Energy Harvesting
Energy Harvesting
Energy Harvesting
MATERIALS SCIENCE
M19: Energy Harvesting
Name............................. College..........................
Dr. Sohini Kar-Narayan
Michaelmas Term 2014-15
2014 15
Recommended textbooks:
Energy Harvesting for Autonomous Systems - Stephen Beeby and Neil White, Artech
House.
Energy Autonomous Micro and Nano Systems Marc Belleville and Cyril
Condemine, Wiley.
Energy Materials Duncan Bruce, Dermot OHare, Richard Walton, Wiley.
Energy Harvesting Technologies Shashank Priya, Daniel Inman, Springer
Energy-autonomous systems
Power requirements
Ambient power sources
Energy storage
Role of Materials
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Introduction
Energy harvesting from ambient sources for self-powered
micro/nanoelectronic devices.
Bulky batteries
Energy-autonomous systems
Advances in low-power electronics and energy harvesting could make the powering of autonomous
systems from ambient energy sources a reality.
Autonomous systems commonly refer to wireless sensor nodes (WSN) devices that can be deployed
to monitor parameters of interest and to report these observations back, often to a central data collector
known as a sink. [More generally, the term can be used to include small-power consumer electronics
including mobile phones, iPods etc.]
Bare minimum requirement of a WSN: 8-bit microcontroller, radio transceiver, sensor and power supply,
additional passive circuitry. Nodes have been conventionally battery-powered, but this limits their useful
lifetime and the activities they can undertake.
Energy harvesting can eliminate the cost and inconvenience of replacing batteries, reduce waste and
potentially enhance the energy-awareness of sensor nodes.
Power requirements
The multibillion dollar portable electronics market is an attractive arena for micro- and macro-scale energy
harvesting when power requirements can be met. For e.g. the average mobile phone has a power
consumption ~1 W during a call and ~ 10 mW in standby.
In situations where energy harvesting is incapable of delivering watts of power, it may permit a nearindefinite standby lifetime or even recharge the device when not in active use. Where battery replacement is
not feasible, energy harvesting could potentially extend the battery life of such devices significantly or even
indefinitely.
Power requirements
The active current draw of sensor nodes is typically several orders of magnitude larger than the sleep current.
Thus, overall power requirement of sensor nodes depends on the duty cycle (DC), i.e. the percentage of one
period in which the node is active.
Energy reduction = (1 DC) (1 Psleep/Pactive)
Submilliwatt average operating powers mean that sensor nodes can potentially be powered for very long
periods by batteries, or indefinitely using harvested energy. The rate of power generation from energy
harvesting devices is typically insufficient to directly power the sensor node in its active mode, so it is necessary
to store the energy in capacitors or rechargeable batteries.
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Sunlight is clean and abundant more energy strikes the Earth in 1 h (4.3 X 1020 J) than all the energy consumed
on the planet in a year (4.1 X 1020 J) !! Solar energy conversion is thus a broad and rapidly exploding research
field, spurred on by government incentives and lower production costs.
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At high noon on a cloudless day, the surface of the Earth typically receives ~ 1000 W of solar power per square
metre (I kW/m2). A cloudy day will provide ~100 W/m2 and ~5 W/m2 will be incident on most surfaces within a welllit room.
Typical solar cells have efficiency values between 5 20 % under standard conditions and will often be much less
efficient under low illumination levels.
The disadvantages of solar power include constraints in terms of positioning, period of operation, incompatibility
with embedded/indoor devices.
Solar energy is commonly used in low-power electronic devices such as calculators. It is also often employed for
isolated noncritical outdoor systems such as parking meters, weather stations and traffic information systems. It is
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less likely to be used in portable high-power systems.
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Thermoelectric devices can be used to convert waste heat from automobiles or industry into useful electricity. They
can also be integrated into autonomous systems to enhance their capability and lifetime by harvesting thermal
energy from the environment. This can even be in the form of human body heat.
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Schematic of a thermoelectric wristwatch. A miniature thermoelectric converter that consists of 2,268 pairs of
Bi2Te3 thermocouples is mounted on the bottom case of the watch. It produces on average 25 W of electricity
from a temperature difference of 23 K generated by body heat. The conversion efficiency is about 0.1%
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Energy storage
There has been tremendous interest in the development of microenergy storage devices, in particular batteries and
electrochemical capacitors, to be used in conjunction with one or more energy harvesters to provide permanent power to
autonomous wireless systems.
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Photovoltaic technology:
Crystalline silicon This forms the basis of established PV technology. Si-based systems maje up ~ 90% of the
current PV market. The raw materials are expensive and require energy-intensive processing (high purity Si
wafers). Polycrystalline solar cells have lower efficiency due to the relative impurity of the Si and therefore
require a larger area.
Thin-film technologies Advantages include ease of manufacture of large area at lower cost, wider range of
applications, attractive appearance, possibility of assembling devices using flexible substrates. Most established
thin-film technology use amorphous Si (a-Si). Others include Cadmium Telluride (CdTe) and Copper Indium
(Gallium) Diselenide (CIGS). Multijunction devices with improved efficiencies.
Emergent technologies These are mostly driven by nanotechnology, including dye-sensitised solar cells,
organic polymer solar cells and bulk-heterojunction solar cells.
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Nanotechnology-driven advances!
End of Lecture 1
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Solar energy harvesting is based on PV cells which generate electric current when exposed to light. PV cells are
based on semiconductor materials mostly.
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Semiconductor basics
A semiconductor has low concentrations of thermally generated intrinsic charge carriers at finite temperatures. It can
be made n-type by adding donor atoms (e.g. phosphorus in silicon) , or p-type by adding acceptor impurities (e.g.
boron in silicon).
When a junction is formed between n- and p-type semiconductors, the concentration gradient of charge carriers at
the junction causes a net diffusion of electrons from n- type material to the p-type material and net diffusion of holes
from p-type material to n-type material, leaving behind a charged depletion region on either side of the junction. This
leads to the formation of an electrostatic field and a built-in voltage across the junction.
This built-in potential is used to separate photo-generated electron-hole pairs that are created when light is incident
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on a p-n junction
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Quantum Efficiency
The "quantum efficiency" is the ratio of the number of carriers collected by the solar cell to the number of photons of a given
energy incident on the solar cell. The quantum efficiency may be given either as a function of wavelength or as energy. If all
photons of a certain wavelength are absorbed and the resulting minority carriers are collected, then the quantum efficiency at
that particular wavelength is unity. The quantum efficiency for photons with energy below the band gap is zero. A quantum
efficiency curve for an ideal solar cell is shown below.
The "external" quantum efficiency (EQE) of a silicon solar cell (above) includes the effect of optical losses such as transmission
and reflection. However, it is often useful to look at the quantum efficiency of the light left after the reflected and transmitted
light has been lost. "Internal" quantum efficiency refers to the efficiency with which photons that are not reflected or
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transmitted out of the cell can generate collectable carriers.
Two major factors at play Absorption of light and Recombination of minority carriers
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Absorption of light
Photons incident on the surface of a semiconductor will be either reflected from the top surface, will be absorbed in the
material or, failing either of the above two processes, will be transmitted through the material. For photovoltaic devices,
reflection and transmission are typically considered loss mechanisms as photons which are not absorbed do not generate
power. If the photon is absorbed it has the possibility of exciting an electron from the valence band to the conduction band. A
key factor in determining if a photon is absorbed or transmitted is the energy of the photon (Eph). Therefore, only if the photon
has enough energy will the electron be excited into the conduction band from the valence band. Photons falling onto a
semiconductor material can be divided into three groups based on their energy compared to that of the semiconductor band
gap:
Eph < Eg : Photons with energy Eph less than the band gap energy EG interact only weakly with the
semiconductor, passing through it as if it were transparent.
