This study proposes the use of a cobalt-based Prussian blue analogue (Co-PBA; potassium cobalt hexacyanoferrate), as an adsorbent for the cost-effective recovery of aqueous ammonium ions. The characterization of Co-PBA involved various techniques, including Fourier-transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, nitrogen adsorption-desorption analysis, and zeta potential. The prepared Co-PBA reached an adsorption equilibrium for ammonium ions within approximately 480 min, which involved both surface adsorption and subsequent diffusion into the interior. The isotherm experiment revealed a maximum adsorption capacity of 37.29 mg/g, with the Langmuir model indicating a predominance of chemical monolayer adsorption. Furthermore, the material consistently demonstrated adsorption efficiency across a range of pH conditions. Notably, adsorption was observed even when competing cations were present. Co-PBA emerges as a readily synthesized adsorbent, underscoring its efficacy in ammonium removal and selectivity toward ammonium.
Transition metal chalcogenides are promising cathode materials for next-generation battery systems, particularly sodium-ion batteries. Ni3Co6S8-pitch-derived carbon composite microspheres with a yolk-shell structure (Ni3Co6S8@C-YS) were synthesized through a three-step process: spray pyrolysis, pitch coating, and post-heat treatment process. Ni3Co6S8@C-YS exhibited an impressive reversible capacity of 525.2 mA h g-1 at a current density of 0.5 A g-1 over 50 cycles when employed as an anode material for sodium-ion batteries. However, Ni3Co6S8 yolk shell nanopowder (Ni3Co6S8-YS) without pitch-derived carbon demonstrated a continuous decrease in capacity during charging and discharging. The superior sodium-ion storage properties of Ni3Co6S8@C-YS were attributed to the pitchderived carbon, which effectively adjusted the size and distribution of nanocrystals. The carbon-coated yolk-shell microspheres proposed here hold potential for various metal chalcogenide compounds and can be applied to various fields, including the energy storage field.
본 연구는 에너지 저장 응용을 위한 PVI-PGMA/LiTFSI 고분자 막 전해질 및 CxNy-C 유연 전극의 합성 및 특성 에 관한 연구이다. 이중 기능을 갖는 PVI-PGMA 공중합체는 우수한 이온 전도성을 나타내었으며, PVI-GMA73/LiTFSI200 막 전해질은 1.0 × 10-3 S cm-1의 최고 전도도를 달성하였다. CxNy-C 전극의 전기화학적 성능을 체계적으로 분석하였으며, C3N2-C는 나노와이어와 다면체로 구성된 높은 연결성을 갖는 하이브리드 구조와 이중 Co/Ni 산화물을 포함하여 풍부한 산 화환원 활성 부위와 이온 확산을 용이하게 하는 특징으로 인해 958 F g-1의 최고용량 및 최소한의 전하 전달 저항(Rct)을 달성 하였다. 흑연 탄소 껍질의 존재는 충전-방전 동안 높은 전기화학적 안정성에 기여하였다. 이러한 결과들은 고성능 에너지 저 장 장치인 슈퍼커패시터 및 리튬 이온 전지와 같은 첨단 에너지 저장 장비에 PVI-PGMA/LiTFSI 고분자 막 전해질과 CxNy-C 전극을 활용하는 잠재력을 보여주었으며, 지속 가능하고 고성능의 에너지 저장 기술을 더욱 발전시키는 길을 열어가 고 있다.
Cobalt is a vital metal in the modern society because of its applications in lithium-ion batteries, super alloys, hard metals, and catalysts. Further, cobalt is a representative rare metal and is the 30th most abundant element in the Earth’s crust. This study reviews the current status of cobalt extraction and recycling processes, along with the trends in its production amount and use. Although cobalt occurs in a wide range of minerals, such as oxides and sulfides of copper and nickel ores, the amounts of cobalt in the minerals are too low to be extracted economically. The Democratic Republic of Congo (DRC) leads cobalt mining, and accounts for 68.9 % of the global cobalt reserves (142,000 tons in 2020). Cobalt is mainly extracted from copper–cobalt and nickel–cobalt concentrates and is occasionally extracted directly from the ore itself by hydro-, pyro-, and electro-metallurgical processes. These smelting methods are essential for developing new recycling processes to extract cobalt from secondary resources. Cobalt is mainly recycled from lithium-ion batteries, spent catalysts, and cobalt alloys. The recycling methods for cobalt also depend on the type of secondary cobalt resource. Major recycling methods from secondary resources are applied in pyro- and hydrometallurgical processes.
