm AVoltage SourceMm alloy particleS-Ni(OH)2 particleMicrobatteryVery large R(0.25-1GΩ)VSecondary:100B Mm|S-Ni(OH)2μmPerformance of single-particle microbatteriesI. Primary Microbattery: Zn|MnO2 dischargeW spearZn particleMnO2 particle1.60 5 10 15 20 25 30 35 Time / minB tt @ 2C1.2 tage (V)AA @ C/330μ a  separator100μm A0.80 50 100 150 200 250 300Volt    Time / hZn - ca. 150 μm diameter; MnO2 - ca. 30 μm mean diameter.THICK LINE:           9M KOH; current: 48 nA (ca. 2C). Thin Line: commercial AA battery. Rate: ca. C/330 Remarkable agreement!   Microperformance = MacroperformanceII. Secondary Microbattery: Metal Hydride (Mm)|Ni(OH)2Alloy particle100 100Ni(OH) particleμm μmSeparator/holding device2 Charge-Discharge CurvesMm alloy particleS-Ni(OH)2 particle1.21.6  oltage / V~1.6CA1.6~3.5Ce / V0 20 40 60 800.8 Vo1 6 0 10 20 30 40 500.81.2B Voltag e100μm0 4 8 12 160.81.2.C~6.2 C    Voltage / VTime / minS-Ni(OH)2 particle ca. 30 μm in diameterMm alloy particle ca. 75 μm mean diameter Tlectrolyte: 9M KOHC i ith M b tt P f ompar son w  acro a ery er ormanceTHICK LINE: Mm|Ni(OH)2 μbatteryMm alloy particleS-Ni(OH)2 particle1.41.6 V   1 01.2  Voltage / V0.0 0.2 0.4 0.6 0.8 1.00.8.V1.6C2C 1C100μmTime / hTHIN LINE Commercial AAA batter :   y:Microperformance very similar to MacroperformanceReal Time Spectroscopic Monitoring of a Single Charge Storage Microparticle: LiMn2O4Objective lensLaser beam(532 nm)SapphirewindowLiMn2O4 MicroparticlelClampExperimentaArrangementPt wire Li foilO-ringW wireWorking Electrode: LiMn2O4 microparticle (~50μm dia.)O-ringsTeflon bushingsElectrolyte:1M LiClO4 in 1:1 (v/v) ethylene carbonate (EC): diethyl carbonate Cu wire(DEC)C li V lt t f Si l LiM O Mi ti lyc c o amme ry o  ng e n2 4 cropar c eElectrolyte: 1M LiClO4 in EC:DEC (1:1 v/v)Scan Rate:20B             ν = 0.11 mV/s10 LASER  OFFONAnA0 OFFLASER urrent, n-20-10  ONB'A'Cu3.6 3.8 4.0 4.2 4.4E, V vs Li/Li+Time resolved In situ Raman    Spectra of single crystal LiMn2O4Dr Junji AkimotoNational Institute of Advanced Industrial Science and Technology Tsukuba, JapanI. Acquire series of in situ Raman spectra whileSODunitEABrecording cyclic voltammetry (ca. 6 mV/spectrum)0.40intensity / Arb. 4.2894.2204.2134.2074.2004 193SOD4 13110y / Arb. unitESODCunit E40 EDnitScattering i4.173.4.1864.1804.1664.1594.1524 144*.ttering intensity4.1244.1184.111intensity / Arb. 4.0624.0554.0694.077SODE/ Arb. unitSOD0ensity / Arb. un4.290E450 500 550 600 650 700 75010Raman shift / cm-14.131.4.138*40 Scat4.1044.0974.0904.0844.077 50 Scattering 4.0494.0424.035*104.1724.166ering Intensity /4.1582Scattering inte4.2234.2174.2114.2044 1984.230450 500 550 600 650 700 750Raman shift / cm-1450 500 550 600 650 700 750Raman shift / cm-14.0284.021*Scatte 4.1514.1454.1394.1324.1264.119450 500 550 600 650 700 75010Raman shift / cm-1.4.1914.1854.1784.172450 500 550 600 650 700 750Raman shift / cm-14.11340II Build up library of spectra as a function of    .            