기계적인 합금화에 의한 Mg-18wt.%Ni 수소저장합금의 개발

송명엽,안동수,권익현,안효준,Song, Myoung-Youp,Ahn, Dong-Su,Kwon, Ik-Hyun,Ahn, Hyo-Jun 한국재료학회 2000 한국재료학회지 Vol.10 No.1

기계적으로 합금처리한 Mg-18wt.%Ni 혼합물의 수소저장특성이 조사되었다. 1h, 3h, 그리고 6h 동안 기계적으로 합금처리한 혼합물들 중에서 6h동안 기계적으로 합금처리한 혼합물(MA 6h sample)이 가장 좋은 활성화, 수소화물 형성.분해 특성을 보인다. 수소화물 형성.분해 cycling을 시킴에 따라 $Mg_2$Ni상이 형성된다. MA 6h sample은 비교적 쉽게 활성화되며, 순수한 Mg나 Mg-10wt.%Ni 합금보다 수소화물 형성속도가 높으나, $Mg_2$Ni 합금보다는 수소화물 형성속도가 약간 낮다. MA 6h sample은 $Mg_2$Ni 합금에 비해 낮은 수소화물 분해속도를 보이지만, 순수한 Mg나 Mg-25wt.%Ni 합금보다는 높은 수소화물 분해속도를 보인다. MA 6h sample은 순수한 Mg나 다른 합금들보다 큰 수소저장용량을 가지고 있다. The hydrogen-storage properties of a mechanically-alloyed Mg-18wt.%Ni mixture were investigated. Among the mixtures mechanically alloyed for 1h, 3h, and 6h, the mixture mechanically alloyed for 6h(MA 6h sample) shows the best properties of activation, hydriding, and dehydriding. The $Mg_2Ni$ phase forms in the mechanically-alloyed Mg-18wt.%Ni mixture along with hydriding-dehydriding cycling. The MA 6h sample is relatively easily activated and has higher hydriding rate than the pure Mg, the Mg-10wt.%Ni alloy, and a little lower hydriding rate than the $Mg_2Ni$alloy. The MA 6h sample lower dehydriding rate than the $Mg_2$Ni alloy but higher dehydriding rate than the pure Mg and the Mg-25wt.%Ni alloy. The MA 6h sample has larger hydrogen-storage capacity than the pure Mg and the other alloys.

Influence of Mechanical Alloying and Hydriding - Dehydriding Cycling on the Hydrogen - Storage Properties of Mg

송명엽(Myoung Youp Song) 한국수소및신에너지학회 1998 한국수소 및 신에너지학회논문집 Vol.9 No.4

The variation of the hydrogen-storage properties of Mg contained in the mechanically-allyed mixture with the weight percentage of nickel in the sample is investigated. The weight percentage of nickel transformed into the Mg₂Ni phase, on the basis of the nickel weight, is highest in the Mg-10 wt.%Ni sample. For the first hydriding cycle, the effect of mechanical alloying on the hydriding rate of Mg is highest in the Mg-25 wt.%Ni sample. After activation, the effects of mechanical alloying and hydriding-dehydriding cycling on the hydriding rate of Mg are highest in the Mg-10 wt.%Ni sample. After sufficient hydriding-dehydriding cycling, the effects on the hydrogen-storage capacity of Mg are highest in the Mg-10 wt.%Ni sample. The effects on the hydriding and dehydriding rates of Mg are highest in the Mg-25 wt.%Ni sample. Mg-25wt.%Ni, followed by Mg-10 wt.%Ni, is the optimum composition which has the best effects on the hydrogen-storage properties of Mg contained in the sample. The mechanical alloying and the hydriding-dehydriding cycling produce many defects, which can act as active nucleation sites, and increase the specific surface area, shortening the diffusion distance of hydrogen.

