A proton conductor is an electrolyte, typically a solid electrolyte, in which H+ [1] are the primary charge carriers.
Acid solutions exhibit proton-conductivity, while pure proton conductors are usually dry solids. Typical materials are polymers or ceramic. Typically, the pores in practical materials are small such that protons dominate direct current and transport of cations or bulk solvent is prevented. Water ice is a common example of a pure proton conductor, albeit a relatively poor one. [2] A special form of water ice, superionic water, has been shown to conduct much more efficiently than normal water ice. [3]
Solid-phase proton conduction was first suggested by Alfred Rene Jean Paul Ubbelohde and S. E. Rogers. in 1950, [4] although electrolyte proton currents have been recognized since 1806.
Proton conduction has also been observed in the new type of proton conductors for fuel cells – protic organic ionic plastic crystals (POIPCs), such as 1,2,4-triazolium perfluorobutanesulfonate [5] and imidazolium methanesulfonate. [6] In particular, a high ionic conductivity of 10 mS/cm is reached at 185 °C in the plastic phase of imidazolium methanesulfonate.
When in the form of thin membranes, proton conductors are an essential part of small, inexpensive fuel cells. The polymer nafion is a typical proton conductor in fuel cells. A jelly-like substance similar to Nafion residing in the ampullae of Lorenzini of sharks has proton conductivity only slightly lower than nafion. [7] [8]
High proton conductivity has been reported among alkaline-earth cerates and zirconate based perovskite materials such as acceptor doped SrCeO3, BaCeO3 and BaZrO3. [9] Relatively high proton conductivity has also been found in rare-earth ortho-niobates and ortho-tantalates as well as rare-earth tungstates. [10]
An electrolyte is a substance that conducts electricity through the movement of ions, but not through the movement of electrons. This includes most soluble salts, acids, and bases, dissolved in a polar solvent like water. Upon dissolving, the substance separates into cations and anions, which disperse uniformly throughout the solvent. Solid-state electrolytes also exist. In medicine and sometimes in chemistry, the term electrolyte refers to the substance that is dissolved.
Nafion is a brand name for a sulfonated tetrafluoroethylene based fluoropolymer-copolymer synthesized in 1962 by Dr. Donald J. Connolly at the DuPont Experimental Station in Wilmington Delaware. Additional work on the polymer family was performed in the late 1960s by Dr. Walther Grot of DuPont. Nafion is a brand of the Chemours company. It is the first of a class of synthetic polymers with ionic properties that are called ionomers. Nafion's unique ionic properties are a result of incorporating perfluorovinyl ether groups terminated with sulfonate groups onto a tetrafluoroethylene (PTFE) backbone. Nafion has received a considerable amount of attention as a proton conductor for proton exchange membrane (PEM) fuel cells because of its excellent chemical and mechanical stability in the harsh conditions of this application.
Proton-exchange membrane fuel cells (PEMFC), also known as polymer electrolyte membrane (PEM) fuel cells, are a type of fuel cell being developed mainly for transport applications, as well as for stationary fuel-cell applications and portable fuel-cell applications. Their distinguishing features include lower temperature/pressure ranges and a special proton-conducting polymer electrolyte membrane. PEMFCs generate electricity and operate on the opposite principle to PEM electrolysis, which consumes electricity. They are a leading candidate to replace the aging alkaline fuel-cell technology, which was used in the Space Shuttle.
An ionic liquid (IL) is a salt in the liquid state at ambient conditions. In some contexts, the term has been restricted to salts whose melting point is below a specific temperature, such as 100 °C (212 °F). While ordinary liquids such as water and gasoline are predominantly made of electrically neutral molecules, ionic liquids are largely made of ions. These substances are variously called liquid electrolytes, ionic melts, ionic fluids, fused salts, liquid salts, or ionic glasses.
A proton-exchange membrane, or polymer-electrolyte membrane (PEM), is a semipermeable membrane generally made from ionomers and designed to conduct protons while acting as an electronic insulator and reactant barrier, e.g. to oxygen and hydrogen gas. This is their essential function when incorporated into a membrane electrode assembly (MEA) of a proton-exchange membrane fuel cell or of a proton-exchange membrane electrolyser: separation of reactants and transport of protons while blocking a direct electronic pathway through the membrane.
