Argyrodite

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Argyrodite
Argyrodite-170093.jpg
General
Category Sulfide mineral
Formula
(repeating unit)
Ag8GeS6
IMA symbol Agy [1]
Strunz classification 2.BA.35
Crystal system Orthorhombic
Crystal class Pyramidal (mm2)
H-M symbol: (mm2)
Space group Pna21
Unit cell a = 15.149, b = 7.476
c = 10.589 [Å]; Z = 4
Identification
ColorBlack, purplish tinge
Crystal habit Pseudo-octahedra or pseudo-cubic, dodecahedra, cubes; radiating crystal aggregates, botryoidal crusts, or massive
Twinning Pseudospinel law {111} penetration twins
Cleavage Absent
Fracture Uneven to conchoidal
Mohs scale hardness2.5
Luster Metallic
Diaphaneity Opaque
Specific gravity 6.2-6.5
Optical propertiesWeakly anisotropic
Pleochroism Weak
References [2] [3]

Argyrodite is an uncommon silver germanium sulfide mineral with formula Ag8GeS6. The color is iron-black with a purplish tinge, and the luster metallic.

Discovered and named by Albin Weisbach in 1886, [4] it is of interest as it was the material from which Clemens Winkler isolated the element germanium, 15 years after it had been postulated by Mendeleev. It was first described for an occurrence in the Himmelsfürst Mine, Erzgebirge, Freiberg, Saxony, Germany. [3]

The Freiberg mineral had previously been imperfectly described by August Breithaupt under the name "Plusinglanz", and Bolivian crystals were incorrectly described in 1849 as crystallized brongniardite. [5]

Isomorphous with argyrodite is the corresponding tin bearing mineral Ag8SnS6, also found in Bolivia as pseudocubic crystals, and known by the name canfieldite. [5] There is also a related mineral, putzite, with composition (Cu4.7Ag3.3)GeS6.

Argyrodite gets its name from the Greek words that loosely translate into "rich in silver". [2]

Argyrodite-type material

The term argyrodite is also used for other materials with a similar crystal structure, in particular lithium based argyrodite-type materials, which have received interest from researchers as a potential solid-state electrolyte for lithium-ion batteries. [6] [7]

They are considered to be of the form:

Li
7-x
BCh
6-x
X
x

With x between 0 and 1, B denoting either phosphor or arsenic, Ch for sulfur or selenium and X for chlorine, bromine or iodine. [6] However, other forms exist and can be grouped into three main categories, halogen-based argyrodites, halogen-based argyrodites doped with additional semi-metal or metal components and halogen-free argyrodites based on Li, P, S along with a semi-metal. [8]

Related Research Articles

<span class="mw-page-title-main">Lithium</span> Chemical element, symbol Li and atomic number 3

Lithium is a chemical element with the symbol Li and atomic number 3. It is a soft, silvery-white alkali metal. Under standard conditions, it is the least dense metal and the least dense solid element. Like all alkali metals, lithium is highly reactive and flammable, and must be stored in vacuum, inert atmosphere, or inert liquid such as purified kerosene or mineral oil. It exhibits a metallic luster. It corrodes quickly in air to a dull silvery gray, then black tarnish. It does not occur freely in nature, but occurs mainly as pegmatitic minerals, which were once the main source of lithium. Due to its solubility as an ion, it is present in ocean water and is commonly obtained from brines. Lithium metal is isolated electrolytically from a mixture of lithium chloride and potassium chloride.

<span class="mw-page-title-main">Sphalerite</span> Zinc-iron sulfide mineral

Sphalerite is a sulfide mineral with the chemical formula (Zn,Fe)S. It is the most important ore of zinc. Sphalerite is found in a variety of deposit types, but it is primarily in sedimentary exhalative, Mississippi-Valley type, and volcanogenic massive sulfide deposits. It is found in association with galena, chalcopyrite, pyrite, calcite, dolomite, quartz, rhodochrosite, and fluorite.

<span class="mw-page-title-main">Lepidolite</span> Light micas with substantial lithium

Lepidolite is a lilac-gray or rose-colored member of the mica group of minerals with chemical formula K(Li,Al)3(Al,Si,Rb)4O10(F,OH)2. It is the most abundant lithium-bearing mineral and is a secondary source of this metal. It is the major source of the alkali metal rubidium.

<span class="mw-page-title-main">Lithium-ion battery</span> Rechargeable battery type

A lithium-ion or Li-ion battery is a type of rechargeable battery which uses the reversible reduction of lithium ions to store energy. The negative electrode of a conventional lithium-ion cell is typically graphite, a form of carbon. This negative electrode is sometimes called the anode as it acts as an anode during discharge. The positive electrode is typically a metal oxide; the positive electrode is sometimes called the cathode as it acts a cathode during discharge. Positive and negative electrodes remain positive and negative in normal use whether charging or discharging and are therefore clearer terms to use than anode and cathode which are reversed during charging.

