Lithium-Ion Aging: Negative Electrode

4.1.
3: Negative-electrode aging processes at particle surface
Lithium-ion aging: Negative electrode
key off: store data

key on: initialize
meas. voltage estimate estimate balance compute
In the next lessons, we’ll seek to describe aging qualitatively.1

current state of state of power
temperature charge (SOC) health (SOH) cells limits
In negative electrode, aging observed at three scales:

loop once each measurement interval while pack is active
At the surface of the electrode particles

Within the electrode particles themselves
Within the composite electrode structure (active
materials; conductive additives; binder; current
collector; porosity; etc)
In this lesson, our focus is on aging mechanisms that take place at particle surfaces
We will assume that a graphitic carbon is used as the negative-electrode active
material, although similar results hold for silicon as well
1
Much of this is from: Vetter et al., “Ageing mechanisms in lithium-ion batteries,” Journal of Power
Sources, 147, 2005, 269–281.
Dr. Gregory L. Plett j University of Colorado Colorado Springs Battery State-of-Health (SOH) Estimation | How does lithium-ion cell health degrade? j 1 of 7
4.1.3: Negative-electrode aging processes at particle surface
Negative electrode aging at surface of particles
key off: store data

key on: initialize
Graphitic negative electrodes operate at voltages outside

electrochemical stability window of electrolyte components

Reductive electrolyte decomposition takes place at the electrode/ electrolyte
interface when the electrode (and cell) is in the charged state
❋✐❧♠
This occurs mainly—but not only—at beginning of ❣r♦✇t❤ ❙♦❧✈❡♥t
cycling, especially during “formation” cycle ❙❊■
✂❧♠
The decomposition products form a “solid-electrolyte
interphase” (SEI) surface film covering the electrode’s
❙♦❧✐❞ ♣❛rt✐❝❧❡ ♦❢
surface ❛❝t✐✈❡ ♠❛t❡r✐❛❧
Properties of SEI
key off: store data
key on: initialize
The SEI is a passivating layer, which slows/prevents further

reaction between graphite and electrolyte

Lithium is consumed when SEI film forms, lowering capacity of cell
SEI is porous, allowing de/intercalation of Li from/to graphite, but increases
resistance of ion transfer
SEI composition is complex and not uniform
Various products form, then decompose, then form more stable products
Breakdown of SEI; regrowth
key off: store data

key on: initialize
High temperatures contribute to breakdown of SEI, which

can lead to new SEI forming on exposed graphite

Pores in SEI also allow some solvent to penetrate to ▲✐t❤✐✉♠ ♣❧❛t✐♥❣
graphite surface, reacting and growing more SEI film ❆♥♦❞❡ ♣♦✐s♦♥✐♥❣ ❙❊■
Trace water in electrolyte combines with ionized ✂❧♠
fluorine to form hydrofluoric acid (HF), which attacks ❆❝✐❞
❛tt❛❝❦
the SEI—new SEI forms
Whenever SEI forms/grows, lithium is lost and so cell ❙♦❧✐❞ ♣❛rt✐❝❧❡ ♦❢
❛❝t✐✈❡ ♠❛t❡r✐❛❧
capacity decreases
Anode poisoning; lithium plating
key off: store data

key on: initialize
meas. voltage estimate estimate compute
Products of positive-electrode degradation also end

balance
up as part of SEI (anode poisoning):

If not electrically conductive, increases resistance ▲✐t❤✐✉♠ ♣❧❛t✐♥❣

❆♥♦❞❡ ♣♦✐s♦♥✐♥❣
Can plug pores, blocking lithium from cycling, ❙❊■
✂❧♠
causing capacity fade ❆❝✐❞
At low temperatures, diffusion in particles slows: ❛tt❛❝❦
If charging is forced, local overpotential can attain ❙♦❧✐❞ ♣❛rt✐❝❧❡ ♦❢

level that causes lithium plating on particle surface ❛❝t✐✈❡ ♠❛t❡r✐❛❧
Capacity irreversibly lost; dendrites can form and

grow, eventually leading to internal short circuit
Summary of surface effects

key off: store data
key on: initialize
Table summarizes surface effects (bold = more severe):

Cause Effect Leads to Enhanced by

Continuous low-rate electrolyte Li loss, Capacity fade, High temperatures,
decomposition builds SEI impedance rise Power fade high cell SOC
Decrease of accessible surface Impedance rise Power fade High temperatures,
area due to SEI growth high cell SOC
Changes in porosity due to Impedance rise Power fade High cycling rate,
volume change and SEI growth high cell SOC
Metallic Li plating, subsequent Lithium (electro- Capacity Low temperature,
electrolyte decomposition lyte) loss (power) fade high charge rates
Credits
key off: store data

key on: initialize

Image of lithium-ion electrode on slide 1 courtesy Sangwoo

Han, used with permission

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4.1.

3: Negative-electrode aging processes at particle surface

Lithium-ion aging: Negative electrode

key off: store data

In the next lessons, we’ll seek to describe aging qualitatively.1

In negative electrode, aging observed at three scales:

At the surface of the electrode particles

4.1.3: Negative-electrode aging processes at particle surface

Negative electrode aging at surface of particles

key off: store data

Graphitic negative electrodes operate at voltages outside

loop once each measurement interval while pack is active

electrochemical stability window of electrolyte components

4.1.3: Negative-electrode aging processes at particle surface

meas. voltage estimate estimate balance compute

The SEI is a passivating layer, which slows/prevents further

loop once each measurement interval while pack is active

reaction between graphite and electrolyte

Breakdown of SEI; regrowth

key off: store data

High temperatures contribute to breakdown of SEI, which

loop once each measurement interval while pack is active

can lead to new SEI forming on exposed graphite

4.1.3: Negative-electrode aging processes at particle surface

Anode poisoning; lithium plating

key off: store data

Products of positive-electrode degradation also end

up as part of SEI (anode poisoning):

If not electrically conductive, increases resistance ▲✐t❤✐✉♠ ♣❧❛t✐♥❣

If charging is forced, local overpotential can attain ❙♦❧✐❞ ♣❛rt✐❝❧❡ ♦❢

Capacity irreversibly lost; dendrites can form and

4.1.3: Negative-electrode aging processes at particle surface

Summary of surface effects

meas. voltage estimate estimate balance compute

Table summarizes surface effects (bold = more severe):

loop once each measurement interval while pack is active

Cause Effect Leads to Enhanced by

key off: store data

Image of lithium-ion electrode on slide 1 courtesy Sangwoo

loop once each measurement interval while pack is active

Han, used with permission

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