Oxonickelates

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Nickel forms a series of mixed oxide compounds which are commonly called nickelates. A nickelate is an anion containing nickel or a salt containing a nickelate anion, or a double compound containing nickel bound to oxygen and other elements. Nickel can be in different or even mixed oxidation states, ranging from +1, +2, +3 to +4. The anions can contain a single nickel ion, or multiple to form a cluster ion. The solid mixed oxide compounds are often ceramics, but can also be metallic. They have a variety of electrical and magnetic properties. Rare-earth elements form a range of perovskite nickelates, in which the properties vary systematically as the rare-earth element changes. Fine tuning of properties is achievable with mixtures of elements, applying stress or pressure, or varying the physical form.

Contents

Inorganic chemists call many compounds that contain nickel centred anions "nickelates". These include the chloronickelates, fluoronickelates, tetrabromonickelates, tetraiodonickelates, cyanonickelates, nitronickelates and other nickel-organic acid complexes such as oxalatonickelates.

Alkali nickelates

The lithium nickelates are of interest to researchers as cathodes in lithium cells, as these substance can hold a variable amount of lithium, with the nickel varying in oxidation state. [1]

Rare-earth nickelates

Rare-earth nickelates with nickel in a +1 oxidation state have an electronic configuration to same as for cuprates and so are of interest to high-temperature superconductor researchers. Other rare-earth nickelates can function as fuel cell catalysts. The ability to switch between an insulating and a conducting state in some of these materials is of interest in the development of new transistors, that have higher on to off current ratios. [2]

The rare-earth nickelates were first made by Demazeau et al. in 1971, by heating a mixture of oxides under high pressure oxygen, or potassium perchlorate. However they were unable to make the cerium, praseodymium, and terbium nickelates. [3] This may be because Ce, Pr and Tb oxidises to 4+ions in those conditions. [4] For two decades after that no one paid attention to them. [4] Many rare-earth nickelates have the Ruddlesden–Popper phase structure.

