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© 2014 HORIBA, Ltd. All rights reserved.© 2014 HORIBA, Ltd. All rights reserved.
© 2014 HORIBA, Ltd. All rights reserved.
Improving Battery Performance through Particle Size Analysis
Particle AnalysisJeffrey Bodycomb, Ph.D.
Date: 02/26/2014
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Outline
Battery history
Particles in batteries
Measurements of particle size
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History
March, 1749, Benjamin Franklin uses term “battery to describe a group of linked capacitors.
2013 National Geographic Article: Supercapacitors Amp Up as an Alternative to Batteries” http://news.nationalgeographic.com/news/energy/2013/08/130821-supercapacitors/
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History
March, 1800 Volta describes producing current with a stack of zinc and copper with brine soaked cloth in between.
Now we have copper/zinc potato batteries.
~200 years later Amos Latteier builds a 5000 pound potato battery (http://latteier.com/potato/)
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Oxford Bell
Battery operated bell at Oxford bell starts ringing in ~1840.
2001 discussed in Annals of Improbable Research (Volume 7, Issue 3).
2014, bell still ringing, we still don’t know how these batteries were made. The key seems to be that the bell requires very little energy so the batteries last a long time.
http://www.physics.ox.ac.uk/history.asp?page=Exhibit1
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Our buddy: Zinc Carbon
1896 from National Carbon Company
Positive terminal is graphite rod surrounded by Mn(IV) oxide/carbon powder. Carbon powder is to increase conductivity.
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But my battery is solid!
A battery is usually solid and quite durable.
But what if we look inside a Li-ion battery?
Anode Cathode
Particles!
20 microns6 microns
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XploRA
ND フィルタホイール
sample対物レンズ
pinholegrating
Videocamera
CCD
Light source
slit
XY stage
Raman Imaging
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Ram
an In
tens
ity
500 1 000 1 500 2 000Raman Shift (cm-1)
Spectra for each point
Image showing spatial distribution
of each material
x
y
~ν
Raman imaging results
Hypercube:
X, Y, shifts
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-20
-15
-10
-5
0
5
10
15
20
25
30
Y (µ
m)
-30 -20 -10 0 10 20 30X (µm)
2 µm
-30
-25
-20
-15
-10
-5
0
5
10
15
20
25
30
Y (ƒ
Êm)
-20 0 20X (ƒÊm)
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0.80
0.90
1.00
1.10
Inte
nsity
(cnt
/sec
)
2 ƒÊm2 ƒÊm2 ƒÊm
X(μm)
Y(μm
)
0.2
0.4
0.6
0.8
1.0
1.2
1.4
Inte
nsity
(cnt
/sec
)
400 600 800 1 000 1 200 1 400 1 600 1 800 2 000Raman Shift (cm -1 )
0.00
0.10
0.20
0.30
0.40
0.50
0.60
Inte
nsity
(cnt
/sec
)
400 600 800 1 000 1 200 1 400 1 600 1 800 2 000Raman Shift (cm -1 )
0.5
1.0
1.5
Inte
nsity
(cnt
/sec
)
400 600 800 1 000 1 200 1 400 1 600 1 800 2 000Raman Shift (cm -1 )
LiCoO2 with extra oxide
carbon
LiCoO2
Raman imaging of Li ion electrodes
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Battery Basics
Chemistry sets potential (voltage)…But the voltage drops due to resistance (electrical and ionic).
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Moving Li
Glow discharge
Look at Li level
Pulsed RF GD OES Depth Profile Analysis of the positive electrode
GD Profiler
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Battery Structure
How do I get electrons and ions to move?
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Microscopic View
LiCoO2
Li moves into CoO2 octahedra slabs
How fast can the LI get in there?
Li
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Particle Size!
Need to consider diffusion of Li+ into CoO2
when considering charge/discharge rate (or power, not energy)!
As particles get smaller, area for diffusion increases
Also area for undesirable side reactions increases
See M. Park, et al., J. Power Sources (2010), doi:10.1016/j.jpowsour.2010.06.060
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Alkaline battery
Graphite particle size
Smaller lowers resistivity at low loadings (5%)
Lowers flex strength
D90’s from 10 to 100 microns
MnO2 powder is~100’s of microns
Anode is Zn powder (D50 of 50~200 microns) in gel
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Measuring graphite
Laser diffraction
Dispersed in 0.01% Tween 20
10 minutes ultrasonic
D50: 3.05 micron
D90: 5.80 micron
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Measuring Zinc Powder
This sample was measured dry by laser diffraction…there is no need to disperse it in liquid.
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Measuring MnO2
Yes, laser diffraction works here as well.
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Size: Particle Diameter (m)0.01 0.1 1 10 100 1000
Colloidal
Suspensions and Slurries
DLS – SZ-100
Electron Microscope
Powders
Fine Coarse
Microscopy PSA300, Camsizer
Laser Diffraction – LA-300, LA-950
Acoustic Spectroscopy
Electrozone Sensing
Disc-Centrifuge
Light Obscuration
0.001
Macromolecules
Nano-Metric
Met
hods
App
sA
pps
Size
sSi
zes
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Laser Diffraction
Measure the variation in scattered intensity with angle to find particle size.
