Lesson1 2 3 Handout

1.2.
3: Negative electrodes for lithium-ion cells
Cell formats
key on: initialize

meas. voltage estimate estimate balance compute
current state of state of power
We begin this lesson by considering cell structure temperature charge (SOC) health (SOH) cells limits
loop once each measurement interval while pack is active
Lithium-ion cells are manufactured in different form factors

Cylindrical cells are. . . err. . . cylindrical (round “jelly roll”)
Prismatic cells are. . . prismatic (flat “jelly roll”)
Pouch cells are also flat, but comprise stacked plates
Cylindrical cells Prismatic cells Pouch cells
Dr. Gregory L. Plett University of Colorado Colorado Springs Introduction to Battery Management Systems | How Lithium-ion Cells Work 1 of 10
1.2.3: Negative electrodes for lithium-ion cells
Electrode coating
key on: initialize

Electrodes in lithium-ion cells of any form factor are of similar temperature charge (SOC) health (SOH) cells limits
structure and are made by similar processes

The active electrode materials are coated on both sides of metallic foils which act
as the current collectors conducting the current into and out of the cell
Positive current collector
Positive electrode active material
Negative current collector

Negative electrode active material
Two basic electrode structures are used, depending on cell form factor:
A stacked structure for use in pouch cells, and
A spiral wound structure for use in cylindrical/prismatic cells
Stacked electrode structure

key on: initialize

Pouch/prismatic cells are often used for high capacity battery temperature charge (SOC) health (SOH) cells limits
applications to optimize the use of space

Pouch designs use a stacked electrode structure in Negative
which the negative- and positive-electrode foils are electrode
cut into individual electrode plates which are stacked
alternately and kept apart by the separator
Separator may be cut to the same size as electrodes
but more often is a long strip wound zig-zag between Positive
alternate electrodes in the stack electrode Separator
All negative-electrode tabs are welded in parallel and to the cell’s negative terminal;
all positive-electrode tabs are welded in parallel and to the cell’s positive terminal
Cylindrical and prismatic electrode structure
key on: initialize

For cylindrical cells the negative- and positive-electrode foils temperature charge (SOC) health (SOH) cells limits
are cut into two long strips which are wound on a cylindrical
mandrel, together with the
separator to hold the electrodes Mandrel Mandrel
apart, to form a jelly roll

Positive
Positive electrode
Most prismatic cells are electrode
constructed similarly, by winding

Negative
electrodes on a flat mandrel electrode Negative
electrode
Separator
Separator
Microscale structure of graphite
key on: initialize

We now start to examine the different materials used in the temperature charge (SOC) health (SOH) cells limits
electrodes of lithium-ion cells, starting with negative electrode

Presently, essentially all commercial
lithium-ion cells use some form of graphite
(C6 ) for the negative-electrode material
Graphite has graphene layers of C6
structures that are tightly bonded
These layers are loosely stacked and there is
room for lithium to intercalate between them
Mesoscale structure of graphite

key on: initialize

Carbon used in negative electrodes can come from natural or temperature charge (SOC) health (SOH) cells limits
synthetic sources (which have somewhat different layering

properties), or from natural “hard” or disordered carbons, which have many small
pockets of graphene layers, arranged in random configurations
Natural or synthetic graphite Hard carbon

These carbons have somewhat different voltage and lifetime properties
Alternate negative-electrode material LTO
key on: initialize

Lithium titanate oxide (Li4 Ti5 O12 , LTO) is an alternative temperature charge (SOC) health (SOH) cells limits
negative-electrode material
It has very different crystal Open-circuit potential of common
negative-electrode materials
structure from graphite 2
In figure, Li is purple; Ti
OCP vs. Li/Li+ (V)

1.5
is orange; O is red; green LTO

polyhedra show fixed
1
Hard carbon
Coke
crystal structure 0.5 MCMB
Lithium diffuses through 0

0 0.2 0.4 0.6 0.8 1
openings in crystal Stoichiometry (unitless)
Disadvantage: high open-circuit potential (making cell voltage low)