Eph = Eg : Photons have just enough energy to create an electron hole pair and are efficiently absorbed.
Eph > Eg : Photons with energy much greater than the band gap are strongly absorbed. However, for
photovoltaic applications, the photon energy greater than the band gap is wasted as electrons quickly
thermalize back down to the conduction band edges.
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Absorption coefficient
The absorption coefficient, D, determines how far into a material light of a particular wavelength can penetrate before it is
absorbed. In a material with a low absorption coefficient, light is only poorly absorbed, and if the material is thin enough, it will
appear transparent to that wavelength. The absorption coefficient depends on the material and also on the wavelength of light
which is being absorbed. Semiconductor materials have a sharp edge in their absorption coefficient, since light which has
energy below the band gap does not have sufficient energy to excite an electron into the conduction band from the valence
band. Consequently this light is not absorbed. The absorption coefficient for several semiconductor materials is shown below.
(T = 300 K)
For photons which have an energy very close to that of the band gap, the absorption is relatively low since only those electrons
directly at the valence band edge can interact with the photon to cause absorption. As the photon energy increases, a larger
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number of electrons can interact with the photon and result in the photon being absorbed.
O nm
D cm-1
Because the light used in photovoltaic applications contains many
different wavelengths, many different generation rates must be taken
into account when designing a solar cell.
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Bulk recombination
Any electron which exists in the conduction band is in a meta-stable state and will eventually stabilize to a lower energy
position in the valence band. When this occurs, it must move into an empty valence band state. Therefore, when the electron
stabilizes back down into the valence band, it also effectively removes a hole. This process is called recombination. There are
three basic types of recombination in the bulk of a single-crystal semiconductor.
Radiative recombination: An electron from the conduction band directly combines with a hole in the valence band and
releases a photon. The emitted photon has an energy similar to the band gap and is therefore only weakly absorbed such
that it can exit the piece of semiconductor. This recombination mechanism dominates in direct bandgap semiconductors. In
radiative recombination.
Shockley-Read-Hall or SRH recombination involves recombination through defects in the crystal lattice. These defects can
either be unintentionally introduced or deliberately added to the material, for example in doping the material.
Auger Recombination involves three carriers. An electron and a hole recombine, but rather than emitting the energy as
heat or as a photon, the energy is given to a third carrier, an electron in the conduction band. This electron then
thermalizes back down to the conduction band edge. This recombination mechanism is most important at high carrier
concentrations caused by heavy doping.
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Diffusion length is the average length a carrier moves between generation and recombination. Semiconductor materials that
are heavily doped have greater recombination rates and consequently, have shorter diffusion lengths. Higher diffusion lengths
are indicative of materials with longer lifetimes, and is therefore an important quality to consider with semiconductor
materials.
where L is the diffusion length in meters, D is the diffusivity in m/s and is the lifetime in
seconds.
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Surface recombination
Areas of defect, such as at the surface of solar cells where the lattice is disrupted, recombination is very high.
Surface recombination is high in solar cells, but can be limited.
Understanding the impacts and the ways to limit surface recombination leads to better and more robust solar cell
designs.
The defects at a semiconductor surface are caused by the interruption to the periodicity of the crystal lattice, which causes
dangling bonds at the semiconductor surface. The reduction of the number of dangling bonds, and hence surface
recombination, is achieved by growing a layer on top of the semiconductor surface which ties up some of these dangling
bonds. This reduction of dangling bonds is known as surface passivation.
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Collection probablility
The "collection probability" describes the probability that a carrier generated by light absorption in a certain region of the
device will be collected by the p-n junction and therefore contribute to the light-generated current, but probability depends on
the distance that a light-generated carrier must travel compared to the diffusion length. Collection probability also depends on
the surface properties of the device. The collection probability of carriers generated in the depletion region is unity as the
electron-hole pair are quickly swept apart by the electric field and are collected. Away from the junction, the collection
probability drops. If the carrier is generated more than a diffusion length away from the junction, then the collection probability
of this carrier is quite low. Similarly, if the carrier is generated closer to a region such as a surface with higher recombination
than the junction, then the carrier will recombine. The impact of surface passivation and diffusion length on collection
probability is illustrated below.
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Nanostructuring as a solution?
LA absorption thickness
LC charge transport thickness
End of Lecture 2
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Shockley-Quesisser Limit
ShockleyQueisser limit or detailed balance limit refers to the calculation of the maximum theoretical efficiency of a solar cell
made from a single pn junction. It was first calculated by William Shockley and Hans Queisser:
William Shockley and Hans J. Queisser, "Detailed Balance Limit of Efficiency of p-n Junction Solar Cells", Journal of Applied
Physics, Volume 32, pp. 510-519 (1961).
The ShockleyQueisser limit is calculated by examining the amount of electrical energy that is extracted per incident photon.
The calculation places maximum solar conversion efficiency around 33.7% assuming a single p-n junction with a band gap of
1.4 eV (under one sun). Therefore, an ideal solar cell with incident solar radiation will generate 337 Wm-2. When the solar
radiation is modelled as 6000 K blackbody radiation the maximum efficiency occurs when the bandgap energy Eg=1.4 eV.
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Shockley-Quesisser Limit
Basic Assumptions
1. One semiconductor material (excluding doping materials) per solar cell.
2. One p-n junction per solar cell.
3. The sunlight is not concentrated - a "one sun" source.
4. All energy is converted to heat from photons greater than the band gap.
In order to overcome the S-Q limit, one must work around one or more of the critical assumptions listed above, i.e.
1. Use more than one semiconductor material in a cell.
2. Use more than one junction in a cell - "multijunction cells".
3. Concentrate the sunlight using concentrators
4. Combine a PV semiconductor with a heat based technology to harvest both forms of energy
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Efficiency losses
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Electrical losses
I
IL
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Electrical losses
Bulk recombination: caused by defects within the semiconductor e.g. structural and intrinsic defects, extrinsic defects due to presence of
impurity atoms. Source materials must be high-purity. For multicrystalline semiconductors, grain boundaries represent a significant
source of recombination.
Biggest trade-off in a solar cell is the decision over thickness. Carrier collection is best for thin devices but photon collection is best
for thick devices.
Surface recombination: caused due to defect chemistry at the surface and concentration of free carriers at surface. Efforts to reduce this
effect include addition of a thin passivating material such as SiO2 to saturate dangling bonds and reduce surface defect density, fieldeffect passivation and creation of back-surface field.
Non-ideal diode behaviour: caused by non-uniform acceptor and donor impurity profiles, thickness variations.
Series resistance: arises due to the resistance of the bulk semiconductor material and contact resistances, and should be as small as
possible.
Parallel resistance: caused by pin-holes that break through thin film p-n junctions, conductive paths that can be formed through grain
boundaries, problems at the edges of devices. Should be as high as possible.
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Optical losses
Any process that leads to photon loss will lead to a decrease in the current that can be generated by a solar cell.
Surface Reflection: Reflection from both top and rear surface of the cell leads to optical losses. Anti-reflection coatings
or surface texturing help to mitigate this problem.
