Siegenite

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Siegenite
Siegenite-261468.jpg
Siegenite from Buick mine, Bixby, Viburnum Trend District, Iron County, Missouri, USA
General
Category Sulfide mineral
Thiospinel group
Spinel structural group
Formula
(repeating unit)		(Ni,Co)3S4
IMA symbol Seg [1]
Strunz classification 2.DA.05
Crystal system Cubic
Crystal class m3m
Space group Fd3m (#227)
Unit cell a = 9.33 Å; V = 810.94Å3
Identification
Formula mass 304.3 - 305 g/mol
ColorLight to steel-grey, violet-gray (tarnished)
Crystal habit As octahedral crystals, granular, massive
Twinning On {111}; polysynthetic
Cleavage Imperfect on {001}
Fracture Irregular to uneven, sub-conchoidal
Mohs scale hardness4.5 - 5.5
Luster Metallic
Streak Grayish black
Diaphaneity Opaque
Density 4.5 - 4.8 g/cm3 (Measured) 4.83 g/cm3 (Calculated)
References [2] [3] [4]

Siegenite (also called grimmite, or nickel cobalt sulfide) is a ternary transition metal dichalcogenide compound with the chemical formula (Ni,Co)3S4. It has been actively studied as a promising material system for electrodes in electrochemical energy applications due to its better conductivity, greater mechanical and thermal stability, and higher performance compared to metal oxides currently in use. [5] Potential applications of this material system include supercapacitors, batteries, electrocatalysis, dye-sensitized solar cells, photocatalysis, glucose sensors, and microwave absorption. [6]

Contents

In synthetic chemistry, a range of chemical compositions with the formula NixCo3−xS4 (0 < x < 3) are often referred to as the siegenite system. However, according to the new IMA list of minerals (updated November 2022), the normal spinel NiCo2S4 is called grimmite, the inverse spinel CoNi2S4 is called siegenite, and the endmembers Ni2+(Ni3+)2S4 and Co2+(Co3+)2S4 are called polydymite and linnaeite, respectively. [7] In 2020, NiCo2S4 (grimmite) is approved as a valid mineral species by the IMA. [8]

Discovery and occurrence

Siegenite was first described in 1850 for an occurrence in the Stahlberg Mine in Müsen, Siegerland, North Rhine-Westphalia, Germany and named for the locality. [2] It occurs in hydrothermal copper-nickel-iron sulfide bearing veins associated with chalcopyrite, pyrrhotite, galena, sphalerite, pyrite, millerite, gersdorffite and ullmannite. [3]

It occurs in a variety of deposits worldwide, including Brestovsko in the central Bosnian Mountains of Serbia; at Kladno in the Czech Republic; Blackcraig, Kirkcudbrightshire, Scotland. In the United States occurrences include the Mine la Motte of Madison County and the Buick mine, Bixby, Iron County and in the Sweetwater mine of Reynolds County in the Lead Belt of Missouri. In Canada, it is known from the Langis mine, Cobalt-Gowganda area, Ontario. In Africa it occurs at Shinkolobwe, Katanga Province and Kilembe, Uganda. In Japan, it is reported from the Kamaishi mine, Iwate Prefecture, and the Yokozuru mine, north Kyushu. It also occurs at Kalgoorlie, Western Australia. [3] It is found at the Browns deposit, Batchelor, Northern Territory, Australia. [2]

Crystal structure

Conventional unit cell of NiCo2S4 looking down at the [100] direction. Gray atoms are Ni, blue atoms are Co, and yellow atoms are S. NiCo2S4 crystal strcuture.png
Conventional unit cell of NiCo2S4 looking down at the [100] direction. Gray atoms are Ni, blue atoms are Co, and yellow atoms are S.

Siegenite is a member of the thiospinel group, which belongs to the cubic space group (#227) and has the Pearson symbol . Similar to normal spinels, a normal thiospinel unit cell consists of eight FCC sub unit cells of two different types, where S2- anions occupy all the FCC lattice points. The first type of sub unit cell has 2+ cations occupying 2 of the 8 tetrahedral sites and 3+ cations occupying 3/2 of the 4 octahedral sites. The second type of sub unit cell has only 3+ cations occupying 5/2 of the 4 octahedral sites. These two types of sub unit cells are alternatively stacked, forming a NaCl-type superstructure.

