巻号一覧
1990 巻 (1990)
- 145 号 p. 220-
- 144 号 p. 171-
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1990 巻, 145 号
選択された号の論文の16件中1～16を表示しています
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―グラファイト層間化合物の複合化塩山 洋, 辰巳 国昭, 相馬 勲, 藤井 禄郎1990 年 1990 巻 145 号 p. 220-227
発行日: 1990/12/10
公開日: 2010/06/28
ジャーナル フリーStage-4 AlCl3-GIC prepared by the standard two-zone method were oxidized galvanostatically in H2SO4. The X-ray diffraction data indicate the stepwise intercalation of H2SO4 into host graphite and no formation of the GBC is observed, whereas AlCl3 is deintercalated in an early step of the reaction. In the case of the stage-4 MoCl5-GIC, the galvanostatic oxidation caused the stepwise bi-intercalation of H2SO4 into the host GIC as well as the displacement of MoCl5 by H2SO4.
Alternatively, AlCl3 vapour was allowed to react with stage-3 FeCl3-GIC. The competition between the displacement reaction of FeCl3 by AlCl3 and the stepwise bi-intercalation of AlCl3 into the stage-3 FeCl3-GIC was observed.
The bi-intercalation process of such a high stage GIC is explained with a schematic chemical potential diagram, comparing the bi-intercalation into stage-2 GIC.抄録全体を表示PDF形式でダウンロード (999K) -
岩下 哲雄, 稲垣 道夫1990 年 1990 巻 145 号 p. 228-237
発行日: 1990/12/10
公開日: 2010/06/28
ジャーナル フリーFor electrochemical reduction of graphite intercalation compounds with sulfuric acid (H2SO4-GICs) synthesized by chemical oxidation in sulfuric acid solution with an excess amount of oxidant, a large amount of electrical quantity was needed much larger than that for the reduction of the compound synthesized by electrochemical oxidation. This experimental result seemed to be explained by the competition between the chemical oxidation to H2SO4-GICs in sulfuric acid solution with the chemical oxidant and the electrochemical reduction of H2SO4-GICs. In the case of nitric acid oxidation, even though H2SO4-GICs was electrochemically reduced to graphite, the graphite was chemically oxidized by opening the circuit and again sulfuric acid was intercalated into the gallery of graphite, accompanying the increase in potential. More than 20 cycles of electrochemical discharging and chemical charging were performed with 4mA discharge current.
Based on this reaction cycle, chemical oxidation to and electrochemical reduction of H2SO4-GICS was constructed a battery by using graphite and lead metal as positive and negative electrodes, respectively. Its discharging showed well-defined plateau and larger capacity than theoretical one was obtained.抄録全体を表示PDF形式でダウンロード (1268K) -
作埜 秀一, 小川 あゆみ, 阿久沢 昇, 高橋 洋一1990 年 1990 巻 145 号 p. 238-242
発行日: 1990/12/10
公開日: 2010/06/28
ジャーナル フリーEffects of starting carbon material (Heat-Treatment Temperature, 1000, 1500, 2000 and 2600°C) and chemical composition of K-GICs on the absorption of tetrahydrofuran (THF) and benzene (Bz) on potassium-graphite intercalation compounds (K-GICs) have been investigated by gravimetry and X-ray diffraction measurements. It is found that THF is absorbed on K-GICs, irrespective of the starting carbon material. On the contrary, benzene absorption is very sensitive to the degree of graphitization of the starting carbon material: No absorption was observed, except for K-GICs prepared from HTT-2600 carbon material. It is also found that as the composition of K-GICs, K/C, decreases, the absorbed amount, M/K (M denotes THF and benzene), increases. It is considered that the decrease of K/C results in the increase of interlayer free volume, where molecules are accomodated.
Absorption of thiophene on cesium-graphite intercalation compounds (Cs-GICs) and on K-GICs prepared from natural graphite flakes were also investigated. Isotherms and effect of composition of Cs-GICs are determined.抄録全体を表示PDF形式でダウンロード (551K) -
Zheng-De Wang, Michio Inagaki1990 年 1990 巻 145 号 p. 243-249
発行日: 1990/12/10
公開日: 2010/06/28
ジャーナル フリーGraphite intercalation compounds with CuCl2 (CuCl2-GICs) were prepared at 380° by the vapor, mixing and molten salt methods. The intercalation process ineach method was followed by weight gain and X-ray powder pattern of the products obtained at each reaction time. The equilibrium stage structure in the CuCl2 -KCl molten salts with different compositions was determined.
