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Thursday, August 8, 2024

Fuel cell

From Wikipedia, the free encyclopedia

https://en.wikipedia.org/wiki/Fuel_cell

A fuel cell is an electrochemical cell that converts the chemical energy of a fuel (often hydrogen) and an oxidizing agent (often oxygen) into electricity through a pair of redox reactions. Fuel cells are different from most batteries in requiring a continuous source of fuel and oxygen (usually from air) to sustain the chemical reaction, whereas in a battery the chemical energy usually comes from substances that are already present in the battery. Fuel cells can produce electricity continuously for as long as fuel and oxygen are supplied.

The first fuel cells were invented by Sir William Grove in 1838. The first commercial use of fuel cells came almost a century later following the invention of the hydrogen–oxygen fuel cell by Francis Thomas Bacon in 1932. The alkaline fuel cell, also known as the Bacon fuel cell after its inventor, has been used in NASA space programs since the mid-1960s to generate power for satellites and space capsules. Since then, fuel cells have been used in many other applications. Fuel cells are used for primary and backup power for commercial, industrial and residential buildings and in remote or inaccessible areas. They are also used to power fuel cell vehicles, including forklifts, automobiles, buses, trains, boats, motorcycles, and submarines.

There are many types of fuel cells, but they all consist of an anode, a cathode, and an electrolyte that allows ions, often positively charged hydrogen ions (protons), to move between the two sides of the fuel cell. At the anode, a catalyst causes the fuel to undergo oxidation reactions that generate ions (often positively charged hydrogen ions) and electrons. The ions move from the anode to the cathode through the electrolyte. At the same time, electrons flow from the anode to the cathode through an external circuit, producing direct current electricity. At the cathode, another catalyst causes ions, electrons, and oxygen to react, forming water and possibly other products. Fuel cells are classified by the type of electrolyte they use and by the difference in start-up time ranging from 1 second for proton-exchange membrane fuel cells (PEM fuel cells, or PEMFC) to 10 minutes for solid oxide fuel cells (SOFC). A related technology is flow batteries, in which the fuel can be regenerated by recharging. Individual fuel cells produce relatively small electrical potentials, about 0.7 volts, so cells are "stacked", or placed in series, to create sufficient voltage to meet an application's requirements. In addition to electricity, fuel cells produce water vapor, heat and, depending on the fuel source, very small amounts of nitrogen dioxide and other emissions. PEMFC cells generally produce fewer nitrogen oxides than SOFC cells: they operate at lower temperatures, use hydrogen as fuel, and limit the diffusion of nitrogen into the anode via the proton exchange membrane, which forms NOx. The energy efficiency of a fuel cell is generally between 40 and 60%; however, if waste heat is captured in a cogeneration scheme, efficiencies of up to 85% can be obtained.

History

The number of patent families (solid lines) and non-patent publications about different electrochemical powersources by year. Also shown as the magenta line is the inflation-adjusted oil price in US$/liter in linear scale.

The first references to hydrogen fuel cells appeared in 1838. In a letter dated October 1838 but published in the December 1838 edition of The London and Edinburgh Philosophical Magazine and Journal of Science, Welsh physicist and barrister Sir William Grove wrote about the development of his first crude fuel cells. He used a combination of sheet iron, copper, and porcelain plates, and a solution of sulphate of copper and dilute acid.In a letter to the same publication written in December 1838 but published in June 1839, German physicist Christian Friedrich Schönbein discussed the first crude fuel cell that he had invented. His letter discussed the current generated from hydrogen and oxygen dissolved in water. Grove later sketched his design, in 1842, in the same journal. The fuel cell he made used similar materials to today's phosphoric acid fuel cell.

In 1932, English engineer Francis Thomas Bacon successfully developed a 5 kW stationary fuel cell. NASA used the alkaline fuel cell (AFC), also known as the Bacon fuel cell after its inventor, from the mid-1960s.

In 1955, W. Thomas Grubb, a chemist working for the General Electric Company (GE), further modified the original fuel cell design by using a sulphonated polystyrene ion-exchange membrane as the electrolyte. Three years later another GE chemist, Leonard Niedrach, devised a way of depositing platinum onto the membrane, which served as a catalyst for the necessary hydrogen oxidation and oxygen reduction reactions. This became known as the "Grubb-Niedrach fuel cell". GE went on to develop this technology with NASA and McDonnell Aircraft, leading to its use during Project Gemini. This was the first commercial use of a fuel cell. In 1959, a team led by Harry Ihrig built a 15 kW fuel cell tractor for Allis-Chalmers, which was demonstrated across the U.S. at state fairs. This system used potassium hydroxide as the electrolyte and compressed hydrogen and oxygen as the reactants. Later in 1959, Bacon and his colleagues demonstrated a practical five-kilowatt unit capable of powering a welding machine. In the 1960s, Pratt & Whitney licensed Bacon's U.S. patents for use in the U.S. space program to supply electricity and drinking water (hydrogen and oxygen being readily available from the spacecraft tanks). In 1991, the first hydrogen fuel cell automobile was developed by Roger E. Billings.

UTC Power was the first company to manufacture and commercialize a large, stationary fuel cell system for use as a cogeneration power plant in hospitals, universities and large office buildings.

In recognition of the fuel cell industry and America's role in fuel cell development, the United States Senate recognized October 8, 2015 as National Hydrogen and Fuel Cell Day, passing S. RES 217. The date was chosen in recognition of the atomic weight of hydrogen (1.008).

Types of fuel cells; design

Fuel cells come in many varieties; however, they all work in the same general manner. They are made up of three adjacent segments: the anode, the electrolyte, and the cathode. Two chemical reactions occur at the interfaces of the three different segments. The net result of the two reactions is that fuel is consumed, water or carbon dioxide is created, and an electric current is created, which can be used to power electrical devices, normally referred to as the load.

At the anode a catalyst ionizes the fuel, turning the fuel into a positively charged ion and a negatively charged electron. The electrolyte is a substance specifically designed so ions can pass through it, but the electrons cannot. The freed electrons travel through a wire creating an electric current. The ions travel through the electrolyte to the cathode. Once reaching the cathode, the ions are reunited with the electrons and the two react with a third chemical, usually oxygen, to create water or carbon dioxide.

Design features in a fuel cell include:

The electrolyte substance, which usually defines the type of fuel cell, and can be made from a number of substances like potassium hydroxide, salt carbonates, and phosphoric acid.
The fuel that is used. The most common fuel is hydrogen.
The anode catalyst, usually fine platinum powder, breaks down the fuel into electrons and ions.
The cathode catalyst, often nickel, converts ions into waste chemicals, with water being the most common type of waste.
Gas diffusion layers that are designed to resist oxidization.

A typical fuel cell produces a voltage from 0.6 to 0.7 V at a full-rated load. Voltage decreases as current increases, due to several factors:

Activation loss
Ohmic loss (voltage drop due to resistance of the cell components and interconnections)
Mass transport loss (depletion of reactants at catalyst sites under high loads, causing rapid loss of voltage).

To deliver the desired amount of energy, the fuel cells can be combined in series to yield higher voltage, and in parallel to allow a higher current to be supplied. Such a design is called a fuel cell stack. The cell surface area can also be increased, to allow higher current from each cell.

Proton-exchange membrane fuel cells

Condensation of water produced by a PEMFC on the air channel wall. The gold wire around the cell ensures the collection of electric current.

In the archetypical hydrogen–oxide proton-exchange membrane fuel cell (PEMFC) design, a proton-conducting polymer membrane (typically nafion) contains the electrolyte solution that separates the anode and cathode sides. This was called a solid polymer electrolyte fuel cell (SPEFC) in the early 1970s, before the proton-exchange mechanism was well understood. (Notice that the synonyms polymer electrolyte membrane and proton-exchange mechanism result in the same acronym.)

On the anode side, hydrogen diffuses to the anode catalyst where it later dissociates into protons and electrons. These protons often react with oxidants causing them to become what are commonly referred to as multi-facilitated proton membranes. The protons are conducted through the membrane to the cathode, but the electrons are forced to travel in an external circuit (supplying power) because the membrane is electrically insulating. On the cathode catalyst, oxygen molecules react with the electrons (which have traveled through the external circuit) and protons to form water.

In addition to this pure hydrogen type, there are hydrocarbon fuels for fuel cells, including diesel, methanol (see: direct-methanol fuel cells and indirect methanol fuel cells) and chemical hydrides. The waste products with these types of fuel are carbon dioxide and water. When hydrogen is used, the CO₂ is released when methane from natural gas is combined with steam, in a process called steam methane reforming, to produce the hydrogen. This can take place in a different location to the fuel cell, potentially allowing the hydrogen fuel cell to be used indoors—for example, in forklifts.

The different components of a PEMFC are

bipolar plates,
electrodes,
catalyst,
membrane, and
the necessary hardware such as current collectors and gaskets.

The materials used for different parts of the fuel cells differ by type. The bipolar plates may be made of different types of materials, such as, metal, coated metal, graphite, flexible graphite, C–C composite, carbon–polymer composites etc. The membrane electrode assembly (MEA) is referred to as the heart of the PEMFC and is usually made of a proton-exchange membrane sandwiched between two catalyst-coated carbon papers. Platinum and/or similar types of noble metals are usually used as the catalyst for PEMFC, and these can be contaminated by carbon monoxide, necessitating a relatively pure hydrogen fuel. The electrolyte could be a polymer membrane.

Proton-exchange membrane fuel cell design issues

Cost: In 2013, the Department of Energy estimated that 80 kW automotive fuel cell system costs of US$67 per kilowatt could be achieved, assuming volume production of 100,000 automotive units per year and US$55 per kilowatt could be achieved, assuming volume production of 500,000 units per year. Many companies are working on techniques to reduce cost in a variety of ways including reducing the amount of platinum needed in each individual cell. Ballard Power Systems has experimented with a catalyst enhanced with carbon silk, which allows a 30% reduction (1.0–0.7 mg/cm²) in platinum usage without reduction in performance. Monash University, Melbourne uses PEDOT as a cathode. A 2011-published study documented the first metal-free electrocatalyst using relatively inexpensive doped carbon nanotubes, which are less than 1% the cost of platinum and are of equal or superior performance. A recently published article demonstrated how the environmental burdens change when using carbon nanotubes as carbon substrate for platinum.
Water and air management(in PEMFCs): In this type of fuel cell, the membrane must be hydrated, requiring water to be evaporated at precisely the same rate that it is produced. If water is evaporated too quickly, the membrane dries, the resistance across it increases, and eventually, it will crack, creating a gas "short circuit" where hydrogen and oxygen combine directly, generating heat that will damage the fuel cell. If the water is evaporated too slowly, the electrodes will flood, preventing the reactants from reaching the catalyst and stopping the reaction. Methods to manage water in cells are being developed like electroosmotic pumps focusing on flow control. Just as in a combustion engine, a steady ratio between the reactant and oxygen is necessary to keep the fuel cell operating efficiently.
Temperature management: The same temperature must be maintained throughout the cell in order to prevent destruction of the cell through thermal loading. This is particularly challenging as the 2H₂ + O₂ → 2H₂O reaction is highly exothermic, so a large quantity of heat is generated within the fuel cell.
Durability, service life, and special requirements for some type of cells: Stationary fuel cell applications typically require more than 40,000 hours of reliable operation at a temperature of −35 to 40 °C (−31 to 104 °F), while automotive fuel cells require a 5,000-hour lifespan (the equivalent of 240,000 km or 150,000 mi) under extreme temperatures. Current service life is 2,500 hours (about 120,000 km or 75,000 mi). Automotive engines must also be able to start reliably at −30 °C (−22 °F) and have a high power-to-volume ratio (typically 2.5 kW/L).
Limited carbon monoxide tolerance of some (non-PEDOT) cathodes.

