FUEL CELLS

-PROTON EXCHANGE MEMBRANE FUEL CELL

--What are they?

Proton exchange membrane fuel cells, also known as polymer electrolyte membrane (PEM) fuel
cells (PEMFC), are a type of fuel cell being developed for transport applications as well as for stationary
and portable fuel cell applications. Each individual fuel cell produces about 0.7V when operating in air.
Then, in order to produce a useful voltage, the electrodes of many cells must be linked in series and we
must ensure that reactant gases can still reach the electrodes and that the resistance of the electrodes has a
minimal effect. As each cell produces only about 0.7V, even a small reduction in this is not good, so cells
are not normally wired up this way.
- Reactions:
- Anode:
2H2 --> 4H+ + 4e- (fast)
- Cathode:
Direct pathway: O2 + 4H+ + 4e- --> 2H2O (kinetically slow)
Indirect pathway: O2 + 2H+ + 2e- H2O2
H2O2 + 2H+ + 2e- 2H2O
- Overall reaction:
2H2 + O2 --> 2H2O
- Relevant parts:
--Fuel: H2
---Specific energy content: 2 kWh/kg
--Membrane (electrolyte): proton-conductive polymer membrane. Its purpose is to separate the anode and
the cathode, to prevent mixing of the fuel and the oxidant and to provide a conductive pathway for protons.
The membrane needs to have high ionic conductivity (and zero electronic conductivity) under cell
operating conditions, long-term chemical and mechanical stability at elevated temperature in oxidizing and
reducing environments, good mechanical strength, with resistance to swelling, low oxidant and low fuel
cross-over, interfacial compatibility with catalyst layers and low cost. In a polymer membrane, the proton
conductivity is strongly dependent on membrane structure and water content.
Ex: Nafion, that is a stable material, has a selective ion permeability, is compatible with current fuel cell
technology and has high proton conductivity under aqueous conditions. But, on the other hand, it has low

conductivity at low water content, poor mechanical strength at high temperatures and is expensive. Nafion
is characterized by presence of isolated spherical ionic clusters that are modified when water is absorbed in
the membrane. When water is absorbed, the membranes hydrophilic domain size increases and the
swelling induces a modification of the cluster structure which become spherical water pools. As more water
is absorbed, the cluster size is connected to each other through the water passage. This way, water and
hydrophilic solvents can penetrate the membrane through water channel and it can also provide the passage
of protons (percolation). The Nafion membrane can be modified to have its characteristics improved:
addition of water-retaining additives, non-conducting inorganic particles, proton conducting inorganic salts
and heteropolyacids, substitution of water with a high boiling proton solvent (if water boiled at 200C,
most of the problems related to PEMFC operation at temperatures greater than 100C would be resolved).
For a H2/air fuel cell, it is needed a membrane with a high proton conductivity at 120C and that
operates without water at elevated temperatures.
---Water management: water is produced at the cathode as a result of the electrochemical reaction and it
is dragged from the anode to cathode by protons moving through the electrolyte (by electroosmotic drag).
But, the water generation and electroosmotic drag create a large concentration gradient, and the water
diffuses back to the anode.
---Gas permeation: the membrane should be impermeable to reactant gases (H2 and O2), but, as the
membrane has a porous structure and water content, and H2 and O2 are soluble in water, some gases
permeate through the membrane.
--Electrode: must be porous because reactant gases are fed from the back and they must reach the
electrode/membrane interface and the catalyst layers (part of porous electrode or part of the membrane,
depending on the manufacturing process). Example: Multilayer Electrode Assembly (MEA), that consists
in multilayer assembly of the membrane sandwiched between two electrodes.

