Ion-selective change storage in three types layered MnO2 films intercalated with different cobalt complexes

IF 3.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Solid State Chemistry Pub Date : 2025-09-10 DOI:10.1016/j.jssc.2025.125659

Ryota Sugawara , Ryosuke Okawa , Ryo Sasaki , Mayumi Abe , Kazuaki Tomono

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Abstract

In this study, layered MnO₂ films intercalated with three types of cobalt complexes; [Co(en)₃], trans-[Co(en)₂Cl₂], and cis-[Co(en)₂Cl₂] were prepared on FTO substrates, forming [Co(en)₃]@MnO₂, trans-[Co(en)₂Cl₂]@MnO₂, and cis-[Co(en)₂Cl₂]@MnO₂, respectively. XRD, EDS, FT-IR, and Raman results confirmed the preparation of layered MnO₂ films with the respective cobalt complexes in the interlayer. Electrochemical measurements (cyclic voltammetry; CV) in Na₂SO₄ electrolyte showed that [Co(en)₃]@MnO₂ film (262 F/g), trans-[Co(en)₂Cl₂]@MnO₂ film (226 F/g) and cis-[Co(en)₂Cl₂]@MnO₂ film (193 F/g), showing high cycle stability and capacitance. During CV measurements, the cobalt complex in [Co(en)₃]@MnO₂ was deintercalated and replaced by hydrated Na ⁺ ions, whereas in trans-[Co(en)₂Cl₂]@MnO₂ and cis-[Co(en)₂Cl₂]@MnO₂, the cobalt complexes retained in the interlayer. These results suggest that Na⁺ ions intercalation/deintercalation dominated in [Co(en)₃]@MnO₂, while SO₄²⁻ ions intercalation/deintercalation occurred in trans-[Co(en)₂Cl₂]@MnO₂ and cis-[Co(en)₂Cl₂]@MnO₂. The ionic property that Na ⁺ ions diffuse more easily in aqueous solution than SO₄²⁻ ions suggests that the [Co(en)₃]@MnO₂ film has a larger capacitance than the trans-[Co(en)₂Cl₂]@MnO₂ film and the cis-[Co(en)₂Cl₂]@MnO₂ film. Electrochemical impedance spectroscopy (EIS), [Co(en)₃]@MnO₂ exhibited a mixed response of capacitive and diffusive behavior associated with Na ⁺ replacement, with a linear region showing a slope of approximately 60° in the Nyquist plot. trans-[Co(en)₂Cl₂]@MnO₂ and cis-[Co(en)₂Cl₂]@MnO₂ showed two semicircles originating from surface and interlayer reactions, followed by a linear region with a slope of about 80°, reflecting surface-capacitive dominance. These features are consistent with the differences in the slope and phase angle observed in the Bode plots, indicating that the EIS response is influenced by ion diffusivity and interlayer structure.

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三种不同钴配合物层状二氧化锰膜的离子选择性变化存储

在本研究中，层状MnO2膜嵌入了三种类型的钴配合物；在FTO衬底上制备了[Co(en)3]、trans-[Co(en)2Cl2]和顺式-[Co(en)2Cl2]，分别形成了[Co(en)3]@MnO2、trans-[Co(en)2Cl2]@MnO2和顺式-[Co(en)2Cl2]@MnO2。XRD， EDS， FT-IR和Raman结果证实了层状MnO2薄膜的制备，层间分别有钴配合物。在Na2SO4电解质中的电化学测试（循环伏安法；CV）表明，[Co(en)3]@MnO2膜（262 F/g）、反式-[Co(en)2Cl2]@MnO2膜（226 F/g）和顺式-[Co(en)2Cl2]@MnO2膜（193 F/g）表现出较高的循环稳定性和电容。在CV测量中，[Co(en)3]@MnO2中的钴配合物被脱嵌并被水合的Na +离子取代，而在反式-[Co(en)2Cl2]@MnO2和顺式-[Co(en)2Cl2]@MnO2中，钴配合物保留在中间层中。结果表明，在[Co(en)3]@MnO2中，Na+离子的插入/脱嵌作用占主导地位，而在反式-[Co(en)2Cl2]@MnO2和顺式-[Co(en)2Cl2]@MnO2中，SO42−离子的插入/脱嵌作用占主导地位。Na +离子比SO42−离子更容易在水溶液中扩散，表明[Co(en)3]@MnO2薄膜比反式-[Co(en)2Cl2]@MnO2薄膜和顺式-[Co(en)2Cl2]@MnO2薄膜具有更大的电容。电化学阻抗谱（EIS）显示，[Co(en)3]@MnO2在Na +置换过程中表现出电容性和扩散性的混合响应，在Nyquist图中线性区呈现出约60°的斜率。反式-[Co(en)2Cl2]@MnO2和顺式-[Co(en)2Cl2]@MnO2表现出两个源自表面和层间反应的半圆，然后是一个斜率约为80°的线性区域，反映了表面电容性优势。这些特征与Bode图中观察到的斜率和相角的差异一致，表明EIS响应受离子扩散率和层间结构的影响。

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来源期刊

Journal of Solid State Chemistry 化学-无机化学与核化学

CiteScore

6.00

自引率

9.10%

发文量

848

审稿时长

25 days

期刊介绍： Covering major developments in the field of solid state chemistry and related areas such as ceramics and amorphous materials, the Journal of Solid State Chemistry features studies of chemical, structural, thermodynamic, electronic, magnetic, and optical properties and processes in solids.