For a normal thiospinel (NiCo2S4), Ni2+ cations occupy 1/8 of the tetrahedral sites to form NiS4 tetrahedra and Co3+ cations occupy 1/2 of the octahedral sites to form CoS6 octahedra. Each tetrahedron shares corners with 12 neighboring octahedra, and each octahedron shares corners with 6 tetrahedra and edges with 6 octahedra. For an inverse thiospinel (CoNi2S4), Ni2+ occupy 1/8 of the octahedral sites and Co3+ occupy 1/4 of the tetrahedra sites and 1/4 of the octahedral sites. For a mixed/complex thiospinel, both metal ions occupy tetrahedral and octahedral sites and can be expressed as (AxB1−x)Td[A2-xBx]OhX4 (0 < x < 1), where A and B are metal ions, x is the degree of inversion, and and denote the tetrahedral and octahedral sites, respectively.

The powder X-ray diffraction (XRD) pattern of siegenite exhibits strong diffraction signals between 20° and 60° 2θ angles. The lattice constant of siegenite is measured to be 9.319 Å based on the strongest reflection at around 32°, corresponding to lattice plane (311), which agrees with the calculated lattice constant of 9.325 Å. [9] [10]

Electronic properties

Unlike many binary and ternary semiconductor oxides, NiCo2S4 exhibits metallic properties and high electrical conductivity, which makes it useful as an electrode material in energy storage devices. The resistivity of NiCo2S4 is ~103 μΩ cm at room temperature and its temperature coefficient of resistivity is positive and stays constant between 40 K and 300 K, which is indicative of a metallic compound. [9] NiCo2S4 also has a very low Seebeck coefficient of 5 μV K−1 and a carrier density of 3.18 × 1022 cm−3 higher than that of silver. [9]

Synthesis

Reported synthetic routes of nickel cobalt sulfide include hydrothermal [11] [12] and solvothermal [13] reactions, solvent-free thermal decomposition of xanthates, [14] SILAR method for thin films, [15] and solution-phase organometallic synthesis. [16] The hydrothermal reaction is the most widely used synthesis method to fabricate intricate nanostructures on highly porous substrates, yielding hierarchical structures that maximize redox-active surface areas and promote high-rate supercapacitive performance of Ni-Co-S-based electrodes.

Applications

Batteries and supercapacitors

(Ni,Co)3S4 is a promising electrode material for batteries and supercapacitors. Since the electronegativity of sulfur is lower than that of oxygen, (Ni,Co)3S4 has a more flexible lattice compared to its oxide counterpart, which allows easier electron and ion transport through the structure. [17] Its high ionic conductivity can be attributed to the abundance of available cation sites in the thiospinel structure, and its high redox activity comes from the highly electrochemically active Ni2+/Ni3+ and Co2+/Co3+ redox couples. In literatures, nanoporous Ni-Co-S composite materials have been shown to have both high specific capacity in Li-based batteries and high capacitance in supercapacitors. [6]

Electrocatalysis

(Ni,Co)3S4 has been considered as an alternative electrocatalyst for HER and OER reactions because of its high conductivity and low cost. It is reported that a overpotential of 87 mV for HER and 251 mV for HER can be achieved using NiCo2S4-based electrode, showing good potential for water splitting applications. [6]

Related Research Articles

<span class="mw-page-title-main">Pentlandite</span> Iron–nickel sulfide

Pentlandite is an iron–nickel sulfide with the chemical formula (Fe,Ni)9S8. Pentlandite has a narrow variation range in nickel to iron ratios (Ni:Fe), but it is usually described as 1:1. In some cases, this ratio is skewed by the presence of pyrrhotite inclusions. It also contains minor cobalt, usually at low levels as a fraction of weight.

