Battery Basics

Principles of Structure and Function

Arbon, CH
25.04.18
Contents

§ Introduction

§ Basic structure

§ Primary characteristics

§ Electrode materials

§ Electrolytes

§ Failure mechanisms

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Introduction
How is chemical energy stored?
Energy density determined by:

q = quantity of charge
(from Lithium or other chemistry)

V = chemical potential energy

storage (voltage between cathode and anode)
Difference of potential
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Introduction
Power

C is the discharge rate of a battery

§ Lithium ion transport

§ Surface area
§ Interfacial resistance

C rate

0.5C = full discharge in 2h

1C = full discharge in 1h
2C = in 30 min
4C = in 15 min
Etc..
discharge

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 Introduction
Cathode & Anode
A cathode in electrochemical systems, is the electrode on which a reduction half-
reaction takes place. (Li-Ion various chemistry)
o In the case of a battery or galvanic cell, reduction occurs spontaneously and
consumes electrons (during discharge), so the cathode is the positive pole.
o In the case of an electrolytic cell, reduction is forced by administering electrons,
so the cathode is the negative pole.
o In electronic devices, the cathode is the negative pole.

An anode in electrochemical systems, is the electrode on which an oxidation half-

reaction takes place. (Li-Ion graphite or graphene or silicon)
o In the case of a battery or galvanic cell, oxidation occurs spontaneously and
produces electrons (during discharge), so the anode is the negative pole.
o In the case of an electrolytic cell, oxidation is forced by forcing out the electrons,
so the anode the positive pole.
o In electronic devices,
October 25th, 2013 the anode is the positive pole. 5
Introduction
Chemistries

Lead acid – Low cost, high reliability

NiMH – successor to NiCd

high power, better energy density

Li-ion – High energy density, higher cost

Potential for improved performance in Li-ion

is very high.

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Introduction For the lead battery the chemical reduction reaction is against H SO
2 4
Lead-acid The potential is 2.1V

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Introduction How does lithium move + ê-
Li-ion cells

§ Lithium is highly electropositive -> high voltage, lower energy of ion formation.

§ Lightweight and single valence ion means easier transport within a solid
-> higher power. Bigger ions (like the one of sodium) à lower power

§ Li is often stored in the anode/cathode through intercalation reactions

cathode anode
discharge

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Charge
 positive electrode as the battery is discharged. Elec
Charging move through an external circuit in the same direct
the lithium ions, driven by an external charger
Charger circuit charging) or by the stored potential chemical e
Anode (available to drive a load) when the battery is discha
Cathode
Is the positive electrode Is the negative electrode
(different chemistry) (graphite or graphene)

Charge

During charging, lithium ions (yellow circles) flow from the positive electrode (Cathode) to the negative electrode
(Anode) through the electrolyte in-between. Electrons also flow from the positive electrode (Cathode) to the
negative electrode (Anode), but take the longer path around the outer circuit (the charger circuit injects
electrons). The electrons and ions combine at the negative electrode (Anode) and deposit lithium there.
When the battery is fully charged, all the lithium ions are stored in the carbon graphite structure or between
layers of graphene (sheets of carbon one atom thick) in the graphite electrode (Anode). In this charged-up state,
the battery is effectively a multi-layer sandwich: graphene layers alternate with lithium ion layers.
When no more ions will flow, the battery is fully charged and ready to use à maximum oxidation state à
maximum battery voltage 4.2V typical. FIGURE 1. LITHIUM ION AND ELECTRON FLOW IN A
October 25th, 2013 LI-ION CYLINDRICAL CELL WITH EXTERNAL
9 CIRCUIT
 Discharging

Load circuit
Cathode Anode
Is the positive electrode Is the negative electrode
(different chemistry) (graphite or graphene)

discharge

During discharging, the ions flow back through the electrolyte from the negative electrode (anode) to the positive
electrode. Electrons flow from the negative electrode (anode) to the positive FIGURE
electrode 1. LITHIUM ION AND ELECTRON FLOW IN A
(cathode) through the
LI-ION CYLINDRICAL CELL WITH EXTERNAL CIRCUIT
outer circuit, powering the external load. When the ions and electrons combine at the positive electrode
(cathode), lithium is deposited there.
As the battery discharges, the ions migrate from the graphite electrode to the Acobalt-oxide electrode (Cathode).
lithium ion is a lithium atom that has been stripped of an electron
When it's fully discharged, all the lithium ions have moved over to the cobalt-oxide electrode
leaving behind on the
a positively charged right. Once
particle.

again, the lithium ions sit in layers, in between layers of cobalt ions and oxideBuchman,
ions. I.When all ofthe
BU-205: Types
1 ionsBattery
Lithium-ion. have University
moved back to the positive electrode (cathode), the battery is fully discharged and needs charging up again à
[Internet]. 2019 April 24 [cited 2019 June 4]. Available from:

lower oxidation state à minimum battery voltage 2.7V typical.