Deep eutectic solvents or DESs are solutions of Lewis or Brønsted acids and bases which form a eutectic mixture. Deep eutectic solvents are highly tunable through varying the structure or relative ratio of parent components and thus have a wide variety of potential applications including catalytic, separation, and electrochemical processes. The parent components of deep eutectic solvents engage in a complex hydrogen bonding network which results in significant freezing point depression as compared to the parent compounds. The extent of freezing point depression observed in DESs is well illustrated by a mixture of choline chloride and urea in a 1:2 mole ratio. Choline chloride and urea are both solids at room temperature with melting points of 302 °C and 133 °C respectively, yet the combination of the two in a 1:2 molar ratio forms a liquid with a freezing point of 12 °C. DESs share similar properties to ionic liquids such as tunability and lack of flammability yet are distinct in that ionic liquids are neat salts composed exclusively of discrete ions. In contrast to ordinary solvents, such as volatile organic compounds, DESs are non-flammable, and possess low vapour pressures and toxicity.
A protonic ceramic fuel cell or PCFC is a fuel cell based around a ceramic, solid, electrolyte material as the proton conductor from anode to cathode. These fuel cells produce electricity by removing an electron from a hydrogen atom, pushing the charged hydrogen atom through the ceramic membrane, and returning the electron to the hydrogen on the other side of the ceramic membrane during a reaction with oxygen. The reaction of many proposed fuels in PCFCs produce electricity and heat, the latter keeping the device at a suitable temperature. Efficient proton conductivity through most discovered ceramic electrolyte materials require elevated operational temperatures around 400-700 degrees Celsius, however intermediate temperature (200-400 degrees Celsius) ceramic fuel cells and lower temperature alternative are an active area of research. In addition to hydrogen gas, the ability to operate at intermediate and high temperatures enables the use of a variety of liquid hydrogen carrier fuels, including: ammonia, and methane. The technology shares the thermal and kinetic advantages of high temperature molten carbonate and solid oxide fuel cells, while exhibiting all of the intrinsic benefits of proton conduction in proton-exchange membrane fuel cells (PEMFC) and phosphoric acid fuel cells (PAFC). PCFCs exhaust water at the cathode and unused fuel, fuel reactant products and fuel impurities at the anode. Common chemical compositions of the ceramic membranes are barium zirconate (BaZrO3), barium cerate (BaCeO3), caesium dihydrogen phosphate (CsH2PO4), and complex solid solutions of those materials with other ceramic oxides. The acidic oxide ceramics are sometimes broken into their own class of protonic ceramic fuel cells termed "solid acid fuel cells".
Nanoionics is the study and application of phenomena, properties, effects, methods and mechanisms of processes connected with fast ion transport (FIT) in all-solid-state nanoscale systems. The topics of interest include fundamental properties of oxide ceramics at nanometer length scales, and fast-ion conductor /electronic conductor heterostructures. Potential applications are in electrochemical devices for conversion and storage of energy, charge and information. The term and conception of nanoionics were first introduced by A.L. Despotuli and V.I. Nikolaichik in January 1992.
In materials science, fast ion conductors are solid conductors with highly mobile ions. These materials are important in the area of solid state ionics, and are also known as solid electrolytes and superionic conductors. These materials are useful in batteries and various sensors. Fast ion conductors are used primarily in solid oxide fuel cells. As solid electrolytes they allow the movement of ions without the need for a liquid or soft membrane separating the electrodes. The phenomenon relies on the hopping of ions through an otherwise rigid crystal structure.
Ionic conductivity is a measure of a substance's tendency towards ionic conduction. Ionic conduction is the movement of ions. The phenomenon is observed in solids and solutions. Ionic conduction is one mechanism of current.
An advanced superionic conductor (AdSIC) in materials science, is a fast-ion conductor that has a crystal structure close to optimal for fast-ion transport (FIT).
A plastic crystal is a crystal composed of weakly interacting molecules that possess some orientational or conformational degree of freedom. The name plastic crystal refers to the mechanical softness of such phases: they resemble waxes and are easily deformed. If the internal degree of freedom is molecular rotation, the name rotor phase or rotatory phase is also used. Typical examples are the modifications Methane I and Ethane I.
Solid-state ionics is the study of ionic-electronic mixed conductor and fully ionic conductors and their uses. Some materials that fall into this category include inorganic crystalline and polycrystalline solids, ceramics, glasses, polymers, and composites. Solid-state ionic devices, such as solid oxide fuel cells, can be much more reliable and long-lasting, especially under harsh conditions, than comparable devices with fluid electrolytes.
