Battery Manufacturing

Why is it important?
Batteries allow for portable energy storage as well as grid scale energy
storage.
In the case of portability, electric cars and cell phones would not be
possible.
In the case of grid scale storage, we need to be able to absorb all of the
inconsistent energy inputs from renewable energy sources.
History
• The history of batteries undoubtably begin with the invention of the
leyden Jar.
• Despite the fact that the leyden (leiden) jar is more closely related to
a capacitor than a battery, it started the ball rolling.
• Benjamin Franklin, coined the term “battery” for a group of leyden
jars connected in series. It was a military term meaning two or more
cannons grouped together.
Luigi Galvani
• Luigi Galvani(1737-1798) in 1790 was doing experiments on frogs and
found out that if two metals (copper and zinc) were joined and
touched a dissected frogs leg the leg would twitch. He called this
animal electricity(incorrectly). It led to both the understanding of the
nervous system as well as the development of batteries.
• The galvanic cell gains its name from the Italian physicist.
Alessandro Volta
• Alesandro Volta(1745-1827). The galvanic or voltaic cell was fully
understood and invented by Volta. Volta and Galvani disagreed on
animal electricity. Volta went on to create a copper zinc battery with
salt solution between the plates to demonstrate that it created
current.
• Volta went on to create batteries called “The Voltaic pile”.
• These batteries were essentially a series of metal discs of differing
metal types, separated by salt solution and connected in series to
create larger voltages.
William Cruickshank
• William Cruickshank improved Volta’s design by reorienting the voltaic
pile and encasing it in a frame. This ensured that there were no short
circuits and made the battery more usable. It was called the trough
battery.
Gaston Plante
• The Frenchman Gaston Plante developed the first rechargeable
battery. It was the lead acid battery consisting of lead and lead dioxide
plates soaking in sulfuric acid. The batteries we use in cars today are
very similar to Plantes designs.
Carl Gassner
• Carl Gassner developed the first dry cell battery. It was a zinc carbon
battery that was very cheap to manufacture. They were also able to
be moved due to the fact that there were no fluids in this cell.
• These batteries enabled portable electronic systems such as radios
and flashlights.
• In 1896 Eveready was producing this battery type.
Alkaline battery
• Between Lewis Urry and Karl Kordesh at Eveready, the Alkaline battery
was developed. It was much safer than the NICD battery, and had
much more energy density than zinc carbon batteries. These batteries
are in use to this day.
Lithium ion
• The lithium ion battery was developed in the 80s by John B
Goodenough and Koichi Mizushima. They had exceptional
rechargeability and energy density. Most batteries in use today for cell
phones, electric cars and laptops are refined versions of this battery
type. Its important to note that these early batteries were highly
flammable.
 Working principle
• Within all batteries a chemical reaction takes place at a controlled
rate. This reaction creates current flow.
• There is usually an anode material which releases electrons, and a
cathode material that absorbs electrons.
• Between the anode material and the cathode material there is an
electrolyte that helps transport ions to and from the anode and the
cathode.
• In a galvanic cell, a salt bridge helps neutralise charge build-up due to
reactions happening at the anode and cathode
Remember
• Oxidation loses electrons and happens at the anode
• Reduction gains electrons at the cathode.
In the example on the previous slide we can see a Zn-Cu
electrochemical cell.
• At the anode, zinc ions move from the anode into the salt solution.
Doing this, increases the charge in the salt solution. To combat this,
negative chloride ions from the salt bridge move into the ZnSO4
solution to neutralize the charge.
• At the cathode, copper begins to plate onto the cathode, removing
positive charge from the copper sulphate solution. To combat this,
potassium from the salt bridge moves into the solution.
• The next question is why does the zinc lose electrons and the copper
gains them.
• It has to do with standard reduction potentials.
• Zinc: Zn2+(aq) + 2e- → Zn(s); E° = -0.76 V
• Copper: Cu2+(aq) + 2e- → Cu(s); E° = +0.34 V
• This is a fancy way of saying that copper prefers to accept electrons at a
higher rate than zinc does. This is due to the fact that copper is more
electronegative and has high ionisation energy. The copper literally pulls
the electrons off zinc. Remember the zinc and the copper are connected
by wire, so the copper pulls the electrons off the zinc via the wire, not via
the salt bridge.
Anode (Zn electrode) - Oxidation half-reaction:
Zn(s) → Zn²⁺(aq) + 2e⁻
The zinc electrode loses electrons and dissolves as zinc ions into the ZnSO4
solution.
Cathode (Cu electrode) - Reduction half-reaction:
Cu²⁺(aq) + 2e⁻ → Cu(s)
The copper ions in the CuSO4 solution gain electrons from the external circuit
and deposit as solid copper on the copper electrode.
