Composition, specifications,

issues and prospects

LITHIUM-ION
BATTERY
 KEY CONTENTS
• Battery specifications: voltage,
capacity, power
• Components and mechanism of a
lithium-ion battery
• Historical developments of LIB
• Designing the anode and electrolyte
• Designing the cathode
• Trends and other issues

Lithium salt production 2

WHAT DO YOU WANT FROM YOUR
BATTERIES?
Desirable characteristics

Powerful
Light weight
Safe
Reasonably priced
Fast charging time
Environmentally friendly
BATTERY SPECIFICIATIONS
11.1V; 4400mAh, 49Wh
BATTERY SPECIFICIATIONS: VOLTAGE
❖Voltage: is defined by how much energy each electron has as
it moves. The voltage or potential of a battery is defined by
difference in electrochemical potential between cathode
and anode.
▪ AA/AAA batteries: Zinc anode and Manganese oxide
cathode → 1.5V
▪ Rechargeable AA/AAA batteries: Metal hydride/Nickel
hydroxide → 1.2V
❖The laptop battery shown here has voltage of 11.1V? Is that
all from redox potential difference? Only partially so.
BATTERY ❖Output voltage higher than the electrochemical potential:

SPECIFICIATIONS: • Certain type of lithium-ion battery has voltage of 3.7V

(exact number depends on the chemicals inside)
VOLTAGE • 3 cells in a series would give accumulate voltage of
3.7 x 3 = 11.1V
• In applications like laptop batteries and car batteries,
where more power is needed, cells are arranged in series
(to boost voltage) and in parallel (to boost capacity)

Series Parallel
BATTERY SPECIFICIATIONS: CAPACITY
• Current: quantifies how many electrons are flowing per
second, unit: Amps (A)
• Capacity is defined as the total amount of electricity
generated due to electrochemical reactions in the battery and
is expressed in ampere hours Ah.
• Correlate directly to the amount of active chemicals in the
cell (i.e, the size & weight of the battery)
• Example: 4400mAh = 4.4Ah, meaning: at 11.1V, this battery
can provide a current of 4.4 Amp for one hour, or 1.0A for
4.4 hour.
BATTERY SPECIFICIATIONS: CAPACITY
• Inconvenient to compare between different batteries
and different devices
→ Thus another way to express amount of energy is
used: power capacity. Power capacity is expressed in
Watt-hours Wh (a unit of energy); Wh = V x Ah
• This laptop battery here:
11.1V x 4.4Ah ≈ 49Wh
• And this AA battery: 1.5V x 2.85 Ah = 4.3 Wh
BATTERY SPECIFICIATIONS IN PRACTICE
• Each device requires a certain voltage → choose the suitable source
• How long your battery will power your device before running out depends on both the power
consumption of the device and the power capacity of the battery
• Duration: Divide capacity (Wh) by power consumption (W)

Activities Power requirement (W)* 49Wh battery will last (h)

Gaming 40-60 0.8-1.2
Photo/video editing 30-40 1.2-1.6
HD video 20-30 1.6-2.5
Normal use 10-15 3.3-4.9
Minimum with screen on 8-10 4.9-6.1
*guidingtech.com
BATTERY SPECIFICIATIONS IN PRACTICE
• High voltage (chemistry dependent) x high capacity (quantity dependent) = high power
• Very frequently when you look up technical specs of your electronic device, this power capacity (in
Wh) is the only thing that shows up
Device MacBook Pro 16-inch (2023) Dell XPS 15 (2023)
Battery type Li-Po Not clearly mentioned (Li something)
Battery power 100 86
capacity (Wh)
• How long a battery last also strongly
depends on level of power
consumption
BATTERY DESIGN CONSIDERATIONS

Powerful Light weight Safe

Li: High energy density!

Reasonably Fast charging Environmentally

priced time friendly
Choosing the right materials is key to all these requirements!
 KEY CONTENTS
• Battery specifications: voltage,
capacity, power
• Components and mechanism of a
lithium-ion battery
• Historical developments of LIB
• Designing the anode and electrolyte
• Designing the cathode
• Trends and other issues

Lithium salt production 13

COMPONENTS OF A BATTERY
❖3 main parts of a battery:
• Anode: oxidation happens→ prefer a
(strong) reductant
• Cathode: reduction happens → prefer
a (strong) oxidant
• Electrolyte: a medium through which
ions move → many requirements
related to speed of movements and A generic galvanic cell, electron flows
safety issues. start from anode during discharge
COMPONENTS OF A BATTERY
❖The electrochemical reaction inside has
an ionic and an electronic component.
• The electrolyte transports the ionic
component (ions) inside a cell
• This forces the electronic component
(electrons) to traverse an external
circuit.