Advantage: nearly indestructible — very long life
Future negative-electrode material silicon
key on: initialize

Silicon is a very promising negative-electrode material temperature charge (SOC) health (SOH) cells limits
Using graphite, one can store up to one Li per six C atoms;

using silicon, one can (in principle) store four Li per every Si atom!
Therefore, energy density using silicon electrodes can be much higher
Unfortunately, while volume change for a charge/discharge cycle for graphite is
around 10 %, it is around 400 % for silicon
Therefore, silicon electrodes tend to fracture quickly
and have short lives
Possible workarounds: mix graphite with silicon, or
build small forests of silicon nanowires with space
in-between to allow for expansion
Summary
key on: initialize

Lithium-ion cells are manufactured in pouch, prismatic, and temperature charge (SOC) health (SOH) cells limits
cylindrical form factors

In any of these cases, current-collector metal foils are generally coated on both
sides with electrode active materials
In the negative electrode, the most common active material is some form of carbon:
natural or synthetic graphite, or hard carbon
Lithium titanate oxide (LTO) is an alternative material, which greatly increases cell
longevity, but is costly and significantly lowers energy density
Future lithium-ion cells will probably include silicon in the negative electrode to
improve energy density (presently, cycle life of silicon is low)
Credits
key on: initialize

Credits for images in this lesson:

temperature charge (SOC) health (SOH) cells limits
Graphite structure on page 5 drawn with VESTA. See, Momma, K.

and Izumi, F., “VESTA 3 for three-dimensional visualization of crystal,
volumetric and morphology data,” Journal of Applied Crystallography, 44, 1272–1276 (2011)
LTO structure on page 7 also drawn with VESTA: See, reference above
Silicon nanostructures on page 8, By Christoph Kubasch (2005) [CC BY-SA 3.0
(http://creativecommons.org/licenses/by-sa/3.0)], via Wikimedia Commons,
https://commons.wikimedia.org/wiki/File:Black_Silicon_-_ASE.jpg

Lesson1 2 3 Handout

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1.2.

3: Negative electrodes for lithium-ion cells

key on: initialize

loop once each measurement interval while pack is active

Lithium-ion cells are manufactured in different form factors

Cylindrical cells Prismatic cells Pouch cells

1.2.3: Negative electrodes for lithium-ion cells

key on: initialize

loop once each measurement interval while pack is active

structure and are made by similar processes

Negative current collector

1.2.3: Negative electrodes for lithium-ion cells

Stacked electrode structure

meas. voltage estimate estimate balance compute

loop once each measurement interval while pack is active

applications to optimize the use of space

Cylindrical and prismatic electrode structure

key on: initialize

loop once each measurement interval while pack is active

apart, to form a jelly roll

constructed similarly, by winding

1.2.3: Negative electrodes for lithium-ion cells

Microscale structure of graphite

key on: initialize

loop once each measurement interval while pack is active

electrodes of lithium-ion cells, starting with negative electrode

1.2.3: Negative electrodes for lithium-ion cells

Mesoscale structure of graphite

meas. voltage estimate estimate balance compute

loop once each measurement interval while pack is active

synthetic sources (which have somewhat different layering

Natural or synthetic graphite Hard carbon

Alternate negative-electrode material LTO

key on: initialize

loop once each measurement interval while pack is active

OCP vs. Li/Li+ (V)

is orange; O is red; green LTO

Lithium diffuses through 0

Disadvantage: high open-circuit potential (making cell voltage low)

1.2.3: Negative electrodes for lithium-ion cells

Future negative-electrode material silicon

key on: initialize

loop once each measurement interval while pack is active

Using graphite, one can store up to one Li per six C atoms;

1.2.3: Negative electrodes for lithium-ion cells

meas. voltage estimate estimate balance compute

loop once each measurement interval while pack is active

cylindrical form factors

key on: initialize

Credits for images in this lesson:

loop once each measurement interval while pack is active

Graphite structure on page 5 drawn with VESTA. See, Momma, K.

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