To obtain the overall reaction, add the two half-reactions:
Zn(s) + Cu²⁺(aq) → Zn²⁺(aq) + Cu(s)
How an Alkaline battery works
Electrochemical cells are useful for explaining how batteries work but
they have limited usefulness. A battery type that is used extensively is
the penlight alkaline battery
How it works
• In this case the anode is once again zinc, and the cathode is manganese dioxide. The
two materials are separated by a semi-permeable layer
• The electrolyte is potassium hydroxide. This is where the battery gets its name from,
the basic nature of the electrolyte. The potassium hydroxide ionizes very easily and
hence it becomes a great option for transporting ions. It is generally sprayed onto the
semipermeable membrane.
• If the circuit is completed there will be a pull from the more electronegative
manganese dioxide which will cause the zinc to ionize.
• The zinc ionizes and releases electrons that are picked up on the current pick up pin
which is usually made of brass.
• When the electron makes it to the cathode it causes the manganese dioxide to react
with water from the electrolyte and release a hydroxide ion as a byproduct.
When the battery is connected to an external circuit, a redox reaction
occurs, and electrons are transferred between the anode and cathode.
The reaction at the anode (Zn) is an oxidation reaction, meaning the
anode loses electrons:
Zn(s) + 2OH-(aq) → Zn(OH)2(s) + 2e-
At the cathode (MnO2), a reduction reaction occurs, meaning the
cathode gains electrons:
2MnO2(s) + 2H2O(l) + 2e- → Mn2O3(s) + 2OH-(aq)
As a result of these reactions, electrons are released from the anode
and flow through the external circuit to the cathode, generating an
electric current. The overall cell reaction can be written as:
Zn(s) + 2MnO2(s) + H2O(l) → Zn(OH)2(s) + Mn2O3(s)
• Hydroxide Ions created at the cathode reactions flow through the
semi-permeable membrane toward the anode where they will
combine with zinc in the oxidation reactions.
• It is important to note that the positive and negative terminal are
separated from each other with a protective cap. This also helps
secure the current pick up pin. Without this electrical insulator there
would be a short circuit between the positive and negative terminals
and useful work could not be gained from the cell.
• The flow of electrons between the negative terminal and the positive
terminal can be converted into useful work.
Lead acid battery
• Lead acid batteries have been used in the automotive industry as an
engine starter power source for decades.
• They have relatively long lifespan and are comparatively cheap.
• This battery type is fundamentally different to previous battery types
in the fact that they are rechargeable.
• The anode material in the lead acid battery is usually lead, while the
cathode is usually lead oxide.
• The electrolyte material is sulphuric acid dissolved in water.
• Due to the fact that the standard electrode potential of lead is lower
than lead oxide, electrons are pulled from the lead.
• The lead then becomes ionized and reacts with sulphate ions in the
electrolyte which plate onto the anode.
• Due to the excess of electrons on the cathode, lead oxide loses two of
its electrons and bonds with sulphate ions and creates lead sulpate and
water as a byproduct.
Rechargeability of lead acid batteries
Unlike alkaline batteries, lead acid batteries can be recharged.

• When power is reversed though the battery, lead sulphate that is

coated onto the anode will resolve into lead metal and sulphate ions.
• On the cathode the plated lead sulphate will resolve back into lead
oxide as electrons are removed.
• This restores the original structure of the cell.
• Its important to note that not all of the lead sulphate gets
reconverted and as a result the system eventually degrades.
Chemical reactions
Here are the half-cell reactions for the lead-acid battery:
1.Anode (Negative electrode, Discharge): Lead (Pb) is oxidized to lead sulfate (PbSO4) with the release of
electrons.
• Pb (s) + HSO4- (aq) → PbSO4 (s) + H+ (aq) + 2e-
2.Cathode (Positive electrode, Discharge): Lead dioxide (PbO2) is reduced to lead sulfate (PbSO4) by
accepting electrons.
• PbO2 (s) + 3H+ (aq) + HSO4- (aq) + 2e- → PbSO4 (s) + 2H2O (l)
• These reactions are reversible, so during the charging process, the reverse reactions occur:
1.Anode (Negative electrode, Charge): Lead sulfate (PbSO4) is reduced to lead (Pb) with the consumption of
electrons.
• PbSO4 (s) + H+ (aq) + 2e- → Pb (s) + HSO4- (aq)
2.Cathode (Positive electrode, Charge): Lead sulfate (PbSO4) is oxidized to lead dioxide (PbO2) by releasing
electrons.
• PbSO4 (s) + 2H2O (l) → PbO2 (s) + 3H+ (aq) + HSO4- (aq) + 2e-
Lithium ion battery
• Lithium ion batteries are different to standard electrochemical
batteries due to the fact that they rely on intercalation and
deintercalation to deal with charge balance.