LISICON is an acronym for LIthiumSuper Ionic CONductor, which refers to a family of solids with the chemical formula Li2+2xZn1−xGeO4.
NASICON is an acronym for sodium (Na) super ionic conductor, which usually refers to a family of solids with the chemical formula Na1+xZr2SixP3−xO12, 0 < x < 3. In a broader sense, it is also used for similar compounds where Na, Zr and/or Si are replaced by isovalent elements. NASICON compounds have high ionic conductivities, on the order of 10−3 S/cm, which rival those of liquid electrolytes. They are caused by hopping of Na ions among interstitial sites of the NASICON crystal lattice.
Caesium bisulfate or cesium hydrogen sulfate is an inorganic compound with the formula CsHSO4. The caesium salt of bisulfate, it is a colorless solid obtained by combining Cs2SO4 and H2SO4.
Mixed conductors, also known as mixed ion-electron conductors(MIEC), are a single-phase material that has significant conduction ionically and electronically. Due to the mixed conduction, a formally neutral species can transport in a solid and therefore mass storage and redistribution are enabled. Mixed conductors are well known in conjugation with high-temperature superconductivity and are able to capacitate rapid solid-state reactions.
A solid-state electrolyte (SSE) is a solid ionic conductor and electron-insulating material and it is the characteristic component of the solid-state battery. It is useful for applications in electrical energy storage (EES) in substitution of the liquid electrolytes found in particular in lithium-ion battery. The main advantages are the absolute safety, no issues of leakages of toxic organic solvents, low flammability, non-volatility, mechanical and thermal stability, easy processability, low self-discharge, higher achievable power density and cyclability. This makes possible, for example, the use of a lithium metal anode in a practical device, without the intrinsic limitations of a liquid electrolyte thanks to the property of lithium dendrite suppression in the presence of a solid-state electrolyte membrane. The use of a high capacity anode and low reduction potential, like lithium with a specific capacity of 3860 mAh g−1 and a reduction potential of -3.04 V vs SHE, in substitution of the traditional low capacity graphite, which exhibits a theoretical capacity of 372 mAh g−1 in its fully lithiated state of LiC6, is the first step in the realization of a lighter, thinner and cheaper rechargeable battery. Moreover, this allows the reach of gravimetric and volumetric energy densities, high enough to achieve 500 miles per single charge in an electric vehicle. Despite the promising advantages, there are still many limitations that are hindering the transition of SSEs from academia research to large-scale production, depending mainly on the poor ionic conductivity compared to that of liquid counterparts. However, many car OEMs (Toyota, BMW, Honda, Hyundai) expect to integrate these systems into viable devices and to commercialize solid-state battery-based electric vehicles by 2025.
Lithium lanthanum zirconium oxide (LLZO, Li7La3Zr2O12) or lithium lanthanum zirconate is a lithium-stuffed garnet material that is under investigation for its use in solid-state electrolytes in lithium-based battery technologies. LLZO has a high ionic conductivity and thermal and chemical stability against reactions with prospective electrode materials, mainly lithium metal, giving it an advantage for use as an electrolyte in solid-state batteries. LLZO exhibits favorable characteristics, including the accessibility of starting materials, cost-effectiveness, and straightforward preparation and densification processes. These attributes position this zirconium-containing lithium garnet as a promising solid electrolyte for all-solid-state lithium-ion rechargeable batteries.
Lithium aluminium germanium phosphate, typically known with the acronyms LAGP or LAGPO, is an inorganic ceramic solid material whose general formula is Li
1+xAl
xGe
2-x(PO
4)
3. LAGP belongs to the NASICON family of solid conductors and has been applied as a solid electrolyte in all-solid-state lithium-ion batteries. Typical values of ionic conductivity in LAGP at room temperature are in the range of 10–5 - 10–4 S/cm, even if the actual value of conductivity is strongly affected by stoichiometry, microstructure, and synthesis conditions. Compared to lithium aluminium titanium phosphate (LATP), which is another phosphate-based lithium solid conductor, the absence of titanium in LAGP improves its stability towards lithium metal. In addition, phosphate-based solid electrolytes have superior stability against moisture and oxygen compared to sulfide-based electrolytes like Li
10GeP
2S
12 (LGPS) and can be handled safely in air, thus simplifying the manufacture process. Since the best performances are encountered when the stoichiometric value of x is 0.5, the acronym LAGP usually indicates the particular composition of Li
1.5Al
0.5Ge
1.5(PO
4)
3, which is also the typically used material in battery applications.