Czochralski process vs

Float Zone: two

growth techniques for
mono-crystalline
silicon

Silicon is the most abundant solid element on earth,

being second only to oxygen and it makes up more than
25% of the earth’s crust. However, it rarely occurs in
elemental form, virtually all of it is existing as compounds.

In this lecture the question will be answered how very

pure sand (SiO2) is converted into mono-crystalline silicon
and later on into silicon detectors. After a description of the
different growth techniques for mono-crystalline silicon
with special interest in the material used in this work it is
shown which kind of detectors have been used and how
they have been produced.
The material requirements for the manufacturing of
silicon particle detectors used for high energy physics
applications have to meet two basic demands: high
resistivity and high minority carrier lifetime. A very high
resistivity (> l Kohm/cm) is needed in order to fully
deplete the detector bulk with a thickness of about 200 -
300 um by an adequate voltage below about 300 V.

Together with the demand for a reasonable price and a

homogeneous resistivity distribution, not only over a
single wafer but also over the whole ingot, Float Zone
silicon is the best choice of material and is therefore
exclusively used for detector applications today. Further
requirements for detector grade silicon are often a high
minority carrier lifetime and a very low bulk generation
current in order to avoid detector noise.

However, these requirements should not be taken too

strictly for particle detectors that will be exposed to severe
radiation levels since already after small radiation fluences
the lifetimes are reduced by orders of magnitude and
therefore the good initial lifetime qualities are of no use
any more.

In the search for radiation harder material and in order to

perform radiation tests on an as wide as possible range
of material also silicon grown by the Czochralski has been
investigated in this lecture.

While for the epitaxial technique the price and the

substrate problem might rule out largely its application as
detector material the Czochralski method could become
of interest for the production of radiation hard material if
it is possible to make high resistivity (> 1 KOhm/cm) CZ
commercially available.

In this section the production of silicon with the two

growth techniques mentioned above will shortly be
reviewed with special interest in the high resistivity silicon
production and the possibilities of defect engineering
respectively the controlled incorporation of impurities
into the crystal.

NEW  Czochralski process on silicon and the bright future of graphene

Czochralski silicon (Cz)

The vast majority of the commercially grown silicon is
Czochralski silicon due to the better resistance of the
wafers to thermal stress, the speed of production, the low
cost and the high oxygen concentration that offers the
possibility of Internal Gettering. The industrial standard
crystals range in diameter from 75 to 200 mm, are
typically l m long and of < 100> orientation. In the
following a short review is given.

Standard CZ

The Czochralski method is named after J. Czochralski, who

determined the crystallisation velocity of metals by
pulling mono- and polycrystals against gravity out of a
melt which is held in a crucible. The pull-from-melt
method widely employed today was developed by Teal
and Little in 1950 . A schematic diagram of a Czochralski-
Si grower, called puller, is shown in Fig. 2.1. The puller
consists of three main components:

a) a furnace, which includes a fused-silica crucible, a

graphite susceptor, a rotation mechanism (clockwise as
shown), a heating element, and a power supply;
b) a crystal-pulling mechanism, which includes a seed
holder and a rotation mechanism (counter-Clockwise);
and
c) an ambient control, which includes a gas source (such
as argon), a flow control and an exhaust system.
The Czochralski method begins by melting high purity
polysilicon (SGS) with additional dopants as required for
the final resistivity in the rotating quartz crucible. A single
crystal silicon seed is placed on the surface and gradually
drawn upwards while simultaneously being rotated.

This draws the molten silicon after it which solidifies into

a continuous crystal extending from the seed.
Temperature and pulling speed are adjusted to first neck
the crystal diameter down to several millimetres, which
eliminates dislocations generated by the seed/melt
contact shock, and then to widen the crystal to full
diameter.

During the production process the quartz crucible (SiO2)

gradually dissolves, releasing large quantities of oxygen
into the melt. More than 99% of this is lost as SiO gas
from the molten surface, but the rest stays in the melt
and can dissolve into the single crystal silicon.

Another impurity, however with smaller concentrations,

that is also introduced into the melt by the production
process itself is carbon. The silicon monoxide evaporating
from the melt surface interacts with the hot graphite
susceptor and forms carbon monoxide that re-enters the
melt.