범밀도이론함수(Density Functional Theory, DFT) 기반의 제일원리전산모사는 기저상태의 DFT 에너지를 구하는데 많은 시간소요 및 전산자원을 소모하였다. 이러한 막대한 전산자원의 소모는 DFT 계산에서 고려할 원자수를 수 백개 이 하로 제한되게 되었으며, 이를 해결하기 위해서는 전자구조 계산이 아닌 원자의 환경 내에 원자간 상호작용을 정의 (Force Field, 힘장)하고 이를 통해 주어진 조성 혹은 구조에 따른 에너지를 빠르게 예측 할 수 있어야 한다. 본 논문에서 는 Behler-Parrinello가 제시한 인공신경망 모델을 활용해 인공지능 다원계 힘장을 개발하고 코발트-구리 산화물의 조성에 따른 에너지를 예측하고 안정한 구조를 탐색하는 연구를 수행하였다. 인공신경망 기술로 부터 구리-코발트 산화물에 대 해 15.7 meV/atom의 에너지 오차와 단위거리당 힘 103.6 meV/Å의 정확도를 가지는 인공신경망 포텐셜을 개발하였다. 이 방법으로 빠르고 정확하게 CuCoO 표면구조의 산소 결함률에 따른 생성에너지를 계산할 수 있었고, 에너지 컨벡스 홀을 도시 조성에 따른 안정한 구조를 예측하였다.
Recently, due to high theoretical capacitance and excellent ion diffusion rate caused by the 2D layered crystal structure, transition metal hydroxides (TMHs) have generated considerable attention as active materials in supercapacitors (or electrochemical capacitors). However, TMHs should be designed using morphological or structural modification if they are to be used as active materials in supercapacitors, because they have insulation properties that induce low charge transfer rate. This study aims to modify the morphological structure for high cycling stability and fast charge storage kinetics of TMHs through the use of nickel cobalt hydroxide [NiCo(OH)2] decorated on nickel foam. Among the samples used, needle-like NiCo(OH)2 decorated on nickel foam offers a high specific capacitance (1110.9 F/g at current density of 0.5 A/g) with good rate capability (1110.9 - 746.7 F/g at current densities of 0.5 - 10.0 A/g). Moreover, at a high current density (10.0 A/g), a remarkable capacitance (713.8 F/g) and capacitance retention of 95.6% after 5000 cycles are noted. These results are attributed to high charge storage sites of needle-like NiCo(OH)2 and uniformly grown NiCo(OH)2 on nickel foam surface.
Cobalt (Co) is mainly used to prepare cathode materials for lithium-ion batteries (LIBs) and binder metals for WC-Co hard metals. Developing an effective method for recovering Co from WC-Co waste sludge is of immense significance. In this study, Co is extracted from waste cemented carbide soft scrap via mechanochemical milling. The leaching ratio of Co reaches approximately 93%, and the leached solution, from which impurities except nickel are removed by pH titration, exhibits a purity of approximately 97%. The titrated aqueous Co salts are precipitated using oxalic acid and hydroxide precipitation, and the effects of the precipitating agent (oxalic acid and hydroxide) on the cobalt microstructure are investigated. It is confirmed that the type of Co compound and the crystal growth direction change according to the precipitation method, both of which affect the microstructure of the cobalt powders. This novel mechanochemical process is of significant importance for the recovery of Co from waste WC-Co hard metal. The recycled Co can be applied as a cemented carbide binder or a cathode material for lithium secondary batteries.
Energy storage systems should address issues such as power fluctuations and rapid charge-discharge; to meet this requirement, CoFe2O4 (CFO) spinel nanoparticles with a suitable electrical conductivity and various redox states are synthesized and used as electrode materials for supercapacitors. In particular, CFO electrodes combined with carbon nanofibers (CNFs) can provide long-term cycling stability by fabricating binder-free three-dimensional electrodes. In this study, CFO-decorated CNFs are prepared by electrospinning and a low-cost hydrothermal method. The effects of heat treatment, such as the activation of CNFs (ACNFs) and calcination of CFO-decorated CNFs (C-CFO/ACNFs), are investigated. The C-CFO/ACNF electrode exhibits a high specific capacitance of 142.9 F/g at a scan rate of 5 mV/s and superior rate capability of 77.6% capacitance retention at a high scan rate of 500 mV/s. This electrode also achieves the lowest charge transfer resistance of 0.0063 Ω and excellent cycling stability (93.5% retention after 5,000 cycles) because of the improved ion conductivity by pathway formation and structural stability. The results of our work are expected to open a new route for manufacturing hybrid capacitor electrodes containing the C-CFO/ACNF electrode that can be easily prepared with a low-cost and simple process with enhanced electrochemical performance.
