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
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.
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.
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. This may be because Ce, Pr and Tb oxidises to ions in those conditions. For two decades after that no one paid attention to them. Many rare-earth nickelates have the Ruddlesden–Popper phase structure.
List of oxides
formula | name | other names | structure | Remarks | references |
---|---|---|---|---|---|
LiNiO2 | lithium nickelate | rhombohedral a = 2.88 Å, c = 14.2 Å, density = 4.78 / 4.81 | |||
Li2NiO3 | monoclinic C2/m a = 4.898 Å, b = 8.449 Å, c = 4.9692 Å, β = 109.02°, V = 194.60 Å | Nickel in +4 state | |||
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. | ||
KNiO2 | potassium nickelate | ||||
SrTiNiO3 | strontium titanate nickelate | STN | |||
YNiO3 | yttrium nickelate | monoclinic P21/n; orthorhombic a = 5.516 Å, b = 7.419 Å, c = 5.178 Å, V = 211.9 Å, Z = 4, density = 6.13 | insulator changes to metal under pressure | ||
Y2BaNiO5 | chain nickelate | Orthorhombic Immm, a = 3.7589, b = 5.7604, c = 11.3311 | |||
2H-AgNiO2 | hexagonal P63/mmc, a = 2.93653 Å, b = 2.93653 Å, c = 12.2369 Å, V = 91.384 Å, Z = 2, density = 7.216 g/cm | Ni in +3 state | |||
3R-AgNiO2 | trigonal R32/m, a = 2.9390 Å, c = 18.3700 Å | Ni in +3 state | |||
Ag2NiO2 | silveroxonickelate | trigonal R32/m, a = 2.926 Å, c = 24.0888 Å | lustrous black solid, stable in air; Ni and subvalent Ag2 | ||
Ag3Ni2O4 | hexagonal P63/mmc, a = 2.9331 Å, b = 2.9331 Å, c = 28.31 Å, V = 210.9 Å, Z = 2, density = 7.951 g/cm | electric conductor | |||
BaNiO2 | orthorhombic a = 5.73 Å, b = 9.2 Å, c = 4.73 Å, V = 249 Å, Z = 4 | black | |||
BaNiO3 | hexagonal a = 5.580 Å, c = 4.832 Å, V = 130.4 Å, Z = 2 | black powder dec 730 °C N-type semiconductor; decompose in acid | |||
Ba2Ni2O5 | hexagonal a = 5.72, c = 4.30, density = 6.4 | black needles melt 1200 °C | |||
LaNiO2 | lanthanum nickelite | a = 3.959, c = 3.375 | Ni in +1 state | ||
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 | ||
La2NiO4 | LN | tetragonal a = 3.86 Å, b = 3.86 Å, c = 12.67 Å, V = 188.8 Å, Z = 2, density = 7.05 | |||
La3Ni2O6 | tetragonal a = 3.968 Å, c = 19.32 Å | ||||
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 | |||
La4Ni3O8 | antiferromagnetic below 105 K, mixed valence I and II | ||||
La4Ni3O10 | |||||
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 | ||
CeNiO3 | cerium nickelate | decomposes 1984 °C | |||
PrNiO2 | |||||
PrNiO3 | perovskite | metallic insulator transition=130K | |||
Pr4Ni3O8 | |||||
Pr2BaNiO5 | chain nickelate | Orthorhombic | |||
La2PrNi2O7 | orthorhombic | ||||
La2PrNi2O7 | tetragonal | Superconductor under pressure Tc = 82.5°C | |||
NdNiO3 | neodymium nickelate | perovskite orthorhombic Pbnm, a = 5.38712 Å, b = 5.38267 Å, c = 7.60940 Å | metallic insulator transition=200K | ||
NdNiO2 | orthorhombic a = 5.402 Å, b = 7.608 Å, c = 5.377 Å, V = 221.0 Å, density = 7.54 | ||||
Nd4Ni3O8 | orthorhombic a = 3.9171 Å, b = 3.9171 Å, c = 25.307 Å, V = 388.3 Å, Z = 2, density = 7.54 | ||||
Nd2NiO4 | Cmca a = 5.383 Å, b = 12.342 Å, c = 5.445 Å, V = 361.7 Å, density = 7.55 | ||||
Nd2BaNiO5 | chain nickelate | Orthorhombic Immm, a = 2.8268 Å, b = 5.9272 Å, c = 11.651 Å | |||
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 | |
Sm1.5Sr0.5NiO4 | SSNO | orthorhombic Bmab | giant dielectric constant 100,000 | ||
