• Title/Summary/Keyword: Solution intercalation

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Intercalation of Primary Diamines in the Layered Perovskite Oxides, $HSr_2Nb_3o_{10}$

  • 홍영식;김시중
    • Bulletin of the Korean Chemical Society
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    • v.17 no.8
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    • pp.730-735
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    • 1996
  • The layered perovskite oxide, KSr2Nb3O10, was synthesized. The interlayer potassium cations were readily exchanged by protons in hydrochloric acid solution to give the protonation compound, HSr2Nb3O10·0.5H2O. The intercalation compounds, [NH3(CH2)nNH3]xSr2Nb3O10, were also obtained by acid-base reactions between the protonation compound and organic bases, 1,n-alkyldiamines. The interlayer distances in the intercalation compounds were linearly increased with the increase of the number of carbon (Δc/Δn=1.05 Å) in 1,n-alkyldiamines. The intercalated alkyldiammonium ions formed a paraffin-like monolayer with average tilting angle (θ) of ca. 56°. The intercalation reactions occurred stoichiometrically. The thermal decomposition process of the intercalation compounds showed distinct three steps due to the desorption of hydrated water, the decomposition of organic moiety, and the decomposition of Sr-related compounds.

Mechanism of Intercalation Compounds in Graphite with Hydrogen Sulfate (II. Study of Intermediate Phase between 2 stage and 1 stage in Graphite Hydrogen Sulfate) (흑연에 황산을 Intercalation 시킬 때의 Mechanism 규명 (II. 화학적 방법에 의한 Graphite Salts의 중간상에 관한 연구))

  • 고영신
    • Journal of the Korean Ceramic Society
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    • v.25 no.4
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    • pp.408-414
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    • 1988
  • This thesis is 2nd thesis from "Mechanism of Intercalation Compounds in Graphite with Hydrogen sulfate(J. Korea Cer. Soc. Vol. 22. No.6, 1985). We have oxidized natural Graphite flakes(0.1~0.2mm., Kropfm hl passau in Deutchland. S40) with a solution of CrO3 in H2SO4. Whilst persulfate ions were intercalated, too, below 7$^{\circ}C$, no evidence for intercalation of a peroxo compound was found at 22$^{\circ}C$. The reaction was interrupted after various times by filtering and washing with concentrated H2SO4. X-ray diffraction showed that the 2nd stage compound had already been formed after 2 minutes. We could only follow further oxidation to the blue stage compound which was completed after 35 minutes. We have found six distinct intermediate stage between 2nd stage and 1 stage. Experiments are described on the formation of intermediate stage color and X-ray diffraction analysis.ysis.

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Preparation of Porous Silica-Pillared Montmorillonite: Simultaneous Intercalation of Amine-Tetraethylorthosilicate into H-Montmorillonite and Intra-Gallery Amine-Catalyzed Hydrolysis of Tetraethylorthosilicate

  • Gwon, O Yun;Park, Gyeong Won;Jeong, Sun Yeong
    • Bulletin of the Korean Chemical Society
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    • v.22 no.7
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    • pp.678-684
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    • 2001
  • Porous silica-pillared montmorillonites were prepared by simultaneous intercalation of dodecylamine-TEOS [tetraethylorthosilicate, Si(OC2H5)4] into the H-montmorillonite and intragallery amine-catalyzed hydrolysis of TEOS. Mixtures of the H-montmorillonite, dodecylamine and TEOS at molar ratios of 1 : 2 : 15-30 and 1 : 2-6 : 20 resulted to swollen and viscous gel once at room temperature, allowing intercalation compounds which dodecylamine and TEOS were simultaneously intercalated into interlayer of H-montmorillonite. The hydrolysis of the gallery TEOS was conducted in water solution for 40 min at room temperature, affording siloxane-pillared H-montmorillonite. Calcination of samples at 500 $^{\circ}C$ in air resulted in silica-pillared montmorillonite with large specific surface areas between 403 and 577 m2 /g, depending on the reaction stoichiometry. The reaction at H-montmorillonite : dodecylamine : TEOS reaction stoichiometries of 1 : 2 : 15 and 1 : 4 : 20 resulted in high specific surface areas and mesopores with a narrow pore size distribution. Result indicates that the intragallery-amine catalyze the hydrolysis of gallery-TEOS and simultaneously have a role of gallery-templated micellar assemblies.

