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The double layered carbon materials were prepared from mesophase pitch, artificial graphite, natural graphite and coke coated with coal-tar pitch. The coal-tar pitch as a coating species was dissolved by organic solvents like toluene and light oil. The coating of coal-tar pitch on the mesophase pitch, artificial graphite, natural graphite and coke was confirmed by increasing of the FWHM (full width at half maximum) of X-ray diffraction and of percentage of hydrogen by CHN analysis. However, the coating layers were not confirmed by SEM. The coated carbonaceous materials were carbonized at 800 to 1000℃ in nitrogen atmosphere, and then graphitized at 2600℃ for using of anode in Li-ion battery. Performance of double layered carbonaceous materials as the anode were carried out at the coin type cell. Performance of anode was measured by the charge and discharge capacity. The capacities of charge and discharge were changed by thermal treatment and kind of precursors. However, the coating methods showed the little differences in charge capacity. The lower heat-treatment at 800℃ showed the higher capacity rather than at 1000℃. And also, the lower capacity shown the graphitized double layered materials rather than carbonized materials. Conclusionally, the performances of anode materials were changed by crystallity, composition, microstructures of carbonaceous materials.
The synthesis of the manganese and chromium compounds which based on redox reactions in solutions are practiced by using different precursors and process. All of the Li[CrxLi(1/3-x/3)Mn(2/3-2x/3)]O2 series were synthesized by solid-state reactions using the pre-perpared manganese and chromium precursors. In Capter. 2, the manganese and chromium oxide nanoparticles were synthesized by redox reactions using the oxidation agent in aqueous solutions. The Li1.252Cr0.244Mn0.504O2 materials having α-NaFeO2 (R3-m) phase were prepared by solid-state reactions with LiOH and the prepared nanoparticles. The materials were calcined at 500℃ and 900℃ for 6 hrs in air, and then quenched to room temperature. The Li1.252Cr0.244Mn0.504O2 material heated at 500℃ exhibits nanocrystalline characteristics and much higher discharge capacity of 268 mAh/g than the fully crystallized material heated at 900℃. Also, the material heated at 500℃ shows clearly the absence of the capacity at near 4.5 V after the first charge process in differential capacity vs. potential curve, indicating that the nanocrystalline Li1.252Cr0.244Mn0.504O2 successfully circumvents the undesirable oxygen loss. In Capter. 3, the manganese and chromium oxide nanoparticles were synthesized by redox reactions using transition metal powders in solutions. The layered Li[CrxLi(1/3-x/3)Mn(2/3-2x/3)]O2 (x=0.054, 0.0142, 0.147 and 0.311) materials having α-NaFeO2 (R-3m) structure were prepared by solid-state reactions with LiOH and the pre-perpared manganese and chromium precursors. The amount of chromium, after removing the traces of Li2CrO4 from the prepared samples is found to be increased with temperature. The Li[CrxLi(1/3-x/3)Mn(2/3-2x/3)]O2 material with x=0.147 exhibits a high discharge capacity of 280 mAh/g in the first cycle and a good reversible capacity of about 250 mAh/g when cycled in voltage range 2.0 - 4.9 V. Whereas, the Li[CrxLi(1/3-x/3)Mn(2/3-2x/3)]O2 material with x=0.311 delivered a very low initial discharge capacity of 98 mAh/g, which is found to be increased up to a discharge capacity of about 260 mAh/g at the 30th cycling. This drastic increase in capacity is attributed to the redox couples of Cr+4/Cr+6 and Cr+3/Cr+4. 