As the crystal is pulled from the melt, the impurity

concentration incorporated into the crystal (solid) is
usually different from the impurity concentration of the
melt (liquid) at the interface. The ratio of these two
concentrations is defined as the equilibrium segregation
coefficient k0 =Cs/c1 where Cs and C1 are the equilibrium
concentrations of the impurity in the solid and liquid near
the interface, respectively.
Figure 2.1: Schematic setup of a Czochralski crystal puller

Oxygen is always the impurity with the highest

concentration in CZ silicon. Typical oxygen and carbon
concentrations are [O] ≈ 5 - 10 10^17cm-3  and [C] ≈ 5 - 10
10^15cm-3, respectively. The solubility of O in Si is ≈
10^18 cm-3 at the melting point but drops by several
orders of magnitude at room temperature, hence there is
a driving force for oxygen precipitation. Furthermore the
high oxygen concentration can lead to the formation of
unwanted electrically active defects.

These are oxygen related thermal double donors (TDD)

and shallow thermal donors (STD) which can seriously
change the resistivity of the material. However, oxygen
has also good properties.

Oxygen acts as a gettering agent for trace metal

impurities in the crystal (Internal Gettering) and it can pin
dislocations which greatly strengthens the crystal. Oxygen
precipitates in the wafer core suppress stacking faults,
and oxygen makes the Si more resistant to thermal stress
during processing. This is the reason why CZ-Si is used for
integrated circuit production, where there are many
thermal processing steps.

However, the most important property of a high oxygen

concentration from the point of view of this work is the
improved radiation hardness. The main problem for the
application as detector grade material arises from the
resistivity of CZ silicon. Due to contamination with boron,
phosphorus and aluminum from the dissolving quartz
Crucible the highest commercially available resistivity is
about l00 Ohmcm for n-type and only slightly higher for
p-type material.

Therefore standard CZ silicon is not suitable for detector

production.

However, first experiments to compensate the natural p-

type background doping by adding a small quantity of
phosphorus to the melt have been performed.

Magnetic Field Applied Cz (MGZ)

MCZ may be the future standard CZ technology since

today’s approaches to solve the challenge of the 300 mm
and later on also the 400 mm crystal diameter are based
on this technology The method is the same as the CZ
method except that it is carried out within a strong
horizontal (HMCZ) or vertical (VMCZ) magnetic field. This
serves to control the convection fluid flow, allowing e.g.
with the HMCZ method to minimise the mixing between
the liquid in the center of the bath with that at the edge.

This effectively creates a liquid silicon crucible around the

central silicon bath, which can trap much of the oxygen
and slow its migration into the crystal. Compared to the
standard CZ a lower oxygen concentration can be
obtained and the impurity distribution is more
homogeneous.
This method offers also the possibility to produce
detector grade silicon with a high oxygen concentration.
Since the technology is still a very young one, it is hard to
get such material with reproducible impurity
concentrations on a commercial basis. However, a first
test material of 4 KΩcm  p-type with an oxygen
concentration of 7 - 8 l017 cm-3 and a carbon
concentration below 2xl016 cm-3 was obtained.

 Continuous Cz (CCZ)

With the CCZ method a continuous supply of molten

polycrystalline silicon is achieved by using a double quartz
crucible. In the first one the crystal is grown and in the
second one, connected to the first one, a reservoir of
molten silicon is kept, that can be refilled by new
polysilicon during the growth process.

This allows for larger crystal length and improves the

throughput and operational costs of the CZ grower.
Furthermore the resulting single crystals have a uniform
resistivity and oxygen concentration and identical thermal
history. In combination with the magnetic field method
the Continuous Magnetic Field Applied CZ technique
(CMCZ) offers the possibility to grow long and large
diameter CZ. However, silicon produced by this
technology has so far not been used for radiation
damage experiments.

Float zone silicon (FZ)

Float-zone silicon is a high-purity alternative to crystals
grown by the Czochralski process. The concentrations of
light impurities, such as carbon and oxygen, are
extremely low. Another light impurity,nitrogen, helps to
control microdefects and also brings about an
improvement in mechanical strength of the wafers, and is
now being intentionally added during the growth stages.

The float zone method

The float Zone (FZ) method is based on the zone-melting

principle and was invented by Theuerer in 1962. A
schematic setup of the process is shown in Fig. 2.2. The
production takes place under vacuum or in an inert
gaseous atmosphere. The process starts with a high-
purity polycrystalline rod and a monocrystalline seed
crystal that are held face to face in a vertical position and
are rotated.