(assembly stack of proton conductive membrane + catalyst electrodes + gas diffusion layers)
The MEA is sandwiched between collector/separator plates. The collector collects and conducts electrical
current and the separator separate gases in the adjacent cells (in multicell configuration). In multicell
configuration it connects (physically and electrically) the cathode of one cell with the anode of an adjacent
cell (this is what is called bipolar plates), provides the pathways for the flow of reactant bases (flow fields)
and gives structural rigidity to the cell.
--Gas diffusion layers (GDL): are conductive and porous sheet of material also known as carbon
cloth/paper, in the PEMFCs, it is crucial for it to remain free of water in order to provide a pathway for
gaseous fuel transport. The GDL is a porous material composed of a dense array of carbon fibres, which
also provides an electrically conductive pathway for current collection. The GDL have some important
roles: provide a pathway for reactant gases from the flow field to the catalyst layer (gases need to access
the entire active area, not just those adjacent to the channels), provide pathway for product water from the
catalyst layer to the flow field channels, electrically connect the catalyst layer to the bipolar plate, allowing
electrons to complete the circuit, conduct heat generated in the electrochemical reactions in the catalyst

layer to the bipolar plate, allowing heat removal and provide mechanical support to the MEA, preventing it
from sagging into the flow field channels. To perform these roles well, the GDL must be sufficiently porous
(to permit the flow of the gas and water), electrically and thermally conductive and, it must be sufficiently
rigid to support MEA but must have some flexibility to maintain good electrical contacts. Generally, carbon
fibre based materials are used. The material is usually made hydrophobic to enhance water removal
because, in practice, flooding is one of the major causes of PEMFC performance degradation.
--Bipolar plates: conductive plates that act as an anode for one cell and as a cathode for the next cell. They
can be made of metal, carbon or conductive composite polymer. It must distribute reactant gases over the
surface of the anode, and O2/air over the cathode. Bipolar plates may also have to carry a cooling fluid and
need to keep all these gases and fluids separate. So, to connect cells electrically in series, they must be
electrically conductive, to separate gasses in adjacent cells, they must be impermeable to gases, they
must have adequate strength to provide structural support for the stack but must be lightweight, they also
have to be thermally conductive to conduct heat from active cells to cooling cells. Besides that, they must
be corrosion resistant, cheap, suitable for mass production, the electrical contacts should be as large as
possible, the plate should be thin to minimise resistance and the gas needs to flow easily across the plate.

--Catalysts:
Anode: usually noble metal such as Pt powder (Pt tolerates only about 50 ppm of CO and a few ppm of
sulfur compounds in fuel) or alloy catalysts that can be used to increase the catalysts Co-tolerance (that
enter into the cell with the hydrogen gas and poisons the catalyst thats why hydrogen fuel needs to be as
pure as possible).
Example: PtRu (Ruthenium increases the affinity for adsorption of oxygen containing species in less
positive potentials).
Pt-(CO)ads + Ru-(OH)ads Ru + Pt + CO2 + 2H+ + 2eCathode: usually Ni powder, but Pt and PtNi alloys can also be used. The catalyst must be reversible, must
have a high oxygen adsorption capacity, stability during the adsorption and reduction, stability in electrode
medium, ability to decompose H2O2, good conductivity and must be cheap.
Example: Pt. Advantages: high work function, ability to catalyse the reduction of oxygen, good resistance
to corrosion and dissolution, high exchange current density. Disadvantages: slow oxygen reduction
reactions due to the formation of OH species at 0.8V, expensive and scarce. The reactivity of Pt depends
on its size and shape. When the size of the particles is reduced, the relative amount of surface atoms in
edge and corner positions increases, these atoms are electrocatalytically more active than other surface
atoms. Reactions:
O2+2Pt Pt2O2
Pt2O2 + H+ + e- Pt2-O2H
Pt2-O2H Pt-OH + Pt-O
Pt-OH + Pt-O + H+ + e- Pt-OH + Pt-OH
Pt-OH + Pt-OH + 2H+ + 2e- 2Pt + 2H2O
- How it works:
Hydrogen fuel is processed at the anode where electrons are separated from protons on the surface of a
platinum-based catalyst. The protons pass through the membrane to the cathode side of the cell while the
electrons travel in an external circuit, generating the electrical output of the cell. On the cathode side,

another metal electrode combines the protons and electrons with oxygen to produce water, which is
expelled as the only waste product; oxygen can be provided in a purified form, or extracted at the electrode
directly from the air.
- Pros: operate at relatively low temperatures (below 100C), sustained operation at high current density,
low weight, compactness, etc.
- Cons: the fuel must be pure and the water management is complex (these could be overcome by using
high temperature PEMFC, where the electrolyte used is not water-based, but a mineral acid-based system
and the HT PEMFC can operate up to 200C), the membrane is expensive, so as the Pt catalyst used.
- Uses and applications: the PEMFC are currently the leading technology for light duty vehicles and
materials handling vehicles, also for stationary and other applications.
(type of PEMFC) DIRECT METHANOL FUEL CELL (DMFCS)