용액 상태에서 산화ㆍ환원 반응에 기초를 둔 망간과 크롬 화합물의 합성은 서로 다른 전구체와 실험과정을 이용하여 실행되었다. 모든 Li[CrxLi(1/3-x/3)Mn(2/3-2x/3)]O2 양극재료들은 미리 준비한 망간과 크롬 전구체를 이용하여 고상 고온법으로 합성하였다. Chapter.2에서는 망간과 크롬 화합물은 수용액 상태에서 산화제를 이용하여 산화ㆍ환원 반응에 의해 합성하였다. α-NaFeO2 (R-3m) 구조를 갖는 Li1.252Cr0.244Mn0.504O2 양극재료는 LiOH 와 얻어진 망간과 크롬 화합물과 함께 고상 고온법으로 준비하였다. 이 양극재료는 500℃ 와 900℃에서 6 시간동안 열처리하고, 상온으로 급냉시켰다. 500℃에서 열처리한 Li1.252Cr0.244Mn0.504O2 양극재료는 nanocrystalline 특성을 보여주었고 900℃에서 열처리한 양극재료보다 더 높은 268 mAh/g 의 방전 용량을 나타냈다. 또한, 500℃에서 열처리한 양극재료는 differential capacity vs. potential 곡선에서 첫 번째 충전 과정 후 4.5 V 근처에서 용량 부재를 명백히 나타냈으며, 이는 nanocrystalline 특성을 지닌 Li1.252Cr0.244Mn0.504O2 양극재료가 바라지않은 산소 손실을 성공적으로 극복했다는 것을 말해주고 있다. Capter. 3에서는 망간과 크롬 화합물은 전이 금속 powder를 이용하여 용액상태에서 산화ㆍ환원 반응에 의해 준비되었다. α-NaFeO2 (R-3m) 구조를 갖는 층상구조인 Li[CrxLi(1/3-x/3)Mn(2/3-2x/3)]O2 (x=0.054, 0.142, 0.147 and 0.311) 양극재료들은 얻어진 망간과 크롬 화합물을 이용하여 고상 고온법에 의해 합성되어졌다. 세척 과정을 통해 Li2CrO4를 제거해줌으로써 Li[CrxLi(1/3-x/3)Mn(2/3-2x/3)]O2 양극재료의 크롬 양은 반응 온도가 올라감에 따라 증가하는 것을 ICP결과에 의해 찾아낼 수 있었다. 크롬 양이 0.147함유한 리튬이온전지 양극재료는 전압영역 2.0 V와 4.9 V 사이에서 초기 싸이클 동안 280 mAh/g 의 높은 방전 용량을 나타냈고, 초기 충전 이후 산소 손실의 부재에 의해 약 250 mAh/g의 우수한 가역적인 용량을 나타내었다. 크롬 양이 0.311 함유한 리튬이온전지 양극재료는 98 mAh/g 의 낮은 초기 방전 용량을 나타내지만, 30번째 싸이클까지 약 260 mAh/g 의 급격한 방전 용량의 증가를 보여주었다. differential capacity vs. potential 곡선은 크롬 양이 0.311 함유한 리튬이온전지 양극재료의 용량 증가가 산화ㆍ환원 짝인 Cr+4/Cr+6 과 Cr+3/Cr+4과 관련이 있을 가능성을 언급해 주고 있다.
Diarylethene이 첨가된 저융점 유-무기 하이브리드 유리의 광변색 특성
Diarylethene were doped in organic-inorganic hybrid low-melting glasses were synthesized through a non-aqueous acid-base reaction process, which consists of network units including a smaller number of bridging oxides, a Si atom having terminating organic functional groups instead of a lone electron pair and a Sn atom to improve chemical durability through P-O-Sn instead of P-O-P linkage. Diarylethene is incoporated into the glasses without any degradation of its functionality. The open form of diarylethene, which is converted from the closed one upon UV-irradiation, is backed into the closed form visible light-irradiation. The rate constant of the photochemical reaction is 31.78×10^(-3)s^(-1)with 400W UV lamp irradiation.
Zeolite를 이용한 저 유전성 기판재료의 특성에 관한 연구
Na-X Zeolite의 이온 교환에 의해 합성한 Anorthite에 New Zealand Kaolin으로 합성한 Codierite를 혼합하여 1030℃의 소결온도로 Anorthite/ Codierite 복합체를 제조하었다. Zeolite의 결정→비정질→결정화 과정을 통하여 Cu, Au, Ag-Pb등의 배선 사용이 가능한 저온에서 치밀한 소결체를 얻을 수 있었다. Cordierite 30wt% 이하 조성에서 유전상수는 5.68-4.53 (1MHz), 열팽창율은 5.68-4.53. 1O^(-6)/℃, 꺽임강도 179- 112Mpa로 high-performed substrate로 우수한 특성을 나타내었다. Anorthite/codierite composites for substrate were fabricated by Anorthite synthesized from Na-X zeolite ion exchanged and Cordierite synthesized from New Zealand Kaolin at 1300℃ By the Crystal→Amorphous→Crystal process of Zeolite, the composites were densified at low sintering temperature in air, allowing cofiring with Cu, Ag, Au and Ag-Pb. Under the composites of 30wt% Cordierite had good properties for high-performed substrate, such as low dielectric constant(5.68-4.53, at 1MHz), low coefficient of thermal expansion(5.68-4.53. 10^(-6) / ℃) and bending strength of 179-112Mpa.