기계적 합금처리된 Mg-25wt.%Ni 혼합물의 수소화물 형성 및 분해에 대한 반응속도론적 연구

송명엽(Myoung Youp Song) 한국수소및신에너지학회 1999 한국수소 및 신에너지학회논문집 Vol.10 No.1

The hydriding and dehydriding kinetics were studied for a Mg-25wt.%Ni mixture which has the most excellent hydrogen-storage characteristics among many mechanically-alloyed mixtures. The hydriding and dehydriding rates were measured and the rate-controlling steps were determined by comparing the hydriding and dehydriding rates with the theoretical rate equations. The rate-controlling step in the hydriding reaction is the Knudsen flow and the ordinary gaseous diffusion of hydrogen molecules through interparticle channels, cracks, etc. in the various ranges of weight percentage of absorbed hydrogen H_a below H_a=4.0. In the H_a range 4.0<H_a≤4.25, the diffusion of hydrogen atoms through the growing hydride layer is considered the rate-controlling step. The rate-controlling step in the dehydriding reaction is the Knudsen flow and the ordinary gaseous diffusion of hydrogen molecules for all the ranges of weight percentage of desorbed hydrogen H_d.

Mg과 Ni의 기계적인 합금화에 의한 수소 저장 합금의 개발

송명엽(Myoung Youp Song) 한국수소및신에너지학회 1996 한국수소 및 신에너지학회논문집 Vol.7 No.2

Samples with the compositions of Mg-10wt.%Ni and Mg-25wt.%Ni were prepared by mechanical alloying in a planetary mill. Mg₂Ni phase was formed in the mixture with hydriding·dehydriding cycling. The activation of Mg-10wt.%Ni and Mg-25wt.%Ni was completed after n=7 and n=6 around, respectively, at 583K, 0∼8barH₂. Mg-10wt.% Ni and Mg-25wt. %Ni are considered as excellent hydrogen-storage materials with very high hydriding rates, high dehydriding rates and relatively large hydrogen-storage capacity. The effets of mechanical alloying and hydriding·dehydriding cycling are considered the augmentation in the density of active nucleation sites and the diminution in the particle size.

A Study on the Hydrogen-Storage Characteristics of a Mechanically-Alloyed 2Mg+Ni Mixture

송명엽(Myoung Youp Song),임호(Ho Rim) 한국수소및신에너지학회 1998 한국수소 및 신에너지학회논문집 Vol.9 No.2

A mixture with a composition Mg₂Ni is mechanically alloyed. Its hydriding and dehydriding properties are compared with those of the intermetallic compound Mg₂Ni prepared by partial melting and sintering. The principal effects of mechanical alloying in a planetary mill and hydriding-dehydriding cycling are considered the enlargement in the specific surface area and the augmentation in the density of defects.

Development of Mg-10wt.%Ni Hydrogen - Storage Alloy by Mechanical Alloying

송명엽(Myoung Youp Song) 한국수소및신에너지학회 1998 한국수소 및 신에너지학회논문집 Vol.9 No.4

The hydriding and dehydriding properties of a Mg-10wt.%Ni mixture, mechanically-alloyed in order to improve the hydriding and dehydriding kinetics of pure Mg, were investigated. The Mg₂Ni phase develops along with hydriding-dehydriding cycling. The principal effects of mechanical alloying in a planetary mill and hydriding-dehydriding cycling are considered to be the augmentation in the density of defects and the enlargement in the specific surface area. The mechanically-alloyed Mg-10wt.%Ni mixture is activated easily. It has much higher hydriding rate and hydrogen-storage capacity and relatively high dehydriding rate as compared with the pure Mg, the Mg-10wt.%Ni alloy, the Mg-25wt.%Ni alloy and the Mg₂Ni alloy.

Electrochemical Properties of Pyrolytic Carbon and Boron-doped Carbon for Anode Materials In Li-ion Secondary Batteries

권익현,송명엽,방의용,한영수,김기태,이재영,Kwon, Ik-Hyun,Song, Myoung-Youp,Bang, Eui-Yong,Han, Young-Soo,Kim, Ki-Tae,Lee, Jai-Young The Korean Electrochemical Society 2002 한국전기화학회지 Vol.5 No.1

