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Materials Science for Electrochemical Devices

Chap. 5 Batteries

2020. 6. 8.

EunAe Cho

Department of Materials Science and Engineering

Korea Advanced Institute of Science and Technology (KAIST)

Energy Conversion &

Storage Materials Laboratory
Contents
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1. Introduction to Batteries

2. Lithium-ion Battery (LIB)

3. Electrochemistry in LIB

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What is Battery?
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• Definition: battery is one or more electrochemical cells that convert

stored chemical energy into electrical energy.

• Basic components:
ü Two electrodes (cathode and anode): both sources of chemical reactions
ü Electrolyte: enabling ion transfer between the two electrodes

DG = -zF(ECathode-Eanode) = -zFEcell

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Primary / Secondary Batteries
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a cell or group of cells for the generation of electrical energy

Primary battery (disposable batteries) intended to be used until exhausted and then discarded.

System • Zinc carbon (flashlights, toys)

• Heavy duty zinc chloride (radios, recorders)
• Alkaline (all of the above)
Active Material Electrical Energy • Lithium (photoflash)
Electrochemical • Silver, mercury oxide (hearing aid, watches)
Redox reactions • Zinc air

a cell or group of cells for the generation of electric energy in which the cell, after
Secondary battery (rechargeable battery) being exhausted, may be restored to its original charged condition by an electric
current flowing in the opposite direction.

System

• Nickel cadmium
Active Material Electrical Energy • Nickel metal hydride
Electrochemical • Alkaline
Redox reactions • Lithium ion
• Lithium ion polymer
• Lead acid

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Primary Batteries: Standard Zinc Carbon Batteries
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• Chemistry
Zinc (-), manganese dioxide (+)
Zinc, ammonium chloride aqueous electrolyte
• Features
+ Inexpensive, widely available
- Inefficient at high current drain
- Poor discharge curve (sloping)
- Poor performance at low temperatures

Zn(s) → Zn2+(aq) + 2 e-
2MnO2(s) + 2 H+(aq) + 2 e- → Mn2O3(s) + H2O(l)
NH4+(aq) + H2O(l) → H+(aq) + NH3(aq)

Zn(s) + 2 MnO2(s) + 2 NH4+(aq) → Mn2O3(s) + Zn(NH3)22+(aq)

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Primary Batteries: Li Batteries
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• Chemistry
• Lithium (-), manganese dioxide (+)
• LiClO4 in propylene carbonate and dimethoxyethane
• Features
+ High operating voltage (3V)
+ High energy density
+ Long shelf life (20 years at 70°C)
+ Capable of high rate discharge
- Expensive

Li(s) → Li+(aq) + e-
MnO2(s) +Li+(aq)+ e- → LiMnO2(s)

Li(s) + MnO2(s) → LiMnO2(s)

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Secondary Batteries
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Secondary Batteries: Lead-acid Batteries
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• Chemistry
Lead
Sulfuric acid electrolyte
• Features
+ Least expensive
+ Durable
- Low energy density
- Toxic
O SLI (Start/Light/Ignition)

Pb(s) + SO42-(aq) ↔ PbSO4(s) + 2e-

PbO2(s) + SO42-(aq) + 4H+ + 2e- ↔ PbSO4(s) + 2H2O (l)

PbO2 (s) + Pb (s) + 2 SO4- (aq) + 4 H+ (aq) ↔ 2 PbSO4 (s) + 2H2O (l)

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Secondary Batteries: Ni-Cd Batteries
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• Chemistry
Cadmium (-), nickel hydroxide (+)
Potassium hydroxide aqueous electrolyte
• Features
+ Rugged, long life, economical
+ Good high discharge rate (for power tools)
- Relatively low energy density
- Memory effects
- Toxic

Cd + 2 H2O à Cd(OH)2 + 2H+ + 2e-

2 NiO(OH) + 2H+ + 2e- à 2 Ni(OH)2

2 NiO(OH) + Cd + 2 H2O ↔ 2 Ni(OH)2 + Cd(OH)2

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Secondary Batteries: Ni-MH Batteries
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an anode

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Secondary Batteries: Li-ion Batteries
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• Chemistry
• Graphite (-), LiCoO2 (+)
• Nonaqueous electrolyte
• Features
+ 40% more capacity than NiCd
+ Flat discharge (like NiCd)
+ Self-discharge 50% less than NiCd
- Expensive
- Safety

● Negative electrode
Cn + xLi+ + xe- ↔ CnLix
● Positive electrode
LiCoO2 ↔ Li1-xCoO2 + xLi+ + xe-

Energy Conversion & LiCoO2 + C6 ↔ Li1-xCoO2 + LixC6

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Secondary Batteries
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Energy Density (Wh/l)

600
Li-ion

• Voltage : 3.6 V
500 Li-ion • Long lifetime, high capacity, low self-discharging
Compactness Cellular
400 Note-PC
Ni-MH

300 Ni-MH • Voltage : 1.2 V

• High power, self-discharging
Audio Visual
200
Ni-Cd Ni-Cd
100 Power-tool • Voltage : 1.2 V
• Memory effect, low self-discharging
Light weight • Cd!!
0
0 25 50 75 100 125 150
Energy Density (Wh/kg)