Top contact shading: Metals reflect light and shadow underlying device. Use of transparent conducting oxides (e.g.
indium tin oxide) or thin metals reduces shading at the expense of increasing RS.
Incomplete absorption: Amount of light absorbed depends on amount of material, and hence thickness. Material cost of
thick cells are higher plus the quality of the materials must be ensured. Light-trapping schemes for cheaper thin-film
designs are required to increase effective optical path length.
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Optical losses
Top surface reflectance: The semiconductor surface itself will reflect a component of light depending on the refractive
index of the semiconductor, the angle of incidence and the wavelength, thereby resulting in reduction in the short-circuit
current. Thus antireflection schemes have to be employed to reduce reflectance. (Bare Si has a high surface relflectance
of over 30%)
Antireflection techniques include:
Thin film coatings Destructive interference between light reflected from the interfaces created by adding one or
more thin films to a surface minimizes reflectance at certain wavelengths. The refractive index and thicknesses of the
layers must be carefully chosen for optimum reflection reduction over the required wavelength range.
Micron-scale texturing - Texturing with featured of dimensions above the wavelength of incident light reduces overall
reflectance by forcing the light to undergo multiple reflections from the inclined walls of the features, with a portion
of this light being coupled into the substrate at each reflection
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Anti-reflection coating
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Texturing
Subwavelength-scale texturing - Reflections occur at an interface between two materials because of a sudden
change in refractive index. By texturing on the sub-wavelength scale at the interface, a more gradual change in
refractive index can be introduced and so such reflections can be significantly reduced. The interface is effectively
blurred resulting in a low reflectance for a broad range of wavelengths.
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Light-trapping schemes
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Module losses
Losses result when a solar cell is encapsulated into a module. Reflectance and absorption losses in encapsulant materials
are low as they tend to have low refractive indices and are chosen for their transparency, e.g. glass.
Arrangement of single crystal silicon solar cells that are generally made from circular wafers gives rise to loss of efficiency
due to sub-optimal use of the surface region of the PV module. Cleaving or sawing to make square or hexagonal wafers is
expensive and wasteful.
Series configuration of individual cells connected to form a module introduces losses. Although voltage is increased, the
current is limited by the worst-performing cell in the array.
Careful placement of module is necessary to ensure all cells receive the same level of irradiance, for e.g. partial shading
must be avoided.
Encapsulation affects heat dissipation, raising the operating temperature and reducing the open-circuit voltage. Severe
overheating can cause cracks due to thermal expansion.
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Textured AR surface
Metal top contact
Staeblar-Wronski (SW) effect refers to the degradation of photocurrent in a-Si:H with exposure to light and is a serious
limitation as cells can lose as much as 10% of their initial efficiency after a few months of use. Original photocurrent
restorable with an anneal of 1500C. SW effect attributed to breaking of SiSi or Si-H bbonds within the random amorphous
network leading to increase in midgap defect density and hence recombination current.
Can be deposited onto flexible polymer substrated due to low deposition temperatures. Efficiency in the range 8 10%.
Devices typically used in pocket calculators have efficiency ~ 5%. Low cost and flexibility of a-Si:H makes it viable for lowpower indoor applications
pin design
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MJ Si cell Efficiency of up to 16 %
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CuInSe2 (CIS), has the highest absorption coefficient across the broadest spectral range. Slightly less than optimum Eg of
1.04 eV can be increased by the addition of gallium to form CuIn1-xGaxSe2 (CIGS). CIGS lab cells have the highest efficiency
record of 19.4%. Disadvantage poor scalability, low yield and high production cost.
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Absorption of light creates excited state in dye which injects an electron into the conduction band of TiO2. Electrons diffuse
through successive nanospheres till they reach the top contact. In order to maintain neutrality, the dye molecule takes an
electron from the electrolyte, forming a positively carged ion that diffuses through the electrolyte to the cathode.
Very efficient system limited by inability to absorb red and infrared photons. DSSC devices are cheap, can be manufactured
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by printing technologies rather than expensive semiconductor technologies.
These devices are in early stages of development and have relatively low efficiency. But these nanodevices can act as
standalone energy harvesting units, possibly to power single CMOS gates.
BHJ Polymer/plastic solar cells: light generates excitons with subsequent separation of charges in the interface between
an electron donor and acceptor blend within the devices active layer. Regions of each material in the device are
separated by only several nanometers, a distance suited for carrier diffusion. BHJs require sensitive control over
materials morphology on the nanoscale. A number of variables, are important including choice of materials, solvents,
and the donor-acceptor weight ratio. (For e.g. poly-3-hexyl thiophene (P3HT), phenyl-C61-butyric acid methyl ester
(PCBM) are used to form P3HT:PCBM solar cells)
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End of Lecture 3
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Organic Photovoltaics
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Organic Photovoltaics
Excitons
When incident photons hit electrons at the ground state, inorganic semiconductors generate free carriers. However, in organic
semiconductors, excited electrons slightly relax (due to lower Coulomb screening) and then form an exciton, a bounded
electron and hole pair.
To make an efficient organic photovoltaic cell, effective dissociation of excitons is a key issue because the binding energy of
the exciton is large.
Solution?
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Nanoparticle hybrids
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Solar Energy Materials and Solar Cells, 117 (2013) 329 335
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End of Lecture 4
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Losses can be incurred, not just within the energy harvesting transducer, but at all stages in this process. The
effectiveness of the transducer is not the only factor - performance can be dominated by losses in the transfer of
energy across these system boundaries.
Commonly used transduction mechanisms: electrostatic, electromagnetic and piezoelectric
Recent advance: Triboelectric transduction mechanism
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Consider a rigid box subjected to the environments vibrations y(t), with a mass m suspended by a spring k. The
relative displacement of mass m with respect to its equilibrium position is represented by z(t) and its natural angular
frequency Zn = (k/m)1/2. Part of the kinetic energy is lost in mechanical damping and the rest is converted to
electricity which is modelled as an electrical damping. Together they are represented by the damping coefficient, cT.
The external excitation is given by y(t) = Ysin(Zt). Assuming the mass of the vibrating source >> m, the differential
equation of motion is described as:
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The maximum energy is extracted when the excitation frequency equals the natural frequency,
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The value of maximum power is indeed finite, as reduction of the damping factor results in increased mass displacement
which is ultimately limited by the size and geometry of the device.
The maximum power that can be extracted by the transduction mechanism can be predicted by accounting for the
parasitic and transducer damping ratios and is given by:
Pe is maximized when parasitic damping equals transducer damping, ]p = ]e. Varying the level of damping provides a
handle on bandwidth response of the generator, which may be useful in practical situations where frequency variations
are common. Pe is proportional to mass, which should therefore be maximised subject to design constraints. For fixed A,
Pe is inversely proportional to Zn, hence it is preferable to operate at the lowest fundamental frequency within the
available vibration spectra. When a generator is coupled to an electrical circuit, losses on the circuit will limit the amount
of useful electrical energy.
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Electromagnetic transduction
Electromagnetic generators are based on Faradays law of electromagnetic induction. When an electric conductor is
moved through a magnetic field, a potential difference, or electromotive force (emf), is induced between the ends of the
conductor. The voltage induced in the conductor (V) is proportional to the time rate of change of the magnetic flux
linkage () of that circuit:
In practice, the conductor is in the form of a coil of length l having N turns, and the magnetic field B is created by
permanent magnets.
