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铱酸锂

铱酸锂
IUPAC名
Lithium iridate
英文名 Lithium iridate
别名 铱(IV)酸锂
识别
CAS号 61232-88-0  checkY
性质
化学式 Li2IrO3
外观 黑色晶体
结构
晶体结构 单斜晶系
C2/m[1]
晶格常数 a = 5.1633(2) Å, b = 8.9294(3) Å, c = 5.1219(2) Å
晶格常数 α = 90°, β = 109.759(3)°, γ = 90°
相关物质
其他阴离子 钌酸锂
铂酸锂
其他阳离子 铱酸钠
若非注明,所有数据均出自标准状态(25 ℃,100 kPa)下。

铱酸锂是一种无机化合物,化学式为Li2IrO3。它是黑色晶体,可以形成三种层状结构,α型、β型和γ型,仅略微不同。它表现出类金属的导电性,其导电性和温度有关,冷却至15 K时顺序从顺磁性改变为反铁磁性

结构

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Li2IrO3通常以α型或β型的晶体形式出现,而γ相较为少见。α-Li2IrO3的晶体结构由六边形的锂层和边共享的IrO6八面体的蜂窝交替堆叠在锂的中心。相邻层中的偏移导致相对较低的晶体(单斜)对称性。Li2IrO3晶体具有丰富的孪晶缺陷,其中ab晶面围绕c轴旋转120°。[2]

制备

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以Li和Ir为原料合成Li2IrO3,加热时在空气中发生氧化反应。螺旋楼梯状的反应器让不同晶体在不同阶段结晶。[2]
Li2IrO3合成过程中时间-温度表。[2]

Li2IrO3晶体可以通过金属在空气中的煅烧来生长。α型在750~1050℃下形成,加热至更高的温度产生β相。如果将金属替换为更传统的且易于储存或使用的碳酸锂,可以长出更大的晶体。γ-Li2IrO3可以通过煅烧碳酸锂和铱,然后在700~800℃的熔融氢氧化锂中进行退火获得。[2]

性质

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铱酸锂是黑色固体,其导电性温度关系并不大。[1]α和β型都表现出来自Ir4+和磁自旋之间的基塔耶夫交换耦合。这些自旋在低于15 K(奈尔温度TN)时形成反铁磁晶胞,而在此温度以上是顺磁性的。[2]

潜在应用

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铱酸锂可作为锂离子电池的电极材料而有潜在的应用,[1]但由于Ir价格昂贵,廉价的Li2MnO3可作为其替代物而限制了其应用可能。[3]

参考文献

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  1. ^ 1.0 1.1 1.2 O'Malley, Matthew J.; Verweij, Henk; Woodward, Patrick M. Structure and properties of ordered Li2IrO3 and Li2PtO3. Journal of Solid State Chemistry. 2008, 181 (8): 1803. doi:10.1016/j.jssc.2008.04.005. 
  2. ^ 2.0 2.1 2.2 2.3 2.4 Freund, F.; Williams, S. C.; Johnson, R. D.; Coldea, R.; Gegenwart, P.; Jesche, A. Single crystal growth from separated educts and its application to lithium transition-metal oxides. Scientific Reports. 2016, 6: 35362. PMC 5066249可免费查阅. PMID 27748402. arXiv:1604.04551可免费查阅. doi:10.1038/srep35362. 
  3. ^ Yoshio, Masaki; Brodd, Ralph J.; Kozawa, Akiya. Lithium-Ion Batteries: Science and Technologies. Springer Science & Business Media. 17 July 2010: 10 [2017-08-05]. ISBN 978-0-387-34445-4. (原始内容存档于2017-03-21). 
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铱酸锂
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