Chương 6

Ô TÔ CHẠY BẰNG HYDROGEN

I. Tính chất hóa lý của Hydrogen

Hydrogen (H2) is an alternative fuel that can be produced from diverse domestic
resources. Although hydrogen is in its infancy in the market as a transportation fuel,
government and industry are working toward clean, economical, and safe hydrogen
production and distribution for widespread use in fuel cell electric vehicles (FCEVs).
FCEVs are beginning to enter the consumer market in localized regions domestically and
around the world. The market is also developing for buses, material handling equipment
(such as forklifts), ground support equipment, medium- and heavy-duty vehicles, and
stationary applications. For more information, see fuel properties and the Hydrogen
Analysis Resource Center.
Hydrogen is abundant in our environment. It's stored in water (H 2O),
hydrocarbons (such as methane, CH4), and other organic matter. One of the challenges of
using hydrogen as a fuel comes from being able to efficiently extract it from these
compounds.
Currently, steam reforming, combining high-temperature steam with natural gas
to extract hydrogen, accounts for the majority of the hydrogen produced in the United
States. Hydrogen can also be produced from water through electrolysis. This is more
energy intensive but can take advantage of inexpensive excess renewable energy, such as
wind or solar, while avoiding the harmful emissions associated with other kinds of energy
production. The Sustainable Gas Institute has estimated the cost of hydrogen production
through electrolysis at 4–9p per kWh, compared to 2–5p per kWh for steam methane
reformed natural gas with carbon capture and storage.
Hydrogen would enable captured carbon dioxide from industrial processes to be
recycled into chemicals, for example methanol. The George Olah plant in Iceland
recycles over 5000 tonnes of carbon dioxide annually. Named after the 1994 Nobel
chemistry laureate it uses electrolysis to produce hydrogen, which is converted in a
catalytic reaction with carbon dioxide to produce five million litres of methanol. The
carbon dioxde is captured from the flue gas of the neighbouring geothermal power plant.
Although the production of hydrogen may generate emissions affecting air
quality, depending on the source, a FCEV running on hydrogen emits only water vapor
and warm air as exhaust and is considered a zero-emission vehicle.
The interest in hydrogen as an alternative transportation fuel stems from its ability
to power fuel cells in zero-emission FCEVs, its potential for domestic production, its fast
filling time, and the fuel cell's high efficiency. In fact, a fuel cell coupled with an electric
motor is two to three times more efficient than an internal combustion engine running on
gasoline. Hydrogen can also serve as fuel for internal combustion engines. However,
unlike FCEVs, these produce tailpipe emissions and are less efficient.
The energy in 2.2 pounds (1 kilogram) of hydrogen gas is about the same as the
energy in 1 gallon (6.2 pounds, 2.8 kilograms) of gasoline. Because hydrogen has a low
volumetric energy density, it is stored onboard a vehicle as a compressed gas to achieve
the driving range of conventional vehicles. Most current applications use high-pressure
tanks capable of storing hydrogen at either 5,000 or 10,000 pounds per square inch (psi).
For example, the FCEVs in production by automotive manufacturers and available at
dealerships have 10,000 psi tanks. Retail dispensers, which are mostly co-located at
gasoline stations, can fill these tanks in about 5 minutes. Other storage technologies are
under development, including bonding hydrogen chemically with a material such as
metal hydride, or low-temperature sorbent materials.
Somehow or other, we need to cut energy-related carbon dioxide emissions by
60% in the next 30 years, to limit global warming to 2°C. Tackling the challenge is all the
more urgent as the global population grows and gets wealthier. Throw in the damage
being done by the related air pollution, and it’s not surprising that the spotlight is back on
an abundant element that produces no carbon emissions when burned, and has double the
energy density of fossil fuels: hydrogen. The attraction of hydrogen is that it can be used
both as a feedstock and an energy carrier.
Across the world, researchers are trying to improve the efficiency and costs of
producing, storing, transporting and using hydrogen in applications as diverse as heat and
transport. Developments are coming thick and fast: from advances in hydrogen
production to new catalytic materials that could replace platinum in polymer electrolyte
membrane fuel cells that will cut their cost. Demonstrator projects are underway that may
provide the numbers and the technology to show where and how hydrogen can replace
fossil fuels. But at some point politicians will have to make a decision to encourage the
infrastructure to be built.
Japan has already made that commitment, following the tsunami and resulting
nuclear disaster at Fukushima in 2011. It intends to use the 2020 Tokyo Olympics to
showcase the technology with thousands of hydrogen fuel cell vehicles, a network of
filling stations and a hydrogen-powered athletes’ village. Japan’s car makers are selling
hydrogen fuel cell vehicles and Toyota is building a plant to manufacture fuel cell stacks.
Japanese homes are being equipped with fuel cell technology to provide electricity and
plants are being built to make hydrogen using renewable energy. The country will also
import hydrogen, with Australia the seeming front-runner, using its plentiful coal supplies
to make hydrogen and capturing the resulting carbon dioxide emissions.
 II. Pin nhiên liệu (Fuel Cell)
Electrolysis of water
Passing electricity through platinum electrodes to separate water (H2O) into its hydrogen
and oxygen components.
 How does a fuel cell generate electricity?
Using a process which is the reverse of water electrolysis, fuel cells produce water by
combining hydrogen and oxygen, which generates electricity and heat.
Hydrogen is fed to the anode where catalysis releases hydrogen ions (H+) and electrons
(e-). The electrolyte is a material which allows ions to pass through it, but blocks
electrons. The hydrogen ions (H+) released in catalysis travel through the electrolyte to
the cathode while electrons blocked by the electrolyte are taken out to generate
electricity. Oxygen (O2) is fed to the cathode where catalysis separates it into two oxygen
atoms. Those oxygen atoms, electrons (e-) travelling from the load and hydrogen ions
(H+) passing through the electrolyte combine to produce water (H2O).