Electrochemical Lithium Insertion/Extraction for Carbonaceous Thin Film Electrodes in Propylene Carbonate Solution

  • Fukutsuka, Tomokazu;Abe, Takeshi;Inaba, Minoru;Ogumi, Zempachi;Matsuo, Yoshiaki;Sugie, Yosohiro
    • Carbon letters
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    • v.1 no.3_4
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    • pp.129-132
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    • 2001
  • Carbonaceous thin films were prepared from acetylene and argon gases by plasma assisted chemical vapor deposition (Plasma CVD) at 873 K. The carbonaceous thin films were characterized by mainly Raman spectroscopy, and their electrochemical properties were studied by cyclic voltammetry and charge-discharge measurements in propylene carbonate (PC) solution. Raman spectra showed that crystallinity of carbonaceous thin films is correlated by the applied RF power. The difference of the applied RF power also affected on the results of cyclic voltammetry and charge-discharge measurements. In PC solution, intercalation and de-intercalation of lithium ion can occur as well as in the mixed solution of EC and DEC.

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Electrochemical Lithium Intercalation within Graphite from Ionic Liquids containing BDMI+ Cation (BDMI+ 양이온을 함유한 이온성 액체로부터 흑연으로의 전기화학적 리튬 삽입)

  • Lee, You-Shin;Jeong, Soon-Ki;Lee, Heon-Young;Kim, Chi-Su
    • Journal of the Korean Electrochemical Society
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    • v.13 no.3
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    • pp.186-192
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    • 2010
  • In situ electrochemical atomic force microscopy (ECAFM) observations of the surface of highly oriented pyrolytic graphite (HOPG) was performed before and after cyclic voltammetry in lithium bis(fluorosulfonyl)imide (LiTFSI) dissolved in 1-buthyl-2,3-dimethylimidazolium (BDMI)-TFSI to understand the interfacial reactions between graphite and BDMI-based ionic liquids. The formation of blisters and the exfoliation of graphene layers by the intercalation of $BDMI^+$ cations within HOPG were observed instead of reversible lithium intercalation and de-intercalation. On the other hand, lithium ions are reversibly intercalated into the HOPG and de-intercalatied from the HOPG without intercalation of the $BDMI^+$ cations in the presence of 15 wt% of 4.90 mol/$kg^{-1}$ LiTFSI dissolved in propylene carbonate (PC). ECAFM results revealed that the concentrated PC-based solution is a very effective additive for preventing $BDMI^+$ intercalation through the formation of solid electrolyte interface (SEI).

Lithium intercalation into a plasma-enhanced-chemical-vapour-deposited carbon film electrode

  • Pyun Su-II
    • Journal of the Korean Electrochemical Society
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    • v.2 no.1
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    • pp.38-45
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    • 1999
  • Electrochemical lithium intercalation into a PECVD (plasma enhanced chemical vapour deposited) carbon film electrode was investigated in 1 M $LiPF_6-EC$ (ethylene carbonate) and DEC (diethyl carbonate) solution during lithium intercalation and deintercalation, by using cyclic voltammetry supplemented with ac-impedance spectroscopy. The size of the graphitic crystallite in the a- and c-axis directions obtained from the carbon film electrode was much smaller than those of the graphite one, indicating less-developed crystalline structure with hydrogen bonded to carbon, from the results of AES (Auger electron spectroscopy), powder XRD (X-ray diffraction) method, and FTIR(Fourier transform infra-red) spectroscopy. It was shown from the cyclic voltammograms and ac-impedance spectra of carbon film electrode that a threshold overpotential was needed to overcome an activation barrier to entrance of lithium into the carbon film electrode, such as the poor crystalline structure of the carbon film electrode showing disordered carbon and the presence of residual hydrogen in its structure. The experimental results were discussed in terms of the effect of host carbon structure on the lithium intercalation capability.

Electrochemical Characteristic on Lithium Intercalation into the Interface between Organic Electrolyte and Amorphous WO3 Thin Film Prepared by e-beam Evaporation Method (e-beam 증발법으로 제조된 비정질 WO3박막과 전해질 계면으로 삽입되는 리튬의 층간 반응에 관한 전기화학적 특성)

  • Min, Byoung-Chul;Sohn, Tae-Won;Ju, Jeh-Beck
    • Applied Chemistry for Engineering
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    • v.8 no.6
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    • pp.1022-1028
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    • 1997
  • This work was performed to study the characteristics of electrochemical intercalation reactions occurring at the interface between the organic electrolyte and tungsten trioxide thin film (thickness of $4000{\AA}$) prepared by e-beam evaporation method as cathodically coloring oxide with regard to the electrochromism by the intercalating reactions of the lithium cation in the 1M $LiClO_4/PC$ organic solution. The characteristics of electrochemical intercalation reactions were investigated by various DC electrochemical methods such as cathodic Tafel polarization test, multiple and the single sweep cyclic voltammetry and the coulomety titrations method. The surfaces of thin films were observed with the patterns of X ray diffraction after the coloring and bleaching reactions. In comparison with the previous results that $WO_3$ thin film intersely detached from the surface of electrode when the hydrogen cation was intercalated into $WO_3$ thin film in the o.1N $H_2SO_4$ aqueous solution, the intercalation reaction of lithium cation into $WO_3$ thin film in the 1M $LiClO_4/PC$ organic solution was shown that the stable bleaching and coloration was appeared within 1.0V of the applied overpotential. When the overpotential of electrochromic reaction for lithium cation in the 1M $LiClO_4/PC$ organic solution had been applied up to 1.5V, the accumulation phenomenon of lithium in amorphous $WO_3$ thin film layer occurred because the inserted lithium into amorphous $WO_3$ thin layer for coloring process was not fully removed from the thin layer to the electrolyte during bleaching process. It was found that there is a limitation of applied overpotential for coloring process by the reduction of the current densities of bleaching and coloration after few number of coloring and bleaching cycles.