-Fuel: CH3OH (liquid). It can be supplied to the cell in two ways: passive (reactant into cell by
gravitational, capillary forces or hydraulically more simple and cheaper) or active (reactant into cell by
special pumps more uniform supply).
-Advantages: handling CH3OH (liquid) is safer than handling H2 (gas). It can be stored in cheap plastic
containers and is an excellent carrier fuel that hydrogen can be extracted from to power fuel cells. The
DMFCs are seen as a candidate to eventually replace lithium-ion battery because they can produce a high
amount of energy in a small space over a long period of time.
-Disadvantages: anode and cathode needs Pt catalysts (Pt tolerates only about 50 ppm of CO and a few
ppm of sulfur compounds in fuel), gas humidification is required, the membrane is expensive, some
methanol pass through the membrane without producing electricity (methanol crossover), and efficiency is
low.
-Specific energy content: 6 kWh/kg (higher than H2 but less than gasoline 10 kWh/kg)
-Components: polymer membrane as electrolyte (usually Nafion), peripheral equipments needed are
similar to PEMFCs (bipolar plate, MEA), CCM (catalyst coated membrane, it is a proton-conducting
membrane plus two electrodes), GDL (gas diffusion layer, it can be carbon cloth or paper with carbon
particle filter and Teflon), anode and cathode plate (it can be done with graphite, carbon composite or metal
with machined or stamped flow field), gaskets and seals (seals around edge of structure). Both the anode
and cathode can have Pt particles (same usage as for PEMFCs). But, as CH3OH oxidation produces CO, Pt
catalyst is poisoned. This way, Ru or Au can be added to increase the catalytic activity towards the oxygen
reduction reactions and to increase CO tolerance:
H2O (Ru) OH* + H+ + eOH* + CO CO2 + H+ + e-Reactions:

Anode:
CH3OH + H2O 6H+ + 6e- + CO2
Slow oxidation, with considerable polarisation at the negative electrode, what generates lower working
voltage of the fuel cell.
Cathode:
3/2O2 + 6H+ + 6e- 3H2O
Overall reaction:
CH3OH + 3/2O2 2H2O + CO2
The reaction occurs in several stages:
CH3OH COHads + 3Hads
COHads + 3OHads CO2 + 2H2O
Ionization of Hads and the anodic formation of OHads from water molecules are the steps producing
current:
Hads H+ + eH2O OHads + H+ + eAs we can see, H2O is needed for the reaction, so pure CH3OH cannot be used. So, H2O has to be pumped
in, what limits the power achievable. The concentration of CH3OH must be between 1M and 3M because
higher concentrations cause diffusion to the cathode and lower concentrations limit the maximum
attainable currents. The H2O is lost at the anode and every proton formed drags from 2 to 5 water
molecules.
-Efficiency: ~40%
-Operating temperature: 60-120C
-Applications: due to the relatively low range of operating temperature, this fuel cell is attractive for tiny
to mid-sized applications, like mobile plants, such as small fuel cells for portable devices (PCs, mobile
phones, etc) where energy and power density are more important than efficiency.
-Difference from other fuel cells: the anode catalyst itself draws the H2 from the liquid CH3OH
eliminating the need for a fuel reformer. Hydrogen fuel can be supplied in two ways - either directly as
pure hydrogen gas or through a "fuel reformer" that converts hydrocarbon fuels such as methanol, natural
gas, or gasoline into hydrogen-rich gas. CO2 is produced at the anode and not at the cathode.
(type of PEMFC) INDIRECT (OR REFORMED) METHANOL FUEL CELL (RMFCS)
The fuel CH3OH is reformed before being fed into the fuel cell.