EuNiO3 | europium nickelate | perovskite orthorhombic a = 5.466 Å, b = 7.542 Å, c = 5.293 Å, V = 218.2 Å, Z = 4, density = 7.87 | metallic insulator transition=460K | ||
GdNiO3 | gadolinium nickelate | perovskite orthorhombic a = 0.5492 Å, b = 0.7506 Å, c = 0.5258 Å, V = 216.8 Å, Z = 4, density = 8.09 | metallic insulator transition=510.9K | ||
Gd2NiO4 | digadolinium nickelate | Orthorhombic a = 3.851 Å, b = 3.851 Å, c = 6.8817 Å, V = 187.5 Å, Z = 2, density = 7.75 | |||
BaGd2NiO5 | barium digadolinium nickelate | chain nickellate | ?orthorhombic | low thermal conductance | |
Tb2BaNiO5 | chain nickelate | Orthorhombic | |||
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 | ||
Dy2BaNiO5 | chain nickelate | Orthorhombic | |||
HoNiO3 | holmium nickelate | perovskite orthorhombic a = 3.96 Å, b = 3.96 Å, c = 5.04 Å, V = 212 Å Z = 4, density=8.51 | metallic insulator transition=560K | ||
Ho2BaNiO5 | chain nickelate | Orthorhombic Immm, a = 3.764 Å, b = 5.761 Å, c=11.336 Å | |||
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 | ||
Er2BaNiO5 | chain nickelate | Orthorhombic Immm a = 3.7541 Å, b = 5.7442 Å c=11.3019 Å V=243.71 Å Z=2 | |||
TmNiO3 | thulium nickelate | orthorhombic a = 5.495 Å, b = 7.375 Å, c = 5.149 Å V = 208.7 Z = 4 density = 8.77 | |||
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 | ||
YbNiO3 | ytterbium nickelate | Orthorhombic a = 5.496 Å, b = 7.353 Å, c = 5.131 Å Z=4 V=207.4 Å density=8.96 | |||
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 | ||
LuNiO3 | lutetium nickelate | perovskite a = 5.499 Å, b = 7.356 Å, c = 5.117 Å, V = 207 Å, Z = 4, density = 9.04 | metallic insulator transition=600K | ||
Lu2BaNiO5 | Orthorhombic Pnma | ||||
TlNiO3 | thallium nickelate(III) | perovskite a = 5.2549 Å, b = 5.3677 Å, c = 7.5620 Å, V = 213.3 Å | |||
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 Å | Ni in +2 state, Bi in +3 and +5; stable 5–420K, antiferromagnetic |
See also
- Nickel manganese oxides for what are considered nickel manganates
References
- ^ Shinova, Elitza; Zhecheva, Ekaterina; Stoyanova, Radostina; Bromiley, Geoffrey D. (May 2005). "High-pressure synthesis of solid solutions between trigonal LiNiO2 and monoclinic LiO2". Journal of Solid State Chemistry. 178 (5): 1661–1669. Bibcode:2005JSSCh.178.1661S. doi:10.1016/j.jssc.2005.03.007.
- Notman, Nina (December 2014). "Edging towards silicon-free transistors". Materials Today. 17 (10): 473. doi:10.1016/j.mattod.2014.10.034.
- 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.
- ^ 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.
- ^ Dyer, Lawrence D.; Borie, Bernard S.; Smith, G. Pedro (March 1954). "Alkali Metal-Nickel Oxides of the Type MNiO2". Journal of the American Chemical Society. 76 (6): 1499–1503. doi:10.1021/ja01635a012.
- Komath, M.; Cherian, K. A.; Kulkarni, S. K.; Ray, A. (1994). "The role of sodium nickelate in the metastable recrystallization of diamond". Diamond and Related Materials. 4 (1): 20–25. Bibcode:1994DRM.....4...20K. doi:10.1016/0925-9635(94)90064-7.
- Hofmann, K. A.; Hiendlmaier, H. (July 1906). "Sauerstoffübertragung durch brennendes Kalium". Berichte der Deutschen Chemischen Gesellschaft. 39 (3): 3184–3187. doi:10.1002/cber.190603903136.
- Lee, Ke-Jing; Wang, Li-Wen; Chiang, Te-Kung; Wang, Yeong-Her (26 October 2015). "Effects of Electrodes on the Switching Behavior of Strontium Titanate Nickelate Resistive Random Access Memory". Materials. 8 (10): 7191–7198. Bibcode:2015Mate....8.7191L. doi:10.3390/ma8105374. PMC 5455395. PMID 28793630.
