4.1.

4: Negative-electrode aging processes in bulk and composite electrode

Negative electrode aging in bulk

key off: store data

key on: initialize
meas. voltage estimate estimate balance compute

 Aging/degradation occurs inside negative-electrode particles

current state of state of power
temperature charge (SOC) health (SOH) cells limits

loop once each measurement interval while pack is active

 Dis/charging causes (anisotropic) particle volume ❙♦❧✈❡♥t

❝♦✲✐♥t❡r❝❛❧❛t✐♦♥
changes (usually less than 10 %)
❙❊■
●❛s ❡✈♦✲
 Strain can lead to cracking of particles, more SEI ❧✉t✐♦♥
✂❧♠
formation on exposed graphite ❙♦❧✐❞
♣❛rt✐❝❧❡
 Cracking of SEI itself, and more SEI formation on ♦❢ ❛❝t✐✈❡
exposed graphite ❈r❛❝❦✐♥❣ ♠❛t❡r✐❛❧

 Graphite exfoliation (layers flaking off) due to solvent cointercalation with lithium is
considered to have a bigger impact
 Solvent reacting with graphite inside particles releases gasses, accelerates cracking

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4.1.4: Negative-electrode aging processes in bulk and composite electrode

Negative electrode aging in composite electrode

key off: store data

key on: initialize
meas. voltage estimate estimate compute

 Stresses and strains within electrodes can cause

balance
current state of state of power
temperature charge (SOC) health (SOH) cells limits

mechanical and electronic contact loss:

loop once each measurement interval while pack is active

❆❝t✐✈❡ ♠❛t❡r✐❛❧s
 Between graphite particles ❈♦♥❞✉❝t✐✈❡ ❛❞❞✐t✐✈❡
 Between current collector and particles ❇✐♥❞❡r
 Between binder and particles
 Between binder and current collector
 Results in higher impedance and can result in ❈✉rr❡♥t ❝♦❧❧❡❝t♦r
capacity loss if particles become electrically
disconnected from current collector
 Porosity of electrode can be reduced by volume changes and growth of SEI,
impeding movement of lithium ions in electrolyte, increasing resistance

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4.1.4: Negative-electrode aging processes in bulk and composite electrode

Current-collector corrosion
key off: store data
key on: initialize

meas. voltage estimate estimate balance compute

 At low voltages (near 1:5 V) copper current collector can

current state of state of power
temperature charge (SOC) health (SOH) cells limits

corrode, releasing Cu2C into electrolyte:

loop once each measurement interval while pack is active

 Reduced current-collector/particle contact, higher cell resistance

 Corrosion products that deposit on electrode particles have poor electronic
conductivity, giving higher film resistance
 Leads to nonuniform current and potential distributions across cell plate area,
accelerates aging in parts of the cell, gives preference toward lithium plating
 Copper also makes a metallic annealing site that can accelerate lithium plating,
dendrite growth, and hence short circuits

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4.1.4: Negative-electrode aging processes in bulk and composite electrode

Summary of aging in bulk, composite electrode

key off: store data

key on: initialize
meas. voltage estimate estimate balance compute

 Table summarizes bulk/composite effects (bold = more severe)

current state of state of power
temperature charge (SOC) health (SOH) cells limits

loop once each measurement interval while pack is active

Cause Effect Leads to Enhanced by

Solvent cointercalation, gas Loss of active Capacity Overcharge
evolution, graphite exfoliation material, Li loss fade
Contact loss b/w particles Loss of active Capacity High rate, low
due to volume changes material fade cell SOC
Decomposition of binder Li loss, loss of mech- Capacity High SOC,
anical stability fade high temperatures
Current collector corrosion Impedance rise; Pwr. fade; Overdischarge,
nonuniform current accelerates low cell SOC
and potentials aging

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