<span class="mw-page-title-main">Lithium-ion battery</span> Type of rechargeable battery

A lithium-ion or Li-ion battery is a type of rechargeable battery that uses the reversible intercalation of Li+ ions into electronically conducting solids to store energy. In comparison with other commercial rechargeable batteries, Li-ion batteries are characterized by higher specific energy, higher energy density, higher energy efficiency, a longer cycle life, and a longer calendar life. Also noteworthy is a dramatic improvement in lithium-ion battery properties after their market introduction in 1991: over the following 30 years, their volumetric energy density increased threefold while their cost dropped tenfold. In late 2024 global demand passed 1 Terawatt-hour per year, while production capacity was more than twice that.

<span class="mw-page-title-main">Ullmannite</span> Nickel antimony sulfide mineral

Ullmannite or Nickel glance is a nickel antimony sulfide mineral with formula: NiSbS. Considerable substitution occurs with cobalt and iron in the nickel site along with bismuth and arsenic in the antimony site. A solid solution series exists with the high cobalt willyamite.

<span class="mw-page-title-main">Skutterudite</span> Cobalt arsenide mineral

Skutterudite is a cobalt arsenide mineral containing variable amounts of nickel and iron substituting for cobalt with the ideal formula CoAs3. Some references give the arsenic a variable formula subscript of 2–3. High nickel varieties are referred to as nickel-skutterudite, previously chloanthite. It is a hydrothermal ore mineral found in moderate to high temperature veins with other Ni-Co minerals. Associated minerals are arsenopyrite, native silver, erythrite, annabergite, nickeline, cobaltite, silver sulfosalts, native bismuth, calcite, siderite, barite and quartz. It is mined as an ore of cobalt and nickel with a by-product of arsenic.

<span class="mw-page-title-main">Nickel(II) carbonate</span> Chemical compound

Nickel(II) carbonate describes one or a mixture of inorganic compounds containing nickel and carbonate. From the industrial perspective, an important nickel carbonate is basic nickel carbonate with the formula Ni4CO3(OH)6(H2O)4. Simpler carbonates, ones more likely encountered in the laboratory, are NiCO3 and its hexahydrate. All are paramagnetic green solids containing Ni2+ cations. The basic carbonate is an intermediate in the hydrometallurgical purification of nickel from its ores and is used in electroplating of nickel.

<span class="mw-page-title-main">Polydymite</span> Supergene thiospinel sulfide mineral

Polydymite, Ni2+Ni23+S4, is a supergene thiospinel sulfide mineral associated with the weathering of primary pentlandite nickel sulfide.

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

Carrollite, CuCo2S4, is a sulfide of copper and cobalt, often with substantial substitution of nickel for the metal ions, and a member of the linnaeite group. It is named after the type locality in Carroll County, Maryland, US, at the Patapsco mine, Sykesville.

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

Lithium iron phosphate or lithium ferro-phosphate (LFP) is an inorganic compound with the formula LiFePO
4. It is a gray, red-grey, brown or black solid that is insoluble in water. The material has attracted attention as a component of lithium iron phosphate batteries, a type of Li-ion battery. This battery chemistry is targeted for use in power tools, electric vehicles, solar energy installations and more recently large grid-scale energy storage.

<span class="mw-page-title-main">Lithium cobalt oxide</span> Chemical compound

Lithium cobalt oxide, sometimes called lithium cobaltate or lithium cobaltite, is a chemical compound with formula LiCoO
2. The cobalt atoms are formally in the +3 oxidation state, hence the IUPAC name lithium cobalt(III) oxide.

<span class="mw-page-title-main">Cobalt sulfide</span> Chemical compound

Cobalt sulfide is the name for chemical compounds with a formula CoxSy. Well-characterized species include minerals with the formulas CoS, CoS2, Co3S4, and Co9S8. In general, the sulfides of cobalt are black, semiconducting, insoluble in water, and nonstoichiometric.

Spin states when describing transition metal coordination complexes refers to the potential spin configurations of the central metal's d electrons. For several oxidation states, metals can adopt high-spin and low-spin configurations. The ambiguity only applies to first row metals, because second- and third-row metals are invariably low-spin. These configurations can be understood through the two major models used to describe coordination complexes; crystal field theory and ligand field theory.

<span class="mw-page-title-main">Hexagonal crystal family</span> Union of crystal groups with related structures and lattices

In crystallography, the hexagonal crystal family is one of the six crystal families, which includes two crystal systems and two lattice systems. While commonly confused, the trigonal crystal system and the rhombohedral lattice system are not equivalent. In particular, there are crystals that have trigonal symmetry but belong to the hexagonal lattice.

