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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


Lithium-Ion Batteries
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.

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BET Surface Area


Particle Size
Particle Shape

Summary

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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
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Graphite Anode Materials


Joint Forces for Best Solutions

More than 10 Years Cooperation

World Largest Synthetic Graphite Anode Production


& Leading Edge Technology Know How
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Graphite Powder Processing for High Performance


Lithium-Ion Batteries
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.

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BET Surface Area


Particle Size
Particle Shape

Summary

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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

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separator

Li+ ions flow


Discharge

Cathode

Electrolyte

Li+ ions

Graphite-Anode

Cu current collector

Al current collector

electrons flow

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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.
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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

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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

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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
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Safety

Purity
Cycle Stability
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Graphite Powder Processing for High Performance


Lithium-Ion Batteries
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.

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BET Surface Area


Particle Size
Particle Shape

Summary

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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)

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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
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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

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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
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Li+
Li+

Particle size distribution and


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

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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
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high

Potatoparticle shape

Flakyparticle shape
Low

Compaction Pressure

high

Potato shape particle generates


higher film packing density at
lower compaction pressures

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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

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Graphite Powder Processing for High Performance


Lithium-Ion Batteries
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.

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BET Surface Area


Particle Size
Particle Shape

Summary

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Graphite Powder Processing for High Performance


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)
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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.

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