Where, Rload, Rcoil and Lcoil are the load resistance, coil resistance and coil inductance respectively. Thus Rload can be used
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to adjust ce to match cp and therefore maximise power.
While macroscale, high performance bulk magnets, and multi-turn and macroscale coils are readily available, there
remain challenges for fabrication of MEMS scale systems due to the poor properties of planar magnets. The number of
turns that can be achieved with planar coils are limited the assembly and alignment of wafer-scale (sub-millimeter)
electromagnetic systems remain a challenge for implementation to MEMS devices.
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Electrostatic generators
These types of generators consist of a variable capacitor whose two plates are electrically isolated from each other by air, a
vacuum, or an insulator. External mechanical vibrations cause the gap between the plates to vary and hence the capacitance
changes. In order to extract energy, the plates must be charged and the mechanical vibrations work against the electrostatic
forces present in the device.
Capacitor Basics:
The capacitance of a capacitor is given by: C = Q/V, where Q is the charge and V is the voltage
It can also be expressed as C = HA/d,
where H is the dielectric permittivity of the materials between the plates, A is the area of the plates and d is the separation
between the plates.
The stored energy is given by E = 0.5QV = 0.5CV2 = 0.5Q2 C
Voltage-
and
Energy gain:
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Electrostatic generators
Electrostatic generators can be classified into three configurations:
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Electrostatic generators are well-suited for MEMS devices but the main drawback is the need for input charge/voltage.
Other problems include high output impedance and voltage, requirement of additional circuitry for signal processing,
parasitic capacitances leading to reduced efficiencies and electrode shorting in wafer-scale applications.
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Piezoelectric Materials
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Piezoelectric Materials
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Piezoelectric Materials
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Piezoelectric Materials
Piezoelectricity relates to the electric displacement D (surface charge per unit area) induced in a material by an applied stress
T. In three dimensions, stress is described by two vectors, applied force Fi and the normal to the area upon which the force
acts Aj. Stress, F/A, is thus a second rank tensor Tij whose diagonal elements represent normal stress and off-diagonal
elements represent shear stress. Electric displacement and electric field are vectors Di and Ej respectively, and the permittivity,
Hij=D/E, is represented by a second rank tensor. Taking T and E as independent variables, D is specified by
where d is the piezoelectric constant of the material and is represented by a third rank tensor. Strain S is a second rank tensor
specified by
where dt is the transpose of d, and s is elastic compliance. The above equations are the piezoelectric constitutive equations.
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Piezoelectric Generator
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Piezoelectric constants
Piezoelectric constants in typical energy-harvesting modes:
Piezoelectric materials
Energy harvesting performance is directly related to the piezoelectric coefficients, but the applied stress or strain is also an
important factor. This is why the coupling between the mechanical source and the piezoelectric material is a critical factor in
determining the energy harvesting performance. The energy output also depends on the ability of the piezoelectric material
to sustain an applied force or to repeatedly undergo a recoverable strain.
End of Lecture 5
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Piezoelectric generator
The domains in a ceramic element are aligned by exposing the element to a strong, DC electric field, usually at a temperature
slightly below the Curie temperature. This is referred to as the poling process. After the poling treatment, domains most
nearly aligned with the electric field expand at the expense of domains that are not aligned with the field,
and the element expands in the direction of the field. When the electric field is removed most of the dipoles are locked into
a configuration of near alignment
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Piezoelectric generator
Piezoelectric vibration harvesters exploit piezoelectric properties of materials. In certain cases, the strain in the piezoelectric
material is created by the inertia of a suspended mass undergoing acceleration, rather than being directly deformed by the
source. There are many ways of achieving this coupling, but perhaps one of the most common is the piezoelectric cantilever
The cantilever is clamped at one end (the root) to the vibration source. A mass is fixed to the other end. When the base
accelerates, the inertia of the tip mass bends the cantilever. Simple bending a piezoelectric element creates equal and
opposite strains on the inside and outside of the bend. These cancel, so no net current is generated. To be effective as a
generator it is necessary to move the piezoelectric layer away from the neutral axis. This is usually accomplished either by
fixing the piezoelectric material to a non-piezoelectric elastic layer, or by joining two piezoelectric layers poled in opposite
directions. These are referred to as unimorph of bimorph configurations as shown in the figure above.
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Piezoelectric structures
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Piezoelectric generator
Practical considerations
Piezoelectric generators are usually operated at or close to resonance, where the amplitude of the oscillation is only limited
by the losses from the mechanical system resulting from the energy harvested as well as internal and external losses due to
friction, internal electrical losses and air damping. This means that the most effective energy harvester does not necessarily
employ the material with the highest piezoelectric coefficients.
For example, lead zirconium titanate (PZT) is obtainable in a range of compositions from hard materials which have low
losses but small piezoelectric coupling, through to soft materials with much higher piezoelectric coupling, but also much
higher losses. In some cases, hard materials with much smaller piezoelectric coefficients can produce larger power output
than soft materials. However, this depends on the magnitude of the electrical power harvested compared to other sources of
loss i.e. the efficiency, and for many systems non-harvested losses dominate.
Crossley, Whiter & Kar-Narayan, Materials Science and Technology 2014 VOL 30 NO 13a 1615
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Piezoelectric Polymers
- Flexible and light
- Ease of fabrication
- Cost-effective
- Lead free
Polyamides (nylons)
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Piezoelectric Polymers
The ferroelectric phase of PVDF
D
poling
stretching
annealing
annealing
poling
J
poling
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Effect of geometry
C. Chang et al, Direct-write piezoelectric polymeric nanogenerator with high energy conversion
efficiency," Nano Letters, vol. 10, no. 2, pp. 726-731, 2010.
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The BaTiO3 nanowire arrays were grown on Ti substrate using a two-step hydrothermal synthesis method.
Adv. Energy Mater. 2014, 4, 1301660
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Nano-piezoelectric generators
Polymer nanogenerators
Flexible
Robust
Cheap
Easy to fabricate
Lead-free
Biocompatible
Acoustic impedance matching
Low piezoelectric constant
Crossley, Whiter & Kar-Narayan, Materials Science and Technology 2014 VOL 30 NO 13a 1615
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Nano-piezoelectric generators
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Electrospinning
> 10 kV
When a sufficiently high voltage is applied to a liquid droplet, the body of the liquid
becomes charged, and electrostatic repulsion counteracts the surface tension and the
droplet is stretched; at a critical point a stream of liquid erupts from the surface.
Electrospinning
Electrospinning is a relatively complex fabrication process
requiring high voltages (550 kV) and specialized equipment.
The associated high electric fields and stretching forces result
in poled nanowires, however this fabrication process often
suffers from poor control over nanowire size-distribution and
alignment, and is yet to be conveniently and cost-effectively
scaled up.
Template Wetting
Simple
Scalable
Versatile
Can form nanotubes or nanowires
Can change dimensions with different
templates
After forming nanowires inside template:
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End of Lecture 6
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Triboelectric generator
The triboelectric effect describes a contact-induced electrification in which a material becomes electrically charged after it
is contacted with a different material through friction.
Tribolelectric generator - a device that converts mechanical energy into electricity using the coupling effects between
triboelectrification and electrostatic induction through the contact separation or relative sliding between two materials
that have opposite tribo-polarity.