<span class="mw-page-title-main">Molybdate</span> Chemical compound of the form –O–MoO₂–O–

In chemistry, a molybdate is a compound containing an oxyanion with molybdenum in its highest oxidation state of +6: O−−Mo(=O)2−O−. Molybdenum can form a very large range of such oxyanions, which can be discrete structures or polymeric extended structures, although the latter are only found in the solid state. The larger oxyanions are members of group of compounds termed polyoxometalates, and because they contain only one type of metal atom are often called isopolymetalates. The discrete molybdenum oxyanions range in size from the simplest MoO2−
4, found in potassium molybdate up to extremely large structures found in isopoly-molybdenum blues that contain for example 154 Mo atoms. The behaviour of molybdenum is different from the other elements in group 6. Chromium only forms the chromates, CrO2−
4, Cr
2O2−
7, Cr
3O2−
10 and Cr
4O2−
13 ions which are all based on tetrahedral chromium. Tungsten is similar to molybdenum and forms many tungstates containing 6 coordinate tungsten.

The thiospinel group is a group of sulfide minerals with a general formula AB2X4 where A is nominally a +2 metal, B is a +3 metal and X is -2 sulfide or similar anion. Thio refers to sulfur and spinel indicates their isometric spinel-like structure.

<span class="mw-page-title-main">Supercapacitor</span> High-capacity electrochemical capacitor

A supercapacitor (SC), also called an ultracapacitor, is a high-capacity capacitor, with a capacitance value much higher than solid-state capacitors but with lower voltage limits. It bridges the gap between electrolytic capacitors and rechargeable batteries. It typically stores 10 to 100 times more energy per unit volume or mass than electrolytic capacitors, can accept and deliver charge much faster than batteries, and tolerates many more charge and discharge cycles than rechargeable batteries.

A lithium ion manganese oxide battery (LMO) is a lithium-ion cell that uses manganese dioxide, MnO
2, as the cathode material. They function through the same intercalation/de-intercalation mechanism as other commercialized secondary battery technologies, such as LiCoO
2. Cathodes based on manganese-oxide components are earth-abundant, inexpensive, non-toxic, and provide better thermal stability.

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 reducing cost.

<span class="mw-page-title-main">NASICON</span> Class of solid materials

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.

Nickel manganese oxides, or nickel manganates, are spinel structure compounds of Nickel, Manganese and Oxygen of the form: Ni(x)Mn(3-x)O(y)

<span class="mw-page-title-main">Lithium nickel manganese cobalt oxides</span> Lithium-ion battery cathode material

Lithium nickel manganese cobalt oxides (abbreviated NMC, Li-NMC, LNMC, or NCM) are mixed metal oxides of lithium, nickel, manganese and cobalt with the general formula LiNixMnyCo1-x-yO2. These materials are commonly used in lithium-ion batteries for mobile devices and electric vehicles, acting as the positively charged cathode.

