Bernd Ketterer Graphite Powder Processing

Graphite Powder Processing
A Key Element for High Performance

Lithium-Ion Batteries
Bernt Ketterer, Ulrich Bosch, Oswin ttinger, DKG-AKK Herbsttagung, 7th November 2014
Graphite Powder Processing for High Performance

Outline
1.
Graphite Anode Materials: Position of SGL & Market Perspectives
2.
Anode Materials for Lithium Batteries: Basic Requirements
3.
Powder Design for High Performance Graphite Anodes, Influences of:
4.
Page 2
BET Surface Area

Particle Size
Particle Shape
Summary
| SGL Group master 0214
For internal use only

SGL Proprietary Information
LIB Anode Materials Overview

Material Share Status 2012
- Artificial and natural graphite

biggest share (total >90%)
- Next generation high capacity
materials (silicon and tin based)
enter the market
- Fast growing market for graphite
anodes in 3C and electromobility
Total Volume in 2012: ~32000t
Source: SGL, Avicenne, Battery Market Development 2012-2025
Page 3

Graphite Anode Materials

Joint Forces for Best Solutions
More than 10 Years Cooperation
World Largest Synthetic Graphite Anode Production

& Leading Edge Technology Know How
Page 4


Outline
1.
2.
3.
4.
Page 5
BET Surface Area

Particle Size
Particle Shape
Summary

Lithium Ion Battery: Basic Working Principle
Li+ ions
Cathode
separator
Li+ ions flow

Charge
Electrolyte
Graphite-Anode
Cu current collector
Al current collector
electrons flow
Polymeric
Binder
Graphite
Cu-foil current collector
Conductive additive
Page 6
separator
Li+ ions flow

Discharge
Cathode
Electrolyte
Li+ ions
Graphite-Anode
Cu current collector
Al current collector
electrons flow

Li-Ion Battery - Graphite as Anode Material

Solid Electrolyte Interface - SEI
First Cycle: Carbon/graphite + Electrolyte Solid Electrolyte Interphase
TEM of Solid Electrolyte Interphase
Schematic drawing of the composition of the SEI

Li2O
Li2O
Li2O
LiF
Li2O
Semicar
Li2CO3bonates
Li2O Li CO
2
3
LiF
Li2O
LiF
Polyole
phines
Electrolyte
Carbon/
Graphite
Polyolephines
(LiPF6 ,Carbonates,etc.)
LiF Li2CO3
SEI formation
consumes Lithium!
Solid Electrolyte Interphase (SEI)

The SEI protects the graphite from solvent co-intercalation Graphite would not work without SEI
Source: TEM: F. Orsini, L. Dupont, B. Beaudoin, S. Grugeon, J.-M. Tarascon, Int. J. Inorg. Mater. 2 (2000), 701 AND E. Peled, D. Golodnitsky and G. Ardel, J. Electrochem. Soc. 144 (1997), L208.
Page 7

Key Parameters of Electrode Materials:

Capacity and Efficiency
1m
Li
Graphite Particle
Surface Electrolyte Interphase

Layer (SEI ):
Passivating layer formed on the
graphite particle surface
Page 8
Capacity:
Capacity loss (1st Cycle Efficiency):
How much lithium is intercalated in

graphite? Depending on:
How much lithium contributes to SEIformation? Depending on:
How many defects are in the graphite?
specific surface (e.g. BET)
Degree of graphitization
particle size and shape

Graphite Anode Materials: Basic Requirements

Battery Level
Material Level
Specific Capacity
(mAh/g)
Gravimetric
Energy Density
Wh/kg
Lightweight
Battery
Voltage Level
Volumetric
Energy Density
1st Cycle Efficiency

Electrode Loading
Wh/l
Power Density
Small Battery
W/kg or W/l
Acceleration
(mAh/cm)
% Inactive Material
Film Swelling
Material & Film Density
(g/cm)
Rate Capability
(Temperature-Dependence)
Particle Size / BET
Directly Influenced by
Graphite Particle
Properties
Page 9
Safety
Purity
Cycle Stability

Outline
1.
2.
3.
4.
Page 10
BET Surface Area

Particle Size
Particle Shape
Summary

Lower BET Surface Area:

Optimized Battery 1st Cycle Efficiency
Coulumbic Efficiency (%)
96
A low BET surface is crucial for:
95
1st cycle Efficiency (low Li losses)
94
Energy density
93
Safety
92
Cycle life
91
Binder demand
90
89
Surface Area (m 2/g)
Page 11

BET Surface
(relative numbers)
Lower the BET Surface Area:

Influence of the milling device
Examples from Different Milling Devices
d50 = const.
Different Milling Devices

Milling type & milling & spheroidisation equipment configuration influence
significantly the particle shape / BET and therefore also the battery performance
Additionally milling & rounding yield is the key element for commercial success
Page 12

Lower the BET Surface Area:

Influence of rounding and the coating
Engineered anode
material
Graphite powder
Graphite
Carbon
coating layer
10 m
10 m
Rounding
2 nm
Coating
Lower BET Suface
Page 13

