Lithium Batteries and Beyond

Milano, XX mese 20XX

Courses for «Green Ambassadors»
Prof. Jie Li, Department of Energy, [email protected]
Outline of the course

I. The rise of lithium batteries: How, why, and perspectives (2 CFU)

- Jie Li (Department of Energy)

II. Long duration storage, battery manufacturing and circularity (3 CFU)

- Prof. Eugenio Gibertini (Department of Chemistry)

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I. The rise of lithium batteries: How, why, and perspectives

1. A Nobel prize for Li-ion batteries – history

2. Battery materials
2.1 Cathode materials
2.2 Anode materials
2.3 Electrolyte
2.4 Other components and electrode design
3. Next generations of lithium batteries
- Li metal batteries, all solid-state LIBs, new concept of aqueous LIBs
6. Beyond lithium batteries
- Na-batteries
II. Long duration storage, battery manufacturing and circularity

Course:
1. Post Li-ion: Li-S, non Li-ion (K+,Mg+), Zn-ion and air batteries
2. Safety of LIBs
3. Recycling and circularity of LIBs
4. Supercapacitors
5. Principles of long-duration energy storage
6. Redox flow batteries
7. Non conventional battery configurations and techniques (micro-batteries, wearables batteries
etc.)
Since you are experienced professor, I’d really like to have your feedback from regarding the topics.

Lab activities:
- Material for LIBs
- Coin cell assembly and testing
- Pouch cell production
- Redox flow batteries: assembly and testing
Lecture 1: A Nobel prize for Li-ion batteries

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The 2019 Chemistry Nobel Prize

for the development of lithium-ion batteries

“This rechargeable battery laid the foundation of

wireless electronics such as cell phones and
laptops. It also makes a fossil fuel-free world
possible, as it is used for everything from
powering electric cars to storing energy from
renewable sources. “

---The Royal Swedish Academy of Sciences

John B. Goodenough, M. Stanley Whittingham, Akira Yoshino

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Why batteries?
Global Warming
20 pounds CO2 Energy Price
Energy Supply
Availability/Resources

A gallon gasoline 14 pounds O2

(6 pounds)
Solutions:
1. Increase the share of renewable energy
Magatrend: sustainable energy 2. Elimination of energy losses, and increase of
energy utilization
3. Less energy conversion processes

Energy supplied by the sun in 1h

corresponds to consumption by man in 1
Year !

Per year: Sun Irradiation: 120,000TW (Tera-Watt)

Energy Consumption: <20TW

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Why batteries?

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History

In 1780, Galvani observed that the frog muscle contracts when the nerve
is posed in contact with a metallic part
“Animal Electricity”

Luigi Galvani (Italy, 1737-1798)

Plate I of the Commentarius (1791 edition), showing the prepared frog and the
electric machine on the left allude to the spark experiment.

Brain Research Bulletin, 1998, 46 (5), 367 9

History
--- the invention of Voltaic pile

Volta demonstrated that when two metals and brine-soaked cloth are
arranged in a circuit, they produce an electric current.

In 1800, Volta observed that by piling up

metallic disks of two types ( copper and
zinc) separated by a felt imbedded with
sulfuric acid, a potential develops at the
plie terminals.

Alessandro Volta (Italy, 1745-1827)

- The “father” of the (Primary) Battery
Drawing of the voltaic pile in different configurations,
from the letter sent from Volta

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History
--- the first rechargeable battery

Johann Wilhelm Ritter (Gemany, 1776-1810)

Participation of electrolyte
- The “father” of the fuel cell technology
Decomposition of water by electricity
In 1802, German scientist Ritter developed a rechargeable
battery, the so called “Ritter” pile. The pile consisted out of
copper electrodes and carton filled with NaCl-solution as
electrolyte/separator system. It was charged with a Volta pile,
thereby electrolyzing H2O into H2 and O2. The produced gases
then recombined to water during discharge.