In this study, the effects of Co content on the microstructure and Charpy impact properties of Fe-Cr-W ferritic/martensitic oxide dispersion strengthened (F/M ODS) steels are investigated. F/M ODS steels with 0–5 wt% Co are fabricated by mechanical alloying, followed by hot isostatic pressing, hot-rolling, and normalizing/tempering heat treatment. All the steels commonly exhibit two-phase microstructures consisting of ferrite and tempered martensite. The volume fraction of ferrite increases with the increase in the Co content, since the Co element considerably lowers the hardenability of the F/M ODS steel. Despite the lowest volume fraction of tempered martensite, the F/M ODS steel with 5 wt% Co shows the highest micro-Vickers hardness, owing to the solid solution-hardening effect of the alloyed Co. The high hardness of the steel improves the resistance to fracture initiation, thereby resulting in the enhanced fracture initiation energy in a Charpy impact test at – 40oC. Furthermore, the addition of Co suppresses the formation of coarse oxide inclusions in the F/M ODS steel, while simultaneously providing a high resistance to fracture propagation. Owing to these combined effects of Co, the Charpy impact energy of the F/M ODS steel increases gradually with the increase in the Co content.
To meet the current demand in the fields of permanent magnets for achieving a high energy density, it is imperative to prepare nano-to-microscale rare-earth-based magnets with well-defined microstructures, controlled homogeneity, and magnetic characteristics via a bottom-up approach. Here, on the basis of a microstructural study and qualitative magnetic measurements, optimized reduction conditions for the preparation of nanostructured Sm-Co magnets are proposed, and the elucidation of the reduction-diffusion behavior in the binary phase system is clearly manifested. In addition, we have investigated the microstructural, crystallographic, and magnetic properties of the Sm-Co magnets prepared under different reduction conditions, that is, H2 gas, calcium, and calcium hydride. This work provides a potential approach to prepare high-quality Sm-Co-based nanofibers, and moreover, it can be extended to the experimental design of other magnetic alloys.
This study investigates the microstructural properties of CoCrFeMnNi high entropy alloy (HEA) oxynitride thin film. The HEA oxynitride thin film is grown by the magnetron sputtering method using nitrogen and oxygen gases. The grown CoCrFeMnNi HEA film shows a microstructure with nanocrystalline regions of 5~20 nm in the amorphous region, which is confirmed by high-resolution transmission electron microscopy (HR-TEM). From the TEM electron diffraction pattern analysis crystal structure is determined to be a face centered cubic (FCC) structure with a lattice constant of 0.491 nm, which is larger than that of CoCrFeMnNi HEA. The HEA oxynitride film shows a single phase in which constituting elements are distributed homogeneously as confirmed by element mapping using a Cs-corrected scanning TEM (STEM). Mechanical properties of the CoCrFeMnNi HEA oxynitride thin film are addressed by a nano indentation method, and a hardness of 8.13 GPa and a Young’s modulus of 157.3 GPa are obtained. The observed high hardness value is thought to be the result of hardening due to the nanocrystalline microstructure.
오염수로부터 자성분리가 가능하며, 방사성 세슘을 효율적으로 제거하기 위한 코발트 페로시아나이드(cobalt ferrocyanide, CoFC) 혹은 니켈 페로시아나이드(nickel ferrocyanide, NiFC)가 도입된 자성입자 흡착제를 제조하였다. Fe3O4 나노 입자는 공침법을 이용해 제조하였고, Co2+와 Ni2+ 이온을 입자 표면에 도입시키기 위해 금속이온과 금속 배위결합(metalcoordination) 을 하는 카르복실기를 포함한 숙신산(succinic acid, SA)을 자성나노입자(magnetic nanoparticles, MNPs) 표 면에 코팅하였다. CoFC와 NiFC는 자성나노입자 표면에 도입된 Co2+ 혹은 Ni2+ 이온이 hexacynoferrate와 결합하여 형성된 다. 제조된 CoFC-MNPs 그리고 NiFC-MNPs는 각각 43.2 emu·g-1, 47.7 emu·g-1의 우수한 포화자화 값을 보여주었다. X- 선 회절분석(XRD), 퓨리에 변환 적외선 분광분석(FT-IR), 나노입자 입도 분석기(DLS), 투과전자현미경(TEM) 등의 분석을 통해 흡착제의 물성을 파악하고, 세슘에 대한 흡착 성능을 알아보았다. 흡착실험을 평가하기 위해 Langmuir/Freundlich 등 온흡착식을 이용해 실험 결과 값을 곡선맞춤 하였고, CoFC-MNPs와 NiFC-MNPs의 최대흡착량(qm)은 각각 15.63 mg·g-1, 12.11 mg·g-1이다. CoFC-MNPs와 NiFC-MNPs는 방사성 세슘에 대해서도 최저 99.09%의 제거율을 가지며, 경쟁이온의 존재에도 방사성 세슘만을 선택적으로 흡착한다.