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Fundamentals of Tribolelectrification
The triboelectric effect is a contact-induced electrification in which a material becomes electrically charged after it
is contacted with a different material through friction. As an example, triboelectric effect is a general cause of
commonly experienced static charging. The sign of the charges to be carried by a material depends on its relative
polarity in comparison to the material to which it will contact.
While the effect has been known for many centuries, the mechanism behind tribolelectrification is still not entirely
clear. It is generally believed that, after two different materials come into contact, a chemical bond is formed
between some parts of the two surfaces, called adhesion, and charges move from one material to the other to
equalize their electrochemical potential. The transferred charges can be electrons or may be ions/molecules.
When separated, some of the bonded atoms have a tendency to keep extra electrons and some a tendency to give
them away, possibly producing triboelectric charges on surfaces.
Materials that usually have strong triboelectrification effect are more likely to be insulators, thus enabling them to
capture the transferred charges and retain them for an extended period of time. The build-up of electrostatic
charges are usually considered to be a negative effect in our daily life and technology developments.
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Choice of materials
Triboelectric Series for some common materials following a tendency to easily lose electrons (Positive) and to gain Electrons
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(Negative)
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where is the triboelectric charge density, 0 is the vacuum permittivity, and d0 is the interlayer distance at a given state.
The net effect is that induced charges accumulate with positive sign on the top electrode and negative sign on the bottom
electrode (see figure on previous slide). The induced charge density (0) when the generator is fully released is given by:
where rk and rp are the relative permittivity of Kapton and PMMA, respectively, and d1 and d2 are the thicknesses of the
Kapton film and the PMMA layer. The maximum value of max is obtained by substituting d3 for d in the equation above.
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TENG performance
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TENG configurations
If is the charge density of the PTFE surface,
1 is the charge density of the Cu surface that
is contacted with PTFE, and 2 is charge
density of the Ag upper surface, then
Effect of nanostructuring
Micro- or nanopatterns can be
generated on surfaces to enhance the
contact area and the effectiveness of
the triboelectrification
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TENG configurations
There are two basic friction processes: normal contact
and lateral sliding. A periodic change in the contact
area between two surfaces leads to a lateral separation
of the charge centers, which creates a voltage drop for
driving the flow of electrons in the external load
TENG configurations
Linear gratings with uniform period are fabricated on
both sliding surfaces. The rows of grating units have
the same size as the intervals in between, with all
rows being electrically connected at both ends by two
buses. The grating patterns on both sliding surfaces
are identical so that they can match well with each
other when aligned. Although the grating design
reduces the total contact area by half, thus seemingly
sacrificing half of the triboelectric charges, it increases
the percentage of the mismatched area to 100% for a
displacement of only a grating unit length rather than
the entire length of the TENG so that it dramatically
increases the transport efficiency of the induced
charges.
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TENG configurations
The working principle of the disk TENG is based on the
triboelectrification and the relative-rotation induced cyclic inplane charge separation between Al and Kapton.
In the relative rotation, the Al surface and Kapton surface slide
relative to each other, so that the electrons will be injected
from the Al foil to the inner surface of the Kapton film, leaving
net positive charges on the Al foil and net negative charges on
the Kapton film.
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TENG configurations
TENG configurations
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Pressure sensor
Touch sensor
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Chemical sensor
Outlook
Triboelectric generators are generating significant interest in the mechanical energy harvesting community
due to the relative simplicity of the materials and processing involved, and the promising output performance
Surface modification may be key to performance optimisation
These types of devices tend to have high output impedence, thus impedence matching may be an issue and
additional power conditioning circuitry will be required.
A major issue is the presence of static charges which may be detrimental for electronic devices in the vicinity
of the nanogenerator.
The field is very new and research in the coming years should strengthen our understanding of the
tribolelectric effect in order to fully harness its potential in mechanical energy harvesting.
End of Lecture 7
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Thermoelectric effects
Thermoelectricity refers to a class of phenomena in which a temperature difference creates an electric potential/current
creates a temperature difference.
Seebeck Effect is the generation of a voltage across a material as a result of a temperature difference and is the principle used
in thermoelectric generators.
Peltier Effect is the opposite generating a temperature difference as a result of an applied voltage/current. This is used for
refrigerant free cooling.
Thomson effect refers to heat being absorbed or produced when current flows in material with a certain temperature
gradient. The heat is proportional to both the electric current and the temperature gradient. This is known as Thomson effect.
Seebeck effect
Peltier effect
Thomson effect
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Thermoelectric effects
Mathematically, the Seebeck effect can be described as
Typically, metals have Seebeck coefficients up to few tens of mV/K, semiconductors can have Seebeck coefficients 1-2 orders
larger in magnitude. A thermoelectric device operated in the Seebeck mode converts heat into electricity and is a generator
The Peltier effect can be described by the following: the rate at which heat is removed from one junction to another
junction is given by
, where I is the current flowing in the circuit and S is the Peltier coefficient (unit V). A
thermoelectric device operated in the Peltier mode pumps heat from one junction to another and can be used as a
refrigerator, e.g. during camping, as portable coolers, for cooling electronic components and small instruments.
The Thompson effect can be mathematically described as
The three thermoelectric coefficients are not independent of each other, but are related by the Kelvin relationships:
The first equation describes the relationship between the Seebeck and Peltier coefficients. This indicates that the materials
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that are suitable for thermoelectric power generation are also suitable for thermoelectric refrigeration.
Thermoelectric generators
In a thermoelectric material there are free electrons or holes which carry both charge and heat.
To a first approximation, the electrons and holes in a thermoelectric semiconductor behave like a gas of charged particles. If a
normal (uncharged) gas is placed in a box within a temperature gradient, where one side is cold and the other is hot, the gas
molecules at the hot end will move faster than those at the cold end. The faster hot molecules will diffuse further than the
cold molecules and so there will be a net build up of molecules (higher density) at the cold end. The density gradient will
drive the molecules to diffuse back to the hot end. In the steady state, the effect of the density gradient will exactly
counteract the effect of the temperature gradient so there is no net flow of molecules.
If the molecules are charged, the build-up of charge at the cold end will also produce a repulsive electrostatic force (and
therefore electric potential) to push the charges back to the hot end. If the free charges are positive (the material is p-type),
positive charge will build up on the cold which will have a positive potential. Similarly, negative free charges (n-type material)
will produce a negative potential at the cold end.
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Thermoelectric generators
The simplest thermoelectric power generator consists of a thermocouple, comprising a p-type and n-type material
connected electrically in series and thermally in parallel.
A thermoelectric module consists of a number of the basic building blocks connected electrically in series but thermally in
parallel and sandwiched between two ceramic plates to maximize voltage output.
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Power output
A thermoelectric generator can be viewed as a thermal battery. The electromotive force of this thermal battery is the
Seebeck voltage Vo = npT. See equivalent circuit below:
, where s = RL/R
. , we can work out the heat flux at the hot junction by considering the
Thermoelectric generators suffer from poor efficiency values. There is tremendous ongoing effort to improve the
thermoelectric figure of merit, and hence efficiency through clever materials engineering.
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For a single material with electrical conductivity V and thermal conductivity N, the thermoelectric figure of merit can be
simplified to an expression that involves only fundamental properties of the material, independent of geometry.
