The Journal of
the Korean Journal of Metals and Materials

The Journal of
the Korean Journal of Metals and Materials

Monthly
  • pISSN : 1738-8228
  • eISSN : 2288-8241

Editorial Office


  1. ๋™์•„๋Œ€ํ•™๊ต ์‹ ์†Œ์žฌ๊ณตํ•™๊ณผ (Department of Materials Science and Engineering, Dong-A University, Busan 49315, Republic of Korea)



SOFC, interconnect, Co coating, electrodeposition, thickness uniformity, microstructure

1. ์„œ ๋ก 

์ตœ๊ทผ ๊ณ ์ฒด์‚ฐํ™”๋ฌผ ์—ฐ๋ฃŒ์ „์ง€ (solid oxide fuel cells: SOFC)๊ฐ€ ๋†’์€ ์—๋„ˆ์ง€ ๋ณ€ํ™˜ ํšจ์œจ์„ ๊ฐ€์ง€๋Š” ์นœํ™˜๊ฒฝ์  ๋ฐœ์ „ ์žฅ์น˜๋กœ ์ฃผ๋ชฉ๋ฐ›๊ณ  ์žˆ๋‹ค[1-4]. SOFC์˜ ์—๋„ˆ์ง€ ๋ณ€ํ™˜ ํšจ์œจ์€ 60% ์ด์ƒ์œผ๋กœ ๋‹ค๋ฅธ ์œ ํ˜•์˜ ์—ฐ๋ฃŒ์ „์ง€์— ๋น„ํ•ด ์šฐ์ˆ˜ํ•˜๋ฉฐ, ํ์—ด์„ ์ด์šฉํ•œ ์—ด๋ณ‘ํ•ฉ ์‹œ์Šคํ…œ ๋“ฑ ๋ณตํ•ฉ ๋ฐœ์ „์— ์ ์šฉํ•  ๊ฒฝ์šฐ 80% ์ด์ƒ์˜ ๋ฐœ์ „ ํšจ์œจ์„ ์–ป์„ ์ˆ˜ ์žˆ๋‹ค๊ณ  ์•Œ๋ ค์ ธ ์žˆ๋‹ค[2]. ๋˜ํ•œ ๋†’์€ ์ž‘๋™ ์˜จ๋„๋กœ ์ธํ•ด ์ˆ˜์†Œ ์™ธ ๋ฉ”ํƒ„, ์•Œ์ฝ”์˜ฌ, ์•”๋ชจ๋‹ˆ์•„ ๋“ฑ์˜ ๋‹ค์–‘ํ•œ ์—ฐ๋ฃŒ๋ฅผ ์‚ฌ์šฉํ•  ์ˆ˜ ์žˆ์–ด, ์ˆ˜์†Œ ๊ณต๊ธ‰๋ง ๊ตฌ์ถ•์„ ์œ„ํ•œ ์ถ”๊ฐ€ ํˆฌ์ž ์—†์ด ๊ธฐ์กด ์—๋„ˆ์ง€์›์˜ ๊ณต๊ธ‰๋ง์„ ํ™œ์šฉํ•˜๋Š” ๊ฒƒ์ด ๊ฐ€๋Šฅํ•˜๋‹ค[3]. ๋˜ํ•œ, SOFC๋Š” ๋‚ด์—ฐ๊ธฐ๊ด€์— ๋น„ํ•˜์—ฌ COx, SOx, ๋ฐ NOx ๋“ฑ๊ณผ ๊ฐ™์€ ๋Œ€๊ธฐ ์˜ค์—ผ๋ฌผ์งˆ ๋ฐฐ์ถœ์ด ๋งค์šฐ ์ ์–ด ํ™˜๊ฒฝ์ ์ธ ์žฅ์ ์ด ํฌ๋‹ค[4].

SOFC์—์„œ ์—ฐ๊ฒฐ์žฌ (interconnect)๋Š” ๊ฐ ์…€์„ ์ „๊ธฐ์ ์œผ๋กœ ์—ฐ๊ฒฐํ•˜๊ณ , ์ธ์ ‘ ์…€๋“ค ๊ฐ„์˜ ์—ฐ๋ฃŒ์™€ ๊ณต๊ธฐ๋ฅผ ๋ถ„๋ฆฌํ•˜๋Š” ์ค‘์š”ํ•œ ์—ญํ• ์„ ํ•˜๋Š” ํ•ต์‹ฌ ๋ถ€ํ’ˆ์ด๋‹ค[5-7]. ์ด๋Ÿฌํ•œ ์—ฐ๊ฒฐ์žฌ์˜ ์†Œ์žฌ๋Š” ๊ณ ์˜จ์˜ ์‚ฐํ™” ๋ฐ ํ™˜์› ๋ถ„์œ„๊ธฐ์—์„œ ์šฐ์ˆ˜ํ•œ ์ „๊ธฐ ์ „๋„์„ฑ๊ณผ ๊ตฌ์กฐ์ , ํ™”ํ•™์  ์•ˆ์ •์„ฑ์„ ๊ฐ€์ ธ์•ผ ํ•˜๋ฉฐ, ๊ณ ์˜จ์—์„œ ์…€ ์Šคํƒ์„ ์ง€์ง€ํ•˜๊ธฐ์— ์ถฉ๋ถ„ํ•œ ์—ด์ , ๊ธฐ๊ณ„์  ๋ฌผ์„ฑ ์—ญ์‹œ ์š”๊ตฌ๋œ๋‹ค. ๋˜ํ•œ ์—ฐ๊ฒฐ์žฌ ์†Œ์žฌ๋Š” ์ธ์ ‘ํ•œ ๋ถ€ํ’ˆ ์†Œ์žฌ์™€์˜ ํ˜ธํ™˜์„ฑ ๋ฐ ๋น„๋ฐ˜์‘์„ฑ์˜ ์กฐ๊ฑด๋“ค์„ ์ถฉ์กฑํ•ด์•ผ ํ•œ๋‹ค[8,9].