The intercalation of CuCl2 proceeded rapidly in the molten salt and by mixing method, though no intercalation was detected by vapor method. This result shows that the transportation step of CuCl2 vapor is excluded in the former two methods, but is rate-determining in the last one. The equilibrium stage structure was 2 in the molten salt, but 1 by mixing method, which was explained by the difference in chemical potential of intercalating species CuCl2. It also depended strongly on the composition of the system, that is, chemical potential of CuCl2. The transient state to the equilibrium was observed to be randomly mixed stages.抄録全体を表示PDF形式でダウンロード (800K) -
渡邊 信淳, 東城 哲朗, 鄭 容宝1990 年 1990 巻 145 号 p. 250-255
発行日: 1990/12/10
公開日: 2010/06/28
ジャーナル フリーIn the operation of fluorine cell, today's essential problems should lower the cell voltage and control the onset of anode effect which is abnormal increase of cell voltage. The cause of above phenomenon is that graphite fluoride of extremely low surface energy is formed on the anode surface by an electrode side reaction. When the electrode surface is partially covered by graphite fluoride, the wettability of anode surface much decreases and the true current density sharply increases. And the anode effect occurs when the value of the surface coverage of the compound reaches to about 0.2.
In this paper, the electrochemical characteristics of a new carbon anode are reported. This carbon electrode has been impregnated by molten fluoride at high temperature and high pressure. The cell voltage of the operation with the new anode was much lower than that of the cell with raw carbon electrode, and more the onset of anode effect did not happen even in such a high current density as 60A/dm2. This means that the surfaceof carbon anode is not entirely covered with graphite fluoride, but covered with fluorine intercalation compound which is not so low surface energy and has rather higher electric conductivity than that of raw carbon. This intercalation compound has been identified with the surface analysises.抄録全体を表示PDF形式でダウンロード (808K) -
鄭 容宝, 大橋 満也, 渡邊 信淳, 田坂 明政1990 年 1990 巻 145 号 p. 256-260
発行日: 1990/12/10
公開日: 2010/06/28
ジャーナル フリー(CF)n-Ni plating is expected to have an excellent physical property as for the water repellency, due to the extremely low surface energy of (CF)n such as 6 ± 3 ergs. cm-2.(CF) n was dispersed with the addition of cationic surfactant to Watt bath.(CF)n was codeposited with nickel on platinum or stainless steel electrochemically from this bath. The state and chemical stability of (CF) n in the nickel matrix was examined by the methods of surface analysis such as EPMA, SEM, X-ray diffraction. The wettability of (CF)n-Ni composite material was estimated from the measurement of the contact angle of water on it.抄録全体を表示PDF形式でダウンロード (3353K) -
大平 雅彦, 稲垣 道夫1990 年 1990 巻 145 号 p. 261-267
発行日: 1990/12/10
公開日: 2010/06/28
ジャーナル フリーThe intercalation reactions in CuCl2-FeCl3 system were studied by gravimetric analysis, X-ray powder diffractometry and energy dispersive X-ray spectroscopy (EDS). The reactions between graphite and a mixture of CuCl2 and FeCl3, between CuCl2-GIC's and FeCl3, and also between FeCl3-GIC's and CuCl2 were examined at 300 and 550°C.At 300°C, where the de-intercalation of CuCl2 or FeCl3 from their GIC's in a sealed tube was negligibly small, it was found that FeCl3 is intercalated into vacant graphite galleries and also exchanged with CuCl2 existing in graphite interlayer spaces, while CuCl2 can be merely exchanged with FeCl3 in graphite interlayer spaces. At 550°C, however, the de-intercalation of the intercalates, the intercalation of CuCl2 or FeCl3 into the vacant graphite galleries and the exchange reaction between FeCl3 and CuCl2 proceeded simultaneously. The formation of a molten salt in the CuCl2-FeCl3 system was observed, which seemed to lower the reactivities of CuCl2 and FeCl3 to graphite. The results of the line analysis by EDS showed that CuCl2 and FeCl3 intercalated seemed to coexist in separated domains. From the present results, the following four processes seemed to affect the formation of the ternary GIC's (Fig. 2); (1) exchange reaction between intercalates and reagents, (2) intercalation of reagents into vacant graphite galleries, (3) de-intercalation reaction from the starting GIC's and (4) formation of molten salt which seemed to lower the reactivities of metal chlorides.抄録全体を表示PDF形式でダウンロード (2907K) -