Reactions
principles of workings of hydrogen fuel cells

Schematic diagram of a modern hydrogen-oxygen fuel cell. Commonly used electrolytes

are NaOH solution, phosphoric acid, or solid oxides. A major limitation of any oxygen-
consuming fuel cell is the slow rate of the reduction of this element at a cathode. The best
cathode surfaces are usually made of platinum, which is a major cost factor in fuel cell
design.
A fuel cell consists of a central electrolyte layer, sandwiched between two catalyst layers.
Various materials for these layers are used, but the basic process is the same. When a
hydrogen atom contacts the negative anode catalyst layer, it splits into a proton and an
electron. The proton passes straight through the central electrolyte layer, while the
electron produces electricity as it passes through an external circuit. The circuit returns
the electrons to the positive side of the electrolyte layer, where they bond again with the
protons and join with an oxygen molecule, creating water in the positive cathode catalyst
layer.
Although fuel cells were not employed for practical purposes until space exploration
began in the 1960's, the principle was first demonstrated in 1839 by Sir William Grove, a
Welsh lawyer and amateur chemist. At the time, it was already known that water could be
decomposed into hydrogen and oxygen by electrolysis; Grove tried recombining the two
gases in a simple apparatus, and discovered what he called "reverse electrolysis"-that is,
the recombination of H2 and O2 into water-causing a potential difference to be generated
between the two electrodes:

anode: H2(g) → 2 H+ + 2e– E° = 0 v

cathode: ½ O2 + 2 H+ + 2e– → H2O(l) E° = +1.23 v
net: H2(g) + ½ O2(g) → H2O(l) E° = +1.23 v

It was not until 1959 that the first working hydrogen-oxygen fuel cell was developed by
Francis Thomas Bacon in England. Modern cells employ an alkaline electrolyte, so the
electrode reactions differ from the one shown above by the addition of OH – to both sides
of the equations (note that the net reaction is the same):

anode: H2(g) + 2 OH– → 2 H2O + 2 e– E° = 0 v

cathode: ½ O2 (g) + 2 H2O + 2 e– → 2 OH– E° = +1.23 v
net: H2(g) + ½ O2(g) → H2O E° = +1.23 v