목 적: 화학수송법으로 성장시킨 Ga2Se3 및 Ga2Se3 : Co2+ 단결정의 광학적 에너지 띠 간격 energy band gap의 온도의존성을 규명하고, 이로부터 기초적 열역학 함수를 추정고자 한다.
방 법: gallium(99.9999 %, 2 mol), selenium(99.9999 %, 3 mol), cobalt(99.99 %, 0.1 mol %) 그리고 수송물질로 iodine(99.99 %, 6 mg/cm3)을 함께 석영관에 넣고 내부를 5×10-6 torr로 유지하면서 봉입하여 성장용 ampoule을 만들었다. 성장용 ampoule을 2단 전기로의 중앙에 위치시키고, 결정 성장측의 잔류불순 물을 깨끗이 제거한 후, 시료 출발측을 890 ℃, 성장측을 780 ℃로 6일간 유지하여 단결정을 성장시켰다. 기초 흡수단 부근에서 에너지 띠 간격의 온도의존성을 구하기 위하여 저온장치(Air Products, SH-4)가 부 착된 UV-VIS-NIR spectrophotometer(Hitachi, U-3501)를 사용하여 광흡수 스펙트럼을 측정하였다. 결과 및 고찰: Ga2Se3 및 Ga2Se3 : Co2+ 단결정들의 광흡수 스펙트럼은 순수한 Ga2Se3 단결정의 경우 570 nm영역에서, Ga2Se3 : Co2+ 단결정의 경우 594 nm영역에서 광흡수가 급격히 증가하여 cobalt를 첨가한 단 결정의 기초 흡수단이 장파장 측으로 이동됨을 볼 수 있었다. 또한 에너지 띠 간격의 온도의존성은 Varshni 가 제안한 실험식으로부터 구하였다.
결 론: 성장된 단결정의 구조는 cubic구조이었고, 이들의 격자상수 값은 Ga2Se3 및 Ga2Se3 : Co2+ 단결정 들에 대하여 각각 a = 5.442 Å, a = 5.672 Å이었다. 광흡수 스펙트럼으로부터 구한 optical energy band gap(Eg)의 band구조는 직접 전이형이었고, 에너지 띠 간격의 온도의존성은 Varshni방정식이 잘 적용되었 다. 이때 구한 상수 값은 Ga2Se3 단결정의 경우 Eg(0) = 2.177 eV, α= 7.8×10-4eV/K, β= 378 K로 주어 지고, Ga2Se3 : Co2+단결정의 경우 Eg(0) = 2.089 eV, α= 1.20×10-3 eV/K, β= 349 K로 주어졌다. 이들 값 으로부터 구한 에너지 띠 간격의 온도의존성으로부터 열역학 함수인 entropy(SCV), heat capacity(CCV), enthalpy(HCV) 값을 추정할 수 있었다.
The cobalt silicides were investigated for employment as a catalytic layer for a DSSC. Using an E-gun evaporation process, we prepared a sample of 100 nm-thick cobalt on a p-type Si (100) wafer. To form cobalt silicides, the samples were annealed at temperatures of 300 oC, 500 oC, and 700 oC for 30 minutes in a vacuum. Four-point probe, XRD, FE-SEM, and CV analyses were used to determine the sheet resistance, phase, microstructure, and catalytic activity of the cobalt silicides. To confirm the corrosion stability, we also checked the microstructure change of the cobalt silicides after dipping into iodide electrolyte. Through the sheet resistance and XRD results, we determined that Co2Si, CoSi, and CoSi2 were formed successfully by annealing at 300 oC, 500 oC, and 700 oC, respectively. The microstructure analysis results showed that all the cobalt silicides were formed uniformly, and CoSi and CoSi2 layers were very stable even after dipping in the iodide electrolyte. The CV result showed that CoSi and CoSi2 exhibit catalytic activities 67 % and 54 % that of Pt. Our results for Co2Si, CoSi, and CoSi2 revealed that CoSi and CoSi2 could be employed as catalyst for a DSSC.