N
A good thermoelectric materials must thus have a large Seebeck coefficient to produce a large voltage for a given
temperature difference, large electrical conductivity to minimize Joule heating, and low thermal conductivity to retain the
heat at the hot junction. i.e. thermal transfer needs to be dominated by electrons NOT phonons. (N = Nel + Nph)
There has to be a compromise between D, V and N in order to maximise Z.
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147
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The discovery of new and exciting thermoelectric materials has spurred the development of novel thermoelectric generators
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Improving ZT
N = Nel + Nph
The higher the electrical conductivity, the higher the value of Nel , according to Wiedemann-Franz law.
Our best bet is therefore to try and minimize Nph . Key strategies include:
- Alloying : create point defects, vacancies, or rattling structures to scatter phonons.
- Complex crystals to separate the phonon-glass from the electron-crystal: In the expression for ZT, thermal conductivity
and electrical conductivity compete. It has been proposed that in order to improve ZT, phonons responsible for thermal
conductivity must experience the material as they would in a glass, i.e. experiencing a high degree of phonon scattering
which lowers the thermal conductivity, while electrons must experience the material as a crystal, i.e. experiencing very little
scattering meaning high electrical conductivity.
Phonon-gas, electron-crystal (PGEC) behaviour
- Multiphase nanocomposites that scatter phonons at the interfaces of nanostructured materials.
- Reduced dimensionality: The Seebeck coefficient heavily depends od the band structure, specifically the number of subbands that contribute and the density of states in each band. Reduced dimensionality, e.g. in quantum wells/dots,
decreases the number of bands and creates a more distribution of density of states in-plane, enhancing the
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thermoelectric properties of the system.
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Nanostructured chalcogenides
Nanostructured superlattices comprising
alternating Bi2Te3 and Sb2Te3 layers produce
a device in which there is good electrical
conductivity but poor thermal conductivity
perpendicular to the layers. The result is an
enhanced ZT (approximately 2.4) at room
temperature for p-type devices.
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However, these technologies are still quite young and suffer from problems such as scalability, cost, reproducibility, toxicity
and availability of constituent materials.
End of Lecture 8 154
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Certain pyroelectric materials can operate at very high temperatures where traditional thermoelectric materials
cannot operate, which may be useful and vital in specific applications.
Pyroelectric harvesters tend to operate at low frequency, typically <1 Hz, due to the slow temperature oscillations in
systems of large thermal mass and heat transfer inertia.
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Pyroelectric materials
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Pyroelectric materials
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Pyroelectric materials
The generated current due to a pyroelectric charge Q is given by:
The ability of small changes in temperature to produce a pyroelectric current has been exploited for infra-red imaging and
motion detection by body heat.
To maximise the pyroelectric current, the pyroelectric material should have a large surface area, large pyroelectric coefficient
and a high rate of temperature change.
In general, ferroelectric materials have larger pyroelectric (and piezoelectric) coefficients compared to non-ferroelectric
materials. However if a ferroelectric material is heated beyond the Curie temperature (TC) it undergoes a phase transition
where the spontaneous polarization and both the pyroelectric (and piezoelectric) behaviour vanish.
While the loss of piezoelectric properties above the Curie temperature is a disadvantage for vibration harvesters, the phase
transition at the Curie temperature has attracted some interest for pyroelectric harvesting since the material has the potential
to discharge a large amount of electrical energy as the level of polarisation falls to zero
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Pyroelectric coefficients
A temperature change alters the degree of polarisation in a pyroelectric materials and leads to an electric current.
The primary pyroelectric effect is relevant to the condition of a perfectly clamped material under constant strain
with a homogenous heat distribution without an external field bias.
Since thermal expansion induces a strain that alters the electric displacement via the piezoelectric effect, in many
cases of measurement and energy harvesting, a secondary pyroelectric effect is present.
Using tensor notation the primary pyroelectric coefficient at constant strain (px), i.e. in the clamped condition, is
related to the pyroelectric coefficient at constant stress (pV) by
For thin-film materials, substrate clamping can reduce the pyroelectric response to a small value compared to its
unclamped value. Thus, it may be beneficial to replace thin films with a nanorod geometry that is less likely to
suffer from substrate clamping.
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Pyroelectric coefficients
For thin-film materials, substrate clamping can reduce the pyroelectric response to a small value compared to its
unclamped value. Thus, it may be beneficial to replace thin films with a nanorod geometry that is less likely to
suffer from substrate clamping.
Equivalent capacitance
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Figures of merit
To maximise the pyroelectric current generated for a given energy input, the FOM is:
The above figures of merit are often used for selection of materials for heat and infra-red detection, but these are not to be
confused with energy harvesting applications where generated energy or power is a key criterion as well as the overall
efficiency of the conversion of thermal energy to electrical energy. For pyroelectric energy harvesting, an electro-thermal
coupling factor has been defined to estimate the effectiveness of thermal harvesting:
Note that these static definitions of figures of merit do not take into account the transient nature of heat transfer and dielectric
losses.
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165
The Carnot cycle for pyroelectric energy harvesting faces significant practical limitations, for example the need
for adiabatic temperature changes and two isothermal paths. The Carnot cycle, while impractical, is often used
for comparative purposes to other cycles.
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k2 values are typically small thus the conversion efficiency is low but the electrical circuits that can be employed are
relatively simple.
One limitation of using simple resistive loading and applying no external electric field is that if a ferroelectric is subjected
to temperatures above the Curie temperature, there will be depolarisation of the material. When the ferroelectric is
subsequently re-cooled below TC, in the absence of an applied electric field, there is no longer any net polarisation
(and therefore no pyroelectric behaviour) since the ferroelectric domains are now randomly aligned. For this reason, while
high pyroelectric activity takes place around the ferroelectric to paraelectric phase transition, resistive generators using
ferroelectrics tend to be limited to temperatures below the Curie temperature and transform only a fraction of the
available heat into electricity
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The synchronised electric charge extraction process involves extracting the charge generated when the maximum temperature is
reached and the stored energy is at a maximum and extracting the charge again when the temperature is a minimum
This cycle is more efficient than resistive cycle and has advantages in that voltage control is not required and no pre-determination
of working temperatures or their control is necessary
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In this case the voltage on the pyroelectric material is switched on an inductor at each maximum or minimum temperature so that
the electric field is rapidly reversed at low loss.
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170
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Hybrid generators
Combining pyroelectric and piezoelectric energy harvesting capabilities
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Hybrid generators
Hybrid generators
End of Lecture 9
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Energy storage
Batteries and electrochemical capacitors have been traditionally employed as power sources for electronic devices where
wired power sources are undesirable or not an option.
The diminishing size of electronic devices has necessitated new means to power them, and energy harvesting from ambient
sources has been identified as one of the key means of achieving self-powered autonomous devices. However, even then,
effective intermediate energy storage is required for all energy harvesting concepts, due to the varying availability of
ambient energy and varying energy requirements of the device.
Microenergy storage devices, such as microbatteries and supercapacitors, can be used in conjunction with one or more
energy harvesters to provide permanent power to autonomous wireless systems. The energy storage system can be chosen
depending on the availability/amount of harvestable energy and the efficiency of the energy harvesting mechanism.
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Energy storage
A capacitor is a device to store the charge in an electric
circuit. It is made up of two conductors separated by a
dielectric material.