Figure 2.2: Schematic setup for the Float Zone (FZ)

process

With a radio frequency field both are partially melted. The

seed is brought up from below to make contact with the
drop of melt formed at the tip of the poly rod. A necking
process is carried out to establish a dislocation free
crystal before the neck is allowed to increase in diameter
to form a taper and reach the desired diameter for
steady-state growth.
 As the molten zone is moved along the polysilicon rod,
the molten silicon solidifies into a single Crystal and,
simultaneously, the material is purified.

Typical oxygen and carbon concentrations in FZ silicon

are below 5 1015 cm-3. FZ crystals are doped by adding
the doping gas phosphine (PH3) or diborane (B2H6) to the
inert gas for n- and p-type, respectively. Unlike CZ growth,
the silicon molten Zone is not in contact with any
substances except ambient gas, which may only contain
doping gas. Therefore FZ silicon can easily achieve much
higher purity and higher resistivity.

Additionally multiple zone refining can be performed on a

rod to further reduce the impurity concentrations. Once
again the effective segregation coefficient k plays an
important role. Boron, for example, has an equilibrium
segregation coefficient of k0 = 0.8. In contrast to this
phosphorus cannot only be segregated (k0 = 0.35) but
also evaporates from the melt at a fairly high rate.

This is the reason why on the one hand it is easier to

produce more homogeneous p-type FZ than n-type FZ
and on the other hand high resistivity p-type silicon can
only be obtained from polysilicon with low boron content.
Dopants with a small k0 like Sn  can be introduced by pill
doping  - holes are drilled into the ingot into which the
dopant is incorporated - or by evaporating a dopant layer
on the whole ingot before the float zoning process.

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Explain Czochralski method (CZ method) for Silicon crystal growth. What
are its advantages?

Components

1. Furnace: It includes fused silicon crucible (SiO2)(SiO2), a graphite susceptor, a rotation mechanism (clockwise),
heating element and power supply.
2. A crystal pulling mechanism: It includes a seed holder and a rotation mechanism counter clockwise.
3. Ambient control: It is very important in growth system. There must not be any oxygen inside the system. The
graphite susceptor and graphite heater will react with oxygen to form CO2CO2. It should not react with Si.
Therefore, oxygen should be removed from the chamber and fill it with Argon. It includes gas source, a flow
control & an exhaust system.
4. Control system: A puller has microprocessor based control system to control the process parameters such as
temperatures, crystal diameter, pull rate & rotation speed.

Working

1. Pieces of EGS (Electronic Grade Silicon) are placed in silicon (SiO2)(SiO2) crucible along with a small amount of
doped silicon & melted. The melt temperature is stabilized at just above the silicon melting point (14170C)
(14170C)
2. A small single crystal seed suitably oriented is suspended over the crucible in a chuck.
3. For growth the seed is lowered into the melt until its end is molten.
4. It is now slowly withdrawn resulting in a single crystal which grows by progressive fusing at the liquid – solid
interface.
5. The crystal orientation of this seed will determine the orientation of the resulting pulled crystal and wafers. The
amount of dopant placed in a crucible with silicon charge will determine the doping concentration in the resulting
crystal.
6. The silicon atoms from the melt bond to the atoms in the seed, lattice plane by lattice plane forming a single
crystal as the seed is pulled upwards.
7. The diameter is controlled by the pull rate. Fast pulling results in smaller diameter crystal.
8. The seed & crucible are rotated in opposite direction to promote more uniform growth.

Advantages

1. Capable of easily producing large diameter crystals from which large diameter wafers can be cut.
2. O2 in interstitial sites improves yield strength up to 6.4×1017O2 concentrations, but if it is more then there is
problem of O2 precipitate. Precipitate attracts metallic impurities as well as it can act as a sink and they are called
gettering centers. For power devices it reduces breakdown voltages.
With a neat diagram explain Float zone technique of crystal growth. What
are its advantages?

Float-zone silicon is a high-purity alternative to crystals grown by the Czochralski process.

The basic idea in float zone (FZ) crystal growth is to move a liquid zone through the material. If properly seeded, a single
crystal may result.

The production takes place under vacuum or in an inert gaseous atmosphere.

The process starts with a high-purity polycrystalline rod is held in a vertical position and is rotated.