저온소성 기판재료용 Anorthite/Cordierite계 소결체의 제조 및 특성
본 연구는 Silicon 반도체 소자와 유사한 열팽창계수를 갖는 기판, 연산속도의 고속화를 위한 신호지연시간의 단축을 위한 저유전율 기판, Cu, Ag, Au 등 금속도체와 동시 소성할 수 있는 저온 소결성 기판의 제조조건을 규명한 것이다. 낮은 열팽창계수와 저온 소성을 위해서는 Zeolite를 이용한 저온에서 anorthite의 합성·소결, 낮은 유전율과 열팽챵계수를 위해서는 New Zealand kaolin을 이용한 cordierite의 합성·소결, 또한, anotrhite/cordierite 복합 소결체를 제조하여 낮은 열팽창계수, 낮은 유전율, 저온 소결 가능성을 확인 하였다. 즉, 저가의 13X-Zeolite의 Na 이온을 Ca 이온으로 치환하여 소결한 anorthite의 최적 소성온도는 1030 ∼ 1060℃ 범위였으며 꺽임강도는 179 ∼ 187 MPa, 유전상수는 1060℃에서 7.11이었다. 열팽창계수는 1030℃이상에서 5.68 ∼ 5.66×10^(-6)/℃의 범위로 일정한 값을 나타내고 있다. 또한 New Zealand kaolin을 주원료로 하여 quartz와 Mg(OH)₂로 cordierite의 소결체를 제조하였을 때 최적 소성온도는 1380℃였으며 열팽창계수는 cordierite 결정의 생성량이 증가할수록 낮아지고 있으며 유전율은 증가하였다. 이때 기공율은 13% 꺽임강도는 53.6 MPa, 유전율은 4.5, 열팽창계수는 5.06×10^(-6)/℃이었다. 13X-Zeolite를 주원료로 하여 얻어진 저온 소성이 가능한 anorthite의 특성과 New Zealnd kaolin을 주원료로 하여 얻어진 cordierite의 특성을 이용하여 anorthite / cordierite 소결체를 제조하였을 때 기판재료로서 가장 적합한 조건은 cordierite 첨가량이 20 ∼ 30wt%, 소성온도는 1060 ∼ 1090℃이었다. 이때 소성수축율은 18.0 ∼ 18.4%, 꺽임강도는 120 ∼ 140 MPa, 열팽창계수는 4.4 ∼ 4.86 ×10^(-6)/℃이었다. 겉보기 비중은 약 2.47 ∼ 2.57 이었으며 유전상수는 약 6.0 ∼ 6.93으로 기존의 alumina 기판에 비하여 낮은 유전율을 나타내었고 열팽창계수는 4.41 ∼ 5.3 × 10^(-6)/℃로 silicon 반도체 소자의 열팽창계수에 근접한 값을 나타내고 있다. 따라서 고성능 기판재료로의 사용이 가능할 것으로 판단된다. The purpose of this study is to search for fabrication condition of low temperature sintering substrate, which has thermal expansion coefficient similar to silicon semiconductor chip, low dielectric constant for reduction of signal delay time to accelerate calculation speed high, and can be sintered simultaneously with metal conductor like Cu, Ag, Au. Using Zeolite to archive low thermal expansion coefficient and low temperature sintering, anorthite was synthersized and sintered at low temperature. Using New Zealand kaolin to archive low dielectric constant and thermal expansion coefficient, cordierite was synthersized and sintered. Also after fabricating anorthite/cordierite composites, low dielectric constant, thermal expansion coefficient and possibility of sintering at low temperature was confirmed. That is, the most suitable sintering temperature of anorthite, (Na ion of low priced 13X-Zeolite was substituted to Ca ion and sintered), is between 1030 and 1060℃. And bending strength is 179 ∼ 187 MPa, dielectric constant is 7.11 at 1060℃. Thermal expansion coefficient appeared to have the fixed value of 5.68 ∼ 5.66 ×10^(-6)/℃ above 1030℃. Moreover, the most suitable sintering temperature of cordierite composites, made mainly of New Zealand kaolin added to quartz and Mg(OH)₂, is 1380℃. Thermal expansion coefficient decreased as quantity of cordierite increased, but dielectric constant increased. At this time, porosity is 1.3%, bending strength is 53.6 MPa, dielectric constant is 4.5 and thermal expansion coefficient is 5.06 ×10^(-6)/℃. When using the characteristics of anorthite, (made mainly of 13X-Zeolite and possible sintering at low temperature), and cordierite, (made mainly of New Zealand kaolin), fabricated anorthite/cordierite composites, the most suitable condition is cordierite 20 ∼ 30 wt%, and sintering temperature is between 1060 and 1090℃. Firing shrinkage is 18.0 ∼ 18.4%, bending strength is 120 ∼ 140 MPa, and thermal expansion coefficient is 4.4 ∼ 4.86 × 10^(-6)/℃. Apparent density is about 2.47 ∼ 2.57, dielectric constant is about 6.0 ∼ 6.93 lower than the existing alumina substrate. The thermal expansion coefficient, 4.41 ∼ 5.3 ×10^(-6)/℃, appeared to be closer to the thermal expansion coefficient of silicon semiconductor chip. Therefore, it is considered as possible high-performance substrate material