Phosphoric acid fuel cell

Phosphoric acid fuel cells (PAFCs) were first designed and introduced in 1961 by G. V. Elmore and H. A. Tanner. In these cells, phosphoric acid is used as a non-conductive electrolyte to pass protons from the anode to the cathode and to force electrons to travel from anode to cathode through an external electrical circuit. These cells commonly work in temperatures of 150 to 200 °C. This high temperature will cause heat and energy loss if the heat is not removed and used properly. This heat can be used to produce steam for air conditioning systems or any other thermal energy-consuming system. Using this heat in cogeneration can enhance the efficiency of phosphoric acid fuel cells from 40 to 50% to about 80%. Since the proton production rate on the anode is small, platinum is used as a catalyst to increase this ionization rate. A key disadvantage of these cells is the use of an acidic electrolyte. This increases the corrosion or oxidation of components exposed to phosphoric acid.

Solid acid fuel cell

Solid acid fuel cells (SAFCs) are characterized by the use of a solid acid material as the electrolyte. At low temperatures, solid acids have an ordered molecular structure like most salts. At warmer temperatures (between 140 and 150 °C for CsHSO₄), some solid acids undergo a phase transition to become highly disordered "superprotonic" structures, which increases conductivity by several orders of magnitude. The first proof-of-concept SAFCs were developed in 2000 using cesium hydrogen sulfate (CsHSO₄). Current SAFC systems use cesium dihydrogen phosphate (CsH₂PO₄) and have demonstrated lifetimes in the thousands of hours.

Alkaline fuel cell

The alkaline fuel cell (AFC) or hydrogen-oxygen fuel cell was designed and first demonstrated publicly by Francis Thomas Bacon in 1959. It was used as a primary source of electrical energy in the Apollo space program. The cell consists of two porous carbon electrodes impregnated with a suitable catalyst such as Pt, Ag, CoO, etc. The space between the two electrodes is filled with a concentrated solution of KOH or NaOH which serves as an electrolyte. H₂ gas and O₂ gas are bubbled into the electrolyte through the porous carbon electrodes. Thus the overall reaction involves the combination of hydrogen gas and oxygen gas to form water. The cell runs continuously until the reactant's supply is exhausted. This type of cell operates efficiently in the temperature range 343–413 K (70 -140 °C) and provides a potential of about 0.9 V. Alkaline anion exchange membrane fuel cell (AAEMFC) is a type of AFC which employs a solid polymer electrolyte instead of aqueous potassium hydroxide (KOH) and it is superior to aqueous AFC.

High-temperature fuel cells

Solid oxide fuel cell

Solid oxide fuel cells (SOFCs) use a solid material, most commonly a ceramic material called yttria-stabilized zirconia (YSZ), as the electrolyte. Because SOFCs are made entirely of solid materials, they are not limited to the flat plane configuration of other types of fuel cells and are often designed as rolled tubes. They require high operating temperatures (800–1000 °C) and can be run on a variety of fuels including natural gas.

SOFCs are unique because negatively charged oxygen ions travel from the cathode (positive side of the fuel cell) to the anode (negative side of the fuel cell) instead of protons travelling vice versa (i.e., from the anode to the cathode), as is the case in all other types of fuel cells. Oxygen gas is fed through the cathode, where it absorbs electrons to create oxygen ions. The oxygen ions then travel through the electrolyte to react with hydrogen gas at the anode. The reaction at the anode produces electricity and water as by-products. Carbon dioxide may also be a by-product depending on the fuel, but the carbon emissions from a SOFC system are less than those from a fossil fuel combustion plant. The chemical reactions for the SOFC system can be expressed as follows:

Anode reaction: 2H₂ + 2O²⁻ → 2H₂O + 4e⁻

Cathode reaction: O₂ + 4e⁻ → 2O²⁻

Overall cell reaction: 2H₂ + O₂ → 2H₂O

SOFC systems can run on fuels other than pure hydrogen gas. However, since hydrogen is necessary for the reactions listed above, the fuel selected must contain hydrogen atoms. For the fuel cell to operate, the fuel must be converted into pure hydrogen gas. SOFCs are capable of internally reforming light hydrocarbons such as methane (natural gas), propane, and butane. These fuel cells are at an early stage of development.

Challenges exist in SOFC systems due to their high operating temperatures. One such challenge is the potential for carbon dust to build up on the anode, which slows down the internal reforming process. Research to address this "carbon coking" issue at the University of Pennsylvania has shown that the use of copper-based cermet (heat-resistant materials made of ceramic and metal) can reduce coking and the loss of performance. Another disadvantage of SOFC systems is the long start-up, making SOFCs less useful for mobile applications. Despite these disadvantages, a high operating temperature provides an advantage by removing the need for a precious metal catalyst like platinum, thereby reducing cost. Additionally, waste heat from SOFC systems may be captured and reused, increasing the theoretical overall efficiency to as high as 80–85%.

The high operating temperature is largely due to the physical properties of the YSZ electrolyte. As temperature decreases, so does the ionic conductivity of YSZ. Therefore, to obtain the optimum performance of the fuel cell, a high operating temperature is required. According to their website, Ceres Power, a UK SOFC fuel cell manufacturer, has developed a method of reducing the operating temperature of their SOFC system to 500–600 degrees Celsius. They replaced the commonly used YSZ electrolyte with a CGO (cerium gadolinium oxide) electrolyte. The lower operating temperature allows them to use stainless steel instead of ceramic as the cell substrate, which reduces cost and start-up time of the system.

Molten-carbonate fuel cell

Molten carbonate fuel cells (MCFCs) require a high operating temperature, 650 °C (1,200 °F), similar to SOFCs. MCFCs use lithium potassium carbonate salt as an electrolyte, and this salt liquefies at high temperatures, allowing for the movement of charge within the cell – in this case, negative carbonate ions.

Like SOFCs, MCFCs are capable of converting fossil fuel to a hydrogen-rich gas in the anode, eliminating the need to produce hydrogen externally. The reforming process creates CO₂ emissions. MCFC-compatible fuels include natural gas, biogas and gas produced from coal. The hydrogen in the gas reacts with carbonate ions from the electrolyte to produce water, carbon dioxide, electrons and small amounts of other chemicals. The electrons travel through an external circuit, creating electricity, and return to the cathode. There, oxygen from the air and carbon dioxide recycled from the anode react with the electrons to form carbonate ions that replenish the electrolyte, completing the circuit. The chemical reactions for an MCFC system can be expressed as follows:

Anode reaction: CO₃²⁻ + H₂ → H₂O + CO₂ + 2e⁻

Cathode reaction: CO₂ + ½O₂ + 2e⁻ → CO₃²⁻

Overall cell reaction: H₂ + ½O₂ → H₂O

As with SOFCs, MCFC disadvantages include slow start-up times because of their high operating temperature. This makes MCFC systems not suitable for mobile applications, and this technology will most likely be used for stationary fuel cell purposes. The main challenge of MCFC technology is the cells' short life span. The high-temperature and carbonate electrolyte lead to corrosion of the anode and cathode. These factors accelerate the degradation of MCFC components, decreasing the durability and cell life. Researchers are addressing this problem by exploring corrosion-resistant materials for components as well as fuel cell designs that may increase cell life without decreasing performance.

MCFCs hold several advantages over other fuel cell technologies, including their resistance to impurities. They are not prone to "carbon coking", which refers to carbon build-up on the anode that results in reduced performance by slowing down the internal fuel reforming process. Therefore, carbon-rich fuels like gases made from coal are compatible with the system. The United States Department of Energy claims that coal, itself, might even be a fuel option in the future, assuming the system can be made resistant to impurities such as sulfur and particulates that result from converting coal into hydrogen. MCFCs also have relatively high efficiencies. They can reach a fuel-to-electricity efficiency of 50%, considerably higher than the 37–42% efficiency of a phosphoric acid fuel cell plant. Efficiencies can be as high as 65% when the fuel cell is paired with a turbine, and 85% if heat is captured and used in a combined heat and power (CHP) system.

FuelCell Energy, a Connecticut-based fuel cell manufacturer, develops and sells MCFC fuel cells. The company says that their MCFC products range from 300 kW to 2.8 MW systems that achieve 47% electrical efficiency and can utilize CHP technology to obtain higher overall efficiencies. One product, the DFC-ERG, is combined with a gas turbine and, according to the company, it achieves an electrical efficiency of 65%.

Electric storage fuel cell

The electric storage fuel cell is a conventional battery chargeable by electric power input, using the conventional electro-chemical effect. However, the battery further includes hydrogen (and oxygen) inputs for alternatively charging the battery chemically.

Comparison of fuel cell types

Fuel cell name	Electrolyte	Qualified power (W)	Working temperature (°C)	Efficiency		Status	Cost (USD/W)
Fuel cell name	Electrolyte	Qualified power (W)	Working temperature (°C)	Cell	System	Status	Cost (USD/W)
Electro-galvanic fuel cell	Aqueous alkaline solution		< 40			Commercial / Research	3-7
Direct formic acid fuel cell (DFAFC)	Polymer membrane (ionomer)	< 50 W	< 40			Commercial / Research	10-20
Alkaline fuel cell	Aqueous alkaline solution	10–200 kW	< 80	60–70%	62%	Commercial / Research	50-100
Proton-exchange membrane fuel cell	Polymer membrane (ionomer)	1 W – 500 kW	50–100 (Nafion) 120–200 (PBI)	50–70%	30–50%	Commercial / Research	50–100
Metal hydride fuel cell	Aqueous alkaline solution		> −20 (50% P_peak @ 0 °C)			Commercial / Research	30-200
Zinc–air battery	Aqueous alkaline solution		< 40			Mass production	150-300
Direct carbon fuel cell	Several different		700–850	80%	70%	Commercial / Research	18
Direct borohydride fuel cell	Aqueous alkaline solution		70			Commercial	400-450
Microbial fuel cell	Polymer membrane or humic acid		< 40			Research	10-50
Upflow microbial fuel cell (UMFC)			< 40			Research	1-5
Regenerative fuel cell	Polymer membrane (ionomer)		< 50			Commercial / Research	200-300
Direct methanol fuel cell	Polymer membrane (ionomer)	100 mW – 1 kW	90–120	20–30%	10–25%	Commercial / Research	125
Reformed methanol fuel cell	Polymer membrane (ionomer)	5 W – 100 kW	250–300 (reformer) 125–200 (PBI)	50–60%	25–40%	Commercial / Research	8.50
Direct-ethanol fuel cell	Polymer membrane (ionomer)	< 140 mW/cm²	> 25 ? 90–120			Research	12
Redox fuel cell^{[broken anchor]} (RFC)	Liquid electrolytes with redox shuttle and polymer membrane (ionomer)	1 kW – 10 MW				Research	12.50
Phosphoric acid fuel cell	Molten phosphoric acid (H₃PO₄)	< 10 MW	150–200	55%	40% Co-gen: 90%	Commercial / Research	4.00–4.50
Solid acid fuel cell	H⁺-conducting oxyanion salt (solid acid)	10 W – 1 kW	200–300	55–60%	40–45%	Commercial / Research	15
Molten carbonate fuel cell	Molten alkaline carbonate	100 MW	600–650	55%	45–55%	Commercial / Research	1000
Tubular solid oxide fuel cell (TSOFC)	O²⁻-conducting ceramic oxide	< 100 MW	850–1100	60–65%	55–60%	Commercial / Research	3.50
Protonic ceramic fuel cell	H⁺-conducting ceramic oxide		700			Research	80
Planar solid oxide fuel cell	O²⁻-conducting ceramic oxide	< 100 MW	500–1100	60–65%	55–60%	Commercial / Research	800
Enzymatic biofuel cells	Any that will not denature the enzyme		< 40			Research	10
Magnesium-air fuel cell	Salt water		−20 to 55	90%		Commercial / Research	15

Glossary of terms in table:

Anode: The electrode at which oxidation (a loss of electrons) takes place. For fuel cells and other galvanic cells, the anode is the negative terminal; for electrolytic cells (where electrolysis occurs), the anode is the positive terminal.
Aqueous solution: Of, relating to, or resembling water; Made from, with, or by water.
Catalyst: A chemical substance that increases the rate of a reaction without being consumed; after the reaction, it can potentially be recovered from the reaction mixture and is chemically unchanged. The catalyst lowers the activation energy required, allowing the reaction to proceed more quickly or at a lower temperature. In a fuel cell, the catalyst facilitates the reaction of oxygen and hydrogen. It is usually made of platinum powder very thinly coated onto carbon paper or cloth. The catalyst is rough and porous so the maximum surface area of the platinum can be exposed to the hydrogen or oxygen. The platinum-coated side of the catalyst faces the membrane in the fuel cell.
Cathode: The electrode at which reduction (a gain of electrons) occurs. For fuel cells and other galvanic cells, the cathode is the positive terminal; for electrolytic cells (where electrolysis occurs), the cathode is the negative terminal.
Electrolyte: A substance that conducts charged ions from one electrode to the other in a fuel cell, battery, or electrolyzer.
Fuel cell stack: Individual fuel cells connected in a series. Fuel cells are stacked to increase voltage.
Matrix: something within or from which something else originates, develops, or takes form.
Membrane: The separating layer in a fuel cell that acts as electrolyte (an ion-exchanger) as well as a barrier film separating the gases in the anode and cathode compartments of the fuel cell.
Molten carbonate fuel cell (MCFC): A type of fuel cell that contains a molten carbonate electrolyte. Carbonate ions (CO₃²⁻) are transported from the cathode to the anode. Operating temperatures are typically near 650 °C.
Phosphoric acid fuel cell (PAFC): A type of fuel cell in which the electrolyte consists of concentrated phosphoric acid (H₃PO₄). Protons (H+) are transported from the anode to the cathode. The operating temperature range is generally 160–220 °C.
Proton-exchange membrane fuel cell (PEM): A fuel cell incorporating a solid polymer membrane used as its electrolyte. Protons (H+) are transported from the anode to the cathode. The operating temperature range is generally 60–100 °C for Low Temperature Proton-exchange membrane fuel cell (LT-PEMFC). PEM fuel cell with operating temperature of 120-200 °C is called High Temperature Proton-exchange membrane fuel cell (HT-PEMFC).
Solid oxide fuel cell (SOFC): A type of fuel cell in which the electrolyte is a solid, nonporous metal oxide, typically zirconium oxide (ZrO₂) treated with Y₂O₃, and O²⁻ is transported from the cathode to the anode. Any CO in the reformate gas is oxidized to CO₂ at the anode. Temperatures of operation are typically 800–1,000 °C.
Solution: An act or the process by which a solid, liquid, or gaseous substance is homogeneously mixed with a liquid or sometimes a gas or solid.; A homogeneous mixture formed by this process; especially : a single-phase liquid system.; The condition of being dissolved.

Efficiency of leading fuel cell types

Theoretical maximum efficiency

The energy efficiency of a system or device that converts energy is measured by the ratio of the amount of useful energy put out by the system ("output energy") to the total amount of energy that is put in ("input energy") or by useful output energy as a percentage of the total input energy. In the case of fuel cells, useful output energy is measured in electrical energy produced by the system. Input energy is the energy stored in the fuel. According to the U.S. Department of Energy, fuel cells are generally between 40 and 60% energy efficient. This is higher than some other systems for energy generation. For example, the internal combustion engine of a car can be about 43% energy efficient. Steam power plants usually achieve efficiencies of 30-40% while combined cycle gas turbine and steam plants can achieve efficiencies above 60%. In combined heat and power (CHP) systems, the waste heat produced by the primary power cycle - whether fuel cell, nuclear fission or combustion - is captured and put to use, increasing the efficiency of the system to up to 85–90%.

The theoretical maximum efficiency of any type of power generation system is never reached in practice, and it does not consider other steps in power generation, such as production, transportation and storage of fuel and conversion of the electricity into mechanical power. However, this calculation allows the comparison of different types of power generation. The theoretical maximum efficiency of a fuel cell approaches 100%, while the theoretical maximum efficiency of internal combustion engines is approximately 58%.

In practice

Values are given from 40% for acidic, 50% for molten carbonate, to 60% for alkaline, solid oxide and PEM fuel cells.

Fuel cells cannot store energy like a battery, except as hydrogen, but in some applications, such as stand-alone power plants based on discontinuous sources such as solar or wind power, they are combined with electrolyzers and storage systems to form an energy storage system. As of 2019, 90% of hydrogen was used for oil refining, chemicals and fertilizer production (where hydrogen is required for the Haber–Bosch process), and 98% of hydrogen is produced by steam methane reforming, which emits carbon dioxide. The overall efficiency (electricity to hydrogen and back to electricity) of such plants (known as round-trip efficiency), using pure hydrogen and pure oxygen can be "from 35 up to 50 percent", depending on gas density and other conditions. The electrolyzer/fuel cell system can store indefinite quantities of hydrogen, and is therefore suited for long-term storage.

Solid-oxide fuel cells produce heat from the recombination of the oxygen and hydrogen. The ceramic can run as hot as 800 °C (1,470 °F). This heat can be captured and used to heat water in a micro combined heat and power (m-CHP) application. When the heat is captured, total efficiency can reach 80–90% at the unit, but does not consider production and distribution losses. CHP units are being developed today for the European home market.

Professor Jeremy P. Meyers, in the Electrochemical Society journal Interface in 2008, wrote, "While fuel cells are efficient relative to combustion engines, they are not as efficient as batteries, primarily due to the inefficiency of the oxygen reduction reaction (and ... the oxygen evolution reaction, should the hydrogen be formed by electrolysis of water).... [T]hey make the most sense for operation disconnected from the grid, or when fuel can be provided continuously. For applications that require frequent and relatively rapid start-ups ... where zero emissions are a requirement, as in enclosed spaces such as warehouses, and where hydrogen is considered an acceptable reactant, a [PEM fuel cell] is becoming an increasingly attractive choice [if exchanging batteries is inconvenient]". In 2013 military organizations were evaluating fuel cells to determine if they could significantly reduce the battery weight carried by soldiers.

In vehicles

In a fuel cell vehicle the tank-to-wheel efficiency is greater than 45% at low loads and shows average values of about 36% when a driving cycle like the NEDC (New European Driving Cycle) is used as test procedure. The comparable NEDC value for a Diesel vehicle is 22%. In 2008 Honda released a demonstration fuel cell electric vehicle (the Honda FCX Clarity) with fuel stack claiming a 60% tank-to-wheel efficiency.

It is also important to take losses due to fuel production, transportation, and storage into account. Fuel cell vehicles running on compressed hydrogen may have a power-plant-to-wheel efficiency of 22% if the hydrogen is stored as high-pressure gas, and 17% if it is stored as liquid hydrogen.

Applications

Power

Stationary fuel cells are used for commercial, industrial and residential primary and backup power generation. Fuel cells are very useful as power sources in remote locations, such as spacecraft, remote weather stations, large parks, communications centers, rural locations including research stations, and in certain military applications. A fuel cell system running on hydrogen can be compact and lightweight, and have no major moving parts. Because fuel cells have no moving parts and do not involve combustion, in ideal conditions they can achieve up to 99.9999% reliability. This equates to less than one minute of downtime in a six-year period.

Since fuel cell electrolyzer systems do not store fuel in themselves, but rather rely on external storage units, they can be successfully applied in large-scale energy storage, rural areas being one example. There are many different types of stationary fuel cells so efficiencies vary, but most are between 40% and 60% energy efficient. However, when the fuel cell's waste heat is used to heat a building in a cogeneration system this efficiency can increase to 85%. This is significantly more efficient than traditional coal power plants, which are only about one third energy efficient. Assuming production at scale, fuel cells could save 20–40% on energy costs when used in cogeneration systems. Fuel cells are also much cleaner than traditional power generation; a fuel cell power plant using natural gas as a hydrogen source would create less than one ounce of pollution (other than CO₂) for every 1,000 kW·h produced, compared to 25 pounds of pollutants generated by conventional combustion systems. Fuel Cells also produce 97% less nitrogen oxide emissions than conventional coal-fired power plants.

One such pilot program is operating on Stuart Island in Washington State. There the Stuart Island Energy Initiative has built a complete, closed-loop system: Solar panels power an electrolyzer, which makes hydrogen. The hydrogen is stored in a 500-U.S.-gallon (1,900 L) tank at 200 pounds per square inch (1,400 kPa), and runs a ReliOn fuel cell to provide full electric back-up to the off-the-grid residence. Another closed system loop was unveiled in late 2011 in Hempstead, NY.

Fuel cells can be used with low-quality gas from landfills or waste-water treatment plants to generate power and lower methane emissions. A 2.8 MW fuel cell plant in California is said to be the largest of the type. Small-scale (sub-5kWhr) fuel cells are being developed for use in residential off-grid deployment.

Cogeneration

Combined heat and power (CHP) fuel cell systems, including micro combined heat and power (MicroCHP) systems are used to generate both electricity and heat for homes (see home fuel cell), office building and factories. The system generates constant electric power (selling excess power back to the grid when it is not consumed), and at the same time produces hot air and water from the waste heat. As the result CHP systems have the potential to save primary energy as they can make use of waste heat which is generally rejected by thermal energy conversion systems. A typical capacity range of home fuel cell is 1–3 kW_el, 4–8 kW_th. CHP systems linked to absorption chillers use their waste heat for refrigeration.

The waste heat from fuel cells can be diverted during the summer directly into the ground providing further cooling while the waste heat during winter can be pumped directly into the building. The University of Minnesota owns the patent rights to this type of system.

Co-generation systems can reach 85% efficiency (40–60% electric and the remainder as thermal). Phosphoric-acid fuel cells (PAFC) comprise the largest segment of existing CHP products worldwide and can provide combined efficiencies close to 90%. Molten carbonate (MCFC) and solid-oxide fuel cells (SOFC) are also used for combined heat and power generation and have electrical energy efficiencies around 60%. Disadvantages of co-generation systems include slow ramping up and down rates, high cost and short lifetime. Also their need to have a hot water storage tank to smooth out the thermal heat production was a serious disadvantage in the domestic market place where space in domestic properties is at a great premium.

Delta-ee consultants stated in 2013 that with 64% of global sales the fuel cell micro-combined heat and power passed the conventional systems in sales in 2012. The Japanese ENE FARM project stated that 34.213 PEMFC and 2.224 SOFC were installed in the period 2012–2014, 30,000 units on LNG and 6,000 on LPG.

Fuel cell electric vehicles (FCEVs)

Configuration of components in a fuel cell car

Automobiles

By year-end 2019, about 18,000 FCEVs had been leased or sold worldwide. Three fuel cell electric vehicles have been introduced for commercial lease and sale: the Honda Clarity, Toyota Mirai and the Hyundai ix35 FCEV. Additional demonstration models include the Honda FCX Clarity, and Mercedes-Benz F-Cell. As of June 2011 demonstration FCEVs had driven more than 4,800,000 km (3,000,000 mi), with more than 27,000 refuelings. Fuel cell electric vehicles feature an average range of 505 km (314 mi) between refuelings. They can be refueled in less than 5 minutes. The U.S. Department of Energy's Fuel Cell Technology Program states that, as of 2011, fuel cells achieved 53–59% efficiency at one-quarter power and 42–53% vehicle efficiency at full power, and a durability of over 120,000 km (75,000 mi) with less than 10% degradation. In a 2017 Well-to-Wheels simulation analysis that "did not address the economics and market constraints", General Motors and its partners estimated that, for an equivalent journey, a fuel cell electric vehicle running on compressed gaseous hydrogen produced from natural gas could use about 40% less energy and emit 45% less greenhouse gasses than an internal combustion vehicle.