With a radio frequency the rod is partially melted. The seed is brought up from below to make contact with the drop of melt
formed at the tip of the poly rod.

As the molten zone is moved along the polysilicon rod, the molten silicon solidifies into a single Crystal and, simultaneously,
the material is purified.

FZ crystals are doped by adding the doping gas phosphine (PH3) or diborane (B2H6) to the inert gas for n- and p-type,
respectively.

Unlike CZ growth, the silicon molten Zone is not in contact with any substances except ambient gas, which may only contain
doping gas.

Therefore FZ silicon can easily achieve much higher purity and higher resistivity.

After the heating coils move over the whole polysilicon rod, it converts to a single crystal silicon ingot.
Advantages:

1. When extremely high purity silicon is required the growth technique of choice is float-zone method.
2. There is no need for a crucible and so there is lower melt contamination, especially oxygen and carbon which
cannot be avoided in CZ crystal growth.

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Explain formation of energy bands in solids and explain classification on
the basis of energy band theory.

Formation of energy bands in solids

 1. The solid crystals are formed when the isolated atoms are brought together. Various interactions occur between
the neighboring atoms.
2. At a particular interatomic spacing d, there is a proper balance between forces of attraction to form a crystal. In
this process, the changes occur in the electron energy level configurations.
3. In case of a single atom, there is a single energy for an electron orbit.
4. However, when two atoms are brought close to each other, it leads to intermixing of electrons in the valence shell.
5. As a result, the number of permissible energy levels is formed, which is called an energy band.
6. Three bands are important from the conductivity point of view, which are,
7. Valence band
8. Conduction band
9. Forbidden gap or band
10. The simple energy band diagram, showing these bands is shown in the figure

1. In the normal state, the electrons involved in the covalent bonds in the crystal occupy the valence band and the
conduction band is empty. Hence the electrons in the outermost shell are called valence electrons and the
outermost shell is called valence shell.
2. At higher temperature, these electrons acquire energy and move to the conduction band as electron is not
allowed to occupy any energy state in forbidden gap. These electrons are called free electrons.
3. For any given type of material the forbidden energy gap may be large, small or nonexistent. The classification of
materials as insulators, conductors and semiconductors is mainly dependent on the widths of the forbidden
energy gap.

Classification on the basis of energy theory:

Based on the ability of various materials to conduct current, the materials are classified as conductors, insulators and the
semiconductors.

Conductors

 A material having large number of free electrons can conduct very easily. For example, copper has 8.5x1028 free
electrons per cubic meter which is a very large number. Hence copper is called good conductor.
 Intact, in the metals like copper, aluminum there is no forbidden gap between valence band and conduction
band.
 The two bands overlap. Hence even at room temperature, a large number of electrons are available for
conduction.
 So without any additional energy, such metals contain a large number of free electrons and hence called good
conductors. An energy band diagram for a conductor is shown in the Figure (a).

Insulators

 An insulator has an energy band diagram as shown in the Figure (b).

 In case of such insulating material, there exists a large forbidden gap in between the conduction band and the
valence band.
 Practically it is impossible for an electron to jump from the valence band to the conduction band.
 Hence such materials cannot conduct and called insulators.
  The forbidden gap is very wide, approximately of about 7 eV is present in insulators. For a diamond, which is an
insulator, the forbidden gap is about 6 eV.
 Such materials may conduct only at very high temperatures or if they are subjected to high voltage. Such
conduction is rare and is called breakdown of an insulator. The other insulating materials are glass, wood, mica,
paper etc.

Semiconductors

 Semiconductors are neither insulators nor conductors. The forbidden gap in such materials is very narrow as
shown in Figure (c). Such materials are called semiconductors.
 The forbidden gap is about 1 eV. For such materials, the energy provided by the heat at room temperature is
sufficient to lift the electrons from the valence band to the conduction band.
 Therefore at room temperature, semiconductors are capable of conduction. But at 0 IC or absolute zero (-273 °C),
all the electrons of semiconductor materials find themselves locked in the valence band.

 Hence at 0 IC, the semiconductor materials behave as perfect insulators. In case of semiconductors, forbidden
gap energy depends on the temperature. For silicon and germanium, this energy is given by,

EG=1.21−3.6×10−4×TeV(for Silicon)EG=1.21−3.6×10−4×TeV(for Silicon)

EG=0.785−2.23×10−4×TeV(for Germanium)EG=0.785−2.23×10−4×TeV(for Germanium)

where T = Absolute temperature in K

What is mesomorphic state of matter? Explain with neat diagram

cholesteric phase.