SOFC์˜ ํ˜•ํƒœ ๋ฐ ์šด์ „ ์˜จ๋„์— ๋”ฐ๋ผ ์—ฐ๊ฒฐ์žฌ ์†Œ์žฌ๋กœ์„œ ์„ธ๋ผ๋ฏน ๋˜๋Š” ๊ธˆ์†์ด ์‚ฌ์šฉ๋˜๋Š”๋ฐ, 600 ~ 800 ยฐC์˜ ์ €์˜จ์—์„œ ๋™์ž‘ํ•˜๋Š” ํ‰ํŒํ˜• SOFC์—์„œ๋Š” ๊ธˆ์† ์—ฐ๊ฒฐ์žฌ๊ฐ€ ์ผ๋ฐ˜์ ์œผ๋กœ ์ ์šฉ๋˜๋ฉฐ, ๊ทธ ์†Œ์žฌ๋กœ์„œ Cr์˜ ํ•จ์œ ๋Ÿ‰์ด ๋†’์€ ํŽ˜๋ผ์ดํŠธ๊ณ„ ์Šคํ…Œ์ธ๋ฆฌ์Šค๊ฐ• ์†Œ์žฌ๊ฐ€ ๋„๋ฆฌ ์‚ฌ์šฉ๋œ๋‹ค[5-11]. ๊ทธ๋Ÿฐ๋ฐ, SOFC์˜ ์šด์ „ ํ™˜๊ฒฝ์—์„œ ํŽ˜๋ผ์ดํŠธ๊ณ„ ์Šคํ…Œ์ธ๋ฆฌ์Šค๊ฐ• ์—ฐ๊ฒฐ์žฌ์˜ ํ‘œ๋ฉด์—์„œ Cr ์‚ฐํ™”๋ฌผ์˜ ๋‘๊ป˜๊ฐ€ ์ฆ๊ฐ€ํ•˜์—ฌ ์—ฐ๊ฒฐ์žฌ์˜ ๊ณ„๋ฉด ์ €ํ•ญ์„ ์ฆ๊ฐ€์‹œํ‚ค๋ฉฐ, ๋˜ํ•œ ์ด๋Ÿฌํ•œ ๊ณ„๋ฉด ์‚ฐํ™”๋ฌผ๋กœ๋ถ€ํ„ฐ ํœ˜๋ฐœ๋œ Cr์€ ๊ณต๊ธฐ๊ทน ๋‚ด์— ์ฆ์ฐฉ๋˜์–ด ์‚ฐ์†Œ์˜ ์ „๊ธฐํ™”ํ•™์  ํ™˜์› ๋ฐ˜์‘์„ ์ €ํ•ดํ•˜๋Š” ํ˜„์ƒ์„ ์œ ๋ฐœํ•œ๋‹ค[6,7,10]. ์ด์—, ๊ธˆ์† ์—ฐ๊ฒฐ์žฌ์˜ ์ „๊ธฐ์  ํŠน์„ฑ์„ ์œ ์ง€ํ•˜๋ฉด์„œ Cr ํœ˜๋ฐœ์„ ๋ฐฉ์ง€ํ•˜๊ธฐ ์œ„ํ•ด ๊ธˆ์† ์—ฐ๊ฒฐ์žฌ ํ‘œ๋ฉด์— ์ด์ข… ์†Œ์žฌ์˜ ๋ณดํ˜ธ ์ฝ”ํŒ…๋ง‰์„ ์ ์šฉํ•˜๋Š” ์—ฐ๊ตฌ๊ฐ€ ํ™œ๋ฐœํžˆ ์ง„ํ–‰๋˜๊ณ  ์žˆ๋‹ค[6,7].

