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Oxonickelates

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For the most common nickel oxide, see Nickel(II) oxide.

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.

Alkali nickelates

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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

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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

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formula name other names structure Remarks references
LiNiO2 lithium nickelate rhombohedral a = 2.88 Å, c = 14.2 Å, density = 4.78 / 4.81 [5]
Li2NiO3 monoclinic C2/m a = 4.898 Å, b = 8.449 Å, c = 4.9692 Å, β = 109.02°, V = 194.60 Å3 Nickel in +4 state [1]
NaNiO2 sodium nickelate monoclinic 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 Å Carbon dissolved in the molten salt can precipitate diamond. [5][6]
KNiO2 potassium nickelate [5][7]
SrTiNiO3[dubious – discuss] strontium titanate nickelate STN [8]
YNiO3 yttrium nickelate monoclinic P21/n; orthorhombic a = 5.516 Å, b = 7.419 Å, c = 5.178 Å, V = 211.9 Å3, Z = 4, density = 6.13 insulator changes to metal under pressure [9][10]
Y2BaNiO5 chain nickelate Orthorhombic Immm, a = 3.7589, b = 5.7604, c = 11.3311 [11][12]
2H-AgNiO2 hexagonal P63/mmc, a = 2.93653 Å, b = 2.93653 Å, c = 12.2369 Å, V = 91.384 Å3, Z = 2, density = 7.216 g/cm3 Ni in +3 state [13]
3R-AgNiO2 trigonal R32/m, a = 2.9390 Å, c = 18.3700 Å Ni in +3 state [13][14]
Ag2NiO2 silveroxonickelate trigonal R32/m, a = 2.926 Å, c = 24.0888 Å lustrous black solid, stable in air; Ni3+ and subvalent Ag2+ [14]
Ag3Ni2O4 hexagonal P63/mmc, a = 2.9331 Å, b = 2.9331 Å, c = 28.31 Å, V = 210.9 Å3, Z = 2, density = 7.951 g/cm3 electric conductor [15]
BaNiO2 orthorhombic a = 5.73 Å, b = 9.2 Å, c = 4.73 Å, V = 249 Å3, Z = 4 black [16]
BaNiO3 hexagonal a = 5.580 Å, c = 4.832 Å, V = 130.4 Å3, Z = 2 black powder dec 730 °C N-type semiconductor; decompose in acid [16][17]
Ba2Ni2O5 hexagonal a = 5.72, c = 4.30, density = 6.4 black needles melt 1200 °C [16][17]
LaNiO2 lanthanum nickelite a = 3.959, c = 3.375 Ni in +1 state [18]
LaNiO3 lanthanum nickelate a = 5.4827 Å, b = 5.4827 Å, c = 3.2726 Å, γ = 120°, V = 345.5, Z = 6, density = 7.08 metallic, no insulating transition polar metal [19]
La2NiO4 LN tetragonal a = 3.86 Å, b = 3.86 Å, c = 12.67 Å, V = 188.8 Å3, Z = 2, density = 7.05 [20][21]
La3Ni2O6 tetragonal a = 3.968 Å, c = 19.32 Å [20]
La3Ni2O7 a = 5.3961 Å, b = 5.4498 Å, c = 20.522 Å, V = 603.5, Z = 4, density = 7.1 superconductor under pressure Tc=80K [20][22][23]
La4Ni3O8 antiferromagnetic below 105 K, mixed valence I and II [20][24]
La4Ni3O10 [24]
La2−xSrxNiO4 LSN a 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 = 1.2 polarization-specific metal [25]
CeNiO3 cerium nickelate decomposes 1984 °C [26]
PrNiO2 [20]
PrNiO3 perovskite metallic insulator transition=130K [27]
Pr4Ni3O8 [20]
Pr2BaNiO5 chain nickelate Orthorhombic [11]
La2PrNi2O7 orthorhombic [28]
La2PrNi2O7 tetragonal Superconductor under pressure Tc = 82.5°C [28]
