© 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 Analysis
Je...
© 2014 HORIBA, Ltd. All rights reserved.
Outline
Battery history
Particles in batteries
Measurements of particle size
© 2014 HORIBA, Ltd. All rights reserved.
History
 March, 1749, Benjamin
Franklin uses term
“battery to describe a
group o...
© 2014 HORIBA, Ltd. All rights reserved.
History
 March, 1800 Volta describes
producing current with a
stack of zinc and ...
© 2014 HORIBA, Ltd. All rights reserved.
Oxford Bell
 Battery operated bell at Oxford
bell starts ringing in ~1840.
 200...
© 2014 HORIBA, Ltd. All rights reserved.
Our buddy: Zinc Carbon
1896 from National Carbon Company
Positive terminal is g...
© 2014 HORIBA, Ltd. All rights reserved.
But my battery is solid!
A battery is usually solid and quite durable.
But what...
© 2014 HORIBA, Ltd. All rights reserved.
XploRA
ND フィルタ
ホイール
sample
対物レンズ
pinholegrating
Video
camera
CCD
Light source
sl...
© 2014 HORIBA, Ltd. All rights reserved.
RamanIntensity
500 1 000 1 500 2 000
Raman Shift (cm-1)
Spectra for each
point
Im...
© 2014 HORIBA, Ltd. All rights reserved.
-20
-15
-10
-5
0
5
10
15
20
25
30
Y(µm)
-30 -20 -10 0 10 20 30
X (µm)
2 µm
-30
-2...
© 2014 HORIBA, Ltd. All rights reserved.
Battery Basics
Chemistry sets potential (voltage)…
But the voltage drops due to r...
© 2014 HORIBA, Ltd. All rights reserved.
Moving Li
Glow discharge
Look at Li level
Pulsed RF GD OES
Depth Profile Analy...
© 2014 HORIBA, Ltd. All rights reserved.
Battery Structure
How do I get electrons and ions to move?
© 2014 HORIBA, Ltd. All rights reserved.
Microscopic View
LiCoO2
Li moves into CoO2 octahedra slabs
How fast can the LI...
© 2014 HORIBA, Ltd. All rights reserved.
Particle Size!
 Need to consider diffusion of Li+ into CoO2
when considering cha...
© 2014 HORIBA, Ltd. All rights reserved.
Alkaline battery
 Graphite particle size
 Smaller lowers
resistivity at low
loa...
© 2014 HORIBA, Ltd. All rights reserved.
Measuring graphite
 Laser diffraction
 Dispersed in 0.01% Tween 20
 10 minutes...
© 2014 HORIBA, Ltd. All rights reserved.
Measuring Zinc Powder
This sample was measured dry by laser
diffraction…there is ...
© 2014 HORIBA, Ltd. All rights reserved.
Measuring MnO2
Yes, laser diffraction works here as well.
© 2014 HORIBA, Ltd. All rights reserved.
Size: Particle Diameter (m)
0.01 0.1 1 10 100 1000
Colloidal
Suspensions and Slu...
© 2014 HORIBA, Ltd. All rights reserved.
Laser Diffraction
Measure the variation in scattered intensity with angle
to find...
© 2014 HORIBA, Ltd. All rights reserved.
LA-950 Optics
© 2014 HORIBA, Ltd. All rights reserved.
Scattered Intensity and Size
As diameter increases, intensity (per particle) incr...
© 2014 HORIBA, Ltd. All rights reserved.
Li Battery Materials
Cathode Materials:
•Lithium cobalt oxide LiCoO2
•Lithium nic...
© 2014 HORIBA, Ltd. All rights reserved.
Repeatability (measure same material)
Below are results from measuring to differe...
© 2014 HORIBA, Ltd. All rights reserved.
Instrument to Instrument Agreement
Two different instruments
LA #1 LA #2 diff
LiM...
© 2014 HORIBA, Ltd. All rights reserved.
Lot Median Size (μm)
No.1 11.3
No.2 11.8
No.3 12.2
No.4 12.5
No.5 11.9
No.1
No.2
...
© 2014 HORIBA, Ltd. All rights reserved.
MeasurementGoalSampleState
Association: Electrostatic, Van der Waals, etc.
Primar...
© 2014 HORIBA, Ltd. All rights reserved.
Large Scale Storage
Sodium sulfur battery
Molten sodium and sulfur at 300 C.
L...
© 2014 HORIBA, Ltd. All rights reserved.
Fused White Alumina
In aqueous 0.2% hexametaphosphate
To measure alumina accurate...
© 2014 HORIBA, Ltd. All rights reserved.
Dispersants: More than just water
line ultrasonic mode1(μm) mode 2(μm)
―― none 12...
© 2014 HORIBA, Ltd. All rights reserved.
ultrasound
0 min
10 min
small ball mill media Large ball mill media
72μm
6μm
12μm...
© 2014 HORIBA, Ltd. All rights reserved.
Dynamic:
particles flow past camera
1 – 3000 um
Static:
particles fixed on slide,...