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Market Share of Secondary Batteries
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LIB (small-sized)

Etc.
NiMH/NiCd
LIB (EV)

Lead-acid
LIB (ESS)

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Megatrend of LIB
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∼ Wh

IT devices

EV

∼ MWh ∼ kWh

Paradigm of LIB : From small to large powers

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Further Advances in Batteries
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chart from Enevate Corporation | Innovating Energy Storage

http://www.estquality.com/technology

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Li-ion Batteries (LIB)

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Li-ion Battery
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Load
e

Li +
Negative e e Positive
-
current X current
collector collector
Li salt/solvent/
separator film

Li1-xC6 LixCoO2
negative positive
electrode electrode

Anode: LiC6 ßà Li+ + C6 + e-

Cathode: Co(IV)O2 + Li+ + e- ßà LiCo(III)O2
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Structure & Reaction Mechanism of Li-ion Battery
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+
+
Li
Co
O

Energy Conversion & Anode (Graphite) Cathode (LiCoO2)

Storage Materials Laboratory
Structure & Reaction Mechanism of Li-ion Battery – Charging
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e-
Li+
e+-
+

C6 + xLi+ + xe- à LixC6 LiCoO2 à xLi+ + xe- + Li1-xCoO2

+

+
+
Li
Co
O

Energy Conversion & Anode (Graphite) Cathode (LiCoO2)

Storage Materials Laboratory
Structure & Reaction Mechanism of Li-ion Battery – Charging
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e-
Li+
e+-
+

e+- e+-
+ e+- e+-
e+-
+
+
e+- Li
-
e+ Co
O

Energy Conversion & Anode (Graphite) Cathode (LiCoO2)

Storage Materials Laboratory
Structure & Reaction Mechanism of Li-ion Battery – Discharging
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e-
Li+
e+-

LixC6 à C6 + xLi+ + xe- xLi+ + xe- + Li1-xCoO2 → LiCoO2

+

+
+
Li
Co
O

Energy Conversion & Anode (Graphite) Cathode (LiCoO2)

Storage Materials Laboratory
Structure & Reaction Mechanism of Li-ion Battery – Discharging
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e-
Li+

e+-
e+- +

- e+- +
e+

+
e+- +
e+- Li
e+- Co
O
-
e+

Energy Conversion & Anode (Graphite) Cathode (LiCoO2)

Storage Materials Laboratory
Structure of Commercial Li-ion Batteries
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Charging

C6 + xLi+ + xe- à LixC6

LiCoO2 à xLi+ + xe- + Li1-xCoO2

Discharging

LixC6 à C6 + xLi+ + xe-

LixC Li1-xCoO2 xLi+ + xe- + Li1-xCoO2 → LiCoO2

charge
LiCoO2 + C6 Li1-xCoO2 + LixC6
discharge

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What is LIB composed of?
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Discharge Cathode
Anode
Graphite LiCoO2

Separator Charge Electrolyte

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Components of Li-ion Batteries
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Laminate type due to lower ionic conductivity of organic electrolyte than aqueous one
(~10-2 S/cm, ~2 order of magnitude lower)

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Lithium-metal batteries vs. lithium-ion batteries
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Lithium-metal batteries

Lithium-metal batteries are primary or secondary batteries that have lithium metal as an anode.
- Primary lithium-metal batteries have been used since being commercialized in the 1970s.
- The production of secondary lithium-metal batteries, which were commercialized in the
1980s, was suspended by reason of combustion.

Formation of Li dendrite upon cycling → Internal short in the batteries → unsafe

Li+
Li+
Li+
Li+ Li+
Li+ Li+
Short
Li+
Li Li+ Li Li+ Li Li
separator

Lithium-ion batteries

Lithium-ion batteries are secondary batteries that have graphite instead of lithium metal as an
anode.

No formation of Li dendrite upon cycling → safe

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Electrochemistry in LIB

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Batteries in Your Life
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18650, 7,000 batteries

Voltage:10.95V; 3.6-3.7 V, 3,400 mAh, ∼12,000 Wh

3.82 V, 6.91 Wh, 2,716 mAh Capacity: 6,000mAh/65Wh; (4.35 V-2.75 V)
6 Cell
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Key Properties
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• Voltage • Capacitye
V

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 Terminologies
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• Principal terminology
ü Capacity (Q): the ability to store electric charge, and the unit is Ah or C.
(capacity = current(A) × time (h) = Ah, mAh = 1/1000 Ah)

ü Energy (E): the capacity to do work, and the unit is Wh or J

(energy = capacity (Ah) × voltage (V) = Wh)

ü Power (P): the rate of doing work or converting energy, and the unit is W or J/sec
(power = energy (J) / time (sec) = capacity (C) × voltage (V) / time (sec)
= current (A) × voltage (V) = W)

ü C-rate: Rate of charge or discharge expressed as C/R, where R is the number of

hours required to completely charge/discharge its nominal capacity.
(C/10: Full of charge or discharge takes 10 hours)

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Standard Electrode Potentials at 25 C
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Charge-discharge profiles (voltage-capacity plot)
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A diagram in which x-axis stands for time or capacity, and y-axis cell voltage.
Charge-discharge profiles is useful to find out voltage change under constant current
density applied during charge-discharge.