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LA-950 Optics
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Scattered Intensity and Size
As diameter increases, intensity (per particle) increases and location of first peak shifts to smaller angle.
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Li Battery Materials
Cathode Materials:•Lithium cobalt oxide LiCoO2•Lithium nickel oxide LiNiO2•Lithium manganese oxide LiMn2O4•Lithium iron phosphate LiFePO4Anode Materials•Carbon C•Lithium Li•Lithium titanate Li2TiO3
LA Series Laser Diffraction
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Repeatability (measure same material)
Below are results from measuring to different lithium compounds. Each compound was measured ten times and the relative standard deviation was found.
Sample Run 1 Run 2 Run 3 Run 4 Run 5 Run 6 Run 7 Run 8 Run 9 Run 10 Average RSD
LiMn2O4 9.75 9.93 9.75 9.66 9.83 9.78 9.76 9.75 9.79 9.60 9.76 0.90%
Li2TiO3 16.7 16.6 16.7 16.6 16.7 16.6 16.8 16.8 16.8 16.9 16.7 0.51%
Samples were measured in aqueous suspension. The mixing level and circulation level were both set to 3 during measurement.
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Instrument to Instrument Agreement
Two different instruments
LA #1 LA #2 diff
LiMn2O4 9.75 9.64 0.1
Li2TiO3 16.7 16.9 0.2
D50 values
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Lot Median Size (μm)
No.1 11.3No.2 11.8No.3 12.2No.4 12.5No.5 11.9
No.1
No.2
No.3
No.4
No.5
Here, 5 different lots of lithium cobalt oxide (LiCoO2) were measured. Note that there is some variation between the lots.
Lithium ion material lot to lot variation
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Measu
rem
ent G
oal
Sam
ple
State
Association: Electrostatic, Van der Waals, etc.
PrimaryTertiary Secondary
Agglomerate size
particle size
Ultrasound, mixing, dispersant.
disperion
Dispersion
stability Zeta Potential
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Large Scale Storage
Sodium sulfur battery
Molten sodium and sulfur at 300 C.
Load leveling (store wind/solar power) for the grid
BASE – Beta alumina solid electrolyte
Alumina lid (to keep out moisture among other things
Both require alumina. And particle size is important.
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Fused White AluminaIn aqueous 0.2% hexametaphosphate
To measure alumina accurately we need to use the built in ultrasonic probe to break up loose aggregates.
Fused White Alumina
Effect of ultrasound
No ultrasonic 1 minute 3 minute
5 minute10 minute
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Dispersants: More than just water
line ultrasonic mode1(μm) mode 2(μm)
―― none 12.96 72.69
―― 5 0.23 7.16
―― 10 0.24 6.08
Some materials are not readily dispersed in water and should be measured in another dispersant.
Here we use NMP.
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ultrasound
0 min
10 min
small ball mill media Large ball mill media72μm
6μm
12μm
0.2μm
162μm8μm
108μm8μm
Evaluating ball milling (and ultrasound)
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Dynamic:particles flow past camera
1 – 3000 um
Static:particles fixed on slide,
stage moves slide
0.5 – 1000 um2000 um w/1.25 objective
Image Analysis: Two Approaches
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Data Evaluation
BinarizeFind Edges
Analyze Each Particle
Output Distribution
Raw Image
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Features
Use gravity, or, better, vacuum (from a compressed air supply and venturi) in order to draw particles through instrument. Vacuum
helps keep the windows clean.
36© Retsch Technology GmbH
Dynamic Image Analysis:
Moving Particles
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Reproducibility
Metal powder by Camsizer XT
xc_min [µm]10 15 20 25 30 35 40 45 500
10
20
30
40
50
60
70
80
90
Q3 [%]
0
1
2
3
4
5
6
7
8
9
q3 [%/µm]
Cookson-#8-30kPa_vvv_ZOOM_xc_min_MvCookson-#8-30kPa_TP1_vvv_ZOOM_xc_miCookson-#8-30kPa_TP2_vvv_ZOOM_xc_miCookson-#13-30kPa_TP1_vvv_ZOOM_xc_mCookson-#13-30kPa_TP2_vvv_ZOOM_xc_mCookson-#13-30kPa_vvv_ZOOM_xc_min_MCookson-#27-30kPa_TP1_vvv_ZOOM_xc_mCookson-#27-30kPa_TP2_vvv_ZOOM_xc_mCookson-#27-30kPa_vvv_ZOOM_xc_min_M
Tin and Lead Solder Powder
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Particle Shape
Image capture with PSA300
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Concluding Comments
Battery performance depends on particle size.
Particle size can be determined by a number of techniques including laser diffraction and image analysis.
Questions?
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Questions?
www.horiba.com/us/particle
Jeffrey Bodycomb, Ph.D.
Jeff.Bodycomb@Horiba.com
labinfo@horiba.com
866-562-4698
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Thank you
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