Quicker Charge/Discharge:
Influence of the Particle Size
Li+
Specific Capacity in mAh/g
375
Li+
Graphite with
medium
particle size
325
275
225
Medium D 50
Value (i.e . 20 m)
175
very small D50

value (i.e . 10 m)
125
75
25
0
slow
Log (Dis. - )/Charging Time
High Energy
Graphite with
very small
particle size
quick
High Power
Smaller anode particle size distribution is beneficial for quicker LIB

charging. However Formation of higher surface area
Page 14
Li+
Li+
Particle size distribution and

shape
d50 between 10 and 30 m
d90< 70 m
Low amount of fine particle fraction

Quicker Charge/Discharge:
Influence of the Particle Shape
Li+
Li+
Flaky
Flaky Graphite
Particles
Potato Shaped
Graphite Particles
Potato
Cu-current collector
How fast is lithium intercalated in graphite? Depending on particle orientation in the electrode
Page 15

high
Potatoparticle shape
Flakyparticle shape
Low
Compaction Pressure
high
Potato shape particle generates

higher film packing density at
lower compaction pressures
Page 16
Electrode Film Density
Electrode Film Density
High Film Density for Improved Energy Density:

Influence of Particle Shape & Particle Size Distribution
Particle
Size
0,1
1
10
Size
0,1Particle
1
10
Density
+ 20%
Bimodal / broader particle size

distribution can generate higher film
packing densities. However, BET need to
be kept low, otherwise efficiency loss


Outline
1.
2.
3.
4.
Page 17
BET Surface Area

Particle Size
Particle Shape
Summary


Lithium-Ion Batteries Key Elements - Summary
Particle Size Distribution
Energy
Density
Particle
Size
Quick Yield
Charge Costs
Cycle
Life
1st Cycle
Efficiency
Particle
Surface
(coating)
Particle Shape
(BET)
Page 18

Thank you
for your attention!
Copyright SGL CARBON SE

Registered trademarks of SGL CARBON SE
Important note:
This presentation may contain forward-looking statements based on the information currently available to us and on our current projections
and assumptions. By nature, forward-looking statements involve known and unknown risks and uncertainties, as a consequence of which
actual developments and results can deviate significantly from these forward-looking statements. Forward-looking statements are not to be
understood as guarantees. Rather, future developments and results depend on a number of factors; they entail various risks and
unanticipated circumstances and are based on assumptions which may prove to be inaccurate. These risks and uncertainties include, for
example, unforeseeable changes in political, economic, legal, and business conditions, particularly relating to our main customer industries,
such as electric steel production, to the competitive environment, to interest rate and exchange rate fluctuations, to technological
developments, and to other risks and unanticipated circumstances. Other risks that in our opinion may arise include price developments,
unexpected developments connected with acquisitions and subsidiaries, and unforeseen risks associated with ongoing cost savings
programs. SGL Group does not intend or assume any responsibility to revise or otherwise update these forward-looking statements.
Page 20


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Graphite Powder Processing

A Key Element for High Performance

Graphite Powder Processing for High Performance

Graphite Anode Materials: Position of SGL & Market Perspectives

Anode Materials for Lithium Batteries: Basic Requirements

Powder Design for High Performance Graphite Anodes, Influences of:

BET Surface Area

| SGL Group master 0214

For internal use only

LIB Anode Materials Overview

- Artificial and natural graphite

| SGL Group master 0214

For internal use only

Graphite Anode Materials

More than 10 Years Cooperation

World Largest Synthetic Graphite Anode Production

| SGL Group master 0214

For internal use only

Graphite Powder Processing for High Performance

Graphite Anode Materials: Position of SGL & Market Perspectives

Anode Materials for Lithium Batteries: Basic Requirements

Powder Design for High Performance Graphite Anodes, Influences of:

BET Surface Area

| SGL Group master 0214

For internal use only

Lithium Ion Battery: Basic Working Principle

Li+ ions flow

Cu-foil current collector

| SGL Group master 0214

Li+ ions flow

For internal use only

Li-Ion Battery - Graphite as Anode Material

Schematic drawing of the composition of the SEI

Solid Electrolyte Interphase (SEI)

| SGL Group master 0214

For internal use only

Key Parameters of Electrode Materials:

Surface Electrolyte Interphase

Capacity loss (1st Cycle Efficiency):

How much lithium is intercalated in

How much lithium contributes to SEIformation? Depending on:

How many defects are in the graphite?

specific surface (e.g. BET)

particle size and shape

| SGL Group master 0214

For internal use only

Graphite Anode Materials: Basic Requirements

1st Cycle Efficiency

Particle Size / BET

| SGL Group master 0214

SGL Proprietary Information

Graphite Powder Processing for High Performance

Graphite Anode Materials: Position of SGL & Market Perspectives

Anode Materials for Lithium Batteries: Basic Requirements

Powder Design for High Performance Graphite Anodes, Influences of:

BET Surface Area

| SGL Group master 0214

For internal use only

Lower BET Surface Area:

Coulumbic Efficiency (%)

A low BET surface is crucial for:

1st cycle Efficiency (low Li losses)

Surface Area (m 2/g)

| SGL Group master 0214