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WIR SCHAFFEN WISSEN – HEUTE FÜR MORGEN
Enhanced rate performance in electrode materials for lithium-ion batteries
Juliette Billaud, Florian Bouville, Tommaso Magrini, Fabio Bargardi, Claire Villevieille, André R. Studart
International Battery Seminar & Exhibit
March 20-23, 2017
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SLS
SINQ
The Paul Scherrer Institut
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New, better performing materials?
Engineering of existing materials?
Reduced charging times
More autonomy
Low cost
Lifetime
Safety
New, better performing materials?
Engineering of existing materials?
Lithium-ion batteries
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Lithium-ion batteries
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LiCoO2
Graphite
Specific energy
= Specific charge
* Voltage
Slow rates
Low loadings
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The example of graphite
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ca. 95% of commercial rechargeable Li-ion batteries
Low volumetric expansion (10%)
Reasonable specific charge
Low potential
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Graphite vs. fast cycling
Page 6 M. Hess, PhD Thesis No. 21240, ETH Zürich Electrodes: SFG6 graphite - ca. 50 µm - 4 mg
Limitation from
stage dense 2 to 1
Limitation from stage 1-2 but
compensated by following transitions
50 mV
overpotential
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Graphite vs. different electrode thicknesses?
Page 7 M. Hess, PhD Thesis No. 21240, ETH Zürich
Despite graphite’s:
low cost,
good reversibility,
high energy density
Graphite does not limit discharge performance but
does limit charge performance
Problem: diffusion of Li+ through thick
electrodes
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Page 8 Buqa et al., Journal of The Electrochemical Society, 152, A474 (2005)
Graphite vs. particle size & electrode thickness
What improvements have been made so far?
Diffusion of Li in graphite:
very anisotropic
(only within the
crystallographic basal
plane)
SFG 44 (ca. 40 µm) SFG 6 (2-5 µm)
Thin
electrodes
Thick
electrodes High tortuosity
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Use of smaller graphite flakes
Improvements for graphite so far
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Tran et al., Journal of applied electrochemistry (1996)
Aurbach et al., Solid State Ionics (2002)
Use of particles with different morphologies
Other approach, cheaper? Reduction of tortuosity?
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Tortuosity?
Page 10
𝜏 =𝐿′
𝐿
Graphics: M. Magrini
Ebner et al., Journal of the Electrochemical Society, 162, A3064 (2015)
Tortuosity = 1
Tortuosity > 1
L’ : Path of a Li+ that intercalates
through an electrode
L : Thickness of the electrode
Average ratio of the length of the actual path taken between
two points and the straight distance between them
Lower tortuosity believed to increase the accessibility of
the intercalation planes of graphite to the Li+
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Tortuosity – homogeneisation strategy
Page 11 Doyle et al., Journal of the Electrochemical Society (1996)
Credit: Tommaso Magrini
𝐷𝑒𝑓𝑓 =𝜀
𝜏𝐷0
(diffusion coefficient) (effective diffusion
coefficient)
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Use of magnetic alignment with
sacrificial solids
How to reduce the tortuosity?
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Freeze-casting
Sander et al., Nature Energy (2016) Bahrami et al., Green Chem. (2017)
Co-extrusion with a sacrificial pore former
Bae et al., Advanced Materials (2013)
Can we work directly on the active materials to optimise the architecture?
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Reduction of the tortuosity by magnetic alignment
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Fe3O4 nanoparticles
Only 0.01 – 0.5 vol. % Fe3O4 needed
Studart, Erb, Libanori, Patent WO2011120643, 2011
Erb et al. Science. 2012
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Principle of the magnetic alignment
Page 14 Erb et al. Science. 2012
Can we apply this to battery materials…?
Bouville, Le Ferrand et al. Nature Materials. 2015
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Approach to reduce the tortuosity
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Li+
Li+
Aligning perpendicular to the current collector:
- Enhances accessibility of intercalation planes
- Reduces tortuosity of electrolyte in intercalation direction
Shorter and easier pathway
for Li diffusion, even in
thick/highly loaded
electrodes
Simple, scalable and
inexpensive
technique consisting
in applying a low
magnetic field during
fabrication of anode
x 20
Hrot
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Electrodes preparation
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Slurry preparation:
80% graphite flakes
10% PVP
10% super P
Magnet: 100 mT
J. Billaud, F. Bouville et al., Nature Energy, 1, 16097 (2016)
Graphite used: SFG44
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XRD
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Degree of alignment probed by tracking the intensity of the
(002) Bragg peak (corresponding to the basal plane spacing)
C. E. Banks and R. G. Compton, The Analyst, 131, 15 (2006)
(002)
In-plane alignment of the flakes
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Cross-section SEM
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Aligned electrodes Non-aligned electrodes
Orientation not totally random…
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FIB-tomography
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𝐷𝑒𝑓𝑓 =𝜀
𝜏𝐷0
Non-aligned electrodes Aligned electrodes
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Rate capability tests
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Galvanostatic profiles
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Galvanostatic profiles
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Overpotential increased by two times more for non-aligned electrodes
Aligned Non-aligned
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Long term cycling on thick electrodes
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Current collector
Current collector
27% Qth
18% Qth
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Effect of the calendering on the alignment
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Intensity of the (002) peak does not increase
until the thickness is reduced of 30 %
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Compression with SEM
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Initial
thickness
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Conclusions and outlook
Page 26
Simple and cheap method to align graphite particles and decrease tortuosity of the lithium
paths
High loading electrodes for fast rate cycling obtained
Performance improved solely by changing the inner architecture of the electrode
But:
- large graphite flakes
- high porosity electrodes calendering allows densification by 30%, tests in progress
- optimisation of the process (carbon, binder, ..)
Many more materials to look at!
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Acknowledgements
BatMat group at the PSI
Complex materials group at the ETHZ
Thank you for your
attention!
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