In 2015, Toyota introduced its first fuel cell vehicle, the Mirai, at a price of $57,000. Hyundai introduced the limited production Hyundai ix35 FCEV under a lease agreement. In 2016, Honda started leasing the Honda Clarity Fuel Cell. In 2020, Toyota introduced the second generation of its Mirai brand, improving fuel efficiency and expanding range compared to the original Sedan 2014 model.

In 2024, Mirai owners filed a class action lawsuit in California over the lack of availability of hydrogen available for fuel cell electric cars, alleging, among other things, fraudulent concealment and misrepresentation as well as violations of California’s false advertising law and breaches of implied warranty.

Criticism

Some commentators believe that hydrogen fuel cell cars will never become economically competitive with other technologies or that it will take decades for them to become profitable. Elon Musk, CEO of battery-electric vehicle maker Tesla Motors, stated in 2015 that fuel cells for use in cars will never be commercially viable because of the inefficiency of producing, transporting and storing hydrogen and the flammability of the gas, among other reasons. In 2012, Lux Research, Inc. issued a report that stated: "The dream of a hydrogen economy ... is no nearer". It concluded that "Capital cost ... will limit adoption to a mere 5.9 GW" by 2030, providing "a nearly insurmountable barrier to adoption, except in niche applications". The analysis concluded that, by 2030, PEM stationary market will reach $1 billion, while the vehicle market, including forklifts, will reach a total of $2 billion. Other analyses cite the lack of an extensive hydrogen infrastructure in the U.S. as an ongoing challenge to Fuel Cell Electric Vehicle commercialization.

In 2014, Joseph Romm, the author of The Hype About Hydrogen (2005), said that FCVs still had not overcome the high fueling cost, lack of fuel-delivery infrastructure, and pollution caused by producing hydrogen. "It would take several miracles to overcome all of those problems simultaneously in the coming decades." He concluded that renewable energy cannot economically be used to make hydrogen for an FCV fleet "either now or in the future." Greentech Media's analyst reached similar conclusions in 2014. In 2015, CleanTechnica listed some of the disadvantages of hydrogen fuel cell vehicles. So did Car Throttle. A 2019 video by Real Engineering noted that, notwithstanding the introduction of vehicles that run on hydrogen, using hydrogen as a fuel for cars does not help to reduce carbon emissions from transportation. The 95% of hydrogen still produced from fossil fuels releases carbon dioxide, and producing hydrogen from water is an energy-consuming process. Storing hydrogen requires more energy either to cool it down to the liquid state or to put it into tanks under high pressure, and delivering the hydrogen to fueling stations requires more energy and may release more carbon. The hydrogen needed to move a FCV a kilometer costs approximately 8 times as much as the electricity needed to move a BEV the same distance.

A 2020 assessment concluded that hydrogen vehicles are still only 38% efficient, while battery EVs are 80% efficient. In 2021 CleanTechnica concluded that (a) hydrogen cars remain far less efficient than electric cars; (b) grey hydrogen – hydrogen produced with polluting processes – makes up the vast majority of available hydrogen; (c) delivering hydrogen would require building a vast and expensive new delivery and refueling infrastructure; and (d) the remaining two "advantages of fuel cell vehicles – longer range and fast fueling times – are rapidly being eroded by improving battery and charging technology." A 2022 study in Nature Electronics agreed. A 2023 study by the Centre for International Climate and Environmental Research (CICERO) estimated that leaked hydrogen has a global warming effect 11.6 times stronger than CO₂.

Buses

As of August 2011, there were about 100 fuel cell buses in service around the world. Most of these were manufactured by UTC Power, Toyota, Ballard, Hydrogenics, and Proton Motor. UTC buses had driven more than 970,000 km (600,000 mi) by 2011. Fuel cell buses have from 39% to 141% higher fuel economy than diesel buses and natural gas buses.

As of 2019, the NREL was evaluating several current and planned fuel cell bus projects in the U.S.

Trains

Train operators may use hydrogen fuel cells in trains in an effort to save the costs of installing overhead electrification and to maintain the range offered by diesel trains. They have encountered expenses, however, due to fuel cells in trains lasting only three years, maintenance of the hydrogen tank and the additional need for batteries as a power buffer. In 2018, the first fuel cell-powered trains, the Alstom Coradia iLint multiple units, began running on the Buxtehude–Bremervörde–Bremerhaven–Cuxhaven line in Germany.^[139] Hydrogen trains have also been introduced in Sweden and the UK.

Trucks

In December 2020, Toyota and Hino Motors, together with Seven-Eleven (Japan), FamilyMart and Lawson announced that they have agreed to jointly consider introducing light-duty fuel cell electric trucks (light-duty FCETs). Lawson started testing for low temperature delivery at the end of July 2021 in Tokyo, using a Hino Dutro in which the Toyota Mirai fuel cell is implemented. FamilyMart started testing in Okazaki city.

In August 2021, Toyota announced their plan to make fuel cell modules at its Kentucky auto-assembly plant for use in zero-emission big rigs and heavy-duty commercial vehicles. They plan to begin assembling the electrochemical devices in 2023.

In October 2021, Daimler Truck's fuel cell based truck received approval from German authorities for use on public roads.

Forklifts

A fuel cell forklift (also called a fuel cell lift truck) is a fuel cell-powered industrial forklift truck used to lift and transport materials. In 2013 there were over 4,000 fuel cell forklifts used in material handling in the US, of which 500 received funding from DOE (2012). As of 2024, approximately 50,000 hydrogen forklifts are in operation worldwide (the bulk of which are in the U.S.), as compared with 1.2 million battery electric forklifts that were purchased in 2021.

Most companies in Europe and the US do not use petroleum-powered forklifts, as these vehicles work indoors where emissions must be controlled and instead use electric forklifts. Fuel cell-powered forklifts can be refueled in 3 minutes and they can be used in refrigerated warehouses, where their performance is not degraded by lower temperatures. The FC units are often designed as drop-in replacements.

Motorcycles and bicycles

In 2005, a British manufacturer of hydrogen-powered fuel cells, Intelligent Energy (IE), produced the first working hydrogen-run motorcycle called the ENV (Emission Neutral Vehicle). The motorcycle holds enough fuel to run for four hours, and to travel 160 km (100 mi) in an urban area, at a top speed of 80 km/h (50 mph). In 2004 Honda developed a fuel cell motorcycle that utilized the Honda FC Stack.

Other examples of motorbikes and bicycles that use hydrogen fuel cells include the Taiwanese company APFCT's scooter using the fueling system from Italy's Acta SpA and the Suzuki Burgman scooter with an IE fuel cell that received EU Whole Vehicle Type Approval in 2011. Suzuki Motor Corp. and IE have announced a joint venture to accelerate the commercialization of zero-emission vehicles.

Airplanes

In 2003, the world's first propeller-driven airplane to be powered entirely by a fuel cell was flown. The fuel cell was a stack design that allowed the fuel cell to be integrated with the plane's aerodynamic surfaces. Fuel cell-powered unmanned aerial vehicles (UAV) include a Horizon fuel cell UAV that set the record distance flown for a small UAV in 2007. Boeing researchers and industry partners throughout Europe conducted experimental flight tests in February 2008 of a manned airplane powered only by a fuel cell and lightweight batteries. The fuel cell demonstrator airplane, as it was called, used a proton-exchange membrane (PEM) fuel cell/lithium-ion battery hybrid system to power an electric motor, which was coupled to a conventional propeller.

In 2009, the Naval Research Laboratory's (NRL's) Ion Tiger utilized a hydrogen-powered fuel cell and flew for 23 hours and 17 minutes. Fuel cells are also being tested and considered to provide auxiliary power in aircraft, replacing fossil fuel generators that were previously used to start the engines and power on board electrical needs, while reducing carbon emissions. In 2016 a Raptor E1 drone made a successful test flight using a fuel cell that was lighter than the lithium-ion battery it replaced. The flight lasted 10 minutes at an altitude of 80 metres (260 ft), although the fuel cell reportedly had enough fuel to fly for two hours. The fuel was contained in approximately 100 solid 1 square centimetre (0.16 sq in) pellets composed of a proprietary chemical within an unpressurized cartridge. The pellets are physically robust and operate at temperatures as warm as 50 °C (122 °F). The cell was from Arcola Energy.

Lockheed Martin Skunk Works Stalker is an electric UAV powered by solid oxide fuel cell.

Boats

The Hydra, a 22-person fuel cell boat operated from 1999 to 2001 on the Rhine river near Bonn, Germany, and was used as a ferry boat in Ghent, Belgium, during an electric boat conference in 2000. It was fully certified by the Germanischer Lloyd for passenger transport. The Zemship, a small passenger ship, was produced in 2003 to 2013. It used a 100 kW Polymer Electrolyte Membrane Fuel Cells (PEMFC) with 7 lead gel batteries. With these systems, alongside 12 storage tanks, fuel cells provided an energy capacity of 560 V and 234 kWh. Made in Hamburg, Germany, the FCS Alsterwasser, revealed in 2008, was one of the first passenger ships powered by fuel cells and could carry 100 passengers. The hybrid fuel cell technology that powered this ship was produced by Proton Motor Fuel Cell GmbH.

In 2010, the MF Vågen was first produced, utilizing 12 kW fuel cells and 2- to 3-kilogram metal hydride hydrogen storage. It also utilizes 25 kWh lithium batteries and a 10 kW DC motor. The Hornblower Hybrid debuted in 2012. It utilizes a diesel generator, batteries, photovoltaics, wind power, and fuel cells for energy. Made in Bristol, a 12-passenger hybrid ferry, Hydrogenesis, has been in operation since 2012. The SF-BREEZE is a two-motor boat that utilizes 41 × 120 kW fuel cells. With a type C storage tank, the pressurized vessel can maintain 1200 kg of LH2. These ships are still in operation today. In Norway, the first ferry powered by fuel cells running on liquid hydrogen was scheduled for its first test drives in December 2022.

The Type 212 submarines of the German and Italian navies use fuel cells to remain submerged for weeks without the need to surface. The U212A is a non-nuclear submarine developed by German naval shipyard Howaldtswerke Deutsche Werft. The system consists of nine PEM fuel cells, providing between 30 kW and 50 kW each. The ship is silent, giving it an advantage in the detection of other submarines.

Portable power systems

Portable fuel cell systems are generally classified as weighing under 10 kg and providing power of less than 5 kW. The potential market size for smaller fuel cells is quite large with an up to 40% per annum potential growth rate and a market size of around $10 billion, leading a great deal of research to be devoted to the development of portable power cells. Within this market two groups have been identified. The first is the microfuel cell market, in the 1-50 W range for power smaller electronic devices. The second is the 1-5 kW range of generators for larger scale power generation (e.g. military outposts, remote oil fields).

Microfuel cells are primarily aimed at penetrating the market for phones and laptops. This can be primarily attributed to the advantageous energy density provided by fuel cells over a lithium-ion battery, for the entire system. For a battery, this system includes the charger as well as the battery itself. For the fuel cell this system would include the cell, the necessary fuel and peripheral attachments. Taking the full system into consideration, fuel cells have been shown to provide 530 Wh/kg compared to 44 Wh/kg for lithium-ion batteries. However, while the weight of fuel cell systems offer a distinct advantage the current costs are not in their favor. while a battery system will generally cost around $1.20 per Wh, fuel cell systems cost around $5 per Wh, putting them at a significant disadvantage.

As power demands for cell phones increase, fuel cells could become much more attractive options for larger power generation. The demand for longer on time on phones and computers is something often demanded by consumers so fuel cells could start to make strides into laptop and cell phone markets. The price will continue to go down as developments in fuel cells continues to accelerate. Current strategies for improving micro fuel cells is through the use of carbon nanotubes. It was shown by Girishkumar et al. that depositing nanotubes on electrode surfaces allows for substantially greater surface area increasing the oxygen reduction rate.