A generic galvanic cell, electron flows

start from anode during discharge
COMPONENTS OF A LITHIUM-ION BATTERY
Graphite – anode (hosts the Li metal)
Lithium
Oxygen
Cathode
A transition metal (hosts the Li+
ions)
(usually Co or Mn)

“How we made the Li-ion rechargeable battery”

by John B. Goodenough
Published online: 9 March 2018
https://doi.org/10.1038/s41928-018-0048-6
DISCHARGE AND RECHARGE A LITHIUM-ION BATTERY
SEI?
Solid Electrolyte
Interface

Reduction of what?

Discharging (when the battery is in use) Charging (when the battery is being charged)
DISCHARGE AND RECHARGE A LITHIUM-ION BATTERY

Metal oxide shelves Graphite shelves

 KEY CONTENTS
• Battery specifications: voltage,
capacity, power
• Components and mechanism of a
lithium-ion battery
• Historical developments of LIB
• Designing the anode & electrolyte
• Designing the cathode
• Trends and other issues

Lithium salt production 20

TECHNICAL DEVELOPMENT TIMELINE
Based on the short review by Goodenough
❑ 1960s: Primary (non-rechargeable) Lithium metal batteries
• Lots of research on rechargeable batteries (the only commercially viable option at the time was
the lead/acid type)
• The most stable cells used an alkaline electrolyte and a layered nickel oxyhydroxide (NiOOH)
as the cathode into which H+ is inserted reversibly to form the hydroxide Ni(OH)2
• Issue: aqueous electrolyte limits the voltage
❑ 1967: Joseph Kummer and Neill Weber (Ford Motor Company) discovered fast sodium-ion
diffusion above 300 °C in a ceramic electrolyte and invented a sodium–sulfur rechargeable
• Issue: high operating temperature
• Significance: inspired research into solid electrolyte and new battery design based on movement
of alkaline metal ions
❑ Late 1960s: Goodenough started works on battery and developed a solid electrolyte with fast Na+
conductivity at MIT
TECHNICAL DEVELOPMENT TIMELINE
Based on the short review by Goodenough
❑ Early 1970s: oil crisis, more focus on rechargeable batteries
• Li anode was known, and intake/release of sodium ions was proven possible → tried to make
a lithium version
• Note: ionic radius Li+ 0.076nm, Na+ 0.102nm
❑ 1976: Whittingham (Exxon Mobil) developed rechargeable battery with Li metal anode and
LiTiS2 cathode
• Issue: recharging caused lithium metal to build up on the anode → internal short circuit → fire
→ project abandoned.
• Goodenough moved to University of Oxford
❑ Late 1970s: Goodenough developed cathodes based on LiCoO2 and LiNiO2, showed that half of
the lithium can be extracted without structural change in these materials
❑ 1985: Yoshino Akira developed rechargeable batteries with LiCoO2 cathode and Li-graphite
anode
❑ 1991: Sony commercialized rechargeable Lithium-ion batterie
 KEY CONTENTS
• Battery specifications: voltage,
capacity, power
• Components and mechanism of a
lithium-ion battery
• Historical developments of LIB
• Designing the anode
• Designing the cathode
• Trends and other issues

Lithium salt production 23

THE ANODE: OXIDATION OF LI TO LI +
❖ Intrinsic properties of lithium metal:
• Lightest metal,
Lithium button batteries
• Extremely low electrode potential (primary)
Eo Li+/Li = −3.04 V vs. SHE
• High specific capacity (3.86 Ah/g)
→ideal anode material for high-voltage and high-
power batteries.
❖ Lithium metal is used as anode in primary
lithium battery (start in 1960s, commercialized
1970s)
• No big issues here since this is primary battery
(not rechargeable) DOI:10.1149/2.0291711jes
THE ANODE: OXIDATION OF LI TO LI +
Also in the 1970s, Whittingham and Goodenough worked on the cathode materials for
Lithium-ion battery.
When tried in rechargeable setup: Lithium metal build up on anode (dendrite growth,
aka lithium plating), causing internal short circuit and fire hazards