One reason for the interest in fuel cells is that they offer a far more efficient way of
utilizing chemical energy than does conventional thermal conversion. The work
obtainable in the limit of reversible operation of a fuel cell is 229 kJ per mole of H2O
formed. If the hydrogen were simply burned in oxygen, the heat obtainable would be
ΔH = 242 kJ mol–1, but no more than about half of this heat can be converted into work so
the output would not exceed 121 kJ mol –1. This limit is a consequence of the Second Law
of Thermodynamics.
The major limitation of present fuel cells is that the rates of the electrode reactions,
especially the one in which oxygen is reduced, tend to be very small, and thus so is the
output current per unit of electrode surface. Coating the electrode with a suitable catalytic
material is almost always necessary to obtain usable output currents, but good catalysts
are mostly very expensive substances such as platinum, so that the resulting cells are too
costly for most practical uses. There is no doubt that if an efficient, low-cost catalytic
electrode surface is ever developed, the fuel cell would become a mainstay of the energy
economy
III. Sử dụng Hydrogen trên ô tô
 3.1. Lưu trữ Hydrogen nén
The question of how to store hydrogen and move it around efficiently is a pressing one.
Hydrogen’s low density means it has to be stored at pressure, and therefore cooled.
Hydrogen fuel cell vehicles use reinforced carbon fibre tanks with a plastic liner, which
deliver hydrogen at the purity required by fuel cells. There might be more efficient ways
to move hydrogen around, and store it, in bulk. One option is to convert it to ammonia –
an industrial product that is shipped in large quantities all over the world. It has the
highest hydrogen density of fuels used today. Where renewables aren’t available to make
hydrogen directly, ammonia could provide a viable solution.
Siemens and its university partners have just launched an ammonia storage demonstrator
in Oxfordshire, UK, that will run the entire cycle of producing hydrogen from renewable
energy; making ammonia and cracking it back into hydrogen and nitrogen. Current
industrial synthesis of ammonia accounts for 2% of global carbon dioxide emissions, so
to produce it from renewable energy via hydrogen would make a big impact.
According to Ian Wilkinson, programme manager at Siemens, 90% of the energy used to
make ammonia is in the hydrogen production. Cracking it back again will also require
energy but that’s a relatively small part of the equation, he says, especially using catalysis
to bring the temperature down. A 20,000 tonne tank would produce some 50GWh of
electricity assuming a gas turbine with 50% efficiency – as a comparison, Tesla’s
Gigafactory in the US state of Nevada will have a production capacity of around 35GWh.
‘Not many things that are carbon-free give you that amount of energy, for a relatively
compact footprint,’ says Wilkinson.
While ammonia could be burned in a power station – without carbon dioxde emissions –
both it and hydrogen produce nitrogen oxides (NOx) emissions when burnt (ammonia
obviously more so). Reducing emissions is an active research area, and ironically
ammonia itself can clean up NOx emissions under the right conditions.
Another promising technology involves reversible hydrogenation of aromatic
compounds. Chiyoda, an energy company based in Tokyo, Japan, is using toluene:
hydrogenation produces methylcyclohexane (MCH), which can be stored as a liquid at
ambient temperature and pressure. When required, the hydrogen can be liberated through
a process of dehydrogenation, and the toluene recycled. Chiyoda anticipates that Japan’s
existing petroleum distribution infrastructure could be repurposed to handle MCH.
Hydrogenious, a German company spun out of the University of Erlangen–Nuremburg ,
works with dibenzyl toluene. It says 57kg of hydrogen can be stored in one cubic metre
of the liquid carrier – that’s enough to fill about 12 cars.
 3.2. Ô tô sử dụng động cơ đốt trong chạy bằng hydrogen
The properties of hydrogen are detailed in Section 1. The properties that
contribute to its use as a combustible fuel are its:
 wide range of flammability
 low ignition energy
 small quenching distance
 high autoignition temperature
 high flame speed at stoichiometric ratios
 high diffusivity
 very low density

Wide Range of Flammability

Hydrogen has a wide flammability range in comparison with all other fuels.
As a result, hydrogen can be combusted in an internal combustion engine over
a wide range of fuel-air mixtures. A significant advantage of this is that
hydrogen can run on a lean mixture. A lean mixture is one in which the
amount of fuel is less than the theoretical, stoichiometric or chemically ideal
amount needed for combustion with a given amount of air. This is why it is
fairly easy to get an engine to start on hydrogen.
Generally, fuel economy is greater and the combustion reac- tion is more
complete when a vehicle is run on a lean mixture. Additionally, the final
 combustion temperature is generally lower, reducing the amount of pollutants,
such as nitrogen oxides, emitted in the exhaust. There is a limit to how lean
the engine can be run, as lean operation can significantly reduce the power
output due to a reduction in the volumetric heating value of the air/fuel
mixture.

Low Ignition Energy

Hydrogen has very low ignition energy. The amount of energy needed to
ignite hydrogen is about one order of magnitude less than that required for
gasoline. This enables hydrogen engines to ignite lean mixtures and ensures
prompt ignition.
Unfortunately, the low ignition energy means that hot gases and hot
spots on the cylinder can serve as sources of ignition, creating
problems of premature ignition and flashback. Preventing this is one of
the challenges associated with running an engine on hydrogen. The
wide flammability range of hydrogen means that almost any mixture can be
ignited by a hot spot.
Small Quenching Distance
Hydrogen has a small quenching distance, smaller than gasoline.
Consequently, hydrogen flames travel closer to the cylinder wall than other
fuels before they extinguish. Thus, it is more difficult to quench a hydrogen
flame than a gasoline flame. The smaller quenching distance can also increase
the tendency for backfire since the flame from a hydrogen-air mixture more
readily passes a nearly closed intake valve, than a hydrocarbon-air flame.