- García Muñoz, J. L.; Amboage, M.; Hanfland, M.; Alonso, J. A.; Martínez Lope, M. J.; Mortimer, R. (March 2003). "Pressure-induced melting of charge-order in the self-doped mott insulator yttrium nickelate". High Pressure Research. 23 (1–2): 171–175. Bibcode:2003HPR....23..171G. doi:10.1080/0895795031000114430. S2CID 94841772.
- ^ Yamamoto, Susumu; Fujiwara, Takeo (June 2002). "Symmetry consideration and eg bands in NdNiO3 and YNiO3". Journal of Physics and Chemistry of Solids. 63 (6–8): 1347–1351. arXiv:cond-mat/0110431. Bibcode:2002JPCS...63.1347Y. doi:10.1016/S0022-3697(02)00085-9. S2CID 15894552.
- ^ Popova, M. N.; Romanov, E. A.; Klimin, S. A.; Chukalina, E. P.; Mill, B. V.; Dhalenne, G. (2005). "Stark Structure and Exchange Splittings of Nd Ion Levels in Chain Nickelate Nd2BaNiO5" (PDF). Physics of the Solid State. 47 (8): 1497–1503. Bibcode:2005PhSS...47.1497P. doi:10.1134/1.2014500. S2CID 122042627. Retrieved 21 April 2016.
- ^ Alonso, J. A.; Rasines, I.; Rodriguez-Carvajal, J.; Torrance, J. B. (April 1994). "Hole and Electron Doping of R2BaNiO5 (R = Rare Earths)". Journal of Solid State Chemistry. 109 (2): 231–240. Bibcode:1994JSSCh.109..231A. doi:10.1006/jssc.1994.1098.
- ^ Sörgel, Timo; Jansen, Martin (November 2005). "Eine neue, hexagonale Modifikation von AgNiO2" [A New Hexagonal Modification of AgNiO2]. Zeitschrift für Anorganische und Allgemeine Chemie (in German). 631 (15): 2970–2972. doi:10.1002/zaac.200500295.
- ^ Schreyer, Martin; Jansen, Martin (15 February 2002). "Synthesis and Characterization of Ag2NiO2 Showing an Uncommon Charge Distribution". Angewandte Chemie. 114 (4): 665–668. doi:10.1002/1521-3757(20020215)114:4<665::AID-ANGE665>3.0.CO;2-Z.
- Sörgel, Timo; Jansen, Martin (January 2007). "Ag3Ni2O4—A new stage-2 intercalation compound of 2H–AgNiO2 and physical properties of 2H–AgNiO2 above ambient temperature". Journal of Solid State Chemistry. 180 (1): 8–15. Bibcode:2007JSSCh.180....8S. doi:10.1016/j.jssc.2006.08.033. available on ScienceDirect
- ^ Lander, J. J. (1 March 1951). "The crystal structures of NiO·3BaO, NiO·BaO, BaNiO3 and intermediate phases with composition near Ba2Ni2O5; with a note on NiO". Acta Crystallographica. 4 (2): 148–156. doi:10.1107/S0365110X51000441.
- ^ Lander, J. J.; Wooten, L. A. (June 1951). "Barium-Nickel Oxides with Tri- and Tetravalent Nickel". Journal of the American Chemical Society. 73 (6): 2452–2454. doi:10.1021/ja01150a013.
- Crespin, M.; Isnard, O.; Dubois, F.; Choisnet, J.; Odier, P. (April 2005). "LaNiO2: Synthesis and structural characterization". Journal of Solid State Chemistry. 178 (4): 1326–1334. Bibcode:2005JSSCh.178.1326C. doi:10.1016/j.jssc.2005.01.023.
- "Atom Work Inorganic Material Database". Retrieved 23 April 2016.
- ^ Poltavets, Viktor V.; Lokshin, Konstantin A.; Dikmen, Sibel; Croft, Mark; Egami, Takeshi; Greenblatt, Martha (July 2006). "La2Ni2O6: A New Double T′-type Nickelate with Infinite NiO2 Layers". Journal of the American Chemical Society. 128 (28): 9050–9051. doi:10.1021/ja063031o. PMID 16834375.
- "La2NiO4 in K2NiF4 structure". Retrieved 23 April 2016.
- "Details of Selected Material Inorganic Materials Database". Retrieved 23 April 2016.
- Sun, Hualei; Huo, Mengwu; Hu, Xunwu; Li, Jingyuan; Liu, Zengjia; Han, Yifeng; Tang, Lingyun; Mao, Zhongquan; Yang, Pengtao; Wang, Bosen; Cheng, Jinguang; Yao, Dao-Xin; Zhang, Guang-Ming; Wang, Meng (2023-07-12). "Signatures of superconductivity near 80 K in a nickelate under high pressure". Nature. 621 (7979): 493–498. arXiv:2305.09586. doi:10.1038/s41586-023-06408-7. ISSN 0028-0836. PMID 37437603. S2CID 259843168.