탄화수소가스를 고온$(1000^{\circ}C)$에서 열분해 하여 고상화하는 기상 열분해법을 사용하여 저결정질 탄소재를 제조하고 같은 방법으로 붕소를 첨가한 저결정질 탄소재$C_{l-x}B_x(x=0.05,\;0.10,\;0.20)$를 제조하여, 리튬 이온 이차전지의 부극으로서의 전기화학적 특성을 조사하였다. 시료 대 PVDF를 95:5의 무게비로 첨가한 경우, 붕소를 첨가하지 않은 저 결정질 탄소재(x=0.00)는 초기 방전용량 374mAh/g을 나타내었으며, 제 2싸이클부터는 싸이클 성능이 비교적 우수하여 제 10싸이클에서 258mAh/g의 방전용량을 나타내었다. 시료 대 PVDF를 95:5의 무게비로 첨가한 경우, $C_{1-x}B_x(x=0.00,\;0.05,\;0.10\;0.20)$ 시료들 중에서 x=0.05 조성의 시료는 가장 큰 초기 방전용량 860mAh/g을 나타내었으며, 10번째 싸이클에서 181mAh/g의 방전용량을 나타내었다. 제 2싸이클부터 싸이클 성능은 모두가 비슷하게 나타났다 초기방전 용량(PVDF $10wt.\%$ 사용시, 853mAh/g), 싸이클 성능, 방전용량(PVDF $10wt.\%$사용시 10번째 싸이클에서 400mAh/g)면에서 $C_{0.90}B_{0.10}$ 시료가 리튬이온 이차전지의 부극으로서의 가장 우수한 전기화학적 특성을 나타내었다. 합성한 탄소에 NMP를 용매로 한 액상 혼합 바인더(PVDF)를 90:10의 무게비로 첨가한 경우가 95:5의 무게비로 첨가한 경우보다 대체로 모든 조성에서 충$\cdot$방전용량이 크게 나타났다. 붕소가 첨가되어 덜 disordered된 구조가 됨으로써 1.25V보다 낮은 전압 부분에서 평탄구역이 증가하는 것으로 판단된다. 붕소가 첨가된 경우 충$\cdot$방전용량이 제 2싸이클에서부터 급격히 감소하였는데, 이는 첨가된 붕소가 제 1싸이클에서 삽입되는 Li과 일부는 강하게 결합하여 추출이 안되고 일부만이 다시 가역적으로 추출$\cdot$삽입되기 때문으로 생각된다. 붕소 첨가에 의한 충$\cdot$방전용량의 증가는, 붕소가 electron acceptor로 작용하여 삽입된 Li와 붕소-탄소 host 사이의 결합 강도를 증가시킴으로써 붕소치환 된 탄소에서 Li의 전위를 상승시키기 때문에 일어난다고 사려된다. Disordered carbon and boron-substituted disordered carbons $C_{l-x}B_x(x=0.05,\;0.10,\;0.20)$ were synthesized by Pyrolysis of LPG(liquid Propane gas)and $BCl_3$. Their electrochemical properties as anode materials for Li-ion secondary batteries were then investigated. When PVDF is added to the sample in a weight ratio 5 : 95, the disordered carbon with x=0.00 had the first discharge capacity 374 mAh/g. Its cycling performance was relatively good from the second cycle and it had the discharge capacity 258 mAh/g at the 10th cycle. When PVDF is added to the sample in a weight ratio 5 : 95, the sample with x=0.05 among the samples $C_{l-x}B_x(x=0.05,\;0.10,\;0.20)$ exhibited the largest first discharge capacity 860 mAh/g and discharge capacity 181 mAh/g at the 10th cycle. All the samples had similar cycling performances from the second cycle. The sample $C_{0.90}B_{0.10}$ showed the best electrochemical properties as a anode materials fur Li-ion secondary battery from the view points of the first discharge capacity(853 mAh/g when $10w1.\%$ PVDF is used), cycling performance, discharge capacity(400mAh/g at the 10th cycle when $10wt.\%$ PVDF is used). All the samples showed generally larger charge and discharge capacities when $10wt.\%$ PVDF ratter than $5wt.\%$ PVDF is used. The plateau region in the range of voltage lower than 1.25V becomes larger probably since the structure becomes less disordered by the addition of boron. When boron is added, the charge and discharge capacities decreased suddenly at the second cycle. This may be become only a part of Li are reversibly deintercalated and intercalated and a part of Li which are strongly combined with B are not deintercalated. The increases in charge and discharge capacities are considered to be resulted from the increase in the potential of Li in the boron-added carbons, caused by the strengthening of the chemical bond between the intercalated Li and the boron-carbon host since the boron acts as electron acceptor.