High Autoignition Temperature

Hydrogen has a relatively high autoignition temperature. This has important
implications when a hydrogen-air mixture is compressed. In fact, the autoignition
temperature is an important factor in determining what compression ratio an
engine can use, since the temperature rise during compression is related to the
compression ratio. The temperature rise is shown by the equation:

The temperature may not exceed hydrogen’s autoignition temperature without

 causing premature ignition. Thus, the absolute final temperature limits the
compression ratio. The high autoignition temperature of hydrogen allows
larger compression ratios to be used in a hydrogen engine than in a
hydrocarbon engine.
This higher compression ratio is important because it is related to the thermal
efficiency of the system. On the other hand, hydrogen is difficult to ignite in a
compression ignition or diesel configuration, because the temperatures
needed for those types of ignition are relatively high.
High Flame Speed
Hydrogen has high flame speed at stoichiometric ratios. Under these
conditions, the hydrogen flame speed is nearly an order of magnitude higher
(faster) than that of gasoline. This means that hydrogen engines can more
closely approach the thermodynamically ideal engine cycle. At leaner
mixtures, however, the flame velocity decreases significantly.
High Diffusivity
Hydrogen has very high diffusivity. This ability to disperse in air is
considerably greater than gasoline and is advanta- geous for two main
reasons. Firstly, it facilitates the forma- tion of a uniform mixture of fuel and
air. Secondly, if a hydrogen leak develops, the hydrogen disperses rapidly.
Thus, unsafe conditions can either be avoided or minimized.
Low Density
Hydrogen has very low density. This results in two problems when used in an
internal combustion engine. Firstly, a very large volume is necessary to store
enough hydrogen to give a vehicle an adequate driving range. Secondly, the
energy density of a hydrogen-air mixture, and hence the power output, is reduced

Hydrogen can be used advantageously in internal combustion engines as an

additive to a hydrocarbon fuel.
Hydrogen is most commonly mixed with high pressure natural gas for this
purpose since both gases can be stored in the same tank. If hydrogen is
blended with other fuels, it usually has to be stored separately and mixed in
the gaseous state immediately before ignition. In general, it is impractical to
use hydrogen in conjunction with other fuels that also re- quire bulky storage
systems, such as propane.
Gaseous hydrogen cannot be stored in the same vessel as a liquid fuel.
Hydrogen’s low density will cause it to remain on top of the liquid and not
mix. Furthermore, liquid fuels are stored at relatively low pressures so that
 very little hydrogen could be added to the vessel.
Liquid hydrogen cannot be stored in the same vessel as other fuels.
Hydrogen’s low boiling point will freeze other fu- els resulting in fuel “ice”!
Hydrogen can be used in conjunction with compact liquid fuels such as
gasoline, alcohol or diesel provided each are stored separately. In these
applications, the fuel tanks can be formed to fit into unused spaces on the
vehicle. Existing vehicles of this type tend to operate using one fuel or the
other but not both at the same time. One advantage of this strategy is that the
vehicle can continue to operate if hydro- gen is unavailable.
Hydrogen cannot be used directly in a diesel (or “compres- sion ignition”)
engine since hydrogen’s autoignition tempera- ture is too high (this is also
true of natural gas). Thus, diesel engines must be outfitted with spark plugs or
use a small amount of diesel fuel to ignite the gas (known as pilot igni- tion).
Although pilot ignition techniques have been developed for use with natural
gas, no one is currently doing this with hydrogen.
One commercially available gas mixture known as Hythane contains 20%
hydrogen and 80% natural gas. At this ratio, no modifications are required to a
natural gas engine, and studies have shown that emissions are reduced by more
than 20%. Mixtures of more than 20% hydrogen with natu- ral gas can reduce
emissions further but some engine modi- fications are required.
Lean operation of any internal combustion engine is advan- tageous in terms of
oxides of nitrogen emissions and fuel economy
For hydrocarbon engines, lean operation also leads to lower emissions of carbon
monoxide and unburned hydrocarbons. As more oxygen is available than
required to combust the fuel, the excess oxygen oxidizes more carbon monoxide
into carbon dioxide, a less harmful emission. The excess oxygen also helps to
complete the combustion, decreasing the amount of unburned hydrocarbons.
As with hydrogen, the drawback of lean operation with hy- drocarbon fuels is a
reduced power output. Lean operation of hydrocarbon engines has additional
drawbacks. Lean mix- tures are hard to ignite, despite the mixture being above
the LFL of the fuel. This results in misfire, which increases un- burned
hydrocarbon emissions, reduces performance and wastes fuel. Another
disadvantage is the reduced conversion efficiency of 3-way catalytic converters,
resulting in more harmful emissions.
To some extent, mixing hydrogen with other hydrocarbon fuels reduces all of
these drawbacks. Hydrogen’s low ignition energy limit and high burning speed
makes the hydro- gen/hydrocarbon mixture easier to ignite, reducing misfire and
thereby improving emissions, performance and fuel economy. Regarding power
output, hydrogen augments the mixture’s energy density at lean mixtures by
increasing the hydrogen-to-carbon ratio, and thereby improves torque at wide-
open throttle conditions. However, the difficulty associated with storing adequate
amounts of hydrogen can reduce vehicle range