Fuel cells for use in larger scale operations also show much promise. Portable power systems that use fuel cells can be used in the leisure sector (i.e. RVs, cabins, marine), the industrial sector (i.e. power for remote locations including gas/oil wellsites, communication towers, security, weather stations), and in the military sector. SFC Energy is a German manufacturer of direct methanol fuel cells for a variety of portable power systems. Ensol Systems Inc. is an integrator of portable power systems, using the SFC Energy DMFC. The key advantage of fuel cells in this market is the great power generation per weight. While fuel cells can be expensive, for remote locations that require dependable energy fuel cells hold great power. For a 72-h excursion the comparison in weight is substantial, with a fuel cell only weighing 15 pounds compared to 29 pounds of batteries needed for the same energy.

Other applications

Providing power for base stations or cell sites
Emergency power systems are a type of fuel cell system, which may include lighting, generators and other apparatus, to provide backup resources in a crisis or when regular systems fail. They find uses in a wide variety of settings from residential homes to hospitals, scientific laboratories, data centers,
Telecommunication equipment and modern naval ships.
An uninterrupted power supply (UPS) provides emergency power and, depending on the topology, provide line regulation as well to connected equipment by supplying power from a separate source when utility power is not available. Unlike a standby generator, it can provide instant protection from a momentary power interruption.
Smartphones, laptops and tablets for use in locations where AC charging may not be readily available.
Portable charging docks for small electronics (e.g. a belt clip that charges a cell phone or PDA).
Small heating appliances.
Food preservation, achieved by exhausting the oxygen and automatically maintaining oxygen exhaustion in a shipping container, containing, for example, fresh fish.
Sensors, including in Breathalyzers, where the amount of voltage generated by a fuel cell is used to determine the concentration of fuel (alcohol) in the sample.

Fueling stations

According to FuelCellsWorks, an industry group, at the end of 2019, 330 hydrogen refueling stations were open to the public worldwide. As of June 2020, there were 178 publicly available hydrogen stations in operation in Asia. 114 of these were in Japan. There were at least 177 stations in Europe, and about half of these were in Germany. There were 44 publicly accessible stations in the US, 42 of which were located in California.

A hydrogen fueling station costs between $1 million and $4 million to build.

Social Implications

As of 2023, technological barriers to fuel cell adoption remain. Fuel cells are primarily for material handling in warehouses, distribution centers, and manufacturing facilities. They are projected to be useful and sustainable in a wider range applications. But current applications do not often reach lower-income communities, though some attempts at inclusivity are being made, for example in accessibility.

Markets and economics

In 2012, fuel cell industry revenues exceeded $1 billion market value worldwide, with Asian pacific countries shipping more than 3/4 of the fuel cell systems worldwide. However, as of January 2014, no public company in the industry had yet become profitable. There were 140,000 fuel cell stacks shipped globally in 2010, up from 11,000 shipments in 2007, and from 2011 to 2012 worldwide fuel cell shipments had an annual growth rate of 85%. Tanaka Kikinzoku expanded its manufacturing facilities in 2011. Approximately 50% of fuel cell shipments in 2010 were stationary fuel cells, up from about a third in 2009, and the four dominant producers in the Fuel Cell Industry were the United States, Germany, Japan and South Korea. The Department of Energy Solid State Energy Conversion Alliance found that, as of January 2011, stationary fuel cells generated power at approximately $724 to $775 per kilowatt installed. In 2011, Bloom Energy, a major fuel cell supplier, said that its fuel cells generated power at 9–11 cents per kilowatt-hour, including the price of fuel, maintenance, and hardware.

Industry groups predict that there are sufficient platinum resources for future demand, and in 2007, research at Brookhaven National Laboratory suggested that platinum could be replaced by a gold-palladium coating, which may be less susceptible to poisoning and thereby improve fuel cell lifetime. Another method would use iron and sulphur instead of platinum. This would lower the cost of a fuel cell (as the platinum in a regular fuel cell costs around US$1,500, and the same amount of iron costs only around US$1.50). The concept was being developed by a coalition of the John Innes Centre and the University of Milan-Bicocca. PEDOT cathodes are immune to carbon monoxide poisoning.

In 2016, Samsung "decided to drop fuel cell-related business projects, as the outlook of the market isn't good".

Research and development

2005: Georgia Institute of Technology researchers used triazole to raise the operating temperature of PEM fuel cells from below 100 °C to over 125 °C, claiming this will require less carbon-monoxide purification of the hydrogen fuel.

2008: Monash University, Melbourne used PEDOT as a cathode.

2009: Researchers at the University of Dayton, in Ohio, showed that arrays of vertically grown carbon nanotubes could be used as the catalyst in fuel cells. The same year, a nickel bisdiphosphine-based catalyst for fuel cells was demonstrated.

2013: British firm ACAL Energy developed a fuel cell that it said can run for 10,000 hours in simulated driving conditions. It asserted that the cost of fuel cell construction can be reduced to $40/kW (roughly $9,000 for 300 HP).

2014: Researchers in Imperial College London developed a new method for regeneration of hydrogen sulfide contaminated PEFCs. They recovered 95–100% of the original performance of a hydrogen sulfide contaminated PEFC. They were successful in rejuvenating a SO₂ contaminated PEFC too. This regeneration method is applicable to multiple cell stacks.

2019: U.S. Army Research Laboratory researchers developed a two part in-situ hydrogen generation fuel cell, one part for hydrogen generation and the other for electric power generation through an internal hydrogen/air power plant.

2022: Researchers from University of Delaware developed a hydrogen powered fuel cell that is projected to function at lower costs, operating at roughly $1.4/kW. This design removes carbon dioxide from the air feed of hydroxide exchange membrane fuel cells.

History of electrochemistry

From Wikipedia, the free encyclopedia
https://en.wikipedia.org/wiki/History_of_electrochemistry

Electrochemistry, a branch of chemistry, went through several changes during its evolution from early principles related to magnets in the early 16th and 17th centuries, to complex theories involving conductivity, electric charge and mathematical methods. The term electrochemistry was used to describe electrical phenomena in the late 19th and 20th centuries. In recent decades, electrochemistry has become an area of current research, including research in batteries and fuel cells, preventing corrosion of metals, the use of electrochemical cells to remove refractory organics and similar contaminants in wastewater electrocoagulation and improving techniques in refining chemicals with electrolysis and electrophoresis.

Background and dawn of electrochemistry

The 16th century marked the beginning of scientific understanding of electricity and magnetism that culminated with the production of electric power and the Industrial Revolution in the late 19th century.

In the 1550s, English scientist William Gilbert spent 17 years experimenting with magnetism and, to a lesser extent, electricity. For his work on magnets, Gilbert became known as "The Father of Magnetism." His book De Magnete quickly became the standard work throughout Europe on electrical and magnetic phenomena, and made a clear distinction between magnetism and what was then called the "amber effect" (static electricity).

German physicist Otto von Guericke beside his electrical generator while conducting experiment.

In 1663, German physicist Otto von Guericke created the first electrostatic generator, which produced static electricity by applying friction. The generator was made of a large sulfur ball inside a glass globe, mounted on a shaft. The ball was rotated by means of a crank and a static electric spark was produced when a pad was rubbed against the ball as it rotated. The globe could be removed and used as an electrical source for experiments with electricity. Von Guericke used his generator to show that like charges repelled each other.

The 18th century and birth of electrochemistry

In 1709, Francis Hauksbee at the Royal Society in London discovered that by putting a small amount of mercury in the glass of Von Guericke's generator and evacuating the air from it, it would glow whenever the ball built up a charge and his hand was touching the globe. He had created the first gas-discharge lamp.

Between 1729 and 1736, two English scientists, Stephen Gray and Jean Desaguliers, performed a series of experiments which showed that a cork or other object as far away as 800 or 900 feet (245–275 m) could be electrified by connecting it via a charged glass tube to materials such as metal wires or hempen string. They found that other materials, such as silk, would not convey the effect.

By the mid-18th century, French chemist Charles François de Cisternay Du Fay had discovered two forms of static electricity, and that like charges repel each other while unlike charges attract. Du Fay announced that electricity consisted of two fluids: vitreous (from the Latin for "glass"), or positive, electricity; and resinous, or negative, electricity. This was the "two-fluid theory" of electricity, which was opposed by Benjamin Franklin's "one-fluid theory" later in the century.

In 1745, Jean-Antoine Nollet developed a theory of electrical attraction and repulsion that supposed the existence of a continuous flow of electrical matter between charged bodies. Nollet's theory at first gained wide acceptance, but met resistance in 1752 with the translation of Franklin's Experiments and Observations on Electricity into French. Franklin and Nollet debated the nature of electricity, with Franklin supporting action at a distance and two qualitatively opposing types of electricity, and Nollet advocating mechanical action and a single type of electrical fluid. Franklin's argument eventually won and Nollet's theory was abandoned.

In 1748, Nollet invented one of the first electrometers, the electroscope, which showed electric charge using electrostatic attraction and repulsion. Nollet is reputed to be the first to apply the name "Leyden jar" to the first device for storing electricity. Nollet's invention was replaced by Horace-Bénédict de Saussure's electrometer in 1766.

By the 1740s, William Watson had conducted several experiments to determine the speed of electricity. The general belief at the time was that electricity was faster than sound, but no accurate test had been devised to measure the velocity of a current. Watson, in the fields north of London, laid out a line of wire supported by dry sticks and silk which ran for 12,276 feet (3.7 km). Even at this length, the velocity of electricity seemed instantaneous. Resistance in the wire was also noticed but apparently not fully understood, as Watson related that "we observed again, that although the electrical compositions were very severe to those who held the wires, the report of the Explosion at the prime Conductor was little, in comparison of that which is heard when the Circuit is short." Watson eventually decided not to pursue his electrical experiments, concentrating instead upon his medical career.

By the 1750s, as the study of electricity became popular, efficient ways of producing electricity were sought. The generator developed by Jesse Ramsden was among the first electrostatic generators invented. Electricity produced by such generators was used to treat paralysis, muscle spasms, and to control heart rates. Other medical uses of electricity included filling the body with electricity, drawing sparks from the body, and applying sparks from the generator to the body.

Charles-Augustin de Coulomb developed the law of electrostatic attraction in 1781 as an outgrowth of his attempt to investigate the law of electrical repulsions as stated by Joseph Priestley in England. To this end, he invented a sensitive apparatus to measure the electrical forces involved in Priestley's law. He also established the inverse square law of attraction and repulsion magnetic poles, which became the basis for the mathematical theory of magnetic forces developed by Siméon Denis Poisson. Coulomb wrote seven important works on electricity and magnetism which he submitted to the Académie des Sciences between 1785 and 1791, in which he reported having developed a theory of attraction and repulsion between charged bodies, and went on to search for perfect conductors and dielectrics. He suggested that there was no perfect dielectric, proposing that every substance has a limit, above which it will conduct electricity. The SI unit of charge is called a coulomb in his honour.

In 1789, Franz Aepinus developed a device with the properties of a "condenser" (now known as a capacitor.) The Aepinus condenser was the first capacitor developed after the Leyden jar, and was used to demonstrate conduction and induction. The device was constructed so that the space between two plates could be adjusted, and the glass dielectric separating the two plates could be removed or replaced with other materials.

Despite the gain in knowledge of electrical properties and the building of generators, it was not until the late 18th century that Italian physician and anatomist Luigi Galvani marked the birth of electrochemistry by establishing a bridge between muscular contractions and electricity with his 1791 essay De Viribus Electricitatis in Motu Musculari Commentarius (Commentary on the Effect of Electricity on Muscular Motion), where he proposed a "nerveo-electrical substance" in life forms.