© 2014 HORIBA, Ltd. All rights reserved.
Data Evaluation
Binarize
Find Edges
Analyze Each Particle
Output Distribution
Raw...
© 2014 HORIBA, Ltd. All rights reserved.
Features
Use gravity, or, better, vacuum (from a compressed air supply and
ventur...
© 2014 HORIBA, Ltd. All rights reserved.
Reproducibility
Metal powder by Camsizer XT
xc_min [µm]10 15 20 25 30 35 40 45 5...
© 2014 HORIBA, Ltd. All rights reserved.
Particle Shape
Image capture with PSA300
© 2014 HORIBA, Ltd. All rights reserved.
Concluding Comments
Battery performance depends on particle
size.
Particle size...
© 2013 HORIBA, Ltd. All rights reserved.
Questions?
www.horiba.com/us/particle
Jeffrey Bodycomb, Ph.D.
Jeff.Bodycomb@Horib...
© 2014 HORIBA, Ltd. All rights reserved.
Thank you
© 2014 HORIBA, Ltd. All rights reserved.
Danke
Gracias
Большое спасибо
Grazie‫ر‬ْ‫ك‬ُ‫ش‬‫ا‬
Σας ευχαριστούμε
감사합니다
Obrigad...
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Improving Battery Performance Through Particle Size Analysis

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Dr. Jeff Bodycomb of HORIBA Scientific discusses how particle size analysis positively impacts the development and performance of battery materials.

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Improving Battery Performance Through Particle Size Analysis

  1. 1. © 2014 HORIBA, Ltd. All rights reserved. © 2014 HORIBA, Ltd. All rights reserved.
  2. 2. © 2014 HORIBA, Ltd. All rights reserved. Improving Battery Performance through Particle Size Analysis Particle Analysis Jeffrey Bodycomb, Ph.D. Date: 02/26/2014
  3. 3. © 2014 HORIBA, Ltd. All rights reserved. Outline Battery history Particles in batteries Measurements of particle size
  4. 4. © 2014 HORIBA, Ltd. All rights reserved. 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/n ews/energy/2013/08/130821- supercapacitors/
  5. 5. © 2014 HORIBA, Ltd. All rights reserved. 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/)
  6. 6. © 2014 HORIBA, Ltd. All rights reserved. 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
  7. 7. © 2014 HORIBA, Ltd. All rights reserved. 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.
  8. 8. © 2014 HORIBA, Ltd. All rights reserved. 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 microns 6 microns
  9. 9. © 2014 HORIBA, Ltd. All rights reserved. XploRA ND フィルタ ホイール sample 対物レンズ pinholegrating Video camera CCD Light source slit XY stage Raman Imaging
  10. 10. © 2014 HORIBA, Ltd. All rights reserved. RamanIntensity 500 1 000 1 500 2 000 Raman Shift (cm-1) Spectra for each point Image showing spatial distribution of each material x y ~ν Raman imaging results Hypercube: X, Y, shifts
  11. 11. © 2014 HORIBA, Ltd. All rights reserved. -20 -15 -10 -5 0 5 10 15 20 25 30 Y(µm) -30 -20 -10 0 10 20 30 X (µm) 2 µm -30 -25 -20 -15 -10 -5 0 5 10 15 20 25 30 Y(ƒÊm) -20 0 20 X (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 Intensity(cnt/sec) 2 ƒÊm2 ƒÊm2 ƒÊm X(μm) Y(μm) 0.2 0.4 0.6 0.8 1.0 1.2 1.4 Intensity(cnt/sec) 400 600 800 1 000 1 200 1 400 1 600 1 800 2 000 Raman Shift (cm -1 ) 0.00 0.10 0.20 0.30 0.40 0.50 0.60 Intensity(cnt/sec) 400 600 800 1 000 1 200 1 400 1 600 1 800 2 000 Raman Shift (cm -1 ) 0.5 1.0 1.5 Intensity(cnt/sec) 400 600 800 1 000 1 200 1 400 1 600 1 800 2 000 Raman Shift (cm -1 ) LiCoO2 with extra oxide carbon LiCoO2 Raman imaging of Li ion electrodes
  12. 12. © 2014 HORIBA, Ltd. All rights reserved. Battery Basics Chemistry sets potential (voltage)… But the voltage drops due to resistance (electrical and ionic).
  13. 13. © 2014 HORIBA, Ltd. All rights reserved. Moving Li Glow discharge Look at Li level Pulsed RF GD OES Depth Profile Analysis of the positive electrode GD Profiler
  14. 14. © 2014 HORIBA, Ltd. All rights reserved. Battery Structure How do I get electrons and ions to move?
