• 한국분말재료학회지
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• 제19권5호
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• pp.356-361
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• 2012

The ultra-fine and less agglomerated titanium carbonitride particles were successfully synthesized by magnesiothermic reduction with low feeding rate of $TiCl_4+1/4C_2Cl_4$ solution. The sub-stoichiometric titanium carbide ($TiC_{0.5{\sim}0.6}$) particles were produced by reduction of chlorine component by liquid magnesium at $800^{\circ}C$ of gaseous $TiCl_4+1/4C_2Cl_4$ and the heat treatments in vacuum were performed for 5 hours to remove the residual magnesium and magnesium chloride mixed with produced $TiC_{{\sim}0.5}$. The final $TiC_{{\sim}0.5}N_{0{\sim}0.5}$ particle with near 100 nm in mean size and high specific surface area of $65m^2/g$ was obtained by nitrification under nitrogen gas at $1,150^{\circ}C$ for 2 hrs.

• 한국재료학회지
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• 제24권5호
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• pp.243-248
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• 2014

Silicon-carbon composite was prepared by the magnesiothermic reduction of mesoporous silica and subsequent impregnation with a carbon precursor. This was applied for use as an anode material for high-performance lithium-ion batteries. Well-ordered mesoporous silica(SBA-15) was employed as a starting material for the mesoporous silicon, and sucrose was used as a carbon source. It was found that complete removal of by-products ($Mg_2Si$ and $Mg_2SiO_4$) formed by side reactions of silica and magnesium during the magnesiothermic reduction, was a crucial factor for successful formation of mesoporous silicon. Successful formation of the silicon-carbon composite was well confirmed by appropriate characterization tools (e.g., $N_2$ adsorption-desorption, small-angle X-ray scattering, X-ray diffraction, and thermogravimetric analyses). A lithium-ion battery was fabricated using the prepared silicon-carbon composite as the anode, and lithium foil as the counter-electrode. Electrochemical analysis revealed that the silicon-carbon composite showed better cycling stability than graphite, when used as the anode in the lithium-ion battery. This improvement could be due to the fact that carbon efficiently suppressed the change in volume of the silicon material caused by the charge-discharge cycle. This indicates that silicon-carbon composite, prepared via the magnesiothermic reduction and impregnation methods, could be an efficient anode material for lithium ion batteries.

• 자원리싸이클링
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• 제32권2호
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• pp.19-32
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• 2023

본 연구에서는 수소분위기 내 사염화타이타늄의 마그네슘 열환원을 이용한 수소화타이타늄 분말 합성 과정 중 온도 및 소결 조건에 따른 분말 특성 변화를 조사하였다. 수소화타이타늄 생성에 미치는 온도의 영향을 검토하기 위해 1023~1123 K의 1 atm 수소분위기에서 약 30 분간 사염화타이타늄과 마그네슘을 반응시켰다. 환원반응 후 생성된 수소화타이타늄 분말의 소결이 진행되도록 0~120 분간 환원반응 온도를 유지시켰으며, 반응 종료 후 회수된 생성물의 산소농도를 분석하였다. 실험결과, 1023 K에서는 TiH_1.924 이 생성되었으나, 1073K 및 1123 K에서는 TiH_1.924와 TiH_1.5의 혼합물이 생성되었다. 또한, 반응온도가 높을수록 생성된 수소화타이타늄 분말의 수소농도는 감소하였다. 반응온도 및 소결시간이 증가할수록 분말의 산소농도는 감소하였으며, 이는 분말의 비표면적 감소에 기인하였다. 반응온도 1073 K 및 소결시간 120 분 실험조건에서 최저 산소농도 0.246 mass%인 TiH_1.924와 TiH_1.5의 혼합물이 제조되었다.

• 한국표면공학회:학술대회논문집
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• 한국표면공학회 2016년도 추계학술대회 논문집
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• pp.59-75
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• 2016