In his essay, Galvani concluded that animal tissue contained a before-unknown innate, vital force, which he termed "animal electricity," which activated muscle when placed between two metal probes. He believed that this was evidence of a new form of electricity, separate from the "natural" form that is produced by lightning and the "artificial" form that is produced by friction (static electricity). He considered the brain to be the most important organ for the secretion of this "electric fluid" and that the nerves conducted the fluid to the muscles. He believed the tissues acted similarly to the outer and inner surfaces of Leyden jars. The flow of this electric fluid provided a stimulus to the muscle fibres.

Italian physicist Alessandro Volta showing his *"battery"* to French emperor Napoleon Bonaparte in the early 19th century.

Galvani's scientific colleagues generally accepted his views, but Alessandro Volta, the outstanding professor of physics at the University of Pavia, was not convinced by the analogy between muscles and Leyden jars. Deciding that the frogs' legs used in Galvani's experiments served only as an electroscope, he held that the contact of dissimilar metals was the true source of stimulation. He referred to the electricity so generated as "metallic electricity" and decided that the muscle, by contracting when touched by metal, resembled the action of an electroscope. Furthermore, Volta claimed that if two dissimilar metals in contact with each other also touched a muscle, agitation would also occur and increase with the dissimilarity of the metals. Galvani refuted this by obtaining muscular action using two pieces of similar metal. Volta's name was later used for the unit of electrical potential, the volt.

Rise of electrochemistry as branch of chemistry

Scheme of Ritter's apparatus to separate water into hydrogen and oxygen by electrolysis

In 1800, English chemists William Nicholson and Johann Wilhelm Ritter succeeded in separating water into hydrogen and oxygen by electrolysis. Soon thereafter, Ritter discovered the process of electroplating. He also observed that the amount of metal deposited and the amount of oxygen produced during an electrolytic process depended on the distance between the electrodes. By 1801 Ritter had observed thermoelectric currents, which anticipated the discovery of thermoelectricity by Thomas Johann Seebeck.

In 1802, William Cruickshank designed the first electric battery capable of mass production. Like Volta, Cruickshank arranged square copper plates, which he soldered at their ends, together with plates of zinc of equal size. These plates were placed into a long rectangular wooden box which was sealed with cement. Grooves inside the box held the metal plates in position. The box was then filled with an electrolyte of brine, or watered down acid. This flooded design had the advantage of not drying out with use and provided more energy than Volta's arrangement, which used brine-soaked papers between the plates.

In the quest for a better production of platinum metals, two scientists, William Hyde Wollaston and Smithson Tennant, worked together to design an efficient electrochemical technique to refine or purify platinum. Tennant ended up discovering the elements iridium and osmium. Wollaston's effort, in turn, led him to the discovery of the metals palladium in 1803 and rhodium in 1804.

Wollaston made improvements to the galvanic battery (named after Galvani) in the 1810s. In Wollaston's battery, the wooden box was replaced with an earthenware vessel, and a copper plate was bent into a U-shape, with a single plate of zinc placed in the center of the bent copper. The zinc plate was prevented from making contact with the copper by dowels (pieces) of cork or wood. In his single cell design, the U-shaped copper plate was welded to a horizontal handle for lifting the copper and zinc plates out of the electrolyte when the battery was not in use.

In 1809, Samuel Thomas von Soemmering developed the first telegraph. He used a device with 26 wires (1 wire for each letter of the German alphabet) terminating in a container of acid. At the sending station, a key, which completed a circuit with a battery, was connected as required to each of the line wires. The passage of current caused the acid to decompose chemically, and the message was read by observing at which of the terminals the bubbles of gas appeared. This is how he was able to send messages, one letter at a time.

Humphry Davy's work with electrolysis led to conclusion that the production of electricity in simple electrolytic cells resulted from chemical reactions between the electrolyte and the metals, and occurred between substances of opposite charge. He reasoned that the interactions of electric currents with chemicals offered the most likely means of decomposing all substances to their basic elements. These views were explained in 1806 in his lecture On Some Chemical Agencies of Electricity, for which he received the Napoleon Prize from the Institut de France in 1807 (despite the fact that England and France were at war at the time). This work led directly to the isolation of sodium and potassium from their common compounds and of the alkaline earth metals from theirs in 1808.

Hans Christian Ørsted's discovery of the magnetic effect of electric currents in 1820 was immediately recognised as an important advance, although he left further work on electromagnetism to others. André-Marie Ampère quickly repeated Ørsted's experiment, and formulated them mathematically (which became Ampère's law) . Ørsted also discovered that not only is a magnetic needle deflected by the electric current, but that the live electric wire is also deflected in a magnetic field, thus laying the foundation for the construction of an electric motor. Ørsted's discovery of piperine, one of the pungent components of pepper, was an important contribution to chemistry, as was his preparation of aluminium in 1825.

During the 1820s, Robert Hare developed the Deflagrator, a form of voltaic battery having large plates used for producing rapid and powerful combustion. A modified form of this apparatus was employed in 1823 in volatilising and fusing carbon. It was with these batteries that the first use of voltaic electricity for blasting under water was made in 1831.

In 1821, the Estonian-German physicist, Thomas Johann Seebeck, demonstrated the electrical potential in the juncture points of two dissimilar metals when there is a temperature difference between the joints. He joined a copper wire with a bismuth wire to form a loop or circuit. Two junctions were formed by connecting the ends of the wires to each other. He then accidentally discovered that if he heated one junction to a high temperature, and the other junction remained at room temperature, a magnetic field was observed around the circuit.

He did not recognise that an electric current was being generated when heat was applied to a bi-metal junction. He used the term "thermomagnetic currents" or "thermomagnetism" to express his discovery. Over the following two years, he reported on his continuing observations to the Prussian Academy of Sciences, where he described his observation as "the magnetic polarization of metals and ores produced by a temperature difference." This Seebeck effect became the basis of the thermocouple, which is still considered the most accurate measurement of temperature today. The converse Peltier effect was seen over a decade later when a current was run through a circuit with two dissimilar metals, resulting in a temperature difference between the metals.

In 1827 German scientist Georg Ohm expressed his law in his famous book Die galvanische Kette, mathematisch bearbeitet (The Galvanic Circuit Investigated Mathematically) in which he gave his complete theory of electricity.

In 1829 Antoine-César Becquerel developed the "constant current" cell, forerunner of the well-known Daniell cell. When this acid-alkali cell was monitored by a galvanometer, current was found to be constant for an hour, the first instance of "constant current". He applied the results of his study of thermoelectricity to the construction of an electric thermometer, and measured the temperatures of the interior of animals, of the soil at different depths, and of the atmosphere at different heights. He helped validate Faraday's laws and conducted extensive investigations on the electroplating of metals with applications for metal finishing and metallurgy. Solar cell technology dates to 1839 when Becquerel observed that shining light on an electrode submerged in a conductive solution would create an electric current.

Michael Faraday began, in 1832, what promised to be a rather tedious attempt to prove that all electricities had precisely the same properties and caused precisely the same effects. The key effect was electrochemical decomposition. Voltaic and electromagnetic electricity posed no problems, but static electricity did. As Faraday delved deeper into the problem, he made two startling discoveries. First, electrical force did not, as had long been supposed, act at a distance upon molecules to cause them to dissociate. It was the passage of electricity through a conducting liquid medium that caused the molecules to dissociate, even when the electricity merely discharged into the air and did not pass through a "pole" or "center of action" in a voltaic cell. Second, the amount of the decomposition was found to be related directly to the amount of electricity passing through the solution.

These findings led Faraday to a new theory of electrochemistry. The electric force, he argued, threw the molecules of a solution into a state of tension. When the force was strong enough to distort the forces that held the molecules together so as to permit the interaction with neighbouring particles, the tension was relieved by the migration of particles along the lines of tension, the different parts of atoms migrating in opposite directions. The amount of electricity that passed, then, was clearly related to the chemical affinities of the substances in solution. These experiments led directly to Faraday's two laws of electrochemistry which state:

The amount of a substance deposited on each electrode of an electrolytic cell is directly proportional to the amount of electricity passing through the cell.
The quantities of different elements deposited by a given amount of electricity are in the ratio of their chemical equivalent weights.

William Sturgeon built an electric motor in 1832 and invented the commutator, a ring of metal-bristled brushes which allow the spinning armature to maintain contact with the electric current and changed the alternating current to a pulsating direct current. He also improved the voltaic battery and worked on the theory of thermoelectricity.

Hippolyte Pixii, a French instrument maker, constructed the first dynamo in 1832 and later built a direct current dynamo using the commutator. This was the first practical mechanical generator of electric current that used concepts demonstrated by Faraday.

John Daniell began experiments in 1835 in an attempt to improve the voltaic battery with its problems of being unsteady and a weak source of electric current. His experiments soon led to remarkable results. In 1836, he invented a primary cell in which hydrogen was eliminated in the generation of the electricity. Daniell had solved the problem of polarization. In his laboratory he had learned to alloy the amalgamated zinc of Sturgeon with mercury. His version was the first of the two-fluid class battery and the first battery that produced a constant reliable source of electric current over a long period of time.

William Grove produced the first fuel cell in 1839. He based his experiment on the fact that sending an electric current through water splits the water into its component parts of hydrogen and oxygen. So, Grove tried reversing the reaction—combining hydrogen and oxygen to produce electricity and water. Eventually the term fuel cell was coined in 1889 by Ludwig Mond and Charles Langer, who attempted to build the first practical device using air and industrial coal gas. He also introduced a powerful battery at the annual meeting of the British Association for the Advancement of Science in 1839. Grove's first cell consisted of zinc in diluted sulfuric acid and platinum in concentrated nitric acid, separated by a porous pot. The cell was able to generate about 12 amperes of current at about 1.8 volts. This cell had nearly double the voltage of the first Daniell cell. Grove's nitric acid cell was the favourite battery of the early American telegraph (1840–1860), because it offered strong current output.

As telegraphs became more complex, the need for a constant voltage became critical and the Grove device was limited (as the cell discharged, nitric acid was depleted and voltage was reduced). By the time of the American Civil War, Grove's battery had been replaced by the Daniell battery. In 1841 Robert Bunsen replaced the expensive platinum electrode used in Grove's battery with a carbon electrode. This led to large scale use of the "Bunsen battery" in the production of arc-lighting and in electroplating.

Wilhelm Weber developed, in 1846, the electrodynamometer, in which a current causes a coil suspended within another coil to turn when a current is passed through both. In 1852, Weber defined the absolute unit of electrical resistance (which was named the ohm after Georg Ohm). Weber's name is now used as a unit name to describe magnetic flux, the weber.

German physicist Johann Hittorf concluded that ion movement caused electric current. In 1853 Hittorf noticed that some ions traveled more rapidly than others. This observation led to the concept of transport number, the rate at which particular ions carried the electric current. Hittorf measured the changes in the concentration of electrolysed solutions, computed from these the transport numbers (relative carrying capacities) of many ions, and, in 1869, published his findings governing the migration of ions.

In 1866, Georges Leclanché patented a new battery system, which was immediately successful. Leclanché's original cell was assembled in a porous pot. The positive electrode (the cathode) consisted of crushed manganese dioxide with a little carbon mixed in. The negative pole (anode) was a zinc rod. The cathode was packed into the pot, and a carbon rod was inserted to act as a current collector. The anode and the pot were then immersed in an ammonium chloride solution. The liquid acted as the electrolyte, readily seeping through the porous pot and making contact with the cathode material. Leclanché's "wet" cell became the forerunner to the world's first widely used battery, the zinc-carbon cell.

Late 19th century advances and the advent of electrochemical societies

In 1869 Zénobe Gramme devised his first clean direct current dynamo. His generator featured a ring armature wound with many individual coils of wire.