寺井 隆幸, 高橋 洋一1990 年 1990 巻 145 号 p. 268-272
発行日: 1990/12/10
公開日: 2010/06/28
ジャーナル フリーSorption-desorption behavior of isotopic hydrogen gases was investigated on secondstage potassium graphite intercalation compound (K-GIC) prepared from highly oriented pyrolytic graphite (HOPG) flakes. In the first run of hydrogen sorption, little amount of hydrogen was absorbed by KC21±1 at 77K, while H2 gas was absorbed up to 0.65 in the mole ratio of H2 to K in the second run. Absorbed H2 could not be desorbed even by evacuation, and was released with large swelling of the sample by warming up.The swollen sample showed dark blue color, which is characteristic of 2nd-stage K-GIC, and still had great capability of hydrogen sorption. Judging from the absorption isotherms and the data on the changes of enthalpy and entropy of absorption obtained in this study, the swollen sample was considered to have a double porous structure constructed of micropores and macropores.抄録全体を表示PDF形式でダウンロード (1613K) -
中島 剛, 松井 丈雄1990 年 1990 巻 145 号 p. 273-276
発行日: 1990/12/10
公開日: 2010/06/28
ジャーナル フリーVanadium fluoride-graphite intercalation compounds have been prepared under a relatively high vapor pressure of VF5 in a fluorine atmosphere. GISs having larger inter-calate sizes than those for VF5 and VF-6 are abtained under this condition. ESCA and IR spectra indicate that the intercalates of these compounds are VF5 and fluorine. Based on these results, new c-axis structure models have been proposed.抄録全体を表示PDF形式でダウンロード (475K) -
沖野 不二雄1990 年 1990 巻 145 号 p. 277-280
発行日: 1990/12/10
公開日: 2010/06/28
ジャーナル フリーThe F/As molar ratio for the vacuum-stable products obtained following treatment of graphite, at ca. 20°C, with (1) AsF5, (2) AsF5+F2, and (3) O2AsF6 has been established to be 6. Route (1) gives mixtures of first- and second-stage salts Cx AsF6, whereas (2) and (3) readily yield first-stage materials. This is attributed to the greater oxidizing potential of the reagents in (2) and (3). X-ray powder diffraction data for the first-stage compound, C14AsF6 (graphite hexafluoroarsenate) with Ic=7.6 Å, indicate that the F-ligands of AsF6-are nestled in contiguous three-fold sets of C-atom hexagons of a carbon-layer. This requires a staggering of the enclosing carbon-layers. Adjacent pairs of C-atom sheets contain assemblies of AsF6- of short-range order, appropriate for the composition C14AsF6. Aside from the restriction imposed by AsF6- nestling, the carbon-layers are otherwise randomly stacked. The X-ray powder diffraction pattern of C14AsF6 has been simulated by this novel model. Addition of neutral molecules, e. g. AsF5 and AsF3, to C14AsF6 (Ic=7.6Å) produces an un-nestled C14AsF6 1/2; AsF5 (or AsF3) with Ic≅8.0 Å, whose X-ray powder diffraction pattern is indistinguishable from that of CxAsF5 made from graphite and AsF5 without a following evacuation. This process is reversible.抄録全体を表示PDF形式でダウンロード (442K) -
Kazuko Oi, Takayuki Terai, Yoichi Takahashi1990 年 1990 巻 145 号 p. 281-282
発行日: 1990/12/10
公開日: 2010/06/28
ジャーナル フリーSorption behavior of aliphatic hydrocarbons such as ethane and propane by the 2nd-stage cesium-graphite intercalation compound (CsC24) was examined. Both ethane and propane were found to be sorbed at the low temperatures (194-287K) up to the compositions of CsC24 (C2H6) 0.9 and CsC24 (C3H8) 0.7, respectively.