extent of Li+ intercalationSTRUCTURAL INFORMATIONIn situ X-ray diffraction (XRD) for LixMn2O4 (Eriksson et al.) consistent with: 0  • presence of single phase, 1, over range  11+2110 < SOD < 11 % (lattice parameter 8.805 Å ) • presence of different single phase, 2, over range 3535 < SOD < 100 % (lattice parameter 8.125 Å ) 2• coexistence of two phases in intermediate range, 11 < SOD < 35 %  (phase lattice parameters remain fixed)100SOD: State of discharge, equivalent to amount of Li+ in lattice.   SOD = 0 means NO Li+ in lattice i e λ-MnO    , . . 2Total collection time 2 hours. In situ Raman ObservationsI. 0 < SOD < 10 %  Phase 1A• Large drop in intensity during initial stages of discharge of fully charged microparticle SOD0Arb. unit4.289Ewhere Phase 1 undergoes linear lattice expansion as a function of SOD. 0.4tensity / A4.2204.2134.2074 200• Behavior related to changes in electronic properties of λ-MnO2 as Li+ injected into attering int4.173.4.1934.1864.180latticeCause: rapid loss in resonantly enhanced Sca 4.1664.1594.1524.1444 138intensity associated with. λ-MnO2450 500 550 600 650 700 75010Raman shift / cm-14.131.• Most importantly: Correlation between area and extent of Li+ within Phase 1 evident.II 10 < SOD < 40% Coexistence of Phase 1 & 2B.    ,      Rather subtle changes in spectral featuresSODb. unitIDEA4.13110ensity / Arb E• Regard spectrum at extremes in this range as    those of pure Phase 1 & 2*attering inte 4.1244.1184.111    . • Decompose statistically intermediate spectra  Sca 4.1044.0974.0904 084using spectra of pure Phase 1 & 2 as bases (chemometrics) 450 500 550 600 650 700 750*40Raman shift / cm-1.4.077ILLUSTRATIONSA Units Spectroscopic Phase Diagram0 81.02ponent1 ensity, Arb. U0.6.tral Com450 500 550 600 650 70047%53%Inte0.20.4  of SpectWavenumber, cm-1B s10 20 30 40 500.0Fraction y, Arb. UnitsSOD, %Intensity45%55%450 500 550 600 650 700Wavenumber, cm-1B 1.0 nentSPECTROSCOPYELECTROCHEMISTRY01020OFFOFFONA ent, nA0.40.60.82 Spectral Compon13.6 3.8 4.0 4.2 4.4-20-10ONB'A'Curre10 20 30 40 500.00.2Fraction of SSOD, %25 E, V vs Li/Li+2010 70.8Fraction of P ed Charge A) n Phase1ed Charge101504.05 4.10 4.150.6. hase 1 (X1 )NormalizeE (V Li/Li+) ge (μC)FractionNormalize5  vs Charg3.4 3.6 3.8 4.0 4.2 4.40E (V vs Li/Li+)Phase Transition Occurs Over Region in which NO Voltammetric Features ApparentCross-Cutting Science:Basic Science Challenges OpportunitiesMonitor with temporal resolution down to fs elementary  , , and Needs♣,      ,  interfacial events (concerted electron and ion transfer) and bulk events (ion transport within lattice)     Image, in real time and with nm spatial resolution, charge transport in electrodes and devices, including front evolution and moving boundaries in single particlesMonitor, in situ, during charge, discharge and cycling: structure, morphology and composition of the SEI (solid electrolyte interface)electrolyte compositionBasic Research Needs Workshop: Electrical Energy Storage, DOE, 2007

Microbatteries and Advanced Battery Design

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Microbatteries and Advanced Battery Design

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