List of oxides

formulanameother namesstructureRemarksreferences
LiNiO2lithium nickelaterhombohedral a = 2.88 Å, c = 14.2 Å, density = 4.78 / 4.81 [5]
Li2NiO3monoclinic C2/ma = 4.898 Å, b = 8.449 Å, c = 4.9692 Å, β = 109.02°, V = 194.60 Å3Nickel in +4 state [1]
NaNiO2sodium nickelatemonoclinic a = 5.33 Å, b = 2.86 Å, c = 5.59 Å, β = 110°30′, Z = 2, density = 4.74; over 220 °C: rhombohedral a = 2.96 Å, b = 15.77 ÅCarbon dissolved in the molten salt can precipitate diamond. [5] [6]
KNiO2potassium nickelate [5] [7]
SrTiNiO3[ dubious – discuss ]strontium titanate nickelateSTN [8]
YNiO3yttrium nickelatemonoclinic P21/n; orthorhombic a = 5.516 Å, b = 7.419 Å, c = 5.178 Å, V = 211.9 Å3, Z = 4, density = 6.13insulator changes to metal under pressure [9] [10]
Y2BaNiO5chain nickelateOrthorhombic Immm, a = 3.7589, b = 5.7604, c = 11.3311 [11] [12]
2H-AgNiO2hexagonal P63/mmc, a = 2.93653 Å, b = 2.93653 Å, c = 12.2369 Å, V = 91.384 Å3, Z = 2, density = 7.216 g/cm3Ni in +3 state [13]
3R-AgNiO2trigonal R32/m, a = 2.9390 Å, c = 18.3700 ÅNi in +3 state [13] [14]
Ag2NiO2silveroxonickelatetrigonal R32/m, a = 2.926 Å, c = 24.0888 Ålustrous black solid, stable in air; Ni3+ and subvalent Ag2+ [14]
Ag3Ni2O4hexagonal P63/mmc, a = 2.9331 Å, b = 2.9331 Å, c = 28.31 Å, V = 210.9 Å3, Z = 2, density = 7.951 g/cm3electric conductor [15]
BaNiO2orthorhombic a = 5.73 Å, b = 9.2 Å, c = 4.73 Å, V = 249 Å3, Z = 4black [16]
BaNiO3hexagonal a = 5.580 Å, c = 4.832 Å, V = 130.4 Å3, Z = 2black powder dec 730 °C N-type semiconductor; decompose in acid [16] [17]
Ba2Ni2O5hexagonal a = 5.72, c = 4.30, density = 6.4black needles melt 1200 °C [16] [17]
LaNiO2lanthanum nickelitea = 3.959, c = 3.375Ni in +1 state [18]
LaNiO3lanthanum nickelatea = 5.4827 Å, b = 5.4827 Å, c = 3.2726 Å, γ = 120°, V = 345.5, Z = 6, density = 7.08metallic, no insulating transition polar metal [19]
La2NiO4LNtetragonal a = 3.86 Å, b = 3.86 Å, c = 12.67 Å, V = 188.8 Å3, Z = 2, density = 7.05 [20] [21]
La3Ni2O6tetragonal a = 3.968 Å, c = 19.32 Å [20]
La3Ni2O7a = 5.3961 Å, b = 5.4498 Å, c = 20.522 Å, V = 603.5, Z = 4, density = 7.1superconductor under pressure Tc=80K [20] [22] [23]
La4Ni3O8antiferromagnetic below 105 K, mixed valence I and II [20] [24]
La4Ni3O10 [24]
La2−xSrxNiO4LSNa varies from 3.86 to 3.81 as x changes from 0 to 0.5, then ≈ 3.81; c ≈ 12.7 for x ≤ 0.8, the it falls to 12.4 at x = 1.2polarization-specific metal [25]
CeNiO3cerium nickelatedecomposes 1984 °C [26]
PrNiO2 [20]
PrNiO3perovskitemetallic insulator transition=130K [27]
Pr4Ni3O8 [20]
Pr2BaNiO5chain nickelateOrthorhombic [11]
NdNiO3 neodymium nickelate perovskite orthorhombic Pbnm, a = 5.38712 Å, b = 5.38267 Å, c = 7.60940 Åmetallic insulator transition=200K [10] [27]
NdNiO2orthorhombic a = 5.402 Å, b = 7.608 Å, c = 5.377 Å, V = 221.0 Å3, density = 7.54 [20] [28] [29]
Nd4Ni3O8orthorhombic a = 3.9171 Å, b = 3.9171 Å, c = 25.307 Å, V = 388.3 Å3, Z = 2, density = 7.54 [20] [30]
Nd2NiO4Cmca a = 5.383 Å, b = 12.342 Å, c = 5.445 Å, V = 361.7 Å3, density = 7.55 [31]
Nd2BaNiO5chain nickelateOrthorhombic Immm, a = 2.8268 Å, b = 5.9272 Å, c = 11.651 Å [11] [12]
SmNiO3samarium nickelateSNOperovskite Pnma, a = 5.431 Å, b = 7.568 Å, c = 5.336 Å, V = 219.3 Å, Z = 4, density = 7.79metallic insulator transition=400K [27] [32]
Sm1.5Sr0.5NiO4SSNOorthorhombic Bmabgiant dielectric constant 100,000 [33]
EuNiO3europium nickelateperovskite orthorhombic a = 5.466 Å, b = 7.542 Å, c = 5.293 Å, V = 218.2 Å3, Z = 4, density = 7.87metallic insulator transition=460K [27]
GdNiO3gadolinium nickelateperovskite orthorhombic a = 0.5492 Å, b = 0.7506 Å, c = 0.5258 Å, V = 216.8 Å3, Z = 4, density = 8.09metallic insulator transition=510.9K [34]
Gd2NiO4digadolinium nickelateOrthorhombic a = 3.851 Å, b = 3.851 Å, c = 6.8817 Å, V = 187.5 Å3, Z = 2, density = 7.75 [35]
BaGd2NiO5barium digadolinium nickelatechain nickellate?orthorhombiclow thermal conductance [36]
Tb2BaNiO5chain nickelateOrthorhombic [11]
DyNiO3dysprosium nickelateperovskite orthorhombic a = 0.55 Å, b = 0.7445 Å, c = 0.5212 Å V=213.4 Z=4 density=8.38metallic insulator transition=564.1K [27] [34] [37]
Dy2BaNiO5chain nickelateOrthorhombic [11]
HoNiO3holmium nickelateperovskite orthorhombic a = 3.96 Å, b = 3.96 Å, c = 5.04 Å, V = 212 Å3Z = 4, density=8.51metallic insulator transition=560K [34]
Ho2BaNiO5chain nickelateOrthorhombic Immm, a = 3.764 Å, b = 5.761 Å, c=11.336 Å [11] [38]
ErNiO3erbium nickelateperovskite orthorhombic a = 5.514 Å, b =7.381 Å, c = 5.16 V=201 Z=4 density=8.67metallic insulator transition=580K [34] [39]
Er2BaNiO5chain nickelateOrthorhombic Immma = 3.7541 Å, b = 5.7442 Å c=11.3019 Å V=243.71 Å3 Z=2 [11] [12] [40]
TmNiO3thulium nickelateorthorhombic a = 5.495 Å, b = 7.375 Å, c = 5.149 Å V = 208.7 Z = 4 density = 8.77 [41]
Tm2BaNiO5thulium barium nickelateOrthorhombic low temperature Pnmaa = 12.2003 Å b = 5.65845 Å c = 6.9745 Å Z = 4; high T: Immma = 3.75128 b = 5.7214 c = 11.2456Pnma form is brown Immm form is dark green [11] [42]
YbNiO3ytterbium nickelateOrthorhombic a = 5.496 Å, b = 7.353 Å, c = 5.131 Å Z=4 V=207.4 Å3 density=8.96 [43]
Yb2BaNiO5ytterbium barium nickelateOrthorhombic Pnma a = 5.6423 Å, b = 6.9545 Å, c = 12.1583 Å V=477.1 Z=4 density=8.66Pnma form is brown [42]
LuNiO3lutetium nickelateperovskite a = 5.499 Å, b = 7.356 Å, c = 5.117 Å, V = 207 Å3, Z = 4, density = 9.04metallic insulator transition=600K [34] [44]
Lu2BaNiO5Orthorhombic Pnma [12]
TlNiO3thallium nickelate(III)perovskite a = 5.2549 Å, b = 5.3677 Å, c = 7.5620 Å, V = 213.3 Å3 [45]
PbNiO3
BiNiO3bismuth nickelate(III)perovskite triclinic a = 5.3852, b = 5.6498, c = 7.7078 Å, α = 91.9529°, β = 89.8097°, γ = 91.5411, V = 234.29 Å3Ni in +2 state, Bi in +3 and +5; stable 5–420K, antiferromagnetic [46] [47]