October 25th, 2013 10
As the battery charges and discharges, the lithium ions shunt back and forth Tfrom
E C H N Ione
C A L Nelectrode
OTES to the other.
 My notes -2 : 2 more electrons on the shell
+2 : minus 2 electrons on the shell

Chemical reaction Li+1 Co +2/+3/+4 O-2 Li Co O2 à Li0.9 Co O2

There is a transition of the metal in the cathode
Some Li atoms goes to the anode
Charging too much a cell: you could collapse the crystal structure and it damages the battery forever. You
move too much Li atoms to the anode. Overcharging can create unstable conditions inside the battery, increase
pressure, and cause thermal runaway.

Discharging too much a cell: graphite is a very good anode, nothing irreversible will happen in this case,
because the normal structure of the graphite is without Lithium in any case and then emptying completely the
structure doesn't affect his stability. Very deep discharges instead will quickly, permanently damage a Li-ion
battery. Internal metal plating can occur causing a short circuit, making the battery unusable and unsafe.

The Lithium Ion ones must be stored at 30-50% maximum charge for the best results. But it's better to store
when they are fully charged when you're not going to recharge in a few months.

Li+ ions can move easily inside the electrodes if the temperature high.
With larger ions, for example Na, you get lower energy, because ions have more difficulties to move inside the
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electrodes.
 My notes

To store the battery for long time stability, in case of stable graphite anode
This anode is not affected by the state of charge. Then you have to keep in mind the
cathode: Li Co O2 best is if fully “lithiated”: it means discharged à Li atoms are inside
the crystal structure of the cathode, then the crystal structure is preserved à the issue
could be that the cathode becomes Co3 O4: this is cobalt oxide

It seems that to store the battery the best state is to keep discharged ?
Also decompositions inside the electrolyte could occur in case of very high potential.
If the cell is discharged then the potential is at the minimum à no decomposition could occur.

In case of silicon content of the anode, the situation could be different.

October 25th, 2013

 My notes
How to charge LiIon battery
A Li-Ion batt. has a peculiar charging characteristic that most people could not understand and follow. That is
why these batteries have an internal circuit which does the “Dirty” work for you. All you have to do is connect
the battery to the charger. If you do not have an internal circuit-you will have to do the “Dirty” work yourself.
Here goes:
Connect the battery to a suitable power supply, and adjust the current flowing into the battery to be between
10 and 70% of it’s rating(Say the battery is rated at 2 AH, than adjust to .2 to 1.4 amps.)That phase of the
charge will be the “Constant current”step. As the battery voltage will increase, the current flowing into the
battery will decrease. You must watch the current often, and adjust the power supply voltage up to restore the
current to the value you started with.You do this until the battery voltage gets to 4.2 volts/cell(Namely, if you
are charging two batteries connected in series, the total voltage you are looking for is 8.4 volts).At this point,
the battery is about 70% charged. At this point, you switch to a constant voltage charge.You will notice that
the battery voltage will increase beyond the 4.2 volts/cell.You need to watch the voltage often and keep
lowering the power supply voltage to maintain the 4.2 volts/cell.
Charging is complete when the current into the battery reaches 10% of the current you started with(If it was
1.4 amps-it should be 0.14 amps). At this point, the battery is 100% charged.
One more important point. Li-Ion batteries do not like to reach zero volts. If you allow this to happen, EVEN
ONCE-the battery capacity(It’s amp-hours) will drop to about 30% !!!! The built in battery circuit will turn the
battery output off when it’s voltage reaches around 2 volts(Varies w/the manufacturer).You can notice that. Li-
Ion batteries stop working abruptly. They do not dim out as they reach the end of discharge.
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Basic Structure
Opening the black box

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Basic Structure Role of electrolyte and cc
Opening the black box

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Basic Structure
Cathode side – LiCoO2 composite

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 My notes

Replacing transition metal inside the cathode à the cathode will have different propriety

The Li ions are all anode side à high oxidation state à high voltage

Pulling out too fast electrons from one area à local decomposition could happen

The anode must have lowest voltage

The cathode must have the highest voltage
Both characteristics will make a good cell, because of high energy density

Nickel rich cathode chemistry will be the future of LiIon cells.