- ^ Poltavets, Viktor V. (1 January 2010). "Bulk Magnetic Order in a Two-Dimensional" (PDF). Physical Review Letters. 104 (20): 206403. arXiv:1003.3276. Bibcode:2010PhRvL.104t6403P. doi:10.1103/PhysRevLett.104.206403. PMID 20867044. S2CID 14882438. Retrieved 21 April 2016.
- Sreedhar, K.; Rao, C. N. R. (October 1990). "Electrical and magnetic properties of La2−xSrxNiO4: A tentative phase diagram". Materials Research Bulletin. 25 (10): 1235–1242. doi:10.1016/0025-5408(90)90079-H.
- Fratello, V.J.; Berkstresser, G.W.; Brandle, C.D.; Ven Graitis, A.J. (September 1996). "Nickel containing perovskites". Journal of Crystal Growth. 166 (1–4): 878–882. Bibcode:1996JCrGr.166..878F. doi:10.1016/0022-0248(95)00474-2.
- ^ Lafez, P.; Ruello, P.; Edely, M. (2008). "Electrical and Infrared Properties of RF Sputtering of Rare Earth Nickelate (RNiO3) Thin Films with Metal Insulator-Transitions". In Lamont, Paul W. (ed.). Leading-Edge Materials Science Research. Nova Publishers. pp. 277–310. ISBN 9781600217982. Retrieved 21 April 2016.
- ^ Wang, Ningning; Wang, Gang; Shen, Xiaoling; Hou, Jun; Luo, Jun; Ma, Xiaoping; Yang, Huaixin; Shi, Lifen; Dou, Jie; Feng, Jie; Yang, Jie; Shi, Yunqing; Ren, Zhian; Ma, Hanming; Yang, Pengtao (2024-10-17). "Bulk high-temperature superconductivity in pressurized tetragonal La2PrNi2O7". Nature. 634 (8034): 579–584. doi:10.1038/s41586-024-07996-8. ISSN 0028-0836.
- "details of selected material". Atom Work. Retrieved 23 April 2016.
- García-Muñoz, J. L.; Aranda, M. A. G.; Alonso, J. A.; Martínez-Lope, M. J. (28 April 2009). "Structure and charge order in the antiferromagnetic band-insulating phase of NdNiO3". Physical Review B. 79 (13): 134432. Bibcode:2009PhRvB..79m4432G. doi:10.1103/PhysRevB.79.134432.
- "details of selected material". Atom Work. Retrieved 23 April 2016.
- "details of selected material". Atom Work. Retrieved 23 April 2016.
- "materials database 16998". Retrieved 23 April 2016.
- Liu, Xiao Qiang; Wu, Yong Jun; Chen, Xiang Ming; Zhu, Hai Yan (2009). "Temperature-stable giant dielectric response in orthorhombic samarium strontium nickelate ceramics". Journal of Applied Physics. 105 (5): 054104–054104–4. Bibcode:2009JAP...105e4104L. doi:10.1063/1.3082034.
- ^ Gibert, Marta; Catalano, Sara; Fowlie, Jennifer. "Researchkelates". dqmp.unige.ch. Retrieved 21 April 2016.
- "Materials database". Retrieved 23 April 2016.
- Nasani, Narendar; Oliveira Rocha, Carlos Miguel; Kovalevsky, Andrei V.; Otero Irurueta, Gonzalo; Populoh, Sascha; Thiel, Philipp; Weidenkaff, Anke; Neto da Silva, Fernando; Fagg, Duncan P. (8 February 2017). "Exploring the Thermoelectric Performance of BaGd2NiO5 Haldane Gap Materials". Inorganic Chemistry. 56 (4): 2354–2362. doi:10.1021/acs.inorgchem.7b00049. PMID 28177255.
- "materials database". Retrieved 23 April 2016.
- García Matres, E.; Rodríguez Carvajal, J.; Martínez, J.L.; Salinas Sánchez, A.; Sáez Puche, R. (February 1993). "Magnetic structure of Ho2BaNiO5". Solid State Communications. 85 (7): 553–559. Bibcode:1993SSCom..85..553G. doi:10.1016/0038-1098(93)90306-8.
- "materials database". Retrieved 23 April 2016.
- 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.
- "materials database". Retrieved 23 April 2016.
- ^ 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.
- "materials database". Retrieved 23 April 2016.
- "Materials database".
- 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.
- 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.
- 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.
Nickel compounds | |
---|---|
Nickel(0) | |
Nickel(II) | |
Nickel(III) | |
Nickel(IV) |