전 세계적으로 원자력 발전소는 442기가 가동 중이며, 62기가 충원될 예정이다. 원자력 발전소의 증가에 따라 방사성 폐기물 유출에 대한 위험성도 증가하였다. 이러한 이유 때문 에, 방사성 폐기물의 처리는 인간, 동물, 식물을 포함하는 자 연 생태계를 보전하는 관점에서 중요하다. 또한, 방사성 폐 기물 유출은 그 지역뿐만 아니라 전 세계적으로 심각한 문 제를 야기한다. 본 연구는 입체 배양세포에 방사성 핵종원 소 (세슘, 스트론튬, 코발트)를 처리하였고 이에 대한 영향력 을 확인하였다. 입체 배양 구조체는 아가로오스 하이드로겔 을 이용하여 제작했으며 암세포 및 정상세포 (HeLa, HepG2, COS-7)를 사용하여 입체 배양을 실시 하였다. 입체 형태로 세포를 배양한 후 세슘, 스트론튬, 코발트 농도 변화에 따라 세포 생존능력을 분석하였다. 이때 입체 배양세포에서 생존 능력이 단층 배양세포 보다 최대 42% 우수한 것을 확인하였 다. 입체 배양구조체는 세포가 형태 및 생리학적으로 in vivo 환경인 조직과 비슷하게 배양을 가능하게 하였다. 따라서, 입체 배양구조체는 기존의 단층 배양 한계점인 in vivo 환경 에 적용시킬 수 없다는 한계를 극복하였다. 본 입체 배양 기 술이 중금속 독성평가 및 단시간 내에 다수의 물질 분석을 수행하는 고속 대량 스크리닝 기술에 활용될 것으로 기대한 다.
Perforated polygonal cobalt oxide (Co3O4) is synthesized using electrospinning and a hydrothermal methodfollowed by the removal of a carbon nanofiber (CNF) template. To investigate their formation mechanism, thermogravi-metric analysis, field-emission scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy are examined. To obtain the optimum condition of perforated polygonal Co3O4, we pre-pare three different weight ratios of the Co precursor and the CNF template: sample A (Co precursor:CNF template-10:1), sample B (Co precursor:CNF template-3.2:1), and sample C (Co precursor:CNF template-2:1). Among them, sam-ple A exhibits the perforated polygonal Co3O4 with a thin carbon layer (5.7-6.2 nm) owing to the removal of CNF tem-plate. However, sample B and sample C synthesized perforated round Co3O4 and destroyed Co3O4 powders, respectively,due to a decreased amount of Co precursor. The increased amount of the CNF template prevents the formation of polygonalCo3O4. For sample A, the optimized weight ratio of the Co precursor and CNF template may be related to the suc-cessful formation of perforated polygonal Co3O4. Thus, perforated polygonal Co3O4 can be applied to electrode materialsof energy storage devices such as lithium ion batteries, supercapacitors, and fuel cells.
Spherical fine cobalt powders were fabricated by new liquid reduction method. Commercial cobalt sufate heptahydrate was used as raw material. Also ethylene glycol was used as solvent and hydrazine-sodium hypophosphite mixture was used as reduction agent for the new liquid reduction method. A plate shaped cobalt powders with an approximately 300 nm were prepared by a traditional wet ruduction method using distilled water as solvent and hydrazine. Spherical fine cobalt powders with an average size of 1-3 μm were synthesized by a new liquid reduction method in 0.3M cobalt sulfate and 1.5M hydrazine-0.6M sodium hypophosphite mixture at 333K.
In this study, cobalt nanopowder is fabricated by sonochemical polyol synthesis and magnetic separation method. First, sonochemical polyol synthesis is carried out at 220oC for up to 120 minutes in diethylene glycol (C4H10O3). As a result, when sonochemical polyol synthesis is performed for 50 minutes, most of the cobalt precursor (Co(OH)2) is reduced to spherical cobalt nanopowder of approximately 100 nm. In particular, aggregation and growth of cobalt particles are effectively suppressed as compared to common polyol synthesis. Furthermore, in order to obtain finer cobalt nanopowder, magnetic separation method using magnetic property of cobalt is introduced at an early reduction stage of sonochemical polyol synthesis when cobalt and cobalt precursor coexist. Finally, spherical cobalt nanopowder having an average particle size of 22 nm is successfully separated.