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Batteries
Batteries are galvanic cells in which chemical energy from electrochemical reactions is converted to electrical energy that
can be harnessed externally. They contain two chemically different electrodes sandwiching an ion-conducting electrolyte
phase. Upon electrical connection to a load, chemical reactions occur and ions travel across the electrolyte. A
spontaneous flow of electrons occurs in the external circuit from the electrode with the more negative potential to the
more positive electrode, and can therefore be used to power a load such as a device
The energy is typically reported in units of joules (J) or watt-hours (Wh). The total amount of charge extracted from the
battery, or how much that can be stored in the cell, is known as the capacity typically reported as amp-hours (Ah) or
coulombs (C).
These quantities can be normalized with respect to weight, volume, and footprint area. For e.g, electrochemical storage
energy is primarily quantified in terms of the specific energy (Wh/g), the amount of energy stored per unit volume
(Wh/cm3), and the energy stored per unit footprint area occupied on a substrate (Wh/cm2). When comparing
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microdevices the constrained unit is most often the footprint area occupied on a substrate.
Batteries - basics
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Batteries - basics
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Batteries
Primary batteries are those in which the electrochemical reaction is not reversible. They can produce current immediately
on assembly. A primary cell is not rechargeable because the chemical reactions are not reversible and active materials may
not return to their original forms. For e.g. alkaline batteries dependent on the reaction between Zn and MnO2.
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Batteries
Secondary batteries are also known as rechargeable batteries because their electrochemical reactions are electrically
reversible. For e.g. a Li-ion battery in which Li ions move from the negative electrode to the positive electrode during
discharge, and reversely when charging. During discharge the negative electrode is the anode where oxidation takes place
and during charge it turns into the cathode where reduction takes place.
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Li-ion Batteries
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Microbatteries Materials?
Microbattery electrode and electrolyte chemistries are in most cases indistinguishable from those of macrobatteries, the
resulting microbattery performance does not usually scale proportionally because the configurations, materials deposition
and packaging methods used to assemble macrobatteries and are not often feasible in the micro-scale.
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2D Microbatteries
Two-dimensional microbatteries generally are cells configured from successive film depositions, either in planar or stacked
arrangements.
Most thin film, solid-state batteries are fabricated using physical vapor deposition (PVD) tools that deposit materials onto a
substrate via condensation from its vapor phase. PVD tools that have been used for thin film batteries include sputtering
and pulse laser deposition.
Commercial thin film batteries are typically a few cm2 in footprint area with capacities ranging from 10 Ah/cm2 to
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1 mAh/cm2.
2D Microbatteries
Thin film deposition processes can be modified to deposit batteries with active areas under 1 mm2. These processes are
compatible with standard microfabrication methods, and thus thin-film microbatteries can be deposited while
concurrently patterning other wafer-scale components onto the same substrate. Multiple thin-film microbatteries can be
patterned in series and parallel configurations to match voltage and current requirements.
Thick-film microbatteries
Thick film microbatteries have electrode components with thicknesses that are at least an order of magnitude greater
than thin film batteries, but still much thinner than button and coin cell macrobatteries. Therefore, like thin film
microbatteries, thick film microbatteries can be embedded into or on substrates in an inconspicuous fashion.
A commercial solar cell was used to charge a prototype microbattery and more than 2,300 recurring pulse discharges were
extracted from the microbattery without performance degradation. One of the first reported implementations of hybrid
power supply combining an energy harvester with a microbattery in 2006.
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Performance of 2D microbatteries
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3D microbatteries
3D microbatteries function identically to 2D microbatteries, but enhanced electrochemical performance can be achieved
due to the larger amount of electrode and electrolyte interfaces possible, while maintaining short ion transport distances
between electrodes. As a consequence, large areal energy densities are achievable without sacrificing high rate
power performance.
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Performance of 3D microbatteries
End of Lecture 10
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Supercapacitors
Supercapacitors, or electrochemical capacitors, do not have a conventional solid dielectric. Rather, electrostatic storage is
achieved by separation of charge in a Helmholtz double layer at the interface between a conductive electrode and an
electrolyte.
While supercapacitors have energy densities that are approximately 10% of conventional batteries, their power density is
generally 10 to 100 times greater. This results in much shorter charge/discharge cycles than batteries. Additionally, they
will tolerate many more charge and discharge cycles than batteries
Supercapacitors are limited in energy density compared to batteries, but may be appropriate for scenarios requiring
frequent, high-power pulse operation. Can be used in conjunction with batteries to address energy storage needs199of
autonomous systems.
Supercapacitors - background
Conventional capacitors consist of two conducting electrodes separated by an insulating dielectric material. When a voltage
is applied to a capacitor, opposite charges accumulate on the surfaces of each electrode. The charges are kept separate by
the dielectric, thus producing an electric field that allows the capacitor to store energy.
The internal components of the capacitor (e.g., current
collectors, electrodes, and dielectric material) also contribute
to the resistance, which is measured in aggregate by a quantity
known as the equivalent series resistance (ESR). The voltage
during discharge is determined by these resistances. When
measured at matched impedance (R = ESR), the maximum
power Pmax for a capacitor is given by
Conventional capacitors have relatively high power densities, but relatively low energy densities when compared to
electrochemical batteries and to fuel cells.
Supercapacitors are governed by the same basic principles as conventional capacitors. However, they incorporate electrodes
with much higher surface areas A and much thinner dielectrics that decrease the distance D between the electrodes.
Furthermore, by maintaining the low ESR characteristic of conventional capacitors, supercapacitors also are able to achieve
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comparable power densities.
1. power source, 2. collector, 3.polarized electrode, 4. Helmholtz double layer, 5. electrolyte having positive
and negative ions, 6. Separator
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Non-Faradaic
The performance characteristics of an EDLC can be adjusted by changing the nature of its electrolyte. An EDLC can utilize either
an aqueous or organic electrolyte. Aqueous electrolytes, such as H2SO4 and KOH, generally have lower ESR and lower
minimum pore size requirements compared to organic electrolytes, such as acetonitrile. However, aqueous electrolytes also
have lower breakdown voltages. Therefore, in choosing between an aqueous or organic electrolyte, one must consider the
tradeoffs between capacitance, ESR, and voltage.
While the nature of the electrolyte is of great importance in supercapacitor design, the subclasses of EDLCs are distinguished
primarily by the form of carbon they use as an electrode material. Carbon electrode materials generally have higher surface
area, lower cost, and more established fabrication techniques than other commonly used electrode materials such as
conductive polymers and metal oxides.
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Supercapacitor pseudocapacitance
Significantly higher capacitance can be achieved by using pseudocapacitive electrode materials. Unlike high surface area
carbon electrodes, which derive their storage capacity from the electrostatic arrangement of electrolyte ions along their
electrode-electrolyte interfaces, pseudocapacitive materials store energy through Faradaic reactions at these regions.
The redox reactions are reversible within reasonable voltage ranges, thus generally, pseudocapacitive electrodes provide
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higher capacitance in exchange for cycle life and power density.
electrochemical double-layer
204
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Benefiting from the fast reversible Faradaic charge transfer reaction, a higher energy density than EDLCs is delivered by
pseudo-capacitors. The pseudo-capacitive mechanism mainly points to the fast redox reaction carried out at the electrode
surface. Since the surface redox reactions occur only in the top few nanometers in the electrodes surface, nanoengineering
techniques play a significant role in enhancing pseudo-capacitive properties.