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History
--- the invention of lead-acid battery

Cell configuration: PbH2SO4PbO2

charge
Pb + PbO2 + 2H2SO4  2PbSO4 + 2H2O
discharge
During discharge:
Anode (Pb): Pb +HSO4- (aq) - 2 e⁻ → Pb²⁺SO4 + H+ (aq)
Cathode (PbO₂): PbO2 + 2 e⁻ + 3H++ HSO4- (aq) → Pb²⁺SO4+2H2O
Gaston Planté Voltage (single): 2 V
(French, 1834-1889)
In 1859, the French physicist Gaston Planté presented a cell model consisted of a roll of two sheets of pure lead, separated by a linen cloth
and immersed in a cylindrical glass jar of sulfuric acid solution. This is the invention of lead acid battery. In 1860, he presented a set of nine
electrochemical cells to the French Academy of Sciences. Each cell was constructed as his early model and in the same geometry. Planté
demonstrated that he has produced a battery 'of great power’. Moreover, the ‘lead–acid system’ can be recharged electrically and thereby
has proved to be the world's first practical secondary battery.

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History
--- the invention of Zn battery

In 1866, French electrical engineer Leclanché invented a

battery that consisted of a Zn anode and a MnO2 cathode
wrapped in a porous material, dipped in a jar of NH4Cl
solution.
Cell configuration: Zn  NH4Cl MnO2
During discharge:
Anode: Zn - 2e−→ Zn2+
Cathode: 2 MnO2 + 2NH4+ + 2e− → 2 MnO(OH) + 2 NH3 (aq.)
Voltage (single): 1.4 V

Further developed by Carl Gassner (Germany, 1844-1942) that

Georges Leclanché replaced NH4Cl solution by a paste (NH4Cl mixed with Plaster of
(France, 1939-1882) Paris) demonstrated the first dry cell (German patent).

Zn battery: low cost, but can not be recharged

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History
--- the invention of Nickel-Cadmium battery (the first alkaline battery)

400

density ( Wh /l)

Smaller size
Li - ion
300

PLiON TM
Ni -
200
MH
Cell configuration: Cd  KOH  NiOOH

Energy
Ni - Cd
100
During discharge: Lead-
acid
Anode: Cd + 2OH- → Cd(OH)2 + 2e− Lighter weight
Ernst Waldemar Jungner Cathode: 2NiO(OH) + 2H2O + 2e− → 2 Ni(OH)2 +2OH-
0

(Sweden, 1869 –1924) 0 50 100 150 200 250

Voltage: 1.2V Energy density (Wh /Kg)

Vs. lead-acid battery:

• Better physical and chemical stability
• Stable working potential
• Higher energy density: 50 Wh/kg for Ni-Cd cell, 40 Wh/kg for lead-acid battery

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Up to mid-1970s the conventional battery technology was adequate in meeting the requirements of
the consumer electronics and of the automobile markets…. .

Do we need new batteries

The situation changed in the most recent years with the pressing request
of new, advanced-type of batteries, motivated by a series of major events,
namely:
1. the oil crisis
2. the need of improved medical devices
3. the expansion of the consumer electronics market
4. the air pollution in urban areas

The First Pre-Requisite for High-Energy Batteries

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New battery technology
---Numerous material combinations are possible

− Several hundred thousand combinations of electrode

materials have been investigated
− Less than 50 of these electrode material combinations
have been commercialized
− By variation of the electrolyte, even more cell chemistries
are possible
− Different cell chemistries
→different performance characteristics
→different applications

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New battery technology
---Numerous material combinations are possible
High energy batteries: High Voltage + Materials With high capacity and Low Mass

Theoretical Specific Energy [Wh/kg] =

Capacity [Ah] ⋅ Cell Voltage [V]
Active Masses of Anode + Cathode [kg]

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History
--- the invention of Nickel-Metal Hydride (Ni-MH) battery
In 1870s, by replacing cadmium with a hydrogen-absorbing alloy, a nickel metal hydride battery was built, and
the first consumer-grade Ni-MH cells became commercially available in 1989.

CHARGE REACTION DISCHARGE REACTION

e- e- e- e-

Ni(OH)2 Ni(OH)2
OH- OH-

H+ H+ H+ H+
H2O H2O
NiOOH NiOOH

Metal Hydride Electrode Nickel Electrode Metal Hydride Electrode Nickel Electrode
M + H2O + e- → MH + OH- Ni(OH)2 + OH- → MH + OH- → M + H2O + e- NiOOH + H2O + e-→ Ni(OH)2 +
NiOOH + H2O + e- OH-

M: Hydrogen Absorbing intermetallic alloy H: Hydrogen Atom

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History
--- the invention of Nickel-Metal Hydride (Ni-MH) battery