ํŽ˜๋ผ์ดํŠธ๊ณ„ ์Šคํ…Œ์ธ๋ฆฌ์Šค๊ฐ• ์—ฐ๊ฒฐ์žฌ์˜ Cr ํœ˜๋ฐœ์„ ๋ฐฉ์ง€ํ•˜๊ธฐ ์œ„ํ•œ ๋ณดํ˜ธ ์ฝ”ํŒ…๋ง‰์œผ๋กœ๋Š” ์Šคํ”ผ๋„ฌ (spinel) ๊ตฌ์กฐ๋ฅผ ๊ฐ€์ง€๋Š” Co, Mn, Ni, Cu ๋“ฑ์˜ ๊ธˆ์† ์‚ฐํ™”๋ฌผ[11,12], ํฌํ† ๋ฅ˜ ํŽ˜๋กœ๋ธŒ์Šค์นด์ดํŠธ (perovskite) ๊ตฌ์กฐ์˜ ์‚ฐํ™”๋ฌผ, ๊ทธ๋ฆฌ๊ณ  Y, La, Ce์™€ ๊ฐ™์€ ๋ฐ˜์‘์„ฑ ์›์†Œ์˜ ์‚ฐํ™”๋ฌผ ๋“ฑ์ด ์—ฐ๊ตฌ๋˜๊ณ  ์žˆ์œผ๋ฉฐ, ์ด๋“ค ์ค‘ ์Šคํ”ผ๋„ฌ ๊ตฌ์กฐ์˜ ๊ธˆ์† ์‚ฐํ™”๋ฌผ ๋ฐฉ์ง€๋ง‰์ด ํ˜„ ์‹œ์ ์—์„œ ๊ฐ€์žฅ ์œ ๋งํ•œ ๊ฒƒ์œผ๋กœ ํ‰๊ฐ€๋œ๋‹ค. ์ด๋“ค ๊ธˆ์† ์‚ฐํ™”๋ฌผ ๋ฐฉ์ง€ ์ฝ”ํŒ…๋ง‰์„ ํ˜•์„ฑํ•˜๊ธฐ ์œ„ํ•ด์„œ๋Š” ๊ธˆ์† ๋˜๋Š” ์‚ฐํ™”๋ฌผ ๋ฐ•๋ง‰์˜ ์ฆ์ฐฉ์ด ํ•„์š”ํ•˜๋ฉฐ ์ „๊ธฐ๋„๊ธˆ, ๋ฌผ๋ฆฌ์  ๊ธฐ์ƒ ์ฆ์ฐฉ(Physical Vapor Deposition: PVD), ์กธ-๊ฒ”(Sol-Gel) ๋ฐฉ๋ฒ• ๋“ฑ์˜ ๋ฐ•๋ง‰ ์ฆ์ฐฉ ๊ธฐ์ˆ ์ด ์—ฐ๊ตฌ๋˜๊ณ  ์žˆ๋‹ค[6,11,12].

๊ธˆ์† ์—ฐ๊ฒฐ์žฌ ํ‘œ๋ฉด์— ๋ณดํ˜ธ ์ฝ”ํŒ…๋ง‰์„ ํ˜•์„ฑํ•˜๊ธฐ ์œ„ํ•œ ๊ธฐ์ˆ ๋“ค ์ค‘, ์ „๊ธฐ๋„๊ธˆ ๊ธฐ์ˆ [12-19]์„ ์ด์šฉํ•œ ๋ฐ•๋ง‰ ์ฆ์ฐฉ ๋ฐฉ๋ฒ•์ด ๋น„์šฉ์  ์ธก๋ฉด์ด๋‚˜ ๋‹ค์–‘ํ•œ ์†Œ์žฌ์˜ ๋ฐฉ์ง€๋ง‰ ํ˜•์„ฑ ๊ฐ€๋Šฅ์„ฑ์—์„œ ์œ ๋ฆฌํ•œ ๊ธฐ์ˆ ๋กœ ํ‰๊ฐ€๋œ๋‹ค[6]. ์ „๊ธฐ๋„๊ธˆ์€ PVD์™€ ๋‹ฌ๋ฆฌ ์ง„๊ณต ์กฐ๊ฑด์ด ์š”๊ตฌ๋˜์ง€ ์•Š์œผ๋ฉฐ, ์กธ-๊ฒ” ๋ฐฉ๋ฒ•์— ๋น„ํ•ด ๋”์šฑ ์น˜๋ฐ€ํ•œ ๋ฐ•๋ง‰ ํ˜•์„ฑ์ด ๊ฐ€๋Šฅํ•˜๋ฉฐ ์ฆ์ฐฉ ๊ฐ€๋Šฅํ•œ ๋ฌผ์งˆ์˜ ์ œ์•ฝ์ด ๋œํ•˜๋‹ค. ๊ทธ๋Ÿฌ๋‚˜, ์ „๊ธฐ๋„๊ธˆ์œผ๋กœ ํŽ˜๋ผ์ดํŠธ๊ณ„ ์Šคํ…Œ์ธ๋ฆฌ์Šค๊ฐ• ํ‘œ๋ฉด์— ๋ฐ•๋ง‰์„ ํ˜•์„ฑํ•  ๋•Œ, ์ด๋ฏธ ํ˜•์„ฑ๋œ ์ž์—ฐ ์‚ฐํ™”๋ง‰์œผ๋กœ ์ธํ•œ ์Šคํ…Œ์ธ๋ฆฌ์Šค๊ฐ•-๋„๊ธˆ์ธต ๊ฐ„์˜ ๊ณ„๋ฉด ๋ฐ€์ฐฉ๋ ฅ ๋ถ€์กฑ ๋ฌธ์ œ๊ฐ€ ๋ฐœ์ƒํ•  ์ˆ˜ ์žˆ๋‹ค. ๋˜ํ•œ, SOFC ์—ฐ๊ฒฐ์žฌ ํ‘œ๋ฉด์˜ Co, Mn, Ni ๋ฐ ํ•ฉ๊ธˆ ๋„๊ธˆ์— ๋Œ€ํ•œ ์—ฐ๊ตฌ๋Š” ์ƒ๋Œ€์ ์œผ๋กœ ๋ถ€์กฑํ•œ ์ƒํ™ฉ์ด๋‹ค.