Mesomorphic state of matter:-

 Mesomorphic state of matter is a state of matter intermediate between liquid and solid.

 It occurs with the solids having greater tendency to an ordered arrangement.

 It has certain properties of solids like double refraction of light or interference pattern in polarised light.
  It also has some properties of liquid, like surface tension, flow and viscosity.

Cholesteric Phase:-

 Composed of molecules containing a chiral center which produces intermolecular forces that favour alignment
between molecules at a slight angle to one another.

 The structure can be visualized as a stack of very thin 2-D nematic-like layers with the director in each layer
twisted with respect to those above and below forming a continuous helical pattern about the layer normal.

 They organize in layers with no positional ordering within layers, but a director axis which varies with layers.

 The variation of the director axis tends to be periodic in nature.

 The period of this variation (the distance over which a full rotation of 360° is completed) is known as the pitch, p.
This pitch determines the wavelength of light which is reflected.

https://youtu.be/u1TYDh8QRIc

V battery
Flow battery

A flow battery is an electrical storage device that is a cross between a conventional

battery and a fuel cell. (See BU-210: How does the Fuel Cell Work?) Liquid
electrolyte of metallic salts is pumped through a core that consists of a positive and
negative electrode, separated by a membrane. The ion exchange that occurs between
the cathode and anode generates electricity.
Most commercial flow batteries use acid sulfur with vanadium salt as electrolyte; the
electrodes are made of graphite bipolar plates. Vanadium is one of few available
active materials that keep corrosion under control. Flow batteries have been tried that
contain precious metal, such as platinum, which is also used in fuels cells. Research is
continuing to find materials that are low cost and readily available.

Activated by pumps, flow batteries perform best at a size above 20kWh. They are said
to deliver more than 10,000 full cycles and are good for about 20 years. Each cell
produces 1.15–1.55 volts; they are connected in series to achieve the desired voltage
levels. The battery has a specific energy of about 40Wh/kg, which resembles lead
acid. Similar to the fuel cell, the power density and ramp-up speed is moderate. This
makes the battery best suited for bulk energy storage; less for electric power trains
and load leveling that requires quick action.

The electrolyte is stored in tanks. To increase the energy density, the tank sizes can be
doubled using ready-made storage tanks at an estimated cost increase of only 50
percent compared to a new system. When replacing the battery, the electrolyte can be
reused, further saving cost. Problem areas are the membranes that tend to corrode and
are expensive; additives are said to solve this issue. Figure 1 illustrates the flow
battery concept.

Figure 1: Flow
Battery
Electrolyte is stored in tanks and pumped through the core to
generate electricity; charging is the process in reverse. The volume
of electrolyte governs battery capacity.
Vanadium is the 23rd element on the periodic table and is mined in China, Russia and
South Africa. Sun-backed central Nevada may soon become a contributor in the form
of heavily oxidized crumbled rock. Currently, 90 percent of lower grade vanadium is
used as an additive to strengthen steel. Battery scientists, mining companies and
politicians are excited about vanadium becoming a strategic metal for “green energy.”
According to RWTH, Aachen, Germany (2018), the cost of the flow battery is about
$350 per kWh.

For a more precise cost estimation, the flow battery is divided into power cost and
energy cost. The power cost can go above $1,500/kW and consists of stacks, pumps,
pipes and power electronics. The energy cost consisting of tanks and electrolyte
comes in at a bit more than $300/kWh.

Large scale flow batteries exceeding 100kWh have been in use in Japan since 1996.
Some of the biggest current installations boast a capability of several megawatts and a
flow battery for frequency regulation is being installed in Japan that will deliver a
whooping 60MWh.

There is a move towards cost and size reduction. Rather than building a monster
battery resembling a chemical plant, newer systems come in container-sizes of
typically 250kWh that can be stacked. Modern flow batteries are also becoming
common in Europe.

The first patent for a titanium chloride flow battery was granted in July 1954. The
present day vanadium redox battery was patented in 1986 by the University of New
South Wales in Australia. The term “redox” comes from “electron transfer”
of reduction and oxidation.