-Advantages: higher efficiency, smaller fuel cell stacks and no water management.
-Disadvantages: operate at high temperature (200C) and high pressure (25-50 bar) and needs heat
management.
DIRECT ETHANOL FUEL CELL (DEFCS)

-Reactions:
Anode
CH3CH2OH + 3H2O 12H+ + 12e- + 2CO2
Cathode
3O2 + 12H+ + 12e- 6H2O
Overall reaction
CH3CH2OH + 3O2 2CO2 + 6H2O
-Advantages: lower toxicity, EtOH can be obtained by fermentation (already popular in Brazil where there
are EtOH infrastructures).
-Disadvantages: when EtOH is produced by fermentation, the crops for fuel production competes with the
crops for food production (the, arise the questions: which one is better? How to conciliate them?), and it
requires higher working temperature (200C).
PHOSPHORIC ACID FUEL CELL (PAFCS)
-Applications: hospitals and all commercial purposes.
-Components: electrolyte is liquid phosphoric acid saturated in a SiC matrix, electrode is carbon paper and
the catalyst is platinum.
-Electrical efficiency: ~50%
-Advantages: uses relatively low purity H2 as fuel and 85% of the steam can be used for cogeneration, it is
stable, has low electrolyte volatility and its construction is simple.
-Disadvantages: uses expensive Pt as catalyst, has large size and weight, has low power and current
density, has aggressive electrolyte.
-Reactions:
Anode
2H2 4H+ + 4eCathode
O2 + 4H+ + 4e- 2H2O
(occurs at a faster rate than in PEMFCs due to the higher operating temperature)
Overall reaction:
2H2 + O2 2H2O
The water generated (steam) is used for water heating.
-Operating temperature: 150-200 C (this higher temperature imparts a slightly higher tolerance to
impurities, and so, phosphoric acid cells can function with 1-2% CO and a few ppm of sulfur in the
reactant streams.
-Efficiency: up to 50% with potential to reach 70%
MOLTEN CARBONATE FUEL CELL (MCFCS)

A class of fuel cells that work at high temperature (>600 C).

-Components: molten carbonate salt (Na, Li, K, Mg) mixture is used as its electrolyte (at the operating
temperature of about 650 C, it is liquid and good ionic conductor). The electrolyte is suspended in a
porous, insulating and chemically inert ceramic matrix called BETA (beta-alumina solid electrolyte).
-Reactions:
Anode
H2 + CO32- H2O + CO2 + 2eCathode
1/2O2 + CO2 + 2e- CO32Overall reaction
H2 + 1/2O2 H2O
Additional H2 is produced from gas shift reaction
H2O + CO H2 + CO2
The anode process a reaction between H2 and carbonate ions (CO32-) from the electrolyte. The reaction
produces H2O and CO2 while releasing electrons to the anode. The cathode process combines O2 and CO2
from the oxidant stream with electrons from the anode to produce CO32- ions which enter the electrolyte.
The need for CO2 in the oxidant stream requires a system for collecting CO2 from the anode exhaust and
mixing it with the cathode feed stream.
-Advantages: possibility to use the reaction heat to generate additional electricity, high rate of electrode
reactions, little electrode polarization, does not need to use Pt catalysts and Ni catalysts are cheaper, use of
H2 with CO and other impurities, possibility to use CO, natural and bio-gas and petroleum products
directly through internal conversion of these fuels to H2, do not require external reformer to convert energy
dense fuel to H2, and the high temperature limits protect from CO poisoning.
-Disadvantages: the high temperature limit the materials and safe uses of MCFCs, molten carbonates are
highly corrosive and CO32- ions are used up in the reactions, making it necessary to inject carbon dioxide
o compensate.
-Efficiency: ~60% but can reach 85% when wasted heat is used.
SOLID OXIDE FUEL CELL (SOFCS)