๋”ฐ๋ผ์„œ ๋ณธ ์—ฐ๊ตฌ๋Š” ๊ณต๊ธฐ๊ทน/์—ฐ๋ฃŒ๊ทน ํŒจํ„ด์ด ํ˜•์„ฑ๋œ ํŽ˜๋ผ์ดํŠธ๊ณ„ ์Šคํ…Œ์ธ๋ฆฌ์Šค๊ฐ• ์—ฐ๊ฒฐ์žฌ์˜ ํ‘œ๋ฉด์— ๋ฐ€์ฐฉ๋ ฅ์ด ์šฐ์ˆ˜ํ•˜๊ณ  ๋‘๊ป˜๊ฐ€ ๊ท ์ผํ•œ Co ๋ฐ•๋ง‰์„ ํ˜•์„ฑํ•˜๊ธฐ ์œ„ํ•œ Co ์ „๊ธฐ๋„๊ธˆ ๊ธฐ์ˆ [20-23]์„ ๊ฐœ๋ฐœํ•˜๊ณ ์ž ํ•˜์˜€๋‹ค. ์ด๋ฅผ ์œ„ํ•ด ๋จผ์ € ๊ณ„๋ฉด ๋ฐ€์ฐฉ๋ ฅ ํ–ฅ์ƒ์„ ์œ„ํ•ด Co ์ด์˜จ ๊ธฐ๋ฐ˜ ์ŠคํŠธ๋ผ์ดํฌ ๊ณต์ •์„ ๊ฐœ๋ฐœํ•˜์—ฌ ์ฃผ Co ๋„๊ธˆ ๊ณต์ •๊ณผ ๊ฒฐํ•ฉํ•˜์˜€๋‹ค. ๊ทธ๋ฆฌ๊ณ , ๊ฐœ๋ฐœ๋œ ๋‘ ๋‹จ๊ณ„ Co ๋„๊ธˆ๊ธฐ์ˆ ์„ ์ด์šฉํ•˜์—ฌ, ์ฃผ ๋„๊ธˆ๊ณต์ • ์‹œ ์ „๋ฅ˜๋ฐ€๋„๋ฅผ ๋ณ€ํ™”์‹œ์ผœ ๋„๊ธˆํ•œ Co ์ฝ”ํŒ…๋ง‰์˜ ํŒจํ„ด ์œ„์น˜ ๋ณ„ Co ๋„๊ธˆ์ธต์˜ ๋‘๊ป˜์™€ ๋ฏธ์„ธ์กฐ์ง์„ ๋ถ„์„ํ•˜์˜€๊ณ , ๋˜ํ•œ ์‹คํ—˜ํ•œ ๋„๊ธˆ ๊ณต์ •์กฐ๊ฑด์— ๋Œ€ํ•ด ์œ ํ•œ์š”์†Œ๋ฒ• ๊ธฐ๋ฐ˜ ๋„๊ธˆ ์‹œ๋ฎฌ๋ ˆ์ด์…˜์„ ์ˆ˜ํ–‰ํ•˜์˜€๋‹ค. ์ด๋ฅผ ํ†ตํ•ด, ์ „๋ฅ˜ ๋ฐ€๋„์— ๋”ฐ๋ฅธ ์ „๊ธฐํ™”ํ•™์  ๊ฑฐ๋™ ๋ฐ ๋„๊ธˆ์ธต ์„ฑ์žฅ ๋ฉ”์ปค๋‹ˆ์ฆ˜์„ ์ดํ•ดํ•˜๊ณ , ํŒจํ„ด ์œ„์น˜ ๋ณ„ Co ๋„๊ธˆ ๋‘๊ป˜์˜ ์ฐจ์ด๋ฅผ ์œ ๋ฐœํ•˜๋Š” ์ „๊ธฐ๋„๊ธˆ ์ธ์ž๋ฅผ ๊ทœ๋ช…ํ•˜๊ณ ์ž ํ•˜์˜€๋‹ค.

2. ์‹คํ—˜ ๋ฐฉ๋ฒ•

2.1. ํŽ˜๋ผ์ดํŠธ๊ณ„ ์Šคํ…Œ์ธ๋ฆฌ์Šค๊ฐ• ์—ฐ๊ฒฐ์žฌ ๊ธฐํŒ์˜ ์ œ์ž‘ ๋ฐ Co ์ „๊ธฐ๋„๊ธˆ ๋ฐฉ๋ฒ•