Svante August Arrhenius published his thesis in 1884, Recherches sur la conductibilité galvanique des électrolytes (Investigations on the galvanic conductivity of electrolytes). From the results of his experiments, the author concluded that electrolytes, when dissolved in water, become to varying degrees split or dissociated into positive and negative ions. The degree to which this dissociation occurred depended above all on the nature of the substance and its concentration in the solution, being more developed the greater the dilution. The ions were supposed to be the carriers of not only the electric current, as in electrolysis, but also of the chemical activity. The relation between the actual number of ions and their number at great dilution (when all the molecules were dissociated) gave a quantity of special interest ("activity constant").

The race for the commercially viable production of aluminium was won in 1886 by Paul Héroult and Charles M. Hall. The problem many researchers had with extracting aluminium was that electrolysis of an aluminium salt dissolved in water yields aluminium hydroxide. Both Hall and Héroult avoided this problem by dissolving aluminium oxide in a new solvent— fused cryolite (Na₃AlF₆).

Wilhelm Ostwald, 1909 Nobel Laureate, started his experimental work in 1875, with an investigation on the law of mass action of water in relation to the problems of chemical affinity, with special emphasis on electrochemistry and chemical dynamics. In 1894 he gave the first modern definition of a catalyst and turned his attention to catalytic reactions. Ostwald is especially known for his contributions to the field of electrochemistry, including important studies of the electrical conductivity and electrolytic dissociation of organic acids.

Hermann Nernst developed the theory of the electromotive force of the voltaic cell in 1888. He developed methods for measuring dielectric constants and was the first to show that solvents of high dielectric constants promote the ionization of substances. Nernst's early studies in electrochemistry were inspired by Arrhenius' dissociation theory which first recognised the importance of ions in solution. In 1889, Nernst elucidated the theory of galvanic cells by assuming an "electrolytic pressure of dissolution," which forces ions from electrodes into solution and which was opposed to the osmotic pressure of the dissolved ions. He applied the principles of thermodynamics to the chemical reactions proceeding in a battery. In that same year he showed how the characteristics of the current produced could be used to calculate the free energy change in the chemical reaction producing the current. He constructed an equation, known as Nernst Equation, which describes the relation of a battery cell's voltage to its properties.

In 1898 Fritz Haber published his textbook, Electrochemistry: Grundriss der technischen Elektrochemie auf theoretischer Grundlage (The Theoretical Basis of Technical Electrochemistry), which was based on the lectures he gave at Karlsruhe. In the preface to his book he expressed his intention to relate chemical research to industrial processes and in the same year he reported the results of his work on electrolytic oxidation and reduction, in which he showed that definite reduction products can result if the voltage at the cathode is kept constant. In 1898 he explained the reduction of nitrobenzene in stages at the cathode and this became the model for other similar reduction processes.

In 1909, Robert Andrews Millikan began a series of experiments to determine the electric charge carried by a single electron. He began by measuring the course of charged water droplets in an electrical field. The results suggested that the charge on the droplets is a multiple of the elementary electric charge, but the experiment was not accurate enough to be convincing. He obtained more precise results in 1910 with his famous oil-drop experiment in which he replaced water (which tended to evaporate too quickly) with oil.

Jaroslav Heyrovský, a Nobel laureate, eliminated the tedious weighing required by previous analytical techniques, which used the differential precipitation of mercury by measuring drop-time. In the previous method, a voltage was applied to a dropping mercury electrode and a reference electrode was immersed in a test solution. After 50 drops of mercury were collected, they were dried and weighed. The applied voltage was varied and the experiment repeated. Measured weight was plotted versus applied voltage to obtain the curve. In 1921, Heyrovský had the idea of measuring the current flowing through the cell instead of just studying drop-time.

On February 10, 1922, the "polarograph" was born as Heyrovský recorded the current-voltage curve for a solution of 1 mol/L NaOH. Heyrovský correctly interpreted the current increase between −1.9 and −2.0 V as being due to the deposit of Na⁺ ions, forming an amalgam. Shortly thereafter, with his Japanese colleague Masuzo Shikata, he constructed the first instrument for the automatic recording of polarographic curves, which became world-famous later as the polarograph.

In 1923, Johannes Nicolaus Brønsted and Thomas Martin Lowry published essentially the same theory about how acids and bases behave using electrochemical basis.

The International Society of Electrochemistry (ISE) was founded in 1949, and some years later the first sophisticated electrophoretic apparatus was developed in 1937 by Arne Tiselius, who was awarded the 1948 Nobel prize for his work in protein electrophoresis. He developed the "moving boundary," which later would become known as zone electrophoresis, and used it to separate serum proteins in solution. Electrophoresis became widely developed in the 1940s and 1950s when the technique was applied to molecules ranging from the largest proteins to amino acids and even inorganic ions.

During the 1960s and 1970s quantum electrochemistry was developed by Revaz Dogonadze and his pupils.

History of the battery

From Wikipedia, the free encyclopedia

A voltaic pile, the first chemical battery

Batteries provided the primary source of electricity before the development of electric generators and electrical grids around the end of the 19th century. Successive improvements in battery technology facilitated major electrical advances, from early scientific studies to the rise of telegraphs and telephones, eventually leading to portable computers, mobile phones, electric cars, and many other electrical devices.

Students and engineers developed several commercially important types of battery. "Wet cells" were open containers that held liquid electrolyte and metallic electrodes. When the electrodes were completely consumed, the wet cell was renewed by replacing the electrodes and electrolyte. Open containers are unsuitable for mobile or portable use. Wet cells were used commercially in the telegraph and telephone systems. Early electric cars used semi-sealed wet cells.

One important classification for batteries is by their life cycle. "Primary" batteries can produce current as soon as assembled, but once the active elements are consumed, they cannot be electrically recharged. The development of the lead-acid battery and subsequent "secondary" or "chargeable" types allowed energy to be restored to the cell, extending the life of permanently assembled cells. The introduction of nickel and lithium based batteries in the latter half of the 20th century made the development of innumerable portable electronic devices feasible, from powerful flashlights to mobile phones. Very large stationary batteries find some applications in grid energy storage, helping to stabilize electric power distribution networks.

Invention

From the mid 18th century on, before there were batteries, experimenters used Leyden jars to store electrical charge. As an early form of capacitor, Leyden jars, unlike electrochemical cells, stored their charge physically and would release it all at once. Many experimenters took to hooking several Leyden jars together to create a stronger charge and one of them, the colonial American inventor Benjamin Franklin, may have been the first to call his grouping an "electrical battery", a play on the military term for weapons functioning together.

Based on some findings by Luigi Galvani, Alessandro Volta, a friend and fellow scientist, believed observed electrical phenomena were caused by two different metals joined by a moist intermediary. He verified this hypothesis through experiments and published the results in 1791. In 1800, Volta invented the first true battery, storing and releasing a charge through a chemical reaction instead of physically, which came to be known as the voltaic pile. The voltaic pile consisted of pairs of copper and zinc discs piled on top of each other, separated by a layer of cloth or cardboard soaked in brine (i.e., the electrolyte). Unlike the Leyden jar, the voltaic pile produced continuous electricity and stable current, and lost little charge over time when not in use, though his early models could not produce a voltage strong enough to produce sparks. He experimented with various metals and found that zinc and silver gave the best results.

Volta believed the current was the result of two different materials simply touching each other – an obsolete scientific theory known as contact tension – and not the result of chemical reactions. As a consequence, he regarded the corrosion of the zinc plates as an unrelated flaw that could perhaps be fixed by changing the materials somehow. However, no scientist ever succeeded in preventing this corrosion. In fact, it was observed that the corrosion was faster when a higher current was drawn. This suggested that the corrosion was actually integral to the battery's ability to produce a current. This, in part, led to the rejection of Volta's contact tension theory in favor of the electrochemical theory. Volta's illustrations of his Crown of Cups and voltaic pile have extra metal disks, now known to be unnecessary, on both the top and bottom. The figure associated with this section, of the zinc-copper voltaic pile, has the modern design, an indication that "contact tension" is not the source of electromotive force for the voltaic pile.

Volta's original pile models had some technical flaws, one of them involving the electrolyte leaking and causing short-circuits due to the weight of the discs compressing the brine-soaked cloth. A Scotsman named William Cruickshank solved this problem by laying the elements in a box instead of piling them in a stack. This was known as the trough battery. Volta himself invented a variant that consisted of a chain of cups filled with a salt solution, linked together by metallic arcs dipped into the liquid. This was known as the Crown of Cups. These arcs were made of two different metals (e.g., zinc and copper) soldered together. This model also proved to be more efficient than his original piles, though it did not prove as popular.

Another problem with Volta's batteries was short battery life (an hour's worth at best), which was caused by two phenomena. The first was that the current produced electrolyzed the electrolyte solution, resulting in a film of hydrogen bubbles forming on the copper, which steadily increased the internal resistance of the battery (this effect, called polarization, is counteracted in modern cells by additional measures). The other was a phenomenon called local action, wherein minute short-circuits would form around impurities in the zinc, causing the zinc to degrade. The latter problem was solved in 1835 by the English inventor William Sturgeon, who found that amalgamated zinc, whose surface had been treated with some mercury, did not suffer from local action.

Despite its flaws, Volta's batteries provide a steadier current than Leyden jars, and made possible many new experiments and discoveries, such as the first electrolysis of water by the English surgeon Anthony Carlisle and the English chemist William Nicholson.

First practical batteries

Daniell cell

Schematic representation of Daniell's original cell

An English professor of chemistry named John Frederic Daniell found a way to solve the hydrogen bubble problem in the Voltaic Pile by using a second electrolyte to consume the hydrogen produced by the first. In 1836, he invented the Daniell cell, which consists of a copper pot filled with a copper sulfate solution, in which is immersed an unglazed earthenware container filled with sulfuric acid and a zinc electrode. The earthenware barrier is porous, which allows ions to pass through but keeps the solutions from mixing.

The Daniell cell was a great improvement over the existing technology used in the early days of battery development and was the first practical source of electricity. It provides a longer and more reliable current than the Voltaic cell. It is also safer and less corrosive. It has an operating voltage of roughly 1.1 volts. It soon became the industry standard for use, especially with the new telegraph networks.

The Daniell cell was also used as the first working standard for definition of the volt, which is the unit of electromotive force.

Bird's cell

A version of the Daniell cell was invented in 1837 by the Guy's Hospital physician Golding Bird who used a plaster of Paris barrier to keep the solutions separate. Bird's experiments with this cell were of some importance to the new discipline of electrometallurgy.

Porous pot cell

The porous pot version of the Daniell cell was invented by John Dancer, a Liverpool instrument maker, in 1838. It consists of a central zinc anode dipped into a porous earthenware pot containing a zinc sulfate solution. The porous pot is, in turn, immersed in a solution of copper sulfate contained in a copper can, which acts as the cell's cathode. The use of a porous barrier allows ions to pass through but keeps the solutions from mixing.

Gravity cell

In the 1860s, a Frenchman named Callaud invented a variant of the Daniell cell called the gravity cell. This simpler version dispensed with the porous barrier. This reduces the internal resistance of the system and, thus, the battery yields a stronger current. It quickly became the battery of choice for the American and British telegraph networks, and was widely used until the 1950s.

The gravity cell consists of a glass jar, in which a copper cathode sits on the bottom and a zinc anode is suspended beneath the rim. Copper sulfate crystals are scattered around the cathode and then the jar is filled with distilled water. As the current is drawn, a layer of zinc sulfate solution forms at the top around the anode. This top layer is kept separate from the bottom copper sulfate layer by its lower density and by the polarity of the cell.

The zinc sulfate layer is clear in contrast to the deep blue copper sulfate layer, which allows a technician to measure the battery life with a glance. On the other hand, this setup means the battery can be used only in a stationary appliance, or else the solutions mix or spill. Another disadvantage is that a current has to be continually drawn to keep the two solutions from mixing by diffusion, so it is unsuitable for intermittent use.