“A short circuit is an electrical circuit

that allows a current to travel along
an unintended path with no or very Li Li+ +e → Li
anode
low electrical impedance.”
THE ANODE: OXIDATION OF LI TO LI +
THE ANODE: OXIDATION OF LI TO LI+
❖ Solution 1: insert Li in between the layers of
graphite (technical term “intercalate”) 1976
Besenhard reported the first Li-ion-
intercalation based graphite electrode
• Issue 1: much lower capacity compared to pure
lithium (capacity of LiC6 = 0.372 Ah/g) → not
well-received until mass recalls of pure lithium
batteries due to fire.
• Issue 2: Unstable structure as electrolyte also
Layered structure Both Li atoms and
gets intercalated and exfoliates the graphite
of graphite electrolyte molecules get in
THE ANODE: OXIDATION OF LI TO LI+
❖ Solution 2: instead of crystalline graphite, use
petroleum coke, a less crystalline graphite (1985,
Yoshino Akira at Asahi Kasei Corporation, make the
working LIB)
• Issue: even lower capacity due to amorphous region, no
longer 1 Li per 6 C but 1 Li per 12C
❖ Solution 3: change the electrolyte from propylene
carbonate to ethylene carbonate, which forms a more
stable protective layer (more next slide) and doesn’t
exfoliate graphite → back to graphite now
THE ELECTROLYTE: TRANSFERING WITHOUT INTERFERING
❖ Electrolyte in the cell:
• Role: transfers ions between the electrodes
• Desirable: let ions through efficiently
• Undesirable: reacting or impacting the electrodes and
the chemicals there
❖ Concern: redox reaction
• Anode: contains (strong) reductant
• Cathode: contains (strong) oxidant
• Electrolyte might be reduced by the anode chemical
(in this case Li metal) and/or oxidized by the cathode
chemicals
• Li is very strong reductant, so this is a big concern
❖ Fortunately, SEI is here for the rescue
SEI = passivating Solid Electrolyte Interface
THE ELECTROLYTE: TRANSFERING WITHOUT INTERFERING
❖ Remember why stainless steel is stainless?
• Not because it isn’t oxidized, but the oxidized product (oxide of
Cr) forms a protective layer
❖ SEI follows the same concept, electrolyte does get reduced by
lithium, but then the reduced product forms a layer on the
surface of the anode, preventing further reaction.
❖ Original choice: propylene carbonate (PC) PC
• Advantages: can transfer Li+, forms the SEI, low melting point electrolyte
(-48.8oC)
• Issue: SEI layer from PC not tight enough, PC got into the
graphite and degrade it
❖ Solution: use ethylene carbonate instead, it forms tight SEI
layer which prevent reaction of electrolyte while still allows Li
ions to pass
EC
❖ Further improvement: In 1993, Guyomard and Tarascon electrolyte
reported a new electrolyte formulation, LiPF6 in EC/DMC, for
its improved oxidation stability (DMC = dimethylcarbonate)
 KEY CONTENTS
• Battery specifications: voltage,
capacity, power
• Components and mechanism of a
lithium-ion battery
• Historical developments of LIB
• Designing the anode and electrolyte
• Designing the cathode
• Trends and other issues

Lithium salt production 31

THE CATHODE: REQUIREMENTS
❖ What we want:
• High reduction potential (requirement in all
batteries)
• Takes and releases Li+ efficiently (specific for
rechargeable lithium-ion battery)
• Why: Anode reaction during discharge: Li – e →
Li+ , these Li+ cations must be stored somewhere
→ We must collect the Li+ in high concentration on
the electrode, and then be able to release them again
when external current is applied during re-charge
❖ 1960s: scientists showed that this intake and
release was possible with sodium
THE CATHODE: STORING LI +
❖ 1970s: search for a material that could do this with Lithium
• First candidates: conversion type materials: metal fluorides,
sulfides, or oxides (conversion means real chemical bonds are
formed)
• Advantage: takes in lots of Li+ → high capacity
• Disadvantage: unstable structure due to haphazard bond forming
and breaking, each charging circle brings about a different
structures
→Look for materials with room in lattice structure to store Li+
→Whittingham used TiS2, can store and release Li+ without much
change in lattice (first cell demonstrated 1976)
• Issue with Whittingham TiS2: low reduction potential → low
overall battery potential (1976 battery ~2.5V)
THE CATHODE: INTERCALATION MATERIALS
❖ 1979, 1980: Goodenough reported
cathode based on lithium cobalt oxide
LiCoO2 and created rechargeable lithium-
ion battery with 4.0V potential (Yoshino
Akira used this to make the Sony battery)
• Issue: cobalt has low abundance → high
cost
❖ Other transition metal oxides have been used, notably iron and manganese, each with
pros and cons:
• LiMn2O4 lower cost, same potential, but lower stability
• LixFe2(XO4)3 (X = S, Mo, W…) lower cost, stable, but lower potential
• Today, they are all in use but LiCoO2 still the most common, there are versions with
several transition metals involved too.
POTENTIALS OF LIB WITH DIFFERENT CATHODES
The full LIB: discoveries coming together