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 3 Mindat.org - Siegenite
  3. 1 2 3 Handbook of Mineralogy - Siegenite
  4. ↑ Webmineral.com - Siegenite
  5. ↑ "Metal Sulfides for Better Energy Storage". Cornell Research. 2020-08-20. Retrieved 2022-12-12.
  6. 1 2 3 Xue, Gaofei; Bai, Tian; Wang, Weiguo; Wang, Senjing; Ye, Meidan (2022-04-12). "Recent advances in various applications of nickel cobalt sulfide-based materials". Journal of Materials Chemistry A. 10 (15): 8087–8106. doi:10.1039/D2TA00305H. ISSN   2050-7496. S2CID   247370235.
  7. ↑ "List of Minerals". mineralogy-ima.org. 2011-03-21. Retrieved 2022-12-10.
  8. ↑ Škácha, Pavel; Sejkora, Jiří; Plášil, Jakub; Dolníček, Zdeněk; Ulmanová, Jana (2021-04-19). "Grimmite, NiCo2S4, a new thiospinel from Příbram, Czech Republic". European Journal of Mineralogy. 33 (2): 175–187. doi: 10.5194/ejm-33-175-2021 . ISSN   0935-1221.
  9. 1 2 3 Xia, Chuan; Li, Peng; Gandi, Appala Naidu; Schwingenschlögl, Udo; Alshareef, Husam N. (2015-10-13). "Is NiCo 2 S 4 Really a Semiconductor?". Chemistry of Materials. 27 (19): 6482–6485. doi:10.1021/acs.chemmater.5b01843. hdl: 10754/576874 . ISSN   0897-4756.
  10. ↑ "mp-22658: Co2NiS4 (Cubic, Fd-3m, 227)". Materials Project. Retrieved 2022-12-13.
  11. ↑ Chen, Haichao; Jiang, Jianjun; Zhang, Li; Wan, Houzhao; Qi, Tong; Xia, Dandan (2013-09-13). "Highly conductive NiCo2S4 urchin-like nanostructures for high-rate pseudocapacitors". Nanoscale. 5 (19): 8879–8883. doi:10.1039/C3NR02958A. ISSN   2040-3372. PMID   23903234.
  12. ↑ Kumar, Subalakshmi; Sekar, Sankar; Kaliamurthy, Ashok Kumar; Lee, Sejoon (2021-05-01). "Bifunctional rGO-NiCo2S4 MOF hybrid with high electrochemical and catalytic activity for supercapacitor and nitroarene reduction". Journal of Materials Research and Technology. 12: 2489–2501. doi: 10.1016/j.jmrt.2021.04.001 . ISSN   2238-7854.
  13. ↑ Li, Zhong; Yuan, Daqing; Zhu, Shengyun; Fan, Ping; Ma, Hailiang; Zhang, Qiaoli; Wen, Ali; Zhu, Jiliang (2019-05-07). "The multi-structure NiCo2S4 prepared by solvothermal method for supercapacitor accompanied with positron annihilation study". Journal of Applied Physics. 125 (17): 175103. doi:10.1063/1.5087981. ISSN   0021-8979. S2CID   155666428.
  14. ↑ Khan, Malik Dilshad; Murtaza, Ghulam; Revaprasadu, Neerish; O'Brien, Paul (2018-07-10). "Synthesis of chalcopyrite-type and thiospinel minerals/materials by low temperature melts of xanthates". Dalton Transactions. 47 (27): 8870–8873. doi:10.1039/C8DT00953H. ISSN   1477-9234. PMID   29916514.
  15. ↑ Shinde, S. K.; Ramesh, Sivalingam; Bathula, C.; Ghodake, G. S.; Kim, D.-Y.; Jagadale, A. D.; Kadam, A. A.; Waghmode, D. P.; Sreekanth, T. V. M.; Kim, Heung Soo; Nagajyothi, P. C.; Yadav, H. M. (2019-09-23). "Novel approach to synthesize NiCo2S4 composite for high-performance supercapacitor application with different molar ratio of Ni and Co". Scientific Reports. 9 (1): 13717. doi: 10.1038/s41598-019-50165-5 . ISSN   2045-2322. PMC   6757066 . PMID   31548661.
  16. ↑ Feng, Xueting; Jiao, Qingze; Cui, Huiru; Yin, Mengmeng; Li, Qun; Zhao, Yun; Li, Hansheng; Zhou, Wei; Feng, Caihong (2018-09-05). "One-Pot Synthesis of NiCo 2 S 4 Hollow Spheres via Sequential Ion-Exchange as an Enhanced Oxygen Bifunctional Electrocatalyst in Alkaline Solution". ACS Applied Materials & Interfaces. 10 (35): 29521–29531. doi:10.1021/acsami.8b08547. ISSN   1944-8244. PMID   30102862. S2CID   51980053.
  17. ↑ Park, Sang Ho; Sun, Yang-Kook; Park, Ki Soo; Nahm, Kee Suk; Lee, Yun Sung; Yoshio, Masaki (2002-03-20). "Synthesis and electrochemical properties of lithium nickel oxysulfide (LiNiSyO2−y) material for lithium secondary batteries". Electrochimica Acta. 47 (11): 1721–1726. doi:10.1016/S0013-4686(02)00023-3. ISSN   0013-4686.
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