-Components: solid oxide materials (or non-porous ceramic) are used as electrolyte. The electrolyte must
possess a high ionic conductivity and no electrical conductivity in order to oxygen ions migrate through the
electrolyte to the fuel side of the cell. It must be dense to prevent short circuiting of reacting gases through
it and it should be as thin as possible to minimize resistive losses in the cell. And it must be chemically,

thermally and structural stable across a wide temperature range. The anode must meet most of the same
requirements as the cathode in terms of electrical conductivity, thermal expansion compatibility and
porosity, and must function in a reducing atmosphere. So, metals are attractive candidate materials, such as
Ni, that is abundant and affordable and can be combined with YSZ to avoid sinterization of Ni and provide
structural support. The cathode must be porous in order to allow oxygen molecules to reach the
electrode/electrolyte interface, and its conductivity must be all electronic (no ionic) because, this way, the
electrons from the open circuit flow back through the cell via the cathode to reduce the oxygen molecules,
forcing the oxygen ions through the electrolyte.
Interconnect: used when fuel cells are used in combination in order to generate enough voltage and current.
The interconnect functions as the electrical contact to the cathode while protecting it from the reducing
atmosphere of the anode. It must have 100% electrical conductivity, no porosity (to avoid mixing of fuel
and oxygen), thermal expansion compatibility, and must be inertness with respect to the other fuel cell
components. It will be exposed simultaneously to the reducing environment of the anode and the oxidizing
atmosphere of the cathode.
-Operating temperature: 1000 C (so, there is no need for precious-metal catalyst, what reduces costs).
-Reactions:
Anode
H2 + O2- H2O + 2eCathode
1/2O2 + 2e- O2Overall reaction
H2 + 1/2O2 H2O
-Advantages: high efficiency, long-term stability, fuel flexibility, low emissions, relatively low cost
(because it uses currently available fossil fuel, not H2), high temperatures allow SOFCs to reform fuels
internally, which enables the use of a variety of fuels and reduces cost associated with adding a reformer to
the system and SOFCs are not poisoned by CO, which can even be used as fuel.
-Disadvantages: the fuel cell needs to run at high temperatures in order to achieve sufficiently high current
densities and power output. This high temperature also places stringent durability requirements on
materials, what increases their costs.
-Applications: good to big power units (utility applications), but not to transportation and small portable
applications.
-Designs:
Planar: the components are assembled as flat stacks, with air and fuel flowing through channels built into
the cathode and anode.

Tubular: components are assembled as a hollow tube, with the cell constructed in layers around a tubular
cathode. The air flows through the inside of the tube and fuel flows around the exterior.

ALKALINE FUEL CELL (AFCS)

The presence of OH- ions travelling across the electrolyte allow a circuit to be made and electrical energy
to be extracted. The H2O formed at the anode migrates back to the cathode to regenerate OH-. The byproducts are heat and H2O.
-Advantages: AFCs are the cheapest fuel cells to manufacture, the catalyst that is required on the electrode
can be any of a number of different materials that are relatively inexpensive (they are non-noble metal and
metal oxides as NiO, CoO)
-Disadvantages: they are sensitive to CO2 because it reacts with the electrolyte to form a carbonate
(K2CO3) which can decrease the conductivity, because of this, AFCs operates using pure O2 or purified
air.
-Efficiency: 70%
- Operating temperature: 60-220 C
-Reactions:
Anode
H2 + 2OH- 2H2O + 2eCathode
O2 + 2H2O + 4e- 4OHOverall reaction
H2 + O2 2H2O
- Components: KOH as electrolyte.
ENZYMATIC FUEL CELL