VANADIUM REDOX (VRB) FLOW BATTERIES

The Vanadium Redox Battery (VRB®)¹ is a true redox flow battery (RFB), which stores energy by employing
vanadium redox couples (V2+/V3+ in the negative and V4+/V5+ in the positive half-cells). These active
chemical species are fully dissolved at all times in sulfuric acid electrolyte solutions. Like other true RFBs, the
power and energy ratings of Vanadium Redox Batteries are independent of each other and each may be
optimized separately for a specific application. All the other benefits and distinctions of true RFBs compared to
other energy storage systems are realized by VRBs. The first operational vanadium redox battery was
successfully demonstrated at the University of New South Wales in the late 1980s and commercial versions
have been operating on scale for over 8 years.

How Vanadium Flow Redox Batteries Work

During the discharge cycle, V2+ is oxidized to V3+ in the negative half-cell and an electron is released to do
work in the external circuit (either DC or, for AC systems, through an AC/DC converter).

In the positive half-cell, V5+ in the form of VO2+ accepts an electron from the external circuit and is reduced to
V4+ in the form of VO2+. Hydrogen (H+) ions are exchanged between the two half-cells to maintain charge
neutrality. The hydrogen ions diffuse through the anion or cation-ion permeable polymer membrane that
separates the half cells. Charged vanadium species and water can also diffuse across the membrane. The
cross-diffusion results in direct energy loss for that cycle. However, when vanadium is the only element
present on both sides of the cell, this cross diffusion mechanism does not result in permanent capacity loss, as
long as the total vanadium in the system remains constant (i.e., there is no loss due to precipitation).
In a V-only system there is no need to maintain balance between positive and negative sides of the system. In
the positive half-cell, the vanadium is present in solution as oxy-cations. These oxy-cations are vulnerable to
irreversible precipitation as V2O5 if the electrolyte temperature exceeds ~50-60oC. However, when
precipitation occurs, it does so typically in the form of benign compounds, not V2O5.

The normal operating temperature of a VRB is approximately between 10-40oC. Active cooling sub-systems
are employed if ambient temperatures exceed 40-45oC. Being able to cool the system actively is an
advantage since the system can remain operating without risking any damage to it. By contrast, if integrated
cell architectures overheat, the best option is to stop using them until they cool down.

The cell voltage is 1.4-1.6 volts and cell power densities are hundreds mW/cm2 (although Prudent Energy
reports their power densities are higher). The DC-DC efficiency of this battery has been reported in the range
of 60-80%. According to EPRI, the vanadium redox battery is suitable for power systems in the range of 100
kW to 10 MW, with storage durations in the 2-8 hour range.
The vanadium redox battery offers a relatively high cell voltage, which is favorable for higher power and
energy density compared with other true RFBs, like the iron-chromium system. However, the higher voltage
and highly oxidative V5+ electrolyte puts more chemical stress on the materials used in the cell electrodes,
membranes, and fluid handling components. Cross-transport of vanadium ions across the membrane is also
reported as a challenge, and fairly expensive ion-exchange membranes must be used to minimize losses due
to cross-membrane transport. These membranes can be vulnerable to fouling, wherein vanadium ions become
irreversibly trapped in the membrane and increase resistive losses in the cell. On the other hand, lower cost
membranes are under development.

Vanadium is a readily available material, used in steel manufacturing and as a chemical catalyst, which
is found naturally and can also be recovered from various waste streams. The market price of vanadium
as V2O5 has, however, been fairly volatile since 2017 after enjoying several years of low prices..

Why is vanadium used in redox flow batteries?

Vanadium Redox Flow Batteries - How they work

Vanadium has a unique characteristic of having four different stages of oxidation. In each of the four stages,
Vanadium contains a different electrical charge and is therefore used as a catalyst to store energy.
The Vanadium Redox Flow Battery (VRFB from s stands for progressive and innovative flow battery technology. Different oxidation
states of dissolved vanadium ions in the electrolyte (V2+, V3+, V4+, V5+) store or deliver electric energy. The electrolyte is
continuously fed from a tank system into the reaction cell. Depending on the current demand, energy is stored in the electrolyte
(battery charging) or fed into the grid/network (battery discharging). Because the electrolyte flow direction does not have to change
when loading and unloading, the VRFB is very fast in the response time (less than 20ms). It can be switched between charging and
discharging under full load. When the system is in standby mode, only a maximum discharge of the stack takes place. In the
electrolytic tank there is no discharge taking place until the electrolyte will be pumped again through the stack by turning on the
pumps.

