www.iam.kit.edu/wet KIT – The Research University in the Helmholtz Association Performance analysis of Lithium-ion-batteries: status and prospects DPG conference Erlangen March 2018 Ellen Ivers-Tiffée, Philipp Braun, Michael Weiss Karlsruhe Institute of Technology (KIT), Germany
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www.iam.kit.edu/wetKIT – The Research University in the Helmholtz Association
Performance analysis of Lithium-ion-batteries: status and prospectsDPG conference Erlangen
March 2018
Ellen Ivers-Tiffée, Philipp Braun, Michael Weiss
Karlsruhe Institute of Technology (KIT), Germany
Institute for Applied MaterialsMaterials for Electrical and Electronic Engineering
Characterization of Lithium-Ion CellsElectrochemical Impedance Spectroscopy (EIS)
Nyquist Plot:AC Small Signal Perturbation: Frequency Response Analyzer:
System Requirements:
linearitycausality time invariance
Kramers-Kronig Validity Test:
pert
urba
tion
t tEISt
tem
pera
ture
T
startT
endTstart endT T!
ImRe 2 2
0
' ( ')2( ) ''
ZZ d
ImIm 2 2
0
( ')2( ) ''
ZZ d
M. Schönleber, D. Klotz, and E. Ivers-Tiffée, “A Method for Improving theRobustness of linear Kramers-Kronig Validity Tests,” Electrochim. Acta, vol.131, pp. 20–27, 2014.
t
t
( )u t
( )i t
1 2
U
I
0
Z΄
-Z΄΄
12
( )ˆ ( )( ) ˆ( )
jUZ eI
'( ) ''( )Z jZ
synthetic battery-like spectrum
Institute for Applied MaterialsMaterials for Electrical and Electronic Engineering
Modeling of Lithium-Ion CellsTransmission Line Model (TLM)
[1] J. Bisquert, G. Garcia-Belmontea, F. Fabregat-Santiagoa, and A. Compteb,“Anomalous transport effects in the impedance of porous film electrodes,”Electrochemistry Commun., vol. 1, no. 9, pp. 429–435, 1999.
electrolyte
Current collector
1 1 1 1
2 2 2 2 2
1electrode thickness
A
TCT
M
CZ lV a
charge transfer
A
CT
M
Va specific charge transfer resistance
active surface area per unit volume
electrode volume
solid-state diffusion0
0 1
1Diff
diff
Diff IZC D I
l
Finite-Space Warburg Impedance
2Diff
DiffDlj
differential capacity
diffusion length
0
Di
Di
f
ff
fD
l
C
diffusion coefficient
ionic path
21 1
ion A
A
tortuosity (pore)
volume fraction of pores
electrode area
Volume fractions
Tortuosity
Active Surface Area
Particle Size
Diffusion Length
Microstructure parameters:
Institute for Applied MaterialsMaterials for Electrical and Electronic Engineering
Characterization of Lithium-Ion CellsMicrostructure: Anode
Anode: Graphite X-ray nano-tomography:
X-raysource
X-raycamera
sample
M. Ender, J. Joos, A. Weber, and E. Ivers-Tiffée, “Anode microstructures from high-energyand high-power lithium-ion cylindrical cells obtained by X-ray nano-tomography,” J. PowerSources, vol. 269, pp. 912–919, 2014.
electrode thickness lelectrode = 90 µm
volume fraction εgraphite = 0.75
εpore = 0.25
tortuosity pore = 5.12
active surface area agraphite = 0.314 µm-1
particle size dgraphite,vol-av = 12.07 µm
Institute for Applied MaterialsMaterials for Electrical and Electronic Engineering
Characterization of Lithium-Ion CellsMicrostructure: Cathode
Focused ion beam (FIB) tomography: Cathode: NCA/LCO Blend
electron beamGa+ ion beam
sample
e- Ga+
M. Ender, J. Joos, T. Carraro, and E. Ivers-Tiffée, “Three-dimensional reconstruction of acomposite cathode for lithium-ion cells,” Electrochem. commun., vol. 13, no. 2, pp. 166–168, 2011.M. Ender, J. Joos, T. Carraro, and E. Ivers-Tiffée, “Quantitative Characterization of LiFePO4Cathodes Reconstructed by FIB/SEM Tomography,” J. Electrochem. Soc., vol. 159, no. 7,pp. A972–A980, Jan. 2012.
electrode thickness lelectrode = 75 µm
volume fraction εAM = 0.57
εcarbon = 0.17
εpore = 0.26
tortuosity pore = 4.29
active surface area aAM = 0.73 µm-1
particle size dAM,vol-av = 4.06 µm
LiNixCoyAl1-x-yO2 = NCALiCoO2 = LCO
Institute for Applied MaterialsMaterials for Electrical and Electronic Engineering
M. Ender, A. Weber, and E. Ivers-Tiffée, “A novelmethod for measuring the effective conductivityand the contact resistance of porous electrodesfor lithium-ion batteries,” Electrochem. commun.,vol. 34, pp. 130–133, 2013.
M. Ender, J. Joos, T. Carraro, and E. Ivers-Tiffée,“Quantitative Characterization of LiFePO4Cathodes Reconstructed by FIB/SEMTomography,” J. Electrochem. Soc., vol. 159, no.7, pp. A972–A980, Jan. 2012.
ionVa
pse electronicconductivity
volume fractions
tortuosity
electrode thickness
active surface area
particle sizel
conclusion
Electrochemical and microstructure parameters for anode and cathode are
determined
0 5 10 15 20 25 30 35 400
-5
-10
-15
-20
Z'' /
c
m2
Z' / cm2
Institute for Applied MaterialsMaterials for Electrical and Electronic Engineering