Li+ - out Li+ - out

Anode: discharging
Anode: discharging
Cathode: charging
Cathode: charging

Li+ - in Li+ - in
Anode: charging
Anode: charging
Cathode: discharging
Cathode: discharging

S-shaped curve (one-phase reaction, L-shaped curve (two-phase reaction,

solid solution reaction) nucleation and growth reaction)

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Application of Gibbs phase rule to charge-discharge profiles
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Gibbs Phase Rule F = C - P + 2

C: number of components present
P: number of phases present
F: number of degrees of freedom
- the number of intensive thermodynamic parameters that must be specified

Case 1. LiCoO2 Case 2. LiFePO4

F=C-P+2=3-1+2=4 F=C-P+2=4-2+2=4
(components: Li, Co, and O; one phase: (components: Li, Fe, P, and O; two phases:
LixCoO2) LiFePO4, FePO4)
T (temperature) and P (pressure) is fixed; Co : O = T (temperature) and P (pressure) is fixed; Fe : P =
1 : 2 (fixed) 1 : 1 and P : O = 1 : 4 (fixed)
F = 1 (one more degree of freedom) F = 0 (no more degree of freedom)
→ S-shaped curve → L-shaped curve

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Voltage shape – plateau vs. slope
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• The voltage plateau ® Indication of two-phase reaction

Voltage (V)
A/Li1.0A
Li1.0A/Li2.0A
C=2
P=2 Li2.0+dA F=1
F=2 C=2 ® The composition
P=2 within the phase affects
F=2 the properties, voltage.

C=2
P=1
Two intensive properties are F=3
already constant. So, the remaining
F=0
1.0 2.0 x in LixA

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Discharge capacity at various C-rate (Rate-capability)
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Eout = Eth – I × Z
Eout: output voltage,
Eth: theoretical voltage,
I: applied current,
Z: internal impedance of the battery

At high currents (I),

over-potential (I × Z) increases,
that is, Eout decreases

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Cyclic performance of lithium-ion batteries
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ü Upon charge-discharge cycling, the cell's capacity continuously diminishes. The increase
in internal resistance reduces the cell's ability to deliver current.

ü The decrease in discharge capacity means that older batteries do not charge as much as
new ones (charging time required decreases proportionally)

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Why the capacity degradation occurs upon cycling?
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• Decomposition of electrolyte reductively

on the carbonaceous anode

• Prevention of further decomposition of the

electrolyte (Formation of Passivation layer)

• SEI formation
→ Electron consumption
→ Irreversible capacity

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Why the capacity degradation occurs upon cycling?
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The charge transfer resistance and mass transfer resistance in electrode materials depend on
the following factors.

ü Intercalation/deintercalation (LiCoO2,
Li+-ions insertion/extraction LiMn2O4, LiFePO4, graphite)
mechanism in electrode materials ü Decomposition/composition (Metal oxide)
ü Alloying (Sn, Si)

Intrinsic physical property of electrode ü Electronic conductivity

ü Ionic conductivity
materials ü Activation energy for Li+-ions movement

ü Particle size (Nano vs. Micron)

Particle size and morphology of
ü Particle shape (Wire, rod, tube, sphere)
electrode materials ü Particle topology

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Full Cell – “Rocking-Chair”
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Li+ Out
4 Cathode
Li+ In (e.g. LiCoO2)
Cathode capacity (Cc)
3
Voltage (V)

2 Irreversible
capacity Anode capacity (Ca)
Electrolyte decomposition
1 (SEI formation)
Li+ Out
Anode
0 (e.g. Graphite)
Li+ In
0 100 200 300 400

Capacity (mAh/ganode)
Coulombic efficiency = Cdischarge/Ccharge
np ratio = Ca/Cc = ~1.2-1.3 (>1) for avoiding Li plating
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Full Cell – “Rocking-Chair”
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[Charge] [Discharge]
Capacity loss Available capacity

4 4
Voltage (V vs. Li/Li+)

Avoid too high Why Coulombic efficiency

3 potential where 3
should be close to 1
cathode degrades
2 quickly 2 Avoid 0 V where Cu
starts to dissolve
1 Li plating 1
Why np ratio > 1
0 0

0 100 200 300 400 0 100 200 300 400

4 4

3 3
Voltage (V)

2 2

1 1

0 0

0 100 200 300 400 0 100 200 300 400

Capacity (mAh/ganode) Capacity (mAh/ganode)

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Summary
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Discharging process
Li+ Out
Voltage

Energy density = Cell capacity × Cell voltage 4

Li+ In
Cathode capacity (Cc)
Cathode
3

Voltage (V)
2 Irreversible
capacity Anode capacity (Ca)
Cell capacity
Electrolyte decomposition
1 (SEI formation)
Li+ Out
Cell voltage
0
Anode Li+ In
Capacity 0 100 200 300 400

Capacity (mAh/ganode)
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