The SCHMID EverFlow® energy storage technology is designed in such a way, that the
flow rate of the pumps is adjusted according to the necessary energy amount needed at
the current moment in order to achieve the best efficiency possible.
Vanadium Redox Flow Battery, only one element (Vanadium) in the electrolyte for storing energy:

 A chemical element with the symbol V and atomic number 23

 Unique in the periodic table and noteworthy for the accessibility of four adjacent oxidation states: 2+ | 3+ | 4+ | 5+ This
allows the storage of energy with only one element.
 Making use of the different oxidation states of just one element in order to store electrical energy. During the process of
charging and discharging a color change can be observed and thanks to the OCV cell the SCHMID EverFlow ® systems
can determine the exact State of Charge (SoC) at any time.

Watch it on 

SCHMID

and VRFB
Since 2010 SCHMID Energy Systems has been active in research and development of the EverFlow ® energy storage solution based
on Vanadium. All components, including the cell and stack production, are 100% made by SCHMID and are manufactured and
assembled in Freudenstadt in the Black Forest Germany. With more than 50 years of experience in the manufacture of wet chemical
systems SCHMID has the necessary competence and experience for the production of EverFlow ® storage solutions – Expect
Solutions!

History of VRFB
The basics for Redox Flow Cells were developed in the middle of the 20th century by Walther Kangro at the Technical University of
Braunschweig in Germany, when the possibilities of energy storage with redox couples were tested for the first time. In the 1970s,
NASA dealt with the development of this technology. The pure vanadium solution was first proposed in 1978 and developed in the
1980s at the University of New South Wales.
How good are vanadium flow batteries?
Vanadium flow batteries are durable, with an expected lifespan of 25 years or more—and, as noted in the
previous point, there is no degradation of performance even as a battery nears the end of its life.

What are the disadvantages of redox flow batteries?

Their disadvantages are low energy density and low

charge/discharge rates.

Are vanadium batteries better than lithium?

Vanadium batteries have a lower energy density – they are better
at delivering a consistent amount of power over significantly
longer periods. More importantly, a vanadium flow battery can handle
far more charge-discharge cycles than a lithium-ion battery.

What is the problem with flow batteries?

But some of the disadvantages for flow batteries include expensive fluids that are also corrosive or toxic, and the
balance of system costs are relatively high along with the parasitic (on-site) load needed to power the pumps.

What is the problem with flow batteries?

But some of the disadvantages for flow batteries include expensive fluids that are also corrosive or toxic, and the
balance of system costs are relatively high along with the parasitic (on-site) load needed to power the pumps.

The reaction uses the half-reactions:[20]

VO+2 + 2H+ + e− → VO2+ + H2O (E° = +1.00 V[21])

V3+ + e− → V2+ (E° = −0.26 V[22])
 Lithium-ion batteries
Lithium-ion batteries power the lives of millions of people each day. From laptops and cell phones to
hybrids and electric cars, this technology is growing in popularity due to its light weight, high energy
density, and ability to recharge.

So how does it work?

This animation walks you through the process.

Animation created by Sarah Harman and Charles Joyner

THE BASICS

A battery is made up of an anode, cathode, separator, electrolyte, and two current collectors (positive
and negative). The anode and cathode store the lithium. The electrolyte carries positively charged
lithium ions from the anode to the cathode and vice versa through the separator. The movement of
the lithium ions creates free electrons in the anode which creates a charge at the positive current
collector.  The electrical current then flows from the current collector through a device being powered
(cell phone, computer, etc.) to the negative current collector. The separator blocks the flow of
electrons inside the battery.
CHARGE/DISCHARGE

While the battery is discharging and providing an electric current, the anode releases lithium ions to
the cathode, generating a flow of electrons from one side to the other. When plugging in the device,
the opposite happens: Lithium ions are released by the cathode and received by the anode.

ENERGY DENSITY VS. POWER DENSITY

The two most common concepts associated with batteries are energy density and power density.
Energy density is measured in watt-hours per kilogram (Wh/kg) and is the amount of energy the
battery can store with respect to its mass. Power density is measured in watts per kilogram (W/kg)
and is the amount of power that can be generated by the battery with respect to its mass. To draw a
clearer picture, think of draining a pool. Energy density is similar to the size of the pool, while power
density is comparable to draining the pool as quickly as possible. 