Poggendorff cell

The German scientist Johann Christian Poggendorff overcame the problems with separating the electrolyte and the depolariser using a porous earthenware pot in 1842. In the Poggendorff cell, sometimes called Grenet Cell due to the works of Eugene Grenet around 1859, the electrolyte is dilute sulphuric acid and the depolariser is chromic acid. The two acids are physically mixed together, eliminating the porous pot. The positive electrode (cathode) is two carbon plates, with a zinc plate (negative or anode) positioned between them. Because of the tendency of the acid mixture to react with the zinc, a mechanism is provided to raise the zinc electrode clear of the acids.

The cell provides 1.9 volts. It was popular with experimenters for many years due to its relatively high voltage; greater ability to produce a consistent current and lack of any fumes, but the relative fragility of its thin glass enclosure and the necessity of having to raise the zinc plate when the cell is not in use eventually saw it fall out of favour. The cell was also known as the 'chromic acid cell', but principally as the 'bichromate cell'. This latter name came from the practice of producing the chromic acid by adding sulphuric acid to potassium dichromate, even though the cell itself contains no dichromate.

The Fuller cell was developed from the Poggendorff cell. Although the chemistry is principally the same, the two acids are once again separated by a porous container and the zinc is treated with mercury to form an amalgam.

Grove cell

The Welshman William Robert Grove invented the Grove cell in 1839. It consists of a zinc anode dipped in sulfuric acid and a platinum cathode dipped in nitric acid, separated by porous earthenware. The Grove cell provides a high current and nearly twice the voltage of the Daniell cell, which made it the favoured cell of the American telegraph networks for a time. However, it gives off poisonous nitric oxide fumes when operated. The voltage also drops sharply as the charge diminishes, which became a liability as telegraph networks grew more complex. Platinum was and still is very expensive.

Dun cell

Alfred Dun 1885, nitro-muriatic acid (aqua regis) – iron and carbon:

In the new element there can be used advantageously as exciting-liquid in the first case such solutions as have in a concentrated condition great depolarizing-power, which effect the whole depolarization chemically without necessitating the mechanical expedient of increased carbon surface. It is preferred to use iron as the positive electrode, and as exciting-liquid nitro muriatic acid (aqua regis), the mixture consisting of muriatic and nitric acids. The nitro-muriatic acid, as explained above, serves for filling both cells. For the carbon-cells it is used strong or very slightly diluted, but for the other cells very diluted, (about one-twentieth, or at the most one-tenth). The element containing in one cell carbon and concentrated nitro-muriatic acid and in the other cell iron and dilute nitro-muriatic acid remains constant for at least twenty hours when employed for electric incandescent lighting.

Rechargeable batteries and dry cells

Lead-acid

Up to this point, all existing batteries would be permanently drained when all their chemical reactants were spent. In 1859, Gaston Planté invented the lead–acid battery, the first-ever battery that could be recharged by passing a reverse current through it. A lead-acid cell consists of a lead anode and a lead dioxide cathode immersed in sulfuric acid. Both electrodes react with the acid to produce lead sulfate, but the reaction at the lead anode releases electrons whilst the reaction at the lead dioxide consumes them, thus producing a current. These chemical reactions can be reversed by passing a reverse current through the battery, thereby recharging it.

Planté's first model consisted of two lead sheets separated by rubber strips and rolled into a spiral. His batteries were first used to power the lights in train carriages while stopped at a station. In 1881, Camille Alphonse Faure invented an improved version that consists of a lead grid lattice into which is pressed a lead oxide paste, forming a plate. Multiple plates can be stacked for greater performance. This design is easier to mass-produce.

Compared to other batteries, Planté's is rather heavy and bulky for the amount of energy it can hold. However, it can produce remarkably large currents in surges, because it has very low internal resistance, meaning that a single battery can be used to power multiple circuits.

The lead-acid battery is still used today in automobiles and other applications where weight is not a big factor. The basic principle has not changed since 1859. In the early 1930s, a gel electrolyte (instead of a liquid) produced by adding silica to a charged cell was used in the LT battery of portable vacuum-tube radios. In the 1970s, "sealed" versions became common (commonly known as a "gel cell" or "SLA"), allowing the battery to be used in different positions without failure or leakage.

Today cells are classified as "primary" if they produce a current only until their chemical reactants are exhausted, and "secondary" if the chemical reactions can be reversed by recharging the cell. The lead-acid cell was the first "secondary" cell.

Leclanché cell

In 1866, Georges Leclanché invented a battery that consists of a zinc anode and a manganese dioxide cathode wrapped in a porous material, dipped in a jar of ammonium chloride solution. The manganese dioxide cathode has a little carbon mixed into it as well, which improves conductivity and absorption. It provided a voltage of 1.4 volts. This cell achieved very quick success in telegraphy, signaling, and electric bell work.

The dry cell form was used to power early telephones—usually from an adjacent wooden box affixed to fit batteries before telephones could draw power from the telephone line itself. The Leclanché cell can not provide a sustained current for very long. In lengthy conversations, the battery would run down, rendering the conversation inaudible. This is because certain chemical reactions in the cell increase the internal resistance and, thus, lower the voltage.

Zinc-carbon cell, the first dry cell

Many experimenters tried to immobilize the electrolyte of an electrochemical cell to make it more convenient to use. The Zamboni pile of 1812 is a high-voltage dry battery but capable of delivering only minute currents. Various experiments were made with cellulose, sawdust, spun glass, asbestos fibers, and gelatine.

In 1886, Carl Gassner obtained a German patent on a variant of the Leclanché cell, which came to be known as the dry cell because it does not have a free liquid electrolyte. Instead, the ammonium chloride is mixed with plaster of Paris to create a paste, with a small amount of zinc chloride added in to extend the shelf life. The manganese dioxide cathode is dipped in this paste, and both are sealed in a zinc shell, which also acts as the anode. In November 1887, he obtained U.S. patent 373,064 for the same device.

Unlike previous wet cells, Gassner's dry cell is more solid, does not require maintenance, does not spill, and can be used in any orientation. It provides a potential of 1.5 volts. The first mass-produced model was the Columbia dry cell, first marketed by the National Carbon Company in 1896. The NCC improved Gassner's model by replacing the plaster of Paris with coiled cardboard, an innovation that left more space for the cathode and made the battery easier to assemble. It was the first convenient battery for the masses and made portable electrical devices practical, and led directly to the invention of the flashlight.

The zinc–carbon battery (as it came to be known) is still manufactured today.

In parallel, in 1887 Wilhelm Hellesen developed his own dry cell design. It has been claimed that Hellesen's design preceded that of Gassner.

In 1887, a dry-battery was developed by Sakizō Yai (屋井先蔵) of Japan, then patented in 1892. In 1893, Sakizō Yai's dry-battery was exhibited in World's Columbian Exposition and commanded considerable international attention.

NiCd, the first alkaline battery

In 1899, a Swedish scientist named Waldemar Jungner invented the nickel–cadmium battery, a rechargeable battery that has nickel and cadmium electrodes in a potassium hydroxide solution; the first battery to use an alkaline electrolyte. It was commercialized in Sweden in 1910 and reached the United States in 1946. The first models were robust and had significantly better energy density than lead-acid batteries, but were much more expensive.

20th century: new technologies and ubiquity

Size	Year introduced
D	1898
AA	1907
AAA	1911
9V	1956

Nickel-iron

Waldemar Jungner patented a nickel–iron battery in 1899, the same year as his Ni-Cad battery patent, but found it to be inferior to its cadmium counterpart and, as a consequence, never bothered developing it. It produced a lot more hydrogen gas when being charged, meaning it could not be sealed, and the charging process was less efficient (it was, however, cheaper).

Seeing a way to make a profit in the already competitive lead-acid battery market, Thomas Edison worked in the 1890s on developing an alkaline based battery that he could get a patent on. Edison thought that if he produced a lightweight and durable battery electric cars would become the standard, with his firm as its main battery vendor. After many experiments, and probably borrowing from Jungner's design, he patented an alkaline based nickel–iron battery in 1901. However, customers found his first model of the alkaline nickel–iron battery to be prone to leakage leading to short battery life, and it did not outperform the lead-acid cell by much either. Although Edison was able to produce a more reliable and powerful model seven years later, by this time the inexpensive and reliable Model T Ford had made gasoline engine cars the standard. Nevertheless, Edison's battery achieved great success in other applications such as electric and diesel-electric rail vehicles, providing backup power for railroad crossing signals, or to provide power for the lamps used in mines.

Common alkaline batteries

Until the late 1950s, the zinc–carbon battery continued to be a popular primary cell battery, but its relatively low battery life hampered sales. The Canadian engineer Lewis Urry, working for the Union Carbide, first at the National Carbon Co. in Ontario and, by 1955, at the National Carbon Company Parma Research Laboratory in Cleveland, Ohio, was tasked with finding a way to extend the life of zinc-carbon batteries. Building on earlier work by Edison, Urry decided instead that alkaline batteries held more promise. Until then, longer-lasting alkaline batteries were unfeasibly expensive. Urry's battery consists of a manganese dioxide cathode and a powdered zinc anode with an alkaline electrolyte. Using powdered zinc gives the anode a greater surface area. These batteries were put on the market in 1959.

Nickel-hydrogen and nickel metal-hydride

The nickel–hydrogen battery entered the market as an energy-storage subsystem for commercial communication satellites.

The first consumer grade nickel–metal hydride batteries (NiMH) for smaller applications appeared on the market in 1989 as a variation of the 1970s nickel–hydrogen battery. NiMH batteries tend to have longer lifespans than NiCd batteries (and their lifespans continue to increase as manufacturers experiment with new alloys) and, since cadmium is toxic, NiMH batteries are less damaging to the environment.

Alkali metal-ion batteries

Curve of price and capacity of lithium-ion batteries over time; the price of these batteries declined by 97% in three decades.

Lithium is the alkali metal with lowest density and with the greatest electrochemical potential and energy-to-weight ratio. The low atomic weight and small size of its ions also speeds its diffusion, likely making it an ideal battery material. Experimentation with lithium batteries began in 1912 under American physical chemist Gilbert N. Lewis, but commercial lithium batteries did not come to market until the 1970s in the form of the lithium-ion battery. Three volt lithium primary cells such as the CR123A type and three volt button cells are still widely used, especially in cameras and very small devices.

Three important developments regarding lithium batteries occurred in the 1980s. In 1980, an American chemist, John B. Goodenough, discovered the LiCoO₂ (Lithium cobalt oxide) cathode (positive lead) and a Moroccan research scientist, Rachid Yazami, discovered the graphite anode (negative lead) with the solid electrolyte. In 1981, Japanese chemists Tokio Yamabe and Shizukuni Yata discovered a novel nano-carbonacious-PAS (polyacene) and found that it was very effective for the anode in the conventional liquid electrolyte. This led a research team managed by Akira Yoshino of Asahi Chemical, Japan, to build the first lithium-ion battery prototype in 1985, a rechargeable and more stable version of the lithium battery; Sony commercialized the lithium-ion battery in 1991. In 2019, John Goodenough, Stanley Whittingham, and Akira Yoshino, were awarded the Nobel Prize in Chemistry, for their development of lithium-ion batteries.

In 1997, the lithium polymer battery was released by Sony and Asahi Kasei. These batteries hold their electrolyte in a solid polymer composite instead of in a liquid solvent, and the electrodes and separators are laminated to each other. The latter difference allows the battery to be encased in a flexible wrapping instead of in a rigid metal casing, which means such batteries can be specifically shaped to fit a particular device. This advantage has favored lithium polymer batteries in the design of portable electronic devices such as mobile phones and personal digital assistants, and of radio-controlled aircraft, as such batteries allow for a more flexible and compact design. They generally have a lower energy density than normal lithium-ion batteries.

High costs and concerns about mineral extraction associated with lithium chemistry have renewed interest in sodium-ion battery development, with early electric vehicle product launches in 2023.

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