Reduced or black $TiO_{2-x}$ materials with oxygen-deficiency have been achieved by creating oxygen vacancies and/or defects at the surface using different methods. Fascinatingly, they exhibited an extended absorption in VIS and IR instead of only UV light with bandgap decrease from 3.2 (anatase) to ~1 eV. However, despite the dramatic enhancement of optical absorption in black $TiO_{2-x}$ materials, they have failed to show expected visible light-assisted water splitting efficiency. This was ascribed to the high concentration of the surface defects and/or oxygen vacancies, considered as an electron donor to enhance donor density and improve the charge transportation in black $TiO_2$ can also act as charge recombination centers, which eventually decrease photocatalytic activity. Therefore, a black ot reducd $TiO_2$ material with optimized properties would be highly desired for visible light photocatalysis. In this report, a new controlled magnesiothermic reduction has been developed to synthesize reduced black $TiO_{2-x}$ in the presence $H_2/Ar$ for photocatalytic $H_2$ production from methanol-water system. The material possesses an optimum band gap and band position, oxygen vacancies, and surface defects and shows significantly improved optical absorption in the visible and infrared region. The synergistic effects enable the reduced $TiO_{2-x}$ material to show an excellent hydrogen production ability along with long-term stability under the full solar wavelength range of light and visible light, respectively, in the methanol-water system in the presence of Pt as a co-catalyst. These values are superior to those of previously reported black $TiO_2$ materials. On the basis of all the results, it can be realized that the outstanding activity and stability of the reduced of $TiO_{2-x}$ NPs suggest that a balanced combination of different factors like $Ti^{3+}$, surface defects, oxygen vacancy, and recombination center is achieved along with optimized bandgap and band position during the preparation employing magnesiothermic reduction in the presence of $H_2$. The controlled magnesiothermic reduction in the presence of $H_2$ is one of the best alternative ways to produce active and stable $TiO_2-based$ photocatalyst for $H_2$ production.

• Korean Chemical Engineering Research
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• 제54권1호
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• pp.16-21
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• 2016

실리콘의 부피팽창과 낮은 전기전도도를 개선하기 위하여 Silicon/Carbon/CNT 복합체를 제조하였다. Silicon/Carbon/CNT 합성물은 SBA-15를 합성한 후, 마그네슘 열 환원 반응으로 Silicon/MgO를 제조하여 Phenolic resin과 CNT를 첨가하여 탄화하는 과정을 통해 합성하였다. 제조된 Silicon/Carbon/CNT 합성물은 XRD, SEM, BET, EDS를 통해 특성을 분석하였다. 본 연구에서는 충방전, 사이클, 순환전압전류, 임피던스 테스트를 통해 CNT 첨가량에 따른 전기화학적 효과를 조사하였다. $LiPF_6$ (EC:DMC:EMC=1 :1 :1 vol%) 전해액에서 Silicon/Carbon/CNT 음극활물질을 사용하여 제조한 코인셀은 CNT 함량이 7 wt% 일 때 1,718 mAh/g으로 높은 용량을 나타내었다. 코인셀의 사이클 성능은 CNT 첨가량이 증가할수록 개선되었다. 11 wt%의 CNT를 첨가한 Silicon/Carbon/CNT 음극은 두 번째 사이클 이후 83%의 높은 용량 보존율을 나타냄을 알 수 있었다.

• 공업화학
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• 제26권1호
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• pp.80-85
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• 2015

본 연구에서는 리튬이차전지의 음극활물질인 실리콘/탄소 복합소재를 제조하여 전기화학적 특성을 확인하였다. 실리콘/탄소 합성물은 마그네슘의 열 환원 반응을 통해 SBA-15 (Santa Barbara Amorphous material No. 15)를 제조한 후 페놀 수지의 탄화 과정을 통해 합성하였다. 실리콘/탄소를 음극으로 제조하여 충방전, 사이클, 순환전압전류, 임피던스 테스트를 통해 분석하였다. 실리콘에 코팅된 탄소는 전기 전도도를 향상시켜 Rct값을 235 ohm (silicon)에서 30 ohm (실리콘/탄소)으로 낮추었고 리튬의 탈 삽입 시에 발생하는 실리콘의 팽창을 억제하여 전극을 안정화시키는 효과를 보여주었다. 실리콘/탄소 전극을 사용한 리튬이차전지는 1,348 mAh/g의 용량을 나타내었고 50사이클 동안 76%의 안정성을 보여주었다.

• 한국분말재료학회지
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• 제1권2호
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• pp.135-144
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• 1994

Silicon carbide powder was prepared from mixtures of Sangdong silica sand and carbon black by SHS (Self propagating High temperature Synthesis) method which utilizes magnesiothermic reduction of silica. In the powder preparation process, the reacted powder was leached by chloric acid to remove the magnesium oxide and was subsequently roasted to remove free carbon. The impurities were mostly eliminated by hot acid treatment. The resultant SiC powder showed the mean particle size of 0.22 ${\mu}{\textrm}{m}$ and the specific surface area of $66.55 m^2/g$. The SiC powder was mixed with 1 wt% of boron and of carbon to increase densification rate. The mixed powder was pressed and sintered pressurelessly at $2100^{\circ}C$ for 30 min in argon gas. The sintered body showed the hardness of $2550 kg{\cdot}f/mm^2$ and the fracture toughness, KIC of $3.47 MN/m^{3/2}$.