Power density up to 40 W/m2, specific power up to 6 kW/l

-Disadvantages: no full scale implementation, costs (enzymes are very expensive), the enzymes must be
stable to avoid inactivation and inhibition and they have low fuel versatility (enzymes are very specific).
MICROBIAL FUEL CELL (MFCS)
Converts chemical energy, available in a bio-convertible substrate, directly into electricity. To achieve this,
bacteria are used as catalyst to convert substrate into electrons. Bacteria can convert a huge variety of
organic substrates into CO2, H2O and energy. They use this energy to grow and to maintain their
metabolism. However, by using a MFC, part of this microbial energy in the form of electricity may be
harvested.
-Components: anode (substrates such as carbohydrates (glusose, sucrose, cellulose), volatile fatty acids
(formate, acetate), alcohols (ethanol, methanol), amino acids, proteins, etc), cathode, proton or cation
exchange membrane and electrical circuit.
The bacteria live in the anode and convert a substrate such as glucose, acetate, etc, into CO2, protons and
electrons. In aerobic conditions, bacteria use O2 or NO3- as a final electron acceptor to produce water.
However, in the anode no O2 is present, so bacteria need to switch from their natural electron acceptor to
an insoluble acceptor, such as the anode. Due to the ability of bacteria to transfer electrons to an insoluble
electron acceptor, we can use a MFC to collect the electrons originating from the microbial metabolism.
The electron transfer can occur via different components (membrane, soluble electron shuttles, etc). In
anaerobic conditions, electricity can be generated indirectly (via biogas) and directly (without biogas).
-Disadvantages: the microbial nature of the process is affected by electrochemical laws and principles
which generally results in a lowering of the attainable voltage. The losses are to mass transfer, ohmic
losses, activation losses, electrons quenching and competition of parallel metabolic processes. The
biological activity can be inhibited by the products generated, by the medium pH, etc. Biofilm can be
formed on the electrode and it is difficult to control. Good mediators are often toxic. The cathode efficiency
is affected by H2O2 production. And, the membranes to transport protons are costly.

-Example: Sulfate Reducing Fuel Cell

PHOTOVOLTAIC CELLS (PV CELL)

- What is it?
It is a device that converts solar energy directly to electricity. The photovoltaic effect is the
phenomenon that certain materials produce electric current when they are exposed to light.
The sunlight is a primary source of energy, so it is a renewable, free and limitless energy that can be
powered for remote locations. Solar radiation received at the surface oscillates between 275 MW/m2 in the
deserts of Middle East and 75 MW/m2 in the Artic.
-Advantages of solar photovoltaic: converts sunlight directly to electricity (sunlight is the most
abundant renewable resource), there is no moving parts and it has a long lifetime (> 20 years).
-Disadvantages: sunlight is very spread out, it is irregular and unpredictable, the electricity is
difficult to store and it is an expensive technology compared to other means of power generation.

-PV modules are solar cells electrically connected to each other and mounted in a frame. The panels
will supply electricity at a certain voltage, usually a 12V system. So, multiple module can be wired
together to form an array. The larger the area of a panel or array, the more electricity will be produced.
-The installation of PV devices can be gried-tied solar or off-grid solar. In the grid-tied solar, the
PVs arrays are directly connected to the utilities grid, in other words, the array acts like a generator and
produces energy that is first used by the owner and the extra is sold to the operator. And off-grid solar is
when a system is installed and is no longer attached to an electrical operator. The energy generated feeds a
charge controller that monitors the coupled battery bank to maintain fully charged batteries.

-Evolution of PV technology:
-The first generation of PV devices are large-area, single layer p-n junction diode, which are
capable of generating electrical energy from light source with the wavelengths of sunlight. These cells are
typically made using a silicon wafer.
-The second generation is based on the use of thin-film deposits of semiconductors. These devices
are designed to be of high efficiency and to have multiple junction. The most used materials are Cadmium
telluride (CdTe), copper indium gallium selenide (CIGS) and amorphous silicon (A-Si). The most
competitive and cheaper among these is the CdTe technology.
-In the third generation, photovoltaics dont rely on a traditional p-n junction to separate
photogenerated charge carriers.
- Classification of PV technology:
-- Silicon based PVs:
Nowadays, the most important and common semiconductor material for solar cells production is
silicon. It has some important advantages: it is abundant, not poisonous, it is environment friendly, its
waste does not represent any problems, it can be easily melted, handled, and it is fairly easy formed into
monocrystalline form. Furthermore, its electrical properties with endurance of 125 C allow the use of Sibased semiconductor devices even in the most harsh environment and applications. Pure silicon is
produced from sand (SiO2) by reduction in specially design furnaces at 1800 C. The produced material
contains 98-99% of pure Si. To reduce SiO2, carbon electrodes are used: SiO2 + C Si + CO2. But,
processing SiO2 to produce Si is a very high energy process, and it takes over two years for a conventional
solar cell to generate as much energy as was used to make the silicon it contains. Another disadvantage is
that 1.5 tons of CO2 is emitted for each ton of Si produced.
The cells have single layers of p-n diode, so there is just one excitation per photon. The lifetime of
Si PVs is more than 30 years and the energy payback period is in 2-8 years.
Only 77% of solar spectrum is absorbed by silicon, of this, around 30% is used as electrical energy.
Silicon is transparent at wavelengths longer than 1.1 microns, so, 23% of sunlight passes right through it
with no effect, excess photon energy is wasted as heat. So, all together, the maximum efficiency for a
silicon PV is about 23%.
-Disadvantages: Si PVs cells are made in high vacuum and using high temperature, so demands a
lot of energy; the manufacturing costs are high and they are fragile, rigid and thick.
The silicon has four valence electrons, and all electrons are used in bonds, so it is not very
conductive. To overcome this low conductivity, the silicon can be doped by other compounds:
--- p-type silicon: created by doping with compounds containing one less valence electrons than Si, such as
B, Ga, In, Tl This way, only three electrons are available for bonding with 4 adjacent Si atoms.
Therefore, an incomplete bond (hole) can attract an electron from a nearby atom. But, filling one hole
creates another in a different Si atom. This movement of holes is available for conduction.
--- n-type silicon: created by doping the Si with compounds that contain one more valence electrons than
Si, such as P, As This way, since only 4 electrons are required to bond with the 4 adjacent Si atoms, the
5th valence electron is available for conduction.