๊ทธ๋ฆผ 1์— Co ์ „๊ธฐ๋„๊ธˆ์˜ ๋Œ€์ƒ์ด ๋˜๋Š” ํŒจํ„ด ๊ธฐํŒ์˜ ๋„์‹์  ํ˜•์ƒ์„ ๋‚˜ํƒ€๋‚ด์—ˆ๋‹ค. ๊ธฐํŒ์˜ ์†Œ์žฌ๋Š” 430 ํƒ€์ž… ํŽ˜๋ผ์ดํŠธ๊ณ„ ์Šคํ…Œ์ธ๋ฆฌ์Šค๊ฐ•์œผ๋กœ, 3 mm ๋‘๊ป˜์˜ ์Šคํ…Œ์ธ๋ฆฌ์Šค๊ฐ• ํŒ์žฌ์— ๋„ˆ๋น„ 2 mm, ๊นŠ์ด 1 mm์˜ ํŠธ๋ Œ์น˜ ํƒ€์ž… (trench-type) ํŒจํ„ด์„ 2 mm ๊ฐ„๊ฒฉ์œผ๋กœ ๊ธฐ๊ณ„์  ๋ฐ€๋ง ๋ฐฉ๋ฒ•์„ ์ด์šฉํ•˜์—ฌ ํ˜•์„ฑํ•˜์˜€๋‹ค. Co ์ „๊ธฐ๋„๊ธˆ ์ „ ๊ธฐํŒ ํ‘œ๋ฉด์€ ์•„์„ธํ†ค๊ณผ ์—ํƒ„์˜ฌ์„ ์‚ฌ์šฉํ•˜์—ฌ ์„ธ์ฒ™ํ•œ ํ›„, 5% ํ™ฉ์‚ฐ๊ณผ 10% ํƒˆ์ง€์•ก์„ ์ฆ๋ฅ˜์ˆ˜์™€ ํ˜ผํ•ฉํ•œ ์šฉ์•ก์—์„œ 1๋ถ„๊ฐ„ ์ดˆ์ŒํŒŒ ์„ธ์ฒ™์„ ์‹ค์‹œํ•˜์˜€๋‹ค.

์Šคํ…Œ์ธ๋ฆฌ์Šค๊ฐ• ๊ธฐํŒ๊ณผ์˜ ๋ฐ€์ฐฉ๋ ฅ์ด ์šฐ์ˆ˜ํ•œ Co ๋„๊ธˆ์ธต์„ ํ˜•์„ฑ์„ ์œ„ํ•ด, ์Šคํ…Œ์ธ๋ฆฌ์Šค๊ฐ• ๊ธฐํŒ ํ‘œ๋ฉด์— ํ˜•์„ฑ๋œ Cr ์ž์—ฐ ์‚ฐํ™”๋ฌผ์˜ ์ธต์„ ์ œ๊ฑฐํ•˜๋Š” Co ์ด์˜จ ๊ธฐ๋ฐ˜ ์ŠคํŠธ๋ผ์ดํฌ (strike) ๊ณต์ •์„ ์‚ฌ์šฉํ•˜์˜€๋‹ค. ์ผ๋ฐ˜์ ์œผ๋กœ ์Šคํ…Œ์ธ๋ฆฌ์Šค๊ฐ• ๊ธฐํŒ์— ์ถฉ๋ถ„ํ•œ ๋ฐ€์ฐฉ๋ ฅ์„ ๊ฐ€์ง€๋Š” ์ „๊ธฐ๋„๊ธˆ ๋ฐ•๋ง‰์„ ์ฆ์ฐฉํ•˜๊ธฐ ์œ„ํ•ด์„œ Woodโ€™s Ni ์ŠคํŠธ๋ผ์ดํฌ ๊ณต์ •์ด ์‚ฌ์šฉ๋˜์ง€๋งŒ[24], ๋ณธ ์—ฐ๊ตฌ์—์„œ๋Š” Co ๋‹จ์ผ๋ง‰ ํ˜•์„ฑ์„ ์œ„ํ•ด Co ์ด์˜จ ๊ธฐ๋ฐ˜ ์ŠคํŠธ๋ผ์ดํฌ ์šฉ์•ก๊ณผ ๊ณต์ •์„ ๊ฐœ๋ฐœํ•˜์˜€๋‹ค. ์ด๋ฅผ ์œ„ํ•ด, ์—ผํ™”์ฝ”๋ฐœํŠธ (CoCl2ยท6H2O)์™€ ์—ผ์‚ฐ(HCl)์„ ์ฆ๋ฅ˜์ˆ˜์™€ ํ˜ผํ•ฉํ•œ ๋„๊ธˆ ์šฉ์•ก์„ ์‚ฌ์šฉํ•˜์—ฌ 400~600 nm ๋‘๊ป˜์˜ Co ์‹œ๋“œ ์ธต (seed layer)์„ ํ˜•์„ฑํ•˜์˜€๋‹ค. ์ด Co ์ŠคํŠธ๋ผ์ดํฌ ๊ณต์ • ํ›„ ์ฆ‰์‹œ ์ฃผ ๋„๊ธˆ ๊ณต์ •์„ ์ง„ํ–‰ํ•˜์˜€๋‹ค.