NdNiO3 neodymium nickelate perovskite orthorhombic Pbnm, a = 5.38712 Å, b = 5.38267 Å, c = 7.60940 Å metallic insulator transition=200K [10][27]
NdNiO2 orthorhombic a = 5.402 Å, b = 7.608 Å, c = 5.377 Å, V = 221.0 Å3, density = 7.54 [20][29][30]
Nd4Ni3O8 orthorhombic a = 3.9171 Å, b = 3.9171 Å, c = 25.307 Å, V = 388.3 Å3, Z = 2, density = 7.54 [20][31]
Nd2NiO4 Cmca a = 5.383 Å, b = 12.342 Å, c = 5.445 Å, V = 361.7 Å3, density = 7.55 [32]
Nd2BaNiO5 chain nickelate Orthorhombic Immm, a = 2.8268 Å, b = 5.9272 Å, c = 11.651 Å [11][12]
SmNiO3 samarium nickelate SNO perovskite Pnma, a = 5.431 Å, b = 7.568 Å, c = 5.336 Å, V = 219.3 Å, Z = 4, density = 7.79 metallic insulator transition=400K [27][33]
Sm1.5Sr0.5NiO4 SSNO orthorhombic Bmab giant dielectric constant 100,000 [34]
EuNiO3 europium nickelate perovskite orthorhombic a = 5.466 Å, b = 7.542 Å, c = 5.293 Å, V = 218.2 Å3, Z = 4, density = 7.87 metallic insulator transition=460K [27]
GdNiO3 gadolinium nickelate perovskite orthorhombic a = 0.5492 Å, b = 0.7506 Å, c = 0.5258 Å, V = 216.8 Å3, Z = 4, density = 8.09 metallic insulator transition=510.9K [35]
Gd2NiO4 digadolinium nickelate Orthorhombic a = 3.851 Å, b = 3.851 Å, c = 6.8817 Å, V = 187.5 Å3, Z = 2, density = 7.75 [36]
BaGd2NiO5 barium digadolinium nickelate chain nickellate ?orthorhombic low thermal conductance [37]
Tb2BaNiO5 chain nickelate Orthorhombic [11]
DyNiO3 dysprosium nickelate perovskite orthorhombic a = 0.55 Å, b = 0.7445 Å, c = 0.5212 Å V=213.4 Z=4 density=8.38 metallic insulator transition=564.1K [27][35][38]
Dy2BaNiO5 chain nickelate Orthorhombic [11]
HoNiO3 holmium nickelate perovskite orthorhombic a = 3.96 Å, b = 3.96 Å, c = 5.04 Å, V = 212 Å3 Z = 4, density=8.51 metallic insulator transition=560K [35]
Ho2BaNiO5 chain nickelate Orthorhombic Immm, a = 3.764 Å, b = 5.761 Å, c=11.336 Å [11][39]
ErNiO3 erbium nickelate perovskite orthorhombic a = 5.514 Å, b =7.381 Å, c = 5.16 V=201 Z=4 density=8.67 metallic insulator transition=580K [35][40]
Er2BaNiO5 chain nickelate Orthorhombic Immm a = 3.7541 Å, b = 5.7442 Å c=11.3019 Å V=243.71 Å3 Z=2 [11][12][41]
TmNiO3 thulium nickelate orthorhombic a = 5.495 Å, b = 7.375 Å, c = 5.149 Å V = 208.7 Z = 4 density = 8.77 [42]
Tm2BaNiO5 thulium barium nickelate Orthorhombic 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 = 11.2456 Pnma form is brown Immm form is dark green [11][43]
YbNiO3 ytterbium nickelate Orthorhombic a = 5.496 Å, b = 7.353 Å, c = 5.131 Å Z=4 V=207.4 Å3 density=8.96 [44]
Yb2BaNiO5 ytterbium barium nickelate Orthorhombic Pnma a = 5.6423 Å, b = 6.9545 Å, c = 12.1583 Å V=477.1 Z=4 density=8.66 Pnma form is brown [43]
LuNiO3 lutetium nickelate perovskite a = 5.499 Å, b = 7.356 Å, c = 5.117 Å, V = 207 Å3, Z = 4, density = 9.04 metallic insulator transition=600K [35][45]
Lu2BaNiO5 Orthorhombic Pnma [12]
TlNiO3 thallium nickelate(III) perovskite a = 5.2549 Å, b = 5.3677 Å, c = 7.5620 Å, V = 213.3 Å3 [46]
PbNiO3
BiNiO3 bismuth 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 Å3 Ni in +2 state, Bi in +3 and +5; stable 5–420K, antiferromagnetic [47][48]

See also

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References

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