(em laranja: empty conduction band; em azul: filled valence band)

-p-n junction:

Each side starts from an electrically neutral state. Then, negative charges move left and positive
charges move right, thereby a charge imbalance is generated. This creates an electrical field that acts like an
obstacle to further flow of electrons. When all electrons and holes in the depletion layer have combined, a
voltage across the junction is created (built-in potential). So, two concomitant phenomena occur: a
diffusion process that tends to generate more space charge and an electric field generated by the space
charge tends to counteract the diffusion.

A PV device can be a homojunction or a heterojunction device. The homojunction device is made

up of single material altered so that one side is p-type and the other side is n-type (Si PVs) and the p-n
junction is located so that the maximum amount of light is absorbed near it. The heterojunction device is
the one where the junction is formed by contacting two different semiconductors: top layer (high band-gap
material selected for its transparency to light) and bottom layer (low band-gap material that absorbs light).
Besides these two, there is the p-i-n and n-i-p junction that contains a middle intrinsic layer between n-type
and p-type layer where the light generates free electrons and holes.
-Photogeneration: when a photon of light is absorbed by one of the atoms in the n-type doped Si, it
will dislodge an electron, creating a free electron and a hole. If a wire is connected from the cathode (ndoped Si) to the anode (p-doped Si), electrons will flow through it (electric current). The holes created by
the dislodged electron are attracted to the negative charge of n-doped material and migrates to the back
electrical contact. Then, as the electron enters the p-doped Si from the back electrical contact, it combines
with the hole restoring the electrical neutrality.

But, sunlight contains a spectrum of photons of different energy E. If E < Eg (bandgap) the photon are
useless and if E > Eg the excess of energy is heat.
There are two types of Si PV technology:
-Silicon Crystalline Technology: currently makes up 86% of PV market. It is very stable with
module efficiencies of 10-16%. It can be mono crystalline or multi crystalline. The mono crystalline PV
cells are made using saw-cut from single cylindrical crystal of Si and its operating efficiency is up to 15%,
whilst multi crystalline PV cells are cast from ingot of melted and re-crystallised silicon, has an efficiency
of about 12% and accounts for 90% of crystalline Si market.
-Amorphous Silicon PV Cells: due to the manufacturing procedure, these modules are also known
as thin-film solar cells. To make one amorphous silicon PV cell first, a glass substrate is thoroughly
cleaned, then a lower contact layer is applied on it. The surface is then structured (divided into bands) and
so, in vacuum, under high frequency electric field amorphous silicon layer is applied. The surface is rebanded and upper metal electrodes are fixated. This kind of PV cell has an operating efficiency of about
6%.
-- Thin Film Technology:
Thin film modules are constructed by depositing extremely thin layers of photosensitive materials
onto a low-cost backing such as glass, stainless steel or plastic. This technology results in lower production
costs, but lower efficiency rates (from 4% to 11%).
-Advantages: low cost substrate and fabrication process.
-Disadvantages: not very stable.
-- Poly-crystalline PV Cells:
This kind of PV cell can be made of copper indium gallium selenide with band gap to 1eV and have
high absorption coefficient (10^5cm^-1). They have high efficiency levels (>11%). But the manufacturing
process is still immature and slow. If it is made of CdTe, that has a band gap of 1.4eV and high absorption
coefficient, the module efficiency is about 6-9% and the manufacturing process is again immature.
-- Gratzel cells:

A dye, adsorbed on TiO2 (that is cheap and very porous) is excited by light, injecting e- into the
TiO2. The e- leaves the TiO2 and is carried through as current. The electron, then, returns to the device and
reduces the electrolyte. The electrolyte, then, reduces the dye. Example of dye: ruthenium dyes in which
the color changes according to the functional group and so, they can absorb different wavelengths.
-How to prepare TiO2 dye sensitezed solar cells: first, cut and clean TCO (transparent and
conductive oxide) electrode, usually ITO (indium tin oxide), and check the conductive side. Then a layer of
titanium dioxide (TiO2) nanoparticles (in the size of 10-40 nm) must be put on the TCO glass plate. The
titania layer must be sintered and re-firing if it was prepared and stored for long period. After this, the
titania layer must be stained with natural (or synthetic) dyes. After it is dry, another TCO is used as cathode
(carbon or Pt). So, the anode (titania) and the cathode electrodes are put together. Then, the gap between
electrodes must be filled with electrolyte (iodine salt) and the filling holes must be sealed. The last
procedure, then, is to test the solar cell. These solar cells have a power conversion efficiency of 11%.
-Advantages: relatively inexpensive (made in non-vacuum setting mainly at room temperature,
relatively easy and simple manufacturing process), thin, lightweight, flexible, has a short return on
investment (~ 3 months), works even with low light conditions, high price/performance ratio.
-Disadvantages: slightly lower efficiencies, the dye can breakdown, has a slightly larger bandgap
than silicon and liquid electrolyte can leak or degrade (a possible solution maybe is the use of ionic
liquids).
-- Organic photovoltaics:
Are PV cells that use organic molecules (conducting polymers or small organic molecules) for light
absorption and charge transport. There is no p-n junctions but electron donor and electron acceptor and
electron-hole pair are generated by excitons.

-How it works:

The energy difference between the HOMO and LUMO is termed the HOMOLUMO gap. Roughly,
the HOMO level
is
to organic
semiconductors what
the valence
band maximum
is
to
inorganic semiconductors. The same analogy exists between the LUMO level and the conduction
band minimum.
Organic thin-film solar cells from low-molecular weight materials can be fabricated by vacuum
deposition, spin coating, etc. Organic materials having p and n-type conductivities are successively
deposited on a transparent electrode, and then, a metal electrode is deposited on them. Sunlight is absorbed
by organic layers and excitons generated by light absorption are dissociated to electrons and holes at the
interface between p and n-type organic layers. The electrons and holes are collected at the upper and lower
electrodes, respectively, and electricity is generated.
The process of energy generation on an organic PV cell can be simplified by the diagram below:

-Advantages: low-cost materials, lightweight, flexible and customizable at molecular level.

-Disadvantages: 1/3 efficiency of Si solar cells (efficiency has reached 8.3% in 2011 and now is
about 12%) and can suffer of photochemical degradation.
-- Other technologies: the main alternative types of fuel cells are concentrated photovoltaic and flexible
cells. The concentrated photovoltaic is building into concentrating collectors that use a lens to focus the
sunlight onto the cells. The main objective is to use very little of the expensive semiconducting PV material
while collecting as much sunlight as possible. The efficiencies are from 20-30%. The flexible cells are
based on a production process similar to thin film cells, but the active material is deposited in a thin plastic,
so the cell can be flexible. This open the range of applications, especially for building (roof-tiles for
example) and end-consumer applications. The efficiency is around 20.3%.