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Charge-discharge Behaviour of Lithium Ion Secondary Battery Using LiCo$O_2$ Synthesized by a Solution Phase Reaction (액상 반응에 의해 합성한 리튬코발트산화물을 이용한 Lithium ion 2차전지의 충방전 특성)

  • 김상필;조정수;박정후;윤문수;심윤보
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.11 no.11
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    • pp.1049-1054
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    • 1998
  • The LiCo$O_2$ powder was synthesized by a solution phase reaction. This shows a high (003) peak intensity and low (104) or (101) peak intensities in X-ray diffraction spectra. The LiCo$O_2$/Li cell shows an initial discharge capacity of 102.9mAh/g and an average discharge potential or 3.877V at a current density of 50mA/g between 3.0~4.2V. The peaks of dQ/dV plot are associated with Li ion intercalation/deintercalation reaction. To evaluate the cycleability of an actual battery system, cylindrical lithium ion cell was manufactured using graphitized MPCF anode and LiCoO$_2$ cathode. After 100th cycle, this cel maintains 80% capacity of 10th cycle value. The LiCoO$_2$/MPCF cell has a high discharge voltage of 3.6~3.7V and a good cycle life performance on cycling between 4.2~2.7V.

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Chemical Bonding Nature and Mesoporous Structure of Nickel Intercalated Montmorillonite Clay

  • Park, Hye-Mi;Kim, Tae-Woo;Hwang, Seong-Ju;Choy, Jin-Ho
    • Bulletin of the Korean Chemical Society
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    • v.27 no.9
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    • pp.1323-1328
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    • 2006
  • Mesoporous nickel intercalated aluminosilicate nanohybrid has been synthesized through a recombination reaction between the colloidal suspension of exfoliated montmorillonite nanosheets and aqueous nickel acetate solution. According to powder X-ray diffraction and field emission-scanning electron microscopic analyses, the intercalation of nickel species expands significantly the basal spacing of the host montmorillonite clay and the crystallites of the intercalation compound are assembled to form a house-of-card structure. $N_2$ adsorption-desorption isotherm measurements with BJH pore analyses clearly demonstrated that the porosity of the intercalate originates mainly from mesopores (diameter $\sim50\;\AA$) formed by the house-of-card type stacking of clay crystallites. From FT-IR and X-ray absorption spectroscopic analyses, it becomes certain that intercalated nickel ion is stabilized in an isolated $NiO_6$ octahedral unit. The present mesoporous intercalation compound is expected to be applicable as efficient catalysts or absorbents.

Effect of Counter Anions on Solid Electrolyte Interphase Formation on Graphite Electrodes in Propylene Carbonate-based Electrolyte Solutions

  • Song, Hee-Youb;Kim, Seong In;Nogales, Paul Maldonado;Jeong, Soon-Ki
    • Journal of Electrochemical Science and Technology
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    • v.10 no.1
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    • pp.55-60
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    • 2019
  • Herein, the effect of counter anions on the formation of a solid electrolyte interphase (SEI) in a propylene carbonate (PC)-based electrolyte solution was investigated. Although the reversible capacities were different, reversible intercalation and de-intercalation of lithium ions occurred in the graphite negative electrode in the PC-based electrolyte solutions containing 1 M $LiClO_4$, $LiPF_6$, $LiBF_4$, and $LiCF_3SO_3$ at low temperature ($-15^{\circ}C$). This indicated that the surface films acted as an effective SEI to suppress further co-intercalation and decomposition reactions at low temperature. However, the SEIs formed at the low temperature were unstable in 1 M $LiPF_6$ and $LiBF_4/PC$ at room temperature ($25^{\circ}C$). On the other hand, increasing reversible capacity was confirmed in the case of $LiCF_3SO_3/PC$ at room temperature, because the SEI formed at the low temperature was still maintained. These results suggest that counter anions are an important factor to consider for the formation of effective SEIs in PC-based electrolyte solutions.