์ฃผ Co ๋„๊ธˆ ๊ณต์ •์€ ์—ผํ™”์ฝ”๋ฐœํŠธ (CoCl2ยท6H2O)์™€ ๋ถ•์‚ฐ(H3BO3)์„ ์ฆ๋ฅ˜์ˆ˜์™€ ํ˜ผํ•ฉํ•œ ์ „ํ•ด์งˆ ์šฉ์•ก[12,25]์„ ์ด์šฉํ•˜์—ฌ ์ง„ํ–‰๋˜์—ˆ๊ณ , ๋„๊ธˆ ์ค‘ ๋‘ ์ „๊ทน ์‚ฌ์ด์— ์ธ๊ฐ€ํ•˜๋Š” ์ „๋ฅ˜๋ฐ€๋„๋ฅผ ๋‹ฌ๋ฆฌํ•˜๋ฉด์„œ Co ๋ฐ•๋ง‰๋“ค์„ ์ฆ์ฐฉํ•˜์˜€๋‹ค. ์ ์šฉํ•œ ์ „๋ฅ˜๋ฐ€๋„๋Š” 10, 30, 90 mA/cm2 ์˜€์œผ๋ฉฐ, ๊ฐ ์ „๋ฅ˜๋ฐ€๋„ ์กฐ๊ฑด์—์„œ ์ด๋ก ์ ์œผ๋กœ ํ™˜์›๋˜๋Š” Co ์ด์˜จ์˜ ์ด ์ˆ˜๋ฅผ ๊ณ„์‚ฐํ•˜์—ฌ ํ‰ํŒ ๊ธฐ์ค€ 82 ฮผm์˜ ๋„๊ธˆ์ธต์ด ํ˜•์„ฑ๋˜๋„๋ก ๋„๊ธˆ ์‹œ๊ฐ„์„ ๊ฒฐ์ •ํ•˜์˜€๋‹ค. ๋„๊ธˆ ๊ณต์ • ์ค‘ ์šฉ์•ก์€ 200 rpm์œผ๋กœ ํšŒ์ „ํ•˜๋Š” ์ž๊ธฐ ๊ต๋ฐ˜์ž (magnetic stirrer)์— ์˜ํ•ด ๊ต๋ฐ˜๋˜์—ˆ๋‹ค. ์ŠคํŠธ๋ผ์ดํฌ ๋ฐ ์ฃผ ๋„๊ธˆ์„ ์œ„ํ•œ ์ƒ์„ธํ•œ ์šฉ์•ก ์กฐ์„ฑ๊ณผ ๋„๊ธˆ ๊ณต์ • ์กฐ๊ฑด์€ ํ‘œ 1 ๋ฐ 2์— ๊ฐ๊ฐ ์ •๋ฆฌํ•˜์˜€๋‹ค.

Co ๋„๊ธˆ ํ›„, ๋„๊ธˆ๋œ Co ๋ฐ•๋ง‰์˜ ํ‘œ๋ฉด ํ˜•์ƒ๊ณผ ํŠธ๋ Œ์น˜ ํŒจํ„ด ๋‹จ๋ฉด ์ƒ์—์„œ์˜ ๊ตญ๋ถ€์ ์ธ ๋‘๊ป˜๋ฅผ ํ™•์ธํ•˜๊ธฐ ์œ„ํ•ด ์ฃผ์‚ฌ์ „์žํ˜„๋ฏธ๊ฒฝ (๋ชจ๋ธ๋ช…: FEI์‚ฌ Inspect F50)์„ ์‚ฌ์šฉํ•˜์˜€๋‹ค. ๋‹จ๋ฉด ์‹œํŽธ์„ ์–ป๊ธฐ ์œ„ํ•ด, ๋„๊ธˆ๋œ ๊ธฐํŒ์„ ํŠธ๋ Œ์น˜ ํŒจํ„ด์˜ ๊ธธ์ด ๋ฐฉํ–ฅ๊ณผ ์ˆ˜์ง์ด ๋˜๋„๋ก ์ ˆ๋‹จํ•˜๊ณ  ๋งˆ์šดํŒ…ํ•œ ํ›„ ํด๋ฆฌ์‹ฑํ•˜์˜€๋‹ค.

๊ฐ ์ „๋ฅ˜๋ฐ€๋„ ๋ณ„๋กœ ์ฆ์ฐฉ๋œ Co ๋ฐ•๋ง‰์˜ ๊ด‘์—ญ ์ง‘ํ•ฉ์กฐ์ง์„ ์ธก์ •ํ•˜๊ธฐ ์œ„ํ•˜์—ฌ X์„  ํšŒ์ ˆ(XRD) ๋ถ„์„๋ฒ• (๋ชจ๋ธ๋ช…: Malvern Panalytical์‚ฌ EMPYREAN)์„ ์ด์šฉํ•˜์˜€๋‹ค. ํŒจํ„ด ๋‹จ๋ฉด ์ƒ Co ๋ฐ•๋ง‰์˜ ๊ตญ๋ถ€์ ์ธ ์ง‘ํ•ฉ์กฐ์ง ๋ฐ ๋ฏธ์„ธ์กฐ์ง, ์ฆ‰ ๊ฒฐ์ •๋ฆฝ ํ˜•์ƒ๊ณผ ํฌ๊ธฐ๋ฅผ ๋ถ„์„ํ•˜๊ธฐ ์œ„ํ•ด ์ „์žํ›„๋ฐฉ์‚ฐ๋ž€(electron backscatter diffraction: EBSD) ๋ถ„์„ ์‹œ์Šคํ…œ(FEI์‚ฌ Inspect F50 + EDAX์‚ฌ Pegasus with a Hikari EBSD camera + EDAX์‚ฌ OIM Analysis)์„ ์‚ฌ์šฉํ•˜์˜€๋‹ค.