RuO2, an intensively studied pseudo-capacitive electrode with good conductivity, has been the focal point of both the academic
and industrial communities in recent decades. The fast and reversible electron transfer reaction on RuO2 electrode
accompanied by the electro-adsorption of protons in acidic electrolyte can be expressed by:
Supercapacitor materials
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Supercapacitor classification
Each class is characterized by its unique mechanism for storing charge. These are, respectively, non-Faradaic, Faradaic, and a
combination of the two. Faradaic processes, such as oxidation-reduction reactions, involve the transfer of charge between
electrode and electrolyte. A non-Faradaic mechanism, by contrast, does not use a chemical mechanism. Rather, charges are
210
distributed on surfaces by physical processes that do not involve the making or breaking of chemical bonds.
Hybrid Supercapacitor
Hybrid capacitors attempt to exploit the relative advantages and mitigate the relative disadvantages of EDLCs and
pseudocapacitors to realize better performance characteristics. Utilizing both Faradaic and non-Faradaic processes to store
charge, hybrid capacitors have achieved energy and power densities greater than EDLCs without the sacrifices in cycling
stability and affordability that have limited the success of pseudocapacitors
1. Composite electrodes integrate carbon-based materials with either conducting polymer or metal oxide materials and
incorporate both physical and chemical charge storage mechanisms together in a single electrode. The carbon-based materials
facilitate a capacitive double-layer of charge and also provide a high-surface-area backbone that increases the contact
between the deposited pseudocapacitive materials and electrolyte. The pseudocapacitive materials are able to further
increase the capacitance of the composite electrode through Faradaic reactions. Composite electrodes constructed from
carbon nanotubes and polypyrrole, a conducting polymer, have been particularly successful
2. Asymmetric hybrids combine Faradaic and non-Faradaic processes by coupling an EDLC electrode with a pseudocapacitor
electrode. In particular, the coupling of an activated carbon negative electrode with a conducting polymer positive electrode
has received a great deal of attention. The implementation of a negatively charged, activated carbon electrode attempts to
circumvent the lack of an efficient, negatively charged, conducting polymer material.
3. Battery-type hybrids are unique in coupling a supercapacitor electrode with a battery electrode. This specialized
configuration reflects the demand for higher energy supercapacitors and higher power batteries, combining the energy
characteristics of batteries with the power, cycle life, and recharging times of supercapacitors.
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Hybrid Supercapacitor
212
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Supercapacitor microfabrication
Thin film supercapacitor research has largely benefited from the advances in thin film battery research, so parallel trends
in the fabrication processes are often seen.
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End of Lecture 11
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Micropower management
Energy harvesters can be broadly categorized in two groups:
- Thermoelectric generators and PV cells generate a variable DC-output voltage. They require a DCDC-converter with a
variable conversion factor and a controller to provide the battery or the electronics with the correct bias.
- Vibrational energy harvesters on the other hand produce an AC-output voltage. These harvesters require first a
rectifying ACDC-converter stage.
Furthermore, each energy harvester has an operation point where the extracted electrical energy has a maximum. This
maximum power point depends on the individual properties of the energy harvester. Maximum power is achieved by
adapting the input impedance to the maximum power point of the harvester. A controller is required to achieve this.
When the harvester generates less energy than the energy used by the controller and the converters, the power
management system has to shut down and ensure that it does not discharge the output. When there is again sufficient
power available, the power management system has to start up again autonomously. Finally, a battery management
circuit can be needed to ensure safe operating conditions when a battery is charged at the output.
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Maximum power transfer occurs in the case where the load impedance is equal to the source impedance.
However, in an energy-harvester, the definition of the impedance of the source to which the load should be matched is not
generally as trivial as matching the load to a single electrical impedance. The source impedance will be dependent upon the
type of energy harvester used and the conditions under which the harvester operates.
It is therefore useful to specify that the input impedance of the interface circuit to the transducer must be controllable.
Examples of impedance-matching devices include: transformers [turns ratio = (source resistance/ load resistance)],
resistive networks (voltage divider), filters (perfect impedance matching at specific frequencies).
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Standard Dickson 4-stage charge pump: When I1 is low, D1 will charge C1 to Vin. When I1 goes high the top plate of C1 is
pushed up to 2Vin. D1 is then turned off and D2 turned on and C2 begins to charge to 2Vin. On the next clock cycle, I1 goes
low while I2 goes high pushing the top plate of C2 to 3Vin. D2 switches off and D3 switches on, charging C3 to 3Vin and so
on with charge passing up the chain. The final diode-capacitor cell in the cascade is connected to ground rather than a
clock phase and hence is not a multiplier; it is a peak detector which merely provides smoothing
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Half-wave rectification
223
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Micropower management
Bringing it all together!
Block diagram of the capacitive charge pump based power management circuit for converting thermoelectric power
(Doms I, Merken P, Mertens R, Van Hoof C. A capacitive power-management circuit for micropower thermoelectric generators with a
2.1 PW controller. Presented at ISSCC 2008.)
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Micropower management
Control circuit consumes <7 PA
Bennett DA, Selfridge RH, Harb JN, Comer DT. A control circuit for a microsensor hybrid power supply. IEEE Trans Ind Electron 2004;51:7480.
Guyomar D, Badel A, Lefeuvre E, Richard C. Toward energy harvesting using active materials and conversion improvement by nonlinear
processing. IEEE Trans Ultrason Ferroelect Freq Control 2005;52:58495.
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A power source will deliver its maximum power to a load when the load has the same impedance as the internal impedance of
the power source. Unfortunately, batteries are far from the ideal load for a solar array and the mismatch results in major
efficiency losses.
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The maximum power point can change substantially depending on external parameters. It is essential to track the
maximum power point for efficient power transfer, as the operating characteristic of the solar cell changes constantly.
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MPPT matches the voltage of the solar cell at the specified maximum power point (MPP) to the varying battery voltage as
the battery charges up.
Perturb and observe is the most commonly used MPPT method due to its ease of implementation. The controller adjusts
the voltage by a small amount from the array and measures power; if the power increases, further adjustments in that
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direction are tried until power no longer increases.
Sleep/ Standby - the WSN may be consuming as little as 100-300W and can wake-up quickly unless the main crystal
oscillator is turned off.
Listen - the WSN is listening for a packet to arrive, so most of the radio receiver must be on. State-of-the-art power numbers
for WSN communication modules in this mode are within a range from 9 - 40 mW.
Active Rx Receive state, similar to the Listen state, but use of additional circuitry may push power consumption for
transceiver to 50 mW.
Active Tx - in the transmit state, the WSNs active components include the RF power amplifier, which often dominates in highpower transmit systems. State-of-the-art power consumption for SN transceiver module is on average 40mW.
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Duty cycling - consists of waking up the WSN only for the time needed to acquire a new set of samples and then
powering it off immediately afterwards
Adaptive-sensing strategy - is being able to dynamically change the WSN activity to the real dynamics of the process.
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Common network topologies for sensor networks (a) star, (b) tree, with a mix of node types, and (c) mesh with a number of
homogenous nodes.
The software that a node executesincluding the communication protocol, application, and operating systemmust all be
energy-aware, and should be designed to maximize the useful life of the node and of the network as a whole. Energy-aware
design affects every layer of the communication stack, from the modulation scheme used in the physical layer to the highlevel protocols in the application layer.
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, Ptx is the transmission power consumption, Prx is the receive power consumption,
d is the separation distance between the source and sink nodes, is the wavelength, is the path loss exponent
(representing the rate at which the path loss increases with distance), and H is the number of hops.
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End of Lecture 12
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