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Oxonickelates

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.

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.

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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 were first made by Demazeau et al. in 1971, by heating a mixture of oxides under high pressure oxygen, or potassium perchlorate.2 For two decades after that these nickelates received very little attention.3 Many rare-earth nickelates have the Ruddlesden–Popper phase structure.

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.456 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.7

List of oxides

formulanameother namesstructureRemarksreferences
LiNiO2lithium nickelaterhombohedral a = 2.88 Å, c = 14.2 Å, density = 4.78 / 4.818
Li2NiO3monoclinic C2/m a = 4.898 Å, b = 8.449 Å, c = 4.9692 Å, β = 109.02°, V = 194.60 Å3Nickel in +4 state9
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.1011
KNiO2potassium nickelate1213
SrTiNiO3[dubious – discuss]strontium titanate nickelateSTN14
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 pressure1516
Y2BaNiO5chain nickelateOrthorhombic Immm, a = 3.7589, b = 5.7604, c = 11.33111718
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 state19
3R-AgNiO2trigonal R32/m, a = 2.9390 Å, c = 18.3700 ÅNi in +3 state2021
Ag2NiO2silveroxonickelatetrigonal R32/m, a = 2.926 Å, c = 24.0888 Ålustrous black solid, stable in air; Ni3+ and subvalent Ag2+22
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 conductor23
BaNiO2orthorhombic a = 5.73 Å, b = 9.2 Å, c = 4.73 Å, V = 249 Å3, Z = 4black24
BaNiO3hexagonal a = 5.580 Å, c = 4.832 Å, V = 130.4 Å3, Z = 2black powder dec 730 °C N-type semiconductor; decompose in acid2526
Ba2Ni2O5hexagonal a = 5.72, c = 4.30, density = 6.4black needles melt 1200 °C2728
LaNiO2lanthanum nickelitea = 3.959, c = 3.375Ni in +1 state29
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 metal30
La2NiO4LNtetragonal a = 3.86 Å, b = 3.86 Å, c = 12.67 Å, V = 188.8 Å3, Z = 2, density = 7.053132
La3Ni2O6tetragonal a = 3.968 Å, c = 19.32 Å33
La3Ni2O7a = 5.3961 Å, b = 5.4498 Å, c = 20.522 Å, V = 603.5, Z = 4, density = 7.1superconductor under pressure Tc=80K343536
La4Ni3O8antiferromagnetic below 105 K, mixed valence I and II3738
La4Ni3O1039
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 metal40
CeNiO3cerium nickelatedecomposes 1984 °C41
PrNiO242
PrNiO3perovskitemetallic insulator transition=130K43
Pr4Ni3O844
Pr2BaNiO5chain nickelateOrthorhombic45
La2PrNi2O7orthorhombic46
La2PrNi2O7tetragonalSuperconductor under pressure Tc = 82.5°C47
NdNiO3neodymium nickelateperovskite orthorhombic Pbnm, a = 5.38712 Å, b = 5.38267 Å, c = 7.60940 Åmetallic insulator transition=200K4849
NdNiO2orthorhombic a = 5.402 Å, b = 7.608 Å, c = 5.377 Å, V = 221.0 Å3, density = 7.54505152
Nd4Ni3O8orthorhombic a = 3.9171 Å, b = 3.9171 Å, c = 25.307 Å, V = 388.3 Å3, Z = 2, density = 7.545354
Nd2NiO4Cmca a = 5.383 Å, b = 12.342 Å, c = 5.445 Å, V = 361.7 Å3, density = 7.5555
Nd2BaNiO5chain nickelateOrthorhombic Immm, a = 2.8268 Å, b = 5.9272 Å, c = 11.651 Å5657
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=400K5859
Sm1.5Sr0.5NiO4SSNOorthorhombic Bmabgiant dielectric constant 100,00060
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=460K61
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=510.9K62
Gd2NiO4digadolinium nickelateOrthorhombic a = 3.851 Å, b = 3.851 Å, c = 6.8817 Å, V = 187.5 Å3, Z = 2, density = 7.7563
BaGd2NiO5barium digadolinium nickelatechain nickellate?orthorhombiclow thermal conductance64
Tb2BaNiO5chain nickelateOrthorhombic65
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=564.1K666768
Dy2BaNiO5chain nickelateOrthorhombic69
HoNiO3holmium nickelateperovskite orthorhombic a = 3.96 Å, b = 3.96 Å, c = 5.04 Å, V = 212 Å3 Z = 4, density=8.51metallic insulator transition=560K70
Ho2BaNiO5chain nickelateOrthorhombic Immm, a = 3.764 Å, b = 5.761 Å, c=11.336 Å7172
ErNiO3erbium nickelateperovskite orthorhombic a = 5.514 Å, b =7.381 Å, c = 5.16 V=201 Z=4 density=8.67metallic insulator transition=580K7374
Er2BaNiO5chain nickelateOrthorhombic Immm a = 3.7541 Å, b = 5.7442 Å c=11.3019 Å V=243.71 Å3 Z=2757677
TmNiO3thulium nickelateorthorhombic a = 5.495 Å, b = 7.375 Å, c = 5.149 Å V = 208.7 Z = 4 density = 8.7778
Tm2BaNiO5thulium barium nickelateOrthorhombic low temperature Pnma a = 12.2003 Å b = 5.65845 Å c = 6.9745 Å Z = 4; high T: Immm a = 3.75128 b = 5.7214 c = 11.2456Pnma form is brown Immm form is dark green7980
YbNiO3ytterbium nickelateOrthorhombic a = 5.496 Å, b = 7.353 Å, c = 5.131 Å Z=4 V=207.4 Å3 density=8.9681
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 brown82
LuNiO3lutetium nickelateperovskite a = 5.499 Å, b = 7.356 Å, c = 5.117 Å, V = 207 Å3, Z = 4, density = 9.04metallic insulator transition=600K8384
Lu2BaNiO5Orthorhombic Pnma85
TlNiO3thallium nickelate(III)perovskite a = 5.2549 Å, b = 5.3677 Å, c = 7.5620 Å, V = 213.3 Å386
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, antiferromagnetic8788

See also

References

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  2. Demazeau, Gérard; Marbeuf, Alain; Pouchard, Michel; Hagenmuller, Paul (November 1971). "Sur une série de composés oxygènes du nickel trivalent derivés de la perovskite". Journal of Solid State Chemistry (in French). 3 (4): 582–589. Bibcode:1971JSSCh...3..582D. doi:10.1016/0022-4596(71)90105-8. /wiki/Bibcode_(identifier) ↩

  3. Alonso, J. A.; Martínez Lope, M. J.; Casais, M. T.; Martínez, J. L.; Demazeau, G.; Largeteau, A.; García Muñoz, J. L.; Muñoz, A.; Fernández-Díaz, M. T. (September 1999). "High-Pressure Preparation, Crystal Structure, Magnetic Properties, and Phase Transitions in GdNiO3 and DyNiO3 Perovskites". Chemistry of Materials. 11 (9): 2463–2469. doi:10.1021/cm991033k. /wiki/Doi_(identifier) ↩

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