• Korean Chemical Engineering Research
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• 제62권1호
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• pp.19-26
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• 2024

본 연구에서는 리튬이온배터리용 고용량 음극활물질인 실리콘의 부피팽창을 완화하고 사이클 안정성을 향상시키기 위해 SiOx@C 복합소재를 제조하였다. Stӧber 법을 통해 입자 크기가 각각 100, 200, 500 nm인 SiO₂를 합성하였고, 마그네슘 열환원을 통해 SiOx (0≤x≤2)를 제조하였다. 그 후 SiOx에 PVC를 탄화시켜 SiOx와 C의 비율에 따라 SiOx@C 음극활물질을 합성하였다. 제조된 SiOx와 SiOx@C 음극활물질의 물리적 특성은 XRD, SEM, TGA, 라만분광법, XPS, BET를 사용해 분석하였다. 그리고 사이클 테스트, 율속특성, CV, EIS 테스트를 통해 전기화학적 특성을 조사하였다. 입자 크기가 가장 작은 100 nm SiOx에 SiOx:C=70:30으로 탄소를 코팅하여 제조된 SiOx@C-7030은 100 사이클에서 1055 mAh/g의 방전용량과 81.9%의 용량을 유지하여 가장 우수한 전기화학적 특성을 보여주었다. 이는 SiOx 음극활물질 입자의 크기를 줄이고, 탄소를 코팅하여 사이클 안정성을 향상시킬 수 있다는 것을 의미한다.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2012년도 제43회 하계 정기 학술대회 초록집
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• pp.108-109
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• 2012

This talk will begin with the demonstration of facile synthesis of silicon nanostructures using the magnesiothermic reduction on silica nanostructures prepared via self-assembly, which will be followed by the characterization results of their performance for energy storage. This talk will also report the fabrication and characterization of highly porous, stretchable, and conductive polymer nanocomposites embedded with carbon nanotubes (CNTs) for application in flexible lithium-ion batteries. It will be presented that the porous CNT-embedded PDMS nanocomposites are capable of good electrochemical performance with mechanical flexibility, suggesting these nanocomposites could be outstanding anode candidates for use in flexible lithium-ion batteries. Directed self-assembly (DSA) of block copolymers (BCPs) can generate uniform and periodic patterns within guiding templates, and has been one of the promising nanofabrication methodologies for resolving the resolution limit of optical lithography. BCP self-assembly processing is scalable and of low cost, and is well-suited for integration with existing semiconductor manufacturing techniques. This talk will introduce recent research results (of my research group) on the self-assembly of Si-containing block copolymers for the achievement of sub-10 nm resolution, fast pattern generation, transfer-printing capability onto nonplanar substrates, and device applications for nonvolatile memories. An extraordinarily facile nanofabrication approach that enables sub-10 nm resolutions through the synergic combination of nanotransfer printing (nTP) and DSA of block copolymers is also introduced. This simple printing method can be applied on oxides, metals, polymers, and non-planar substrates without pretreatments. This talk will also report the direct formation of ordered memristor nanostructures on metal and graphene electrodes by the self-assembly of Si-containing BCPs. This approach offers a practical pathway to fabricate high-density resistive memory devices without using high-cost lithography and pattern-transfer processes. Finally, this talk will present a novel approach that can relieve the power consumption issue of phase-change memories by incorporating a thin $SiO_x$ layer formed by BCP self-assembly, which locally blocks the contact between a heater electrode and a phase-change material and reduces the phase-change volume. The writing current decreases by 5 times (corresponding to a power reduction of 1/20) as the occupying area fraction of $SiO_x$ nanostructures varies.

• Korean Chemical Engineering Research
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• 제56권4호
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• pp.561-567
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• 2018

본 연구에서는 리튬이온전지 실리콘 음극소재의 사이클 안정성 향상을 위해 실리콘/탄소 음극소재의 전기화학적 특성을 조사하였다. Tetraethyl orthosilicate (TEOS) 로부터 스토버법 및 마그네슘 열 환원법을 통하여 다공성 실리콘을 제조하고, 제조된 다공성 실리콘과 피치의 질량비에 따라 실리콘/탄소 음극소재를 제조하였다. 실리콘/탄소 음극소재의 물리적 특성은 XRD와 TGA를 통해 분석하였다. 1.0 M $LiPF_6$ (EC : DEC = 1 : 1 vol%) 전해액에서 실리콘/탄소 음극소재의 충 방전 사이클, 율속, 순환전압전류, 임피던스 테스트를 통해 전기화학적 특성을 조사하였다. 제조된 실리콘/탄소 음극소재 실리콘 : 탄소 = 5 : 95 일때 453 mAh/g의 향상된 용량을 나타내었으며, 사이클 성능 또한 두 번째 사이클 이후 30 사이클까지 매우 우수한 사이클 안정성을 나타냄을 확인하였다.