Graphite is a very good anode. Adding silicon to graphite, improve the capacity of the anode,
but decrease stability. With silicon the stability of the anode is difficult.

With Li5 Ti4 012 cathode (could be used as anode or cathode): the stability is higher

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 My notes

20% to 80% is a good charging / discharging range of use.

Self discharging:
There is very small electronic conductivity thought the electrolyte à there is very low current
inside the cell à this current discharge the cell.

For liquid electrolyte this current is always there

Long term storage battery are made with solid electrolyte.

Sodium battery (sodium chloride) are solid at normal 20°C temperature and then they are
activated increasing the temperature (it’s necessary to melt the salt)

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 My notes
Battery storage
Temperature
When storing your batteries, keep in mind the temperature can't be extreme. The
recommendation says batteries need to be stored around 15°C. Keep your batteries away from
the sun and choose any cool and dry room for the storage. A battery loses charge capacity when
temperatures are extreme. Keep in mind that batteries self-discharge when they're in storage.
But eneloop rechargeable batteries keep 70% of their capacity even after 10 years of storage.
Charge levels
Always check the charging level before the battery storage. Use separate containers to keep
new and used batteries apart. The Nickel-based batteries (like the eneloop batteries) can be
stored at any state of charge. The Lithium Ion ones must be stored at 30-50% maximum charge
for the best results. But it's better to store when they are fully charged when you're not going to
recharge in a few months.
Humidity
Too high humidity is bad for the storage of batteries. A vapor-proof container is an option to keep
them away from a high humidity environment. The perfect humidity is 35% to 65%. Never put
your batteries in the freezer unless it's recommended by the manufacturer. The condensation in
the fridge can cause damage inside the battery. Keep these factors in mind next time you start
October 25th, 2013 19
with the battery storage.
Basic Structure
Anode side

Anode - Graphite

5 µm 1 µm

LTO, Si
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Basic structure
Electrolyte and separator

§ The separator must provide a physical separation while allowing the electrolyte
to flow freely.

§ Electrolyte solutions are based on the LiPF6 salt dissolved in various carbonate
solvents: EC, DMC, DEC, EMC
§ Additives are added to aid in the formation of proper SEI at the anode and
cathode side. prop-1-ene-1,3-sultone (PES) 1,3,2-dioxathiolane-2,2-dioxide
(DTD), and tris(trimethylsilyl)phosphite (TTSPi)
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Basic structure
Solid-Electrolyte Interface

§ Crucial for stable performance and long cycle lifetime.

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 Cathode materials
Which crystals can store a variable Li amount

Layered Spinel
Li
LiCoO2 LiMn2O4

CoO6

Olivine Tavorite
Fe-O
LiFePO4 LiFeSO4F

PO4
For more information: http://batteryuniversity.com/learn/article/types_of_lithium_ion
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Cathode materials
Voltage profiles

a) Full discharge
b) Half charge
c) Full charge

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 Cathode materials
Playing with composition

§ More Co gives higher voltage

§ More Mn gives higher stability

§ More Ni gives higher capacity

Generally speaking…

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Anode Materials

§ Graphite (carbon) anodes are the most

common due to very low cost, similar voltage
to Li metal and high stability.

§ The capacity of Si is ~10 times higher

however there are many challenges to
overcome mainly due to poor stability.

Integration of Li into the

graphite structure has a
negligable impact of
lattice size.

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Anode Materials
Lithium titanate
Li5Ti4O12

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Anode Materials
Silicon

Each silicon atom can bind up to 4.4 lithium atoms in its fully lithiated
state (Li4.4Si), compared to one lithium atom per 6 carbon atoms for
the fully lithiated graphite (LiC6)

300% volume increase!

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Anode Materials
Lithium Metal

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 Decomposition
Mechanisms for reduced performance

1. Irreversible chemical reactions 2. Isolation of electro-active material

- Lithium plating - Cracking
- SEI growth - blocking of pores
- Transition of cathode materials

Too much discharge leads to crystal instability

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Decomposition
Avoidance measures

§ Moderate charge/discharge rates

§ Promote the formation of stable SEI

§ Avoid deep discharge/charge states

§ Engineer more advanced architectures

§ Synthesise more stable materials for electrolyte and electrodes

And more…

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Future Roadmaps

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Conclusions

1 Lithium chemistry is currently the most promising path for maximizing

the energy density of batteries

2 There is a diverse array of materials and architectures to explore

3 Degradation mechanisms occur for several reasons and are connected

to battery treatment

4 New innovations could lead to x2 or x3 more energy in the future!

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