$Li_2$$CO_3$, ${NiCO_3}$, $CoCO_3$로부터 $LiNi_{1-y}$${Co_y}{O_2}$의 합성 및 전극특성 연구

임호,강성구,장순호,송명엽,Rim, Ho,Kang, Seong-Gu,Chang, Soon-Ho,Song, Myoung-Youp 한국세라믹학회 2001 한국세라믹학회지 Vol.38 No.6

출발 물질로서 L $i_2$C $O_3$, NiC $O_3$, CoC $O_3$를 사용하고 조성과 합성 온도를 변화시켜, 고온 고상법에 의하여 LiN $i_{1-y}$ $Co_{y}$ $O_2$(y=0.1, 0.3, 0.5)를 합성하였다. 합성과 시료들의 결정구조, 미세구조 그리고 전기화학적 특성을 조사하였다. 80$0^{\circ}C$와 8$50^{\circ}C$에서 제조한 L $i_{x}$N $i_{1-y}$ $Co_{y}$ $O_2$는, 삼방정계(space group: R3m)의 $\alpha$-NaFe $O_2$구조로 결정화되어 있는 층상 구조를 형성하였다. LiN $i_{1-y}$ $Co_{y}$ $O_2$(y=0.1, 0.3, 0.5)는 Co의 양이 증가함에 따라 a축과 c축의 크기가 감소하였는데, 이는 코발트 이온의 크기가 니켈 이온의 크기보다 작은데 기인하는 것이다. 그러나 c축과 a축의 크기의 비(c/a)가 증가하였음은 이차원적 구조가 잘 발달됨을 보여준다. 니켈에 대한 코발트의 치환량에 따른 리튬 이온의 삽입/추출 가역성은 코발트의 치환량이 증가하면서 증가하여 y=0.3인 LiN $i_{0.9}$ $Co_{0.1}$ $O_2$에서 대체로 우수하였고 그 이상으로 y값이 증가하면 가역성이 나빠졌다. 80$0^{\circ}C$에서 합성한 LiN $i_{0.9}$ $Co_{0.1}$ $O_2$가 가장 큰 초기 방전 용량 146 mAh/g을 나타내었으며, 싸이클링 성능도 비교적 우수하였다. 8$50^{\circ}C$에서 합성한 LiN $i_{0.9}$ $Co_{0.1}$ $O_2$와 LiN $i_{0.7}$ $Co_{0.3}$ $O_2$가 우수한 싸이클링 성능을 보였다.다. 싸이클링 성능을 보였다.다.보였다.다.

공정 Mg-Ni계 합금 분말의 제조 및 수소저장 특성

홍성현,배종수,임창동,나영상,송명엽,Hong, Seong-Hyeon,Bae, Jong-Soo,Yim, Chang-Dong,Na, Young-Sang,Song, Myoung-Youp 한국수소및신에너지학회 2006 한국수소 및 신에너지학회논문집 Vol.17 No.2

The eutectic Mg-23.5%Ni alloy was casted by melting and solidification. The powders of Mg-23.5%Ni and (Mg-23.5%Ni)-10% iron oxide were prepared by mechanical grinding of casted Mg-Ni alloy and casted Mg-Ni alloy+oxide, respectively. As milling time increases, hydriding and dehydriding rates of Mg-Ni and Mg-Ni-oxide alloy powders increase. The additions of iron oxide to Mg-Ni alloy and Mg-Ni-oxide increase hydriding rates and slightly decrease dehydriding rates.

Mg_51Zn_20의 수소 화합물 형성·분해 반응에 관한 연구

宋明燁 전북대학교 전자산업개발연구소 1990 전자산업연구 Vol.1 No.-

In order to increase the hydriding and dehydriding rates of magnesium which has excellent hydrogen-storage properties, and intermetallic compound of magnesium with zinc, Mg_51Zn_20, is prepared. For the hydriding and dehydriding reactions is used a volumetric apparatus for high pressure, which is designed for hydriding and dehydriding under constant hydrogen pressures. In the early cycles of hydriding reaction Mg_51Zn_20 is decomposed into Mg, MgZn and Mg_2Zn_3, the Mg being hydrided. During subsequent cycles only the magnesium is hydrided and dehydri-ded. In the initial stage of hydriding reaction the nucleation controls the hydriding rates and then the diffusion of hydrogen atoms through growing hydriede layer controls them. Dehydriding rates are controlled by the nucleation of Mg-H solid solution. In addition are studied activation process, equilibrium plateau pressures and microstructures of hydrided samples.