Co ๋ฐ•๋ง‰์ด ์ ์šฉ๋œ ์—ฐ๊ฒฐ์žฌ ๊ธฐํŒ์˜ ๊ณ ์˜จ ์„ฑ๋Šฅ์„ ํ‰๊ฐ€ํ•˜๊ธฐ ์œ„ํ•ด, ๋„๊ธˆ๋œ ํ‰ํŒ ์‹œ๋ฃŒ๋ฅผ 800 ยฐC์—์„œ 100, 300, 500 ์‹œ๊ฐ„ ์—ด์ฒ˜๋ฆฌ ์‹œ ๋ฉด์ €ํ•ญ (area specific resistance: ASR)์˜ ๋ณ€ํ™”๋ฅผ ๋ถ„์„ํ•˜์˜€๋‹ค[26]. ๊ฐ ์กฐ๊ฑด์˜ ์—ด์ฒ˜๋ฆฌ ํ›„ ์‚ฐํ™”๋œ ์‹œํŽธ์˜ ํ‘œ๋ฉด์— Pt ๋ฉ”์‰ฌ๋ฅผ ๋ถ€์ฐฉํ•œ ํ›„ ์ด๋ฅผ ์ „์••/์ „๋ฅ˜ ์†Œ์Šค ๋ฐ ์ธก์ • ์žฅ์น˜ (Yokogawa Electric์‚ฌ GS610)์— ์—ฐ๊ฒฐํ•˜์—ฌ 4 point probe ๋ฐฉ๋ฒ•์„ ์ด์šฉํ•˜์—ฌ ๋ฉด์ €ํ•ญ์„ ์ธก์ •ํ•˜์˜€๋‹ค. ๋ฉด์ €ํ•ญ ์ธก์ • ์‹œ, ์‹œํŽธ์„ 200 ยฐC/hour ์†๋„๋กœ 800 ยฐC๊นŒ์ง€ ๊ฐ€์—ดํ•˜๊ณ  24์‹œ๊ฐ„ ์•ˆ์ •ํ™”ํ•œ ํ›„ 0.2 A ๊ฐ„๊ฒฉ์œผ๋กœ -1 A ~ 1 A๊นŒ์ง€ ์ „๋ฅ˜๋ฅผ ์ธ๊ฐ€ํ•˜๋ฉด์„œ 5๋ถ„ ๊ฐ„๊ฒฉ์œผ๋กœ ์ „๊ธฐ์ €ํ•ญ์„ ์ธก์ •ํ•˜์˜€๋‹ค.

2.2. Co ์ „๊ธฐ๋„๊ธˆ ์‹œ๋ฎฌ๋ ˆ์ด์…˜ ๋ฐฉ๋ฒ•

์‹คํ—˜์„ ํ†ตํ•ด ๊ด€์ฐฐ๋œ ์ „๋ฅ˜๋ฐ€๋„์— ๋”ฐ๋ฅธ ํŒจํ„ด ์œ„์น˜ ๋ณ„ Co ๋ฐ•๋ง‰์˜ ๋‘๊ป˜์™€ ๋ฏธ์„ธ์กฐ์ง์˜ ์ฐจ์ด๋ฅผ ์œ ๋ฐœํ•˜๋Š” ๋„๊ธˆ ์ธ์ž๋ฅผ ํƒ์ƒ‰ํ•˜๊ธฐ ์œ„ํ•ด, ์œ ํ•œ์š”์†Œ๋ฒ•์„ ์ด์šฉํ•˜์—ฌ ์‹คํ—˜ํ•œ ๋„๊ธˆ ๊ณต์ •์„ ์‹œ๋ฎฌ๋ ˆ์ด์…˜ํ•˜์˜€๋‹ค. ์ด๋ฅผ ์œ„ํ•ด ์ƒ์šฉ ์†Œํ”„ํŠธ์›จ์–ด์ธ COMSOL Multiphysicsยฎ (v6.2)๋ฅผ ์‚ฌ์šฉํ•˜์˜€์œผ๋ฉฐ, ๋„๊ธˆ ์šฉ์•ก ๋‚ด์— ์กด์žฌํ•˜๋Š” Co ์ด์˜จ ๋†๋„์— ๋”ฐ๋ฅธ ๊ตญ๋ถ€์ ์ธ ์ „๋ฅ˜๋ฐ€๋„๋ฅผ ๊ณ„์‚ฐํ•˜๊ธฐ ์œ„ํ•ด ํ™œ์„ฑํ™” ๊ณผ์ „์••๊ณผ ๋†๋„ ๊ณผ์ „์••์„ ๊ณ ๋ คํ•œ 3์ฐจ ์ „๋ฅ˜๋ถ„ํฌ ๋ชจ๋ธ์„ ์ ์šฉํ•˜์˜€๋‹ค.