Cell configuration: MH  KOH  NiOOH Energy density diagram

During discharge: 400
Anode: MH + OH- → M + H2O + e-
Cathode: NiOOH + H2O + e-→ Ni(OH)2 + OH-

( Wh /l)
Li - ion

Smaller size
300
Voltage: 1.2V
PLiON TM

density
Ni -
Vs. Ni-Cd battery: 200
• Less environmental effect MH
• Higher energy density: 2-3 time Ni - Cd

Energy
100
Lead -
acid
Lighter weight
0

0 50 100 150 200 250

Energy density ( Wh /Kg)

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History
--- the invention of Li battery
Intercalation material: compounds having a soft structure
with capability of accepting and releasing guest species,
M. Stanley Whittingham (USA, 1941-) e.g., lithium ions and electrons, with reversible changes in
In 1976, Patent on Li/TiS2 cell the crystal and the electronic structure.
--- first example rechargeable lithium batteries

a x y b

TiS2 + xLi+ + xe-  LixTiS2

z

c
To be noticed that the guest specie, here the Li ion, keeps its charge when is
intercalated in the TiS2 structure. Thus, the electrons which arrive to the
Crystal structure of TiS2 intercalating electrode do not reduce the intercalated specie, i.e. Li+, but
rather modify the electronic structure of the intercalating specie, i.e. TiS2 .
Practically, the insert of the ion is accompanied by a variation of the
oxidation state of the transition metal which passes from Ti(IV) to Ti(III).

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History
--- first example rechargeable lithium battery (Li‖TiS2 battery)

Anode : Lithium metal

Cathode: Intercalation electrode, (e.g. TiS2)
Electrolyte: solution of a lithium salt (e.g, LiPF6) in an organic
solvent mixture (e.g., ethylene carbonate - dimetyl carbonate, EC-
DMC mixture)

Total process: xLi + TiS2 → LixTiS2

x= intercalation degree

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History
--- Development of the 1st commercial lithium-ion battery (LIB)

M. Stanley Whittingham John B. Goodenough Akira Yoshino

In 1976, Patent on Li/TiS2 cell In 1980, Replaced TiS2 by LiTMO2 (LiCoO2) to obtained In 1990, developed the first commercial
--- first example rechargeable lithium 4V battery Li-ion battery.
batteries

M. Armand Jeff Dahn

In 1977, replace Li metal by graphite In 1990, constituted the foundation
as anode. of LIB industry.
In 1980, established the concept of
“Rocking Chair Battery”.

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The concept of rocking chair battery

Michel Armand (France, 1946-), in Materials for

Advanced Batteries, D. W. Murphy, J. Broodhead, and B. C.
H. Steele, Editors, p. 145, Plenum Press, New York (1980)

• Lithium ions do not participate to the redox

reactions
• lithium ions "rock" back and forth between
the two electrodes

Rocking chair battery

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The concept of rocking chair battery

Charge process

Electrolyte
Cu Current Collector

AL Current Collector
Graphite anode LiMO2 cathode
SEI CEI

Courtesy of Prof. Scrosati 24

The concept of rocking chair battery
Discharge process

Electrolyte

Cu Current Collector

AL Current Collector
Cu Current
Collector

Graphite anode CEI LiMO2 cathode

SEI

Courtesy of Prof. Scrosati 25

Why Li-ion batteries (LIBs)?

400

density ( Wh /l)

Smaller size
LiLi- ion
300 Environmentally High energy
Long cycle life
friendly density

PLiON TM
Ni -
200
MH low self- Fast charge & No memory
discharge rate discharge effect

Energy
Ni - Cd
100
Li: Lead-
acid
Lightest metal
0 Lighter weight
Low redox potential (-3.045 vs SHE)
High theoretical specific capacity (3860 mAh/g)
0 50 100 150 200 250
Energy density (Wh /Kg)

Secondary battery Average voltage (V) Energy density (Wh/kg) Power density (W/kg) Cycle life Self-discharge (%/month)

Lead-acid 2.0 30-50 150 150 0.3

Ni-Cd 1.2 45-55 170 170 0.25

Ni-MH 1.2 70-80 250 250 0.2

Li-ion 3.6 120-250 300-1500 1000 0.02

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Application of LIBs

Small size battery

Big size battery

In extreme environment

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The history, current state and development of Li-ion batteries

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