The sorption-desorption characteristics were reproducible and the saturation compositions were enhanced with decreasing temperatures, indicating these phenomena to be physisorption.抄録全体を表示PDF形式でダウンロード (224K) -
松浦 基浩, 萩原 亮1990 年 1990 巻 145 号 p. 283-294
発行日: 1990/12/10
公開日: 2010/06/28
ジャーナル フリーA various kinds of interesting ordered form. called by a “hierarchical structure” are found to exist in the natural world. In this paper, we examine the mechanism of a characteristic two-step phase transition observed in CoCl2- and NiCl2-GIC (graphite intercalation compound), magnetic compounds of GIC family which are a series of quasi two-dimensional (2D) complex systems and have been studied extensively, intending to develope some new material with novel characteristics. As the result, the phenomenon is well understood as a hierarchical ordering process realized through two different phase transitions for the second kind in two different scales, like as disorder_??_intra-island (2D) order with inter-island disorder_??_inter-island (3D) order, reflecting the stage structure and island structure which are formed correlatively as a 3D ordered pattern by cooperative interactions among the intercalant atoms or molecules in the intercalation process. In such a way, the present two-step phase transition is considered as a special unique case of a variety of hierarchic structure in the natural world.抄録全体を表示PDF形式でダウンロード (1624K) -
その合成、構造および物理的化学的性質中島 剛1990 年 1990 巻 145 号 p. 295-310
発行日: 1990/12/10
公開日: 2010/06/28
ジャーナル フリーAll the features of fluorine-graphite intercalation compounds, CxFs have been reviewed by citing from the first publication on these compounds to thenewest one. CxFs are synthesized by several different methods in the presence of various kinds of fluorides. The products and their properties strongly depend on the reaction rates. Fluorine intercalation in anhydrous liquid HF or in a large amount of gaseous HF gives stage 1, C2 F-C5 F with semi-ionic C-F bond. On the other hand, the reaction in the presence of a small amount of a volatile fluoride or in the presence of an involatile fluoride yields stage 1-4, C2 F-C16F having more ionic C-F bond on the average. These two groups of CxFs have some differencesin the chemical bonds, structures and electrical conductivities. The present review precisely describes the synthesis, compositions and stage numbers, chemical bonds, structure models, physical and chemical properties, and applications of CxFs.抄録全体を表示PDF形式でダウンロード (1983K) -
インターカラントの種類と挙動田沼 静一1990 年 1990 巻 145 号 p. 311-326
発行日: 1990/12/10
公開日: 2010/06/28
ジャーナル フリーA review on the variety of intercalants of graphite intercalation compounds (GIC) as well as on the peculier behavior of intercalants is given. About a handred kinds of intercalants are listed in the case of single-species intercalation. Intercalation takes place as the gaining of free enthalpy by the attraction between intercalants and graphens mainly by the electrostatic interaction due to the charge transfer. The donor type and acceptor type intercalants make GICs electron rich and hole rich conductors respectively. The charge transfer rate varies from unity to, e.g., 0.02. Staging is the most notable behavior of GIC which can make a c-axis superlattice as large periodic distance as more than 50Å. Staging kinetics due to Daumas-Hérold model, a ‘sliding model’ as the movement of inter-calant sheet and intra-stage fine phase transitions are discussed. Various methods of syntheses of GICs are described. Finally the multi-species intercalation is reviewed giving examples of different methods and different combination of species.抄録全体を表示PDF形式でダウンロード (1982K) -
鏑木 裕, 菱山 幸宥1990 年 1990 巻 145 号 p. 327-338
発行日: 1990/12/10
公開日: 2010/06/28
ジャーナル フリーPDF形式でダウンロード (1611K) -
曽我部 敏明1990 年 1990 巻 145 号 p. 350-351
発行日: 1990/12/10
公開日: 2010/06/28
ジャーナル フリーPDF形式でダウンロード (201K)
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