Tuning Intercalation Sites in Nickel Hexacyanoferrate Using Lattice Nonstoichiometry
Tuning Intercalation Sites in Nickel Hexacyanoferrate Using Lattice Nonstoichiometry
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DOI：
10.1021/cm0515101
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发表时间：
2005-10
影响因子：
8.6
通讯作者：
Xiaogang Hao† and;D. Schwartz
中科院分区：
文献类型：
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作者：
Xiaogang Hao† and;D. Schwartz
可逆的嵌入/脱嵌的铁氰化镍（NiHCF）薄膜中的K+发生在两个能量不同，很大程度上不相互作用，其比例由晶格非化学计量的网站。主成分分析（PCA）是用来关联的化学计量的NiHCF，使用能量色散X-射线光谱（EDS）测量，通过循环伏安法（CV）测量的嵌入过程。众所周知，NiHCF伏安图显示含K+电解质的两个可逆峰;每个峰代表不同的局部阳离子嵌入/脱嵌环境。59个不同的CV-EDS数据集的PCA显示（一阶），两个CV峰的相对大小是成比例的晶格非化学计量比，但峰的位置（能量）在很大程度上是独立的化学计量比。与缺陷相关的位置相比，化学计量晶格中的嵌入位置在能量上是有利的（ΔG −10 kJ/mol K+）。CV峰大小的比例，一个…
Reversible intercalation/deintercalation of K+ in nickel hexacyanoferrate (NiHCF) thin films occurs in two energetically distinct, largely noninteracting, sites whose proportions are set by lattice nonstoichiometry. Principal component analysis (PCA) is used to correlate the stoichiometry of NiHCF, measured using energy-dispersive X-ray spectroscopy (EDS), with intercalation processes measured via cyclic voltammetry (CV). NiHCF voltammograms are well-known to exhibit two reversible peaks for K+-containing electrolytes; each peak represents a different local cation intercalation/deintercalation environment. PCA of 59 different CV-EDS data sets shows (to first order) that the relative sizes of the two CV peaks are proportional to the lattice nonstoichiometry, but the peak locations (energies) are largely independent of stoichiometry. Intercalation sites in stoichiometric lattices are energetically favored compared to sites associated with defects (ΔG ≈ −10 kJ/mol K+). The proportionality of CV peak sizes, a...