The Vehicle Technologies Office works on increasing the energy density of batteries, while reducing
the cost, and maintaining an acceptable power density. For more information on VTO’s battery-related
projects, please visit www.vehicles.energy.gov

Do you know the principle of

operation and construction of Li-
polymer batteries?
Why is lithium-polymer battery good?
Lithium-polymer batteries are highly prevalent in terms of their robust nature and the property of being lightweight
than lithium-ion batteries. Due to their sturdy design, lithium-polymer batteries hold less risk of leakage.

Li-Polymer battery is the most common battery technology we use every day. But do

you know the principle of operation and construction of Li-polymer batteries?

The principle of operation and construction of Li-polymer batteries are identical to

those of Li-ion batteries. These batteries operate on the principle of deintercalation

and intercalation of lithium ions from positive electrode materials to negative
electrode materials.

The sandwich-like cells (Fig. 2) consist of a graphite electrode (negative), a lithium

metal oxide electrode (positive), and a separator layer. The lithium metal oxide is
based on manganese, nickel or cobalt oxide compounds or a mixture of them.
In certain cells with a lower voltage level, iron phosphate is used as an alternative in
the form of Li-iron phosphate cells. The composition affects the properties of the
battery and varies by manufacturer and quality grade.

Fig. 2. Basic construction of Li-ion cells. Diagram: © University of Siegen

Significant criteria that distinguish Li-polymer batteries from other types of cell:

oLi-ion cells have a fixed housing in stainless steel or aluminum. The housing is
usually cylindrical in form (‘round cells’). Rectangular shapes are, however, also
available.

Disadvantages: relatively high tool costs for housing manufacture; restricted

dimensions.

Advantages: robust, mechanically strong housing, making the battery difficult to

damage. A laser welding process seals the cells.

Li-polymer cells, also known as soft or pouch cells have a thin and somewhat ‘soft’
housing –like a pouch – made from deep-drawn aluminum foil. The mostly prismatic
housing can be produced more easily and cheaply than the hard cases of Li-ion cells.
The other components, in wafer-thin layer foils (< 100 µm) can also be mass-
produced at relatively low cost.

The cells are lightweight, thin and can be made in a wide range of shapes and sizes.
Both large formats and heights of less than 1 mm can be achieved. The cells do,
however, require careful mechanical handling.

The housing foil is coated on both sides with plastic. Inside: polyolefins, resistant to
the cell components. Outside: polyamide, resistant to the outer environment. This
waterproof laminate is welded and surrounds the cell comprising cathode, anode, and
separator.

The execution of the deflector in the area of the terrace was a critical point. An
additional foil welded to the deflector increases the sealing in this area of the welding
of the ‘housing’.

o Electrode set: In Li-polymer batteries the electrode set comprises a carbon-based

substance (graphite+additives) pasted onto a metallic substrate. The cathode consists
of threedimensional, lithiated cobalt oxides or nickel/manganese/cobalt (NMC) mixed
oxides, also pasted onto a metallic substrate. Deflectors are present on both
electrodes. They are wound around the core together with the separator, normally a
three-layered polyolefin. The core generally consists of a flat pin in order to create the
rectangular winding. The winding sits in the bottom of the pouch foil, which is partly
folded and laid over the winding. The seal is created by welding the foil.

o Design: An advantage is the almost limitless range of sizes and formats thanks to
the lack of a rigid steel housing and the compact construction. In particular, the
possibility of designing very flat cells sets Li-polymer battery technology apart. Such
batteries can be thinner than 1 mm.

This results in significant design freedom for the end product. Individual dimensions
can be realized even for small batch sizes, while the space reserved for the battery can
be used to its full potential.

o Energy density: The energy density of these cells is higher than that of other types.
Relative to their overall weight, Li-polymer cells have a slightly higher energy density
than Li-ion cells. Like Li-ion batteries, they can be easily connected in parallel to
allow higher capacities.

o Self-discharge: A further advantage of LiPo cells is their relatively low rate of self-
discharge.

They should nevertheless be protected from overcharging, deep discharge and

extreme temperatures.

o Approval: The spread of Li-polymer cells on the market confirms the advantages
and acceptance of this technology. Many of the cells on the market are certified.
Before a particular cell is used, it should be verified whether it has an approval and
whether the manufacturer has the tools required for production