See also

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  40. ↑ Alonso, J. A.; Amador, J.; Rasines, I.; Soubeyroux, J. L. (15 February 1991). "Er2BaNiO5: structure refinement using neutron powder diffraction data". Acta Crystallographica Section C. 47 (2): 249–251. doi:10.1107/S0108270190008873.
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  42. 1 2 Salinas Sánchez, A.; Sáez Puche, R.; Rodríguez Carvajal, J.; Martínez, J.L. (May 1991). "Structural characterization of R2BaNiO5 (R = Tm and Yb): polymorphism for R = Tm". Solid State Communications. 78 (6): 481–488. Bibcode:1991SSCom..78..481S. doi:10.1016/0038-1098(91)90361-X.
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  45. ↑ Kim, Seung-Joo; Demazeau, Gérard; Alonso, José A.; Choy, Jin-Ho (2001). "High pressure synthesis and crystal structure of a new Ni(III) perovskite: TlNiO3". Journal of Materials Chemistry. 11 (2): 487–492. doi:10.1039/b007043m.
  46. ↑ Ishiwata, Shintaro; Azuma, Masaki; Takano, Mikio; Nishibori, Eiji; Takata, Masaki; Sakata, Makoto; Kato, Kenichi (29 November 2002). "High pressure synthesis, crystal structure and physical properties of a new Ni(II) perovskite BiNiO3". Journal of Materials Chemistry. 12 (12): 3733–3737. doi:10.1039/b206022a.
  47. ↑ Pugaczowa-Michalska, M.; Kaczkowski, J. (January 2017). "DFT+U studies of triclinic phase of BiNiO3 and La-substituted BiNiO3". Computational Materials Science. 126: 407–417. doi:10.1016/j.commatsci.2016.10.014.
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