In electrochemistry, a thermogalvanic cell is a kind of galvanic cell in which heat is employed to provide electrical power directly. [1] [2] These cells are electrochemical cells in which the two electrodes are deliberately maintained at different temperatures. This temperature difference generates a potential difference between the electrodes. [3] [4] The electrodes can be of identical composition and the electrolyte solution homogeneous. This is usually the case in these cells. [5] This is in contrast to galvanic cells in which electrodes and/or solutions of different compositions provide the electromotive potential. As long as there is a difference in temperature between the electrodes a current will flow through the circuit. A thermogalvanic cell can be seen as analogous to a concentration cell but instead of running on differences in the concentration/pressure of the reactants they make use of differences in the "concentrations" of thermal energy. [6] [7] [8] The principal application of thermogalvanic cells is the production of electricity from low-temperature heat sources (waste heat and solar heat). Their energetic efficiency is low, in the range of 0.1% to 1% for conversion of heat into electricity. [7]
The use of heat to empower galvanic cells was first studied around 1880. [9] However it was not until the decade of 1950 that more serious research was undertaken in this field. [3]
Thermogalvanic cells are a kind of heat engine. Ultimately the driving force behind them is the transport of entropy from the high temperature source to the low temperature sink. [10] Therefore, these cells work thanks to a thermal gradient established between different parts of the cell. Because the rate and enthalpy of chemical reactions depend directly on the temperature, different temperatures at the electrodes imply different chemical equilibrium constants. This translates into unequal chemical equilibrium conditions on the hot side and on the cold side. The thermocell tries to approach a homogeneous equilibrium and, in doing so, produces a flow of chemical species and electrons. The electrons flow through the path of least resistance (the outer circuit) making it possible to extract power from the cell.
Different thermogalvanic cells have been constructed attending to their uses and properties. Usually they are classified according to the electrolyte employed in each specific type of cell.
In these cells the electrolyte between the electrodes is a water solution of some salt or hydrophylic compound. [5] An essential property of these compounds is that they must be able to undergo redox reactions in order to shuttle electrons from one electrode to the other during the cell operation.
The electrolyte is a solution of some other solvent different from water. [5] Solvents like methanol, acetone, dimethyl sulphoxide and dimethyl formamide have been successfully employed in thermogalvanic cells running on copper sulfate. [11]
In this type of thermocell the electrolyte is some kind of salt with a relatively low melting point. Their use solves two problems. On one hand the temperature range of the cell is much larger. This is an advantage as these cells produce more power the larger the difference between the hot and cold sides. On the other hand, the liquid salt directly provides the anions and cations necessary for sustainment of a current through the cell. Therefore, no additional current-carrying compounds are necessary as the melted salt is the electrolyte itself. [12] Typical hot source temperatures are between 600–900 K, but can get as high as 1730 K. Cold sink temperatures are in the 400–500 K range.
Thermocells in which the electrolyte connecting the electrodes is an ionic material have been considered and constructed too. [5] The temperature range is also elevated as compared to liquid electrolytes. Studied systems fall in the 400–900 K. Some solid ionic materials that have been employed to construct thermogalvanic cells are AgI, PbCl2 and PbBr2.
Given the advantages provided by the working mechanism of thermogalvanic cells, their main application is electricity production under conditions where there is an excess of heat available. In particular thermogalvanic cells are being used to produce electricity in the following areas.
The heat collected from this process generates steam, which can be used in a conventional steam turbine system to make electricity. In contrast to the low-temperature solar thermal systems that are used for air or water heating in domestic or commercial buildings, these solar thermal electricity plants operate at high temperatures, requiring both concentrated sunlight and a large collection area, making the Moroccan desert an ideal location.
This is an alternative approach to the more widely used “photovoltaic” technology for producing electricity from sunlight. In a photovoltaic system, the sunlight is absorbed in the photovoltaic device (commonly called a solar cell) and energy is passed to electrons in the material, converting the solar energy directly into electricity. Sometimes, solar thermal electricity and photovoltaics are portrayed as competing technologies and, while this may be true when deciding on the way forward for a specific site, in general they are complementary, using solar energy as extensively as possible.
Thermogalvanic cells can be used to extract a useful quantity of energy from waste heat sources even when the temperature gradient is less than 100C (sometimes only a few tens of degrees). This is often the case in many industrial areas. [13]
Electrochemistry is the branch of physical chemistry concerned with the relationship between electrical potential difference and identifiable chemical change. These reactions involve electrons moving via an electronically conducting phase between electrodes separated by an ionically conducting and electronically insulating electrolyte.
An electrochemical cell is a device that generates electrical energy from chemical reactions. Electrical energy can also be applied to these cells to cause chemical reactions to occur. Electrochemical cells that generate an electric current are called voltaic or galvanic cells and those that generate chemical reactions, via electrolysis for example, are called electrolytic cells.
A galvanic cell or voltaic cell, named after the scientists Luigi Galvani and Alessandro Volta, respectively, is an electrochemical cell in which an electric current is generated from spontaneous oxidation–reduction reactions. An example of a galvanic cell consists of two different metals, each immersed in separate beakers containing their respective metal ions in solution that are connected by a salt bridge or separated by a porous membrane.
In electrochemistry, standard electrode potential, or , is a measure of the reducing power of any element or compound. The IUPAC "Gold Book" defines it as; "the value of the standard emf of a cell in which molecular hydrogen under standard pressure is oxidized to solvated protons at the left-hand electrode".
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Water splitting is the chemical reaction in which water is broken down into oxygen and hydrogen:
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In electrochemistry, overpotential is the potential difference (voltage) between a half-reaction's thermodynamically determined reduction potential and the potential at which the redox event is experimentally observed. The term is directly related to a cell's voltage efficiency. In an electrolytic cell the existence of overpotential implies that the cell requires more energy than thermodynamically expected to drive a reaction. In a galvanic cell the existence of overpotential means less energy is recovered than thermodynamics predicts. In each case the extra/missing energy is lost as heat. The quantity of overpotential is specific to each cell design and varies across cells and operational conditions, even for the same reaction. Overpotential is experimentally determined by measuring the potential at which a given current density is achieved.
An alkali-metal thermal-to-electric converter is a thermally regenerative electrochemical device for the direct conversion of heat to electrical energy. It is characterized by high potential efficiencies and no moving parts except for the working fluid, which make it a candidate for space power applications.
In battery technology, a concentration cell is a limited form of a galvanic cell that has two equivalent half-cells of the same composition differing only in concentrations. One can calculate the potential developed by such a cell using the Nernst equation. A concentration cell produces a small voltage as it attempts to reach chemical equilibrium, which occurs when the concentration of reactant in both half-cells are equal. Because an order of magnitude concentration difference produces less than 60 millivolts at room temperature, concentration cells are not typically used for energy storage.
A thermoelectric generator (TEG), also called a Seebeck generator, is a solid state device that converts heat directly into electrical energy through a phenomenon called the Seebeck effect. Thermoelectric generators function like heat engines, but are less bulky and have no moving parts. However, TEGs are typically more expensive and less efficient. When the same principle is used in reverse to create a heat gradient from an electric current, it is called a thermoelectric cooler.
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The Glossary of fuel cell terms lists the definitions of many terms used within the fuel cell industry. The terms in this fuel cell glossary may be used by fuel cell industry associations, in education material and fuel cell codes and standards to name but a few.
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