  15. 15. © 2014 HORIBA, Ltd. All rights reserved. Microscopic View LiCoO2 Li moves into CoO2 octahedra slabs How fast can the LI get in there? Li
  16. 16. © 2014 HORIBA, Ltd. All rights reserved. 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
  17. 17. © 2014 HORIBA, Ltd. All rights reserved. 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
  18. 18. © 2014 HORIBA, Ltd. All rights reserved. Measuring graphite  Laser diffraction  Dispersed in 0.01% Tween 20  10 minutes ultrasonic  D50: 3.05 micron  D90: 5.80 micron
  19. 19. © 2014 HORIBA, Ltd. All rights reserved. Measuring Zinc Powder This sample was measured dry by laser diffraction…there is no need to disperse it in liquid.
  20. 20. © 2014 HORIBA, Ltd. All rights reserved. Measuring MnO2 Yes, laser diffraction works here as well.
  21. 21. © 2014 HORIBA, Ltd. All rights reserved. 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 MethodsAppsAppsSizesSizes
  22. 22. © 2014 HORIBA, Ltd. All rights reserved. Laser Diffraction Measure the variation in scattered intensity with angle to find particle size.
  23. 23. © 2014 HORIBA, Ltd. All rights reserved. LA-950 Optics
  24. 24. © 2014 HORIBA, Ltd. All rights reserved. Scattered Intensity and Size As diameter increases, intensity (per particle) increases and location of first peak shifts to smaller angle.
  25. 25. © 2014 HORIBA, Ltd. All rights reserved. Li Battery Materials Cathode Materials: •Lithium cobalt oxide LiCoO2 •Lithium nickel oxide LiNiO2 •Lithium manganese oxide LiMn2O4 •Lithium iron phosphate LiFePO4 Anode Materials •Carbon C •Lithium Li •Lithium titanate Li2TiO3 LA Series Laser Diffraction
  26. 26. © 2014 HORIBA, Ltd. All rights reserved. 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.
  27. 27. © 2014 HORIBA, Ltd. All rights reserved. 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
  28. 28. © 2014 HORIBA, Ltd. All rights reserved. Lot Median Size (μm) No.1 11.3 No.2 11.8 No.3 12.2 No.4 12.5 No.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
  29. 29. © 2014 HORIBA, Ltd. All rights reserved. MeasurementGoalSampleState Association: Electrostatic, Van der Waals, etc. PrimaryTertiary Secondary Agglomerate size particle size Ultrasound, mixing, dispersant. disperi on Dispersion stability Zeta Potential
  30. 30. © 2014 HORIBA, Ltd. All rights reserved. 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.
  31. 31. © 2014 HORIBA, Ltd. All rights reserved. Fused White Alumina In 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
  32. 32. © 2014 HORIBA, Ltd. All rights reserved. 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.
  33. 33. © 2014 HORIBA, Ltd. All rights reserved. ultrasound 0 min 10 min small ball mill media Large ball mill media 72μm 6μm 12μm 0.2μm 162μm 8μm 108μm8μm Evaluating ball milling (and ultrasound)
  34. 34. © 2014 HORIBA, Ltd. All rights reserved. Dynamic: particles flow past camera 1 – 3000 um Static: particles fixed on slide, stage moves slide 0.5 – 1000 um 2000 um w/1.25 objective Image Analysis: Two Approaches
  35. 35. © 2014 HORIBA, Ltd. All rights reserved. Data Evaluation Binarize Find Edges Analyze Each Particle Output Distribution Raw Image
  36. 36. © 2014 HORIBA, Ltd. All rights reserved. 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
  37. 37. © 2014 HORIBA, Ltd. All rights reserved. Reproducibility Metal powder by Camsizer XT xc_min [µm]10 15 20 25 30 35 40 45 50 0 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_Mv Cookson-#8-30kPa_TP1_vvv_ZOOM_xc_mi Cookson-#8-30kPa_TP2_vvv_ZOOM_xc_mi Cookson-#13-30kPa_TP1_vvv_ZOOM_xc_m Cookson-#13-30kPa_TP2_vvv_ZOOM_xc_m Cookson-#13-30kPa_vvv_ZOOM_xc_min_M Cookson-#27-30kPa_TP1_vvv_ZOOM_xc_m Cookson-#27-30kPa_TP2_vvv_ZOOM_xc_m Cookson-#27-30kPa_vvv_ZOOM_xc_min_M Tin and Lead Solder Powder
  38. 38. © 2014 HORIBA, Ltd. All rights reserved. Particle Shape Image capture with PSA300
  39. 39. © 2014 HORIBA, Ltd. All rights reserved. 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?
  40. 40. © 2013 HORIBA, Ltd. All rights reserved. Questions? www.horiba.com/us/particle Jeffrey Bodycomb, Ph.D. Jeff.Bodycomb@Horiba.com labinfo@horiba.com 866-562-4698
  41. 41. © 2014 HORIBA, Ltd. All rights reserved. Thank you
  42. 42. © 2014 HORIBA, Ltd. All rights reserved. Danke Gracias Большое спасибо Grazie‫ر‬ْ‫ك‬ُ‫ش‬‫ا‬ Σας ευχαριστούμε 감사합니다 Obrigado Tacka dig 谢谢ขอบคุณครับ ありがとうございました धन्यवाद நன்ற Cảm ơn
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