• This process is different to standard batteries in the fact that lithium
ions simply leave the matrix of the cathode and make their way to
interstitial sites on the anode. So there is physical transport of ions
across the electrolyte material. The reverse happens during recharge.
• There is a difference in standard reduction potentials between the
anode and cathode which drives electron flow.
There are several types of lithium ion battery material choices but we will
focus on the type that uses a graphite anode and a lithium cobalt oxide
(LiCoO2) cathode.
In the LiCoO2 crystal structure, the cobalt and oxygen ions form edge-
sharing CoO6 octahedra, where each cobalt ion is surrounded by six oxygen
ions, and each oxygen ion is shared by two adjacent CoO6 octahedra. These
CoO6 octahedra layers are stacked along the c-axis of the crystal lattice.
The lithium ions are located between the CoO6 octahedra layers, occupying
the octahedral sites formed by the oxygen ions. The lithium layers are
separated by the CoO6 layers, which provide a pathway for lithium ions to
migrate during the charging and discharging process of a lithium-ion battery.
Structure

Cobalt oxide crystal structure

Lithium ions
In lithium-ion batteries, a type of graphite called natural flake graphite or synthetic graphite is
typically used as the anode material. The choice of graphite depends on factors such as cost,
purity, and performance requirements. Both types of graphite have a similar crystalline
structure, which is composed of layers of carbon atoms arranged in a hexagonal lattice.
The crystal structure of graphite consists of layers of carbon atoms called graphene sheets,
where each carbon atom is bonded to three other carbon atoms, forming a two-dimensional
honeycomb-like pattern. These graphene layers are stacked together with weak van der
Waals forces holding them in place, which allows for easy sliding of the layers relative to one
another.
When a lithium-ion battery is charged, lithium ions from the cathode migrate through the
electrolyte and intercalate between the graphene layers of the graphite anode. The lithium
ions occupy the interstitial sites between the carbon atoms, residing between the graphene
layers. These sites are also known as "gallery sites" or "intercalation sites."
Lithium ion electrolyte
The electrolyte in these batteries is typically a liquid organic solvent
that carries lithium ions from the anode to the cathode (and vice versa
during charging). This solvent usually consists of a mixture of organic
carbonates, such as ethylene carbonate (EC) and diethyl carbonate
(DEC), along with a lithium salt such as lithium hexafluorophosphate
(LiPF6), lithium hexafluoroarsenate monohydrate (LiAsF6), or lithium
perchlorate (LiClO4).
Separator
Traditionally, the separator in lithium-ion batteries is made from a polymer,
such as polyethylene (PE) or polypropylene (PP), or a combination of both.
These materials are chosen for their ability to form microporous
structures, their chemical stability, and their ability to melt and close the
pores to shut down the battery in case of overheating, a feature known as
a "shutdown separator".
More advanced and safer separators are being researched and developed,
including ceramic-coated separators which provide additional safety
features. The ceramic coating is typically made from materials such as
aluminum oxide (Al2O3) or silicon dioxide (SiO2), and it provides improved
thermal stability and resistance to shrinkage at high temperatures.
Solid state batteries
• Solid state batteries have been receiving substantial media coverage
and for good reason.
• This technology promises to extend the lifespan of batteries
substantially. From several years to several decades.
• The cost of grid scale batteries would then be amortized over a much
longer period and hence the affordability of these systems improves.
• Solid state batteries also promise to increase energy density
substantially by allowing for more volatile materials such as sodium to
be incorporated into batteries. This will allow for much lighter
batteries for electric cars.
What makes a battery solid state?
• Regular batteries almost always have a liquid or gel based electrolyte
to transfer ions between the anode and cathode of the battery
• Solid state batteries have a solid electrolyte. This seems to be counter
intuitive. How can ions travel though a solid?
• Generally ions in this case diffuse through the solid using either
substitutional or interstitial sites in the solid.
Types of solid state material
1.Lithium Superionic Conductors (LISICONs): These are lithium-ion conducting solid electrolytes. They are usually composed of lithium,
germanium, phosphorus, and sulfur (Li10GeP2S12 is a common compound). LISICONs offer high ionic conductivity, but their mechanical
properties and stability can be challenging.
2.Lithium phosphorus oxynitride (LiPON): LiPON is a thin-film electrolyte that is widely used in thin-film batteries. It provides a good barrier
against lithium metal dendrites, a significant issue in lithium metal batteries. However, it has lower ionic conductivity compared to some other
solid electrolytes.
3.Garnet-type electrolytes: These electrolytes, such as lithium lanthanum zirconium oxide (LLZO), offer high ionic conductivities and good
stability against lithium metal. They are usually ceramic materials and are often used in all-solid-state lithium batteries. However, processing
these materials can be challenging due to their high sintering temperatures.