<span class="mw-page-title-main">Lithium polymer battery</span> Lithium-ion battery using a polymer electrolyte

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<span class="mw-page-title-main">Covellite</span> Sulfide mineral

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<span class="mw-page-title-main">Clemens Winkler</span> German chemist who discovered germanium

Clemens Alexander Winkler was a German chemist who discovered the element germanium in 1886, solidifying Dmitri Mendeleev's theory of periodicity.

<span class="mw-page-title-main">Freiberg University of Mining and Technology</span> Public university in Freiberg, Saxony, Germany

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<span class="mw-page-title-main">Lithiophilite</span>

Lithiophilite is a mineral containing the element lithium. It is lithium manganese(II) phosphate with chemical formula LiMnPO4. It occurs in pegmatites often associated with triphylite, the iron end member in a solid solution series. The mineral with intermediate composition is known as sicklerite and has the chemical formula Li(Mn,Fe)PO4). The name lithiophilite is derived from the Greek philos (φιλός) "friend," as lithiophilite is usually found with lithium.

<span class="mw-page-title-main">Canfieldite</span>

Canfieldite is a rare silver tin sulfide mineral with formula: Ag8SnS6. The mineral typically contains variable amounts of germanium substitution in the tin site and tellurium in the sulfur site. There is a complete series between canfieldite and its germanium analogue, argyrodite. It forms black orthorhombic crystals which often appear to be cubic in form due to twinning. The most typical form is as botryoidal rounded grape-like masses. Its Mohs hardness is 2.5 and the specific gravity is 6.28. Canfieldite exhibits conchoidal fracturing and no cleavage.

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An Ion gel is a composite material consisting of an ionic liquid immobilized by an inorganic or a polymer matrix. The material has the quality of maintaining high ionic conductivity while in the solid state. To create an ion gel, the solid matrix is mixed or synthesized in-situ with an ionic liquid. A common practice is to utilize a block copolymer which is polymerized in solution with an ionic liquid so that a self-assembled nanostructure is generated where the ions are selectively soluble. Ion gels can also be made using non-copolymer polymers such as cellulose, oxides such as silicon dioxide or refractory materials such as boron nitride.

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Research in lithium-ion batteries has produced many proposed refinements of lithium-ion batteries. Areas of research interest have focused on improving energy density, safety, rate capability, cycle durability, flexibility, and cost.

<span class="mw-page-title-main">NASICON</span>

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.

<span class="mw-page-title-main">Solid-state electrolyte</span>

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 utilization 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 chemical stability against lithium metal, giving it an advantage for use as an electrolyte in solid-state batteries.

<span class="mw-page-title-main">Lithium aluminium germanium phosphate</span> Chemical compound

Lithium aluminium germanium phosphate, typically known with the acronyms LAGP or LAGPO, is an inorganic ceramic solid material whose general formula is Li
1+x
Al
x
Ge
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
10
GeP
2
S
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
1.5
Al
0.5
Ge
1.5
(PO
4
)
3
, which is also the typically used material in battery applications.

References

  1. Warr, L.N. (2021). "IMA–CNMNC approved mineral symbols". Mineralogical Magazine. 85 (3): 291–320. Bibcode:2021MinM...85..291W. doi: 10.1180/mgm.2021.43 . S2CID   235729616.
  2. 1 2 Handbook of Mineralogy
  3. 1 2 Mindat.org
  4. Weisbach, Albin (1886). "Argyrodit, ein neues Silbererz". Neues Jahrbuch für Geologie und Paläontologie. 2: 67.
  5. 1 2 Spencer 1911, p. 488.
  6. 1 2 Raghavan, Prasanth; Fatima, Jabeen (2021-04-05). Ceramic and Specialty Electrolytes for Energy Storage Devices. CRC Press. ISBN   978-1-000-35180-4.
  7. Brinek, Marina; Hiebl, Caroline; Wilkening, H. Martin R. (2020-06-09). "Understanding the Origin of Enhanced Li-Ion Transport in Nanocrystalline Argyrodite-Type Li6PS5I". Chemistry of Materials. 32 (11): 4754–4766. doi:10.1021/acs.chemmater.0c01367. ISSN   0897-4756. PMC   7304077 . PMID   32565618.
  8. Lu, Xin; Tsai, Chih-Long; Yu, Shicheng; He, Hongying; Camara, Osmane; Tempel, Hermann; Liu, Zigeng; Windmüller, Anna; Alekseev, Evgeny V.; Köcher, Simone; Basak, Shibabrata; Lu, Li; Eichel, Rüdiger A.; Kungl, Hans (2022). "Lithium phosphosulfide electrolytes for solid-state batteries: Part II". Functional Materials Letters. 15 (07n08): 2240002. doi:10.1142/S1793604722400021. ISSN   1793-6047.

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