| https://doi.org/10.1038/s41467-020-16259-9 | www.nature.com/naturecommunications
Assembling the LIB: you don’t need Li metal!
• LIBs are assembled in the fully-discharged state, i.e., no lithium on the graphite!
• Then you charge the battery for the first time, Li+ ions move to graphite and combine with electrons to form
Li metal, the SEI is also formed.
 KEY CONTENTS
• Battery specifications: voltage,
capacity, power
• Components and mechanism of a
lithium-ion battery
• Historical developments of LIB
• Designing the anode and electrolyte
• Designing the cathode
• Trends and other issues

Lithium salt production 38

RESEARCH TRENDS
• Desire for higher power density and safer batteries
❖ Some of the past challenges are being revisited:
• Solid electrolyte (remember the 1960s sodium battery with ceramic electrolyte?) → all
solid-state rechargeable batteries (Goodenough is supporting this). The Macbook 16
has a Li-Po battery, Po = polymer electrolyte.
• Conversion-type cathode: was not pursued due to structure-instability, yet still
desirable due to high capacity → lots of work on this the last few years
• And back to lithium itself! Work being done on suppressing the dendrite issue, to bring
back the high capacity (more Li per anode weigh)
❖ New directions: move away from lithium. This is particularly important in energy
storage applications where mobility is not of high priority, but safety and price.
There is a homework regarding battery design consideration that focus on non-Li metals!
IF you want to read more about solid state LIB, go here! 40
 ISSUES
OUTSIDE OF THE
SCIENCE
SOME OTHER
ISSUES:
• Supply
• Environmental impacts of
Lithium “mining”
• Unequal share of profit through
the value chain
• → Social and political unrest
where the natural resources are
located
• Economic impact of shortages of
various component
GLOBAL LI DEPOSIT MAP (@BSG, NOV 2021)
 SUMMARY
• Specification of battery: voltage, capacity, power capacity
• Voltage (V) depends primarily on the redox potentials of the redox pairs inside; and then on how the individual
cells are connected (in series vs in parallel)
• Capacity (Ah) depends on the amount of redox chemicals used, and also boosted in parallel arrangement of cells.
• Power capacity (Wh) = voltage (V) x capacity (Ah), it represent total electrical energy than can be extracted from a
battery; in practice, battery life depends on both power of the battery and consumption rate of the device.
• All batteries need a cathode (reduction), anode (oxidation), and electrolyte (transfer of ions).
• Anode should contain strong reductant, Li is particularly good since it has very low reduction potential, and is the
lightest of all metals, thus very high specific capacity (capacity per mass).
• However, due to issue with dendrite growing (lithium plating) during recharge, Li cannot be used by itself but
stored in graphite instead; this is safer but lowers the specific capacity. There is a research trend on using Li metal
itself, to bring back high specific capacity.
• Electrolytes should transfer the ions efficiently without interfering with the chemicals inside the battery. Originally
PC (propylene carbonate), this has been changed to EC (ethylene carbonate) which forms a protective layer called
SEI to prevent degradation of electrode; recently solid electrolytes have been developed.
• The cathode in LIB should (1) have high reduction potential, (2) take in and release Li+ easily, (3) have structural
stability, (4) reasonably priced. Metal oxides of transition metals are the most common choice, notably of Co, Fe,
Mn, each type with pros and cons.
• Aside from the scientific questions, there are other issues regarding the use of Li and LIB.
46