4.Sulfide-based electrolytes: Examples include lithium sulfide-phosphorous sulfide (Li2S-P2S5) and thio-LISICONs. These materials offer high
lithium-ion conductivities and are easier to process compared to oxide-based electrolytes. However, they are sensitive to moisture and can be
reactive with lithium metal.
5.Polymer electrolytes: These are made from polymers such as polyethylene oxide (PEO) that are doped with lithium salts. They offer good
flexibility, ease of processing, and decent ionic conductivity. However, their conductivity can decrease at lower temperatures, and they can
have stability issues against lithium metal.
6.Composite electrolytes: These materials combine different types of electrolytes, such as ceramics and polymers, in an attempt to combine the
advantages of both. For example, a composite may have the high ionic conductivity of a ceramic and the flexibility of a polymer. However,
optimizing these materials can be complex.
7.NASICON-type electrolytes: Sodium superionic conductor (NASICON)-type materials are often used in sodium-ion batteries. They offer high
ionic conductivities and good stability. Examples include Na3Zr2Si2PO12
What are dendrites and why do solid
electrolytes prevent them?
• Dendrites are microscopic, tree-like structures that can form in rechargeable batteries, such
as lithium-ion batteries, during the charging process. These dendrites form on the electrode,
starting from the lithium metal anode, and grow through the electrolyte towards the cathode.
They're named for their resemblance to the dendrites or "branches" of nerve cells in biology.
• These dendritic formations are problematic because they can cause short-circuits within the
battery. If a dendrite grows large enough to reach from the anode to the cathode, it can
create a path for electricity to flow directly between the two electrodes, bypassing the
electrolyte. This can cause the battery to rapidly discharge, leading to overheating, failure,
and in the worst cases, a fire or explosion.
• Solid-state electrolytes are seen as a potential solution to the dendrite problem in
rechargeable batteries. The reason is that solid electrolytes are generally much harder and
more mechanically resistant than liquid or gel electrolytes. Theoretically, they can resist the
penetration of lithium dendrites, stopping their growth and preventing them from reaching
the cathode and causing a short circuit.
Battery manufacturing techniques
Manufacturing lithium-ion batteries involves several complex steps, each requiring specific machinery and processes. Here's a broad overview
of the main steps involved:
1.Material Preparation: The cathode and anode materials are prepared first. For the cathode, lithium compounds are mixed with other
materials like cobalt, nickel, or manganese. The anode is typically made from graphite. These materials are ground into a fine powder.
2.Electrode Production: The prepared materials are then coated onto a metal foil - typically aluminum for the cathode and copper for the
anode. This process involves creating a slurry by mixing the active materials with a binder and a solvent, and then applying this slurry to the
foil. Once coated, the solvent is evaporated, and the coated foils are compressed to achieve the desired thickness and density. The foils are
then cut into the desired shape and size.
3.Assembly: The anode, cathode, and a separator (a thin piece of material that keeps the anode and cathode from coming into direct contact)
are rolled together and inserted into a battery casing. The separator is soaked with an electrolyte solution that facilitates the movement of
lithium ions between the anode and cathode during charging and discharging.
4.Formation: After assembly, the batteries go through a formation process where they are charged and discharged for the first time. This forms
a solid electrolyte interphase (SEI) on the surface of the anode, which is crucial for the battery's performance and lifespan.
5.Testing and Quality Control: The batteries are then subjected to a series of tests to ensure they meet the required performance, safety, and
reliability standards.
6.Packaging and Shipping: Finally, the batteries are packaged and prepared for shipping.
• The machinery used in these processes includes grinding equipment, coating and drying machines, rolling machines, cutting machines,
assembly equipment, formation and testing equipment, and packaging machines.
• Advanced manufacturing lines may also include
Cylindrical lithium-ion batteries
Cylindrical lithium-ion batteries, such as the popular 18650 or 21700 cells, are manufactured using a roll-
to-roll process. Here's a more detailed explanation of the process:
1.Material Preparation: The cathode and anode materials are prepared, typically by grinding lithium
compounds (for the cathode) and graphite (for the anode) into a fine powder.
2.Electrode Production: The materials are then applied to metallic foils in a roll-to-roll process. The active
material is mixed with a binder and a solvent to create a slurry, which is coated onto the aluminum (for
the cathode) and copper (for the anode) foils. The coated foils are then dried to evaporate the solvent,
and compressed to achieve the desired thickness and density.
3.Assembly: The coated foils are cut to the required width, and then the anode, cathode, and a separator
are assembled together in a "jelly-roll" structure. This involves layering the cathode, separator, and
anode, and then rolling them up together, much like a jelly roll or Swiss roll cake. The roll is then
inserted into a cylindrical casing.
4.Electrolyte Filling and Sealing: The battery casing is filled with an electrolyte solution, and then sealed.
The electrolyte facilitates the movement of lithium ions between the anode and cathode during
charging and discharging