์‹œ๊ฐ„์— ๋”ฐ๋ฅธ ์ „ํ•ด์งˆ ๋‚ด๋ถ€์˜ ์ด์˜จ ๋†๋„๋Š” ์ด์˜จ์˜ ์œ ๋Ÿ‰ ๋ณ€ํ™”์— ์˜ํ•ด ๊ฒฐ์ •๋œ๋‹ค. ์ด์˜จ ์œ ๋Ÿ‰์— ๊ด€๋ จ๋œ ๋ฐฉ์ •์‹์€ ๋Œ€๋ฅ˜ ๋ฐฉ์ •์‹๊ณผ ํ™•์‚ฐ, ์ผ๋ ‰ํŠธ๋กœ๋งˆ์ด๊ทธ๋ ˆ์ด์…˜ (electromigration)์— ์˜ํ•œ ์ด์˜จ ์ด๋™์„ ๋ฌ˜์‚ฌํ•˜๋Š” Nernst-Planck ๋ฐฉ์ •์‹์— ์˜ํ•ด ๋‹ค์Œ๊ณผ ๊ฐ™์ด ์ •์˜๋œ๋‹ค.

(1)
d C i d t = โˆ’ โˆ‡ โ‹… N โ†’ t = โˆ’ โˆ‡ โ‹… ( โˆ’ z i ฮผ i F C i โˆ‡ ฯ• โˆ’ D i โˆ‡ C i + C i u โ†’ )

์œ„ ์‹ (1)์—์„œ Ci๋Š” ์ด์˜จ์˜ ๋†๋„(mol/m3), zi๋Š” ์ด์˜จ ์ „ํ•˜์ˆ˜, ฮผi๋Š” ์ด์˜จ์˜ ์ด๋™๋„ (sยทmol/kg), F๋Š” ํŽ˜๋Ÿฌ๋ฐ์ด ์ƒ์ˆ˜(96, 485 c/mol), Di๋Š” ์ด์˜จ์˜ ํ™•์‚ฐ๊ณ„์ˆ˜ (m2/s), u โ†’ ๋Š” ์œ ์† ๋ฒกํ„ฐ (m/s)์ด๋‹ค.

์ด๋™๋„์˜ ๊ฒฝ์šฐ ํ™•์‚ฐ๊ณ„์ˆ˜๋ฅผ ์ด์šฉํ•œ Einstein ๊ด€๊ณ„์‹์„ ํ†ตํ•˜์—ฌ ๊ณ„์‚ฐ๋˜์–ด ์ง„๋‹ค.

(2)
ฮผ i = D i R T

์œ„ ์‹ (2)์—์„œ R์€ ๊ธฐ์ฒด ์ƒ์ˆ˜ (8.314 J/molยทK)์ด๋‹ค.

๋„๊ธˆ์ธต์˜ ์„ฑ์žฅ์†๋„๋Š” ์Œ๊ทน ํ‘œ๋ฉด์—์„œ ๋ฐœ์ƒ๋˜๋Š” ๊ธˆ์† ์ด์˜จ์˜ ํ™˜์›์ „๋ฅ˜์™€ ์—ฐ๊ด€๋˜์–ด ๋‹ค์Œ ์‹์„ ๋งŒ์กฑํ•œ๋‹ค.

(3)
v = n โ†’ i l o c ฮฉ z i F

์—ฌ๊ธฐ์„œ n โ†’ ๋Š” ์ „๊ทน์— ์ˆ˜์งํ•œ ๋‹จ์œ„ ๋ฒกํ„ฐ์ด๋ฉฐ, iloc๋Š” ๊ตญ๋ถ€์ ์œผ๋กœ ๋ฐœ์ƒ๋œ ํ™˜์›์ „๋ฅ˜๋ฐ€๋„ (A/m2), ฮฉ๋Š” ๊ธˆ์†์˜ ๋ชฐ๋ถ€ํ”ผ(m3/mol)์ด๋‹ค.

์ด๋•Œ iloc๋Š” ๊ณผ์ „์••์— ๋”ฐ๋ฅธ ๋ฐ˜์‘์ „๋ฅ˜๋ฅผ ๋‚˜ํƒ€๋‚ด๋Š” Butler-Volmer ๋ฐฉ์ •์‹์„ ํ†ตํ•ด ํ‘œํ˜„ ๊ฐ€๋Šฅํ•˜๋‹ค.

(4)
i l o c = i 0 ( exp โก ( a a F ฮท R T ) โˆ’ exp โก ( โˆ’ a c F ฮท R T ) )

i0๋Š” ๊ตํ™˜ ์ „๋ฅ˜๋ฐ€๋„์ด๋ฉฐ, ฮฑ๋Š” ์ „์ด๊ณ„์ˆ˜, ฮท๋Š” ํ™œ์„ฑํ™” ๊ณผ์ „์••์„ ์˜๋ฏธํ•œ๋‹ค. ํ™œ์„ฑํ™” ๊ณผ์ „์••์€ ๋‹ค์Œ ์‹์œผ๋กœ ํ‘œํ˜„๋œ๋‹ค.

(5)
ฮท = ฯ• s โˆ’ ฯ• l โˆ’ E e q

ฯ•s, ฯ•l์€ ๊ฐ๊ฐ ์ „๊ทน๊ณผ ๊ทผ์ ‘ํ•œ ์ „ํ•ด์