The real reason that Hydrogen (H2) is not much considered for engines has to do with the
thermodynamic efficiency of engines vs. fuel cells.

1 gallon of gasoline has an energy content of about 130 MegaJoules (MJ).

1 kg of H2 is in the same range (130–140 MJ).

An internal combustion engine (ICE) running on gasoline (the Otto cycle) or Hydrogen
operates at thermodynamic efficiency level of around 20–25%.

A fuel cell that converts H2 and Oxygen into electricity to feed an electric motor operates
at an efficiency level of 60% or even greater. Gasoline (or diesel) cannot be used in a fuel
cell.

Putting these facts together, we see that 1 kg of H2, used in a fuel cell to power an
electric motor is equal to 2.5 to 3 gallons of gasoline, and even greater for urban driving
conditions.

The result is that the fuel cost per mile is equal when the price (at the pump) for 1 kg of
H2 is about 3 times that of 1 gallon of gasoline.

It also means that a vehicle that would have required a 20-gallon gas tank only needs a 7-
kg H2 tank, or about 1/3 of a cubic meter in volume at a relatively low pressure of 250
bar.

3.3. Ô tô sử dụng pin nhiên liệu chạy bằng hydrogen

1. Hydrogen is pumped from the tanks to the stack . . .  2 . . . . where it meets oxygen
from the inlets at the front of the car 3. The reaction in the stack (see detail below)
generates an electrical current 4. The current’s voltage is increased by a boost
converter 5. The electric motor drives the wheels. When the car is coasting or
braking the motor acts as a generator 6. The extra electricity generated by the
motor is stored in a drive battery, which can assist the motor during acceleration
7. The power control unit oversees fuel cell power output and battery discharge
and recharge depending on driving conditions
How hydrogen fuel cells work
A hydrogen fuel cell is a simple machine. The core of the tech is a proton exchange
membrane. On one side of the membrane you have pure hydrogen, and on the other side
you have ordinary air. Ordinary air is about 80-percent nitrogen and 20-percent oxygen,
plus trace amounts of other stuff. The proton exchange membrane is critical, because
hydrogen and oxygen atoms really like to be together. Specifically, two hydrogen atoms
and an oxygen atom always want to get together and create a water molecule.
The membrane will allow hydrogen atoms to pass through to the oxygen, but only if the
hydrogen atom gives up its electron on the way. We cleverly put some highly conductive
metal like platinum on the walls of the fuel cell, so the electrons go there and run all the
way around the fuel cell to get back to their hydrogen atoms; that action creates electrical
current that we can use. When the oxygen and hydrogen are all coupled up and complete
again, we’ve got a water molecule and some electricity for our trouble. If you consider
only the fuel cell, you can get energy without creating any pollution
Yet transitioning to a hydrogen economy has raised some concerns. Because hydrogen is
odorless and burns with a clear flame, leaks can be difficult to detect, although the gas is
so light and disperses so quickly that the chance of an open explosion is considered
minimal. (While many associate hydrogen with the 1937 Hindenburg disaster, the
explosion of the German airship in fact began with ignition of the blimp’s highly
flammable outer covering, not the gas it carried.) Even so, careful engineering is
necessary to ensure that hydrogen fuel cell vehicles are safer than gasoline vehicles,
according to a 1997 Ford Motor Company study.
“Hydrogen is one of the keys to a new energy economy that relies on solar and wind
power rather than fossil fuels,” according to Worldwatch President Chris Flavin. “Private
and public investment in hydrogen technology should be increased substantially. But in
the next few years, the largest reductions in oil demand and greenhouse gas emissions
will come from improved fuel economy and biofuels—both of which are fully
competitive today.”