Bergfeldt, T.

Fischer, J.

Leiste, H.

Rinke, M.

Seifert, H.J.

Strafela, M.

Ulrich, S.

English

Seifert, H. J.

KITopen

1Magnetron sputtered Li-Ni-Mn-Co-O thin film cathodes for lithium-ion batteriesM. Strafela, J. Fischer, H. Leiste, M. Rinke, T. Bergfeldt, S. Ulrich, H.J. SeifertPortfolio Elektrochemische Speicher im System  2014, 14. Oktober 2014, Karlsruhe, GermanyArgon plasmaONi /Mn/CoLiInstitute for Applied Materials – Applied Materials Physics IAM-AWP, Department Composites and Thin FilmsOutlineMotivationThin film synthesis & characterisationSelected resultsSummary and outlookwww.infinitepowersolutions.com (2014)RFPumpsAr22Layered structure – Li(Ni1/3Mn1/3Co1/3)O2Structure and properties:• Theoretical capacity: 290 mAh/g• Voltage versus Li: 2.5 V – 4.3 V• Space group: R3mhexagonal lattice a = b = 0.2867 nm c = 1.4246 nm  α = β = 90° γ = 120°• Layers of closed packed oxygen ions are separated by alternating layers of lithium and transition metal ionsONi /Mn/CoLi3Fabrication of Li-Ni-Mn-Co-O layered structure with high capacity and enhanced Li+ diffusion Nanocrystalline material with optimised chem. compositionOptimization of grain orientation Variation of deposition and growth kineticspressure variation during sputtering Increase of the crystallinity Heat treatment of the films (T = const., t = const.)  Influence pressure during heat treatment in Ar/O2 (80:20) atmosphere on crystallization processGoals for materials developmentTMPicture redesigned “Preferred Orientation of Polycrystalline LiCoO2 Films” J. B. Bates, N. J. Dudney, B. J. Neudecker, F. X. Hart,b H. P. Jun,  S. A. Hackneyc, Journal of The Electrochemical Society, 2000Side view Diffusion coefficients Li0.8CoO2:(003) orientation: ~ 1 x 10-14 cm2s-1(104) orientation: ~ 1 x 10-12 cm2s-1“Orientation dependence of Li-ion diffusion kinetics in LiCoO2 thin films prepared by RF magnetron sputtering” J. Xie, N. Imansishi, T. Matsumura, A. Hirano, Y. Takeda, O. Yamamoto, Solid State Ionics, 200843Characterisation Methods X-ray diffraction (XRD) Raman-spectroscopy Chemical analysis Inductively coupled plasma optical emission spectrometry (ICP-OES) Carrier gas hot extraction (CGHE) Electrochemical analysis galvanostatic cyclingXRDICP-OES“iCap 7600”, T. Bergfeldt, Chemical Analysis Group, 2014Swagelok cells5Experimental procedure2-Step processDeposition conditions:• Leybold Heraeus Z 550 PVD • Argon - atmosphere (non reactive)Thin film constitution:1 – 1.5 µmDeposition parameters:• Power:  RF 100 W • Pressure: 0.2 ; 0.5 ; 2 ; 4 ; 7 ; 10 ; 20 PaHeat treatment:• Temperature: 600 °C• Atmosphere : Ar / O2 (80:20)• Pressure range: 10 mPa, 10 Pa, 150 Pa, 80 kPa• Time: 1 h64Pumps1. Step: Magnetron sputteringVariation of argon working gas pressure Target: Li-Ni-Co-Mn-O (Li-rich) Power: RF 100 W Pressure range: 0.2 ; 0.5 ; 2 ; 4 ; 7 ; 10 ; 20 Pa Working gas: Ar Temperature: unheated (RT) Substrate: Si (001)  / stainless steel RF7As deposited thin filmsChem. composition (ICP-OES / CHGE) – variation of workinggas pressure49.0 48.6 50.3 51.3 51.6 52.0 53.6 46.9 50.06.3 6.6 7.27.7 7.8 7.7 7.18.88.33.4 3.64.2 4.5 4.64.6 4.34.98.37.9 8.28.6 8.98.9 8.8 7.89.98.333.4 32.9 29.727.6 27.1 27.0 27.1 29.4 25.00.2 0.5 2 4 7 10 20 Target0102030405060708090100 Li  Ni  Mn  Co  O  Chem. composition in at%Argon working gas pressure in PaLi(Ni0.33Mn0.33Co0.33)O2Power: 100 WGas: ArTemp.: unheatedAs depositedSubstrate: SiLiNiCoMnO85As deposited thin filmsMicrostructure (XRD) – variation of working gas pressureLayered structureLi(Ni1/3Mn1/3Co1/3)O2JCPDS: 00-056-014715 20 25 30 35 40 45 50 55 60 65Si110018017009012006011015014003a)20 Pa10 Pa7 Pa2 Pa4 Pa0.5 PaXRD - Intensity in arb.u.2 in deg.p = 0.2 Pa Power: 100 WGas: ArTemp.: unheatedAs depositedSubstrate: Si9As deposited thin filmsMicrostructure (Raman spectroscopy) – variation of working gas pressure“Local cationic environment in lithiumnickel–cobalt oxides used ascathode materials for lithium batteries”,C. Julien, Solid State Ionics 2000„Synthesis and characterization of Li Ni1/3Mn1/3Co1/3O2 by wet-chemicalmethod“ X. Zhang, A. Mauger, Q. Lu, H. Groult, L. Perriguard, F. GendronC.M. Julien, Electochimica Acta, 2010A1gEg400 500 600 700551580b)20 Pa10 Pa7 Pa2 Pa4 Pa0.5 PaRaman - Intensity in arb.u.Raman shift in cm-1p = 0.2 PaPower: 100 WGas: ArTemp.: unheatedAs depositedSubstrate: Si10 Battery test (as dep. at 7 Pa): 20 µAhcm-2µm-162. Step: Heat treated thin films 7 PaVariation of heat treatment pressure Sample: Deposited at  7 Pa Temperature: 600 °C Atmosphere: Ar / O2 (80 : 20) Pressure : 10 mPa, 10 Pa, 150 Pa, 80 kPa Time: 1 h Substrate: Stainless steel S 30400Furnace11As deposited thin filmsmicrostructure (XRD) – variation of working gas pressure15 20 25 30 35 40 45 50 55 60 65Si110018017009012006011015014003a)20 Pa10 Pa7 Pa2 Pa4 Pa0.5 PaXRD - Intensity in a.u.2 in deg.p = 0.2 PaLayered structureLi(Ni1/3Mn1/3Co1/3)O2JCPDS : 00-056-0147Power: 100 WGas: ArTemp.: unheatedAs depositedSubstrate: Si127Heat treated thin films 7 Pamicrostructure (XRD) – variation of heat treatment pressure15 20 25 30 35 40 45 50 55 60 65Si10 Pa / SiSS110018017009012006011015014003a)80 kPa150 Pa10 Pa / SSas dep.10 mPaXRD - Intensity in arb.u.2 in deg.Sample: dep. at 7 PaTemp.: 600 °CAtmosphere: Ar / O2 (80 : 20)Time: 1 hSubstrate: Stainless steel S 30400Layered structureLi(Ni1/3Mn1/3Co1/3)O2JCPDS : 00-056-014713Heat treated thin films 7 Pamicrostructure (Raman spectroscopy) - variation heat treatment pressure“Local cationic environment in lithiumnickel–cobalt oxides used ascathode materials for lithium batteries”,C. Julien, Solid State Ionics 2000”Synthesis and characterization of Li Ni1/3Mn1/3Co1/3O2 by wet-chemical method“ X. Zhang, A. Mauger, Q. Lu, H. Groult, L. Perriguard, F. Gendron, C.M. Julien, Electochimica Acta, 2010A1gEgSample: deposited at 7 PaTemperature: 600 °CAtmosphere: Ar / O2 (80 : 20)Time: 1 hSubstrate: Stainless steel S 30400400 500 600 700535595b)80 kPa150 Pa10 Paas dep.10 mPaRaman - Intensity in a.u.Raman shift in cm-1148Summary and Outlook Li-Ni-Mn-Co-O films were successfully deposited with different chemical compositions and microstructures  As deposited unordered layer structure showed discharge capacity of about 20 µAhcm-2µm-1Variation of Li and O concentration up to 5 at% Texture depending on pressure 0.2 Pa – 2 Pa: (018) / (110) 4 Pa – 20 Pa : (012) Pressure during post annealing has an influence on the crystallisation process  During heat treatment the structure transforms into an ordered layer structure Battery tests and investigation of heat treated films and development of a one step process to deposit ordered layer structure Deposition on structured substrates and structuring by different deposition methodsTM15I would like to thank the financial support by the BMBF Portfolio program Our chemical analysis group The members of the  “Department for Composites and Thin Films” and IAM-AWPYou for your attention16

Magnetron sputtered Li-Ni-Mn-Co-O thin film cathodes for lithium-ion batteries

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Magnetron sputtered Li-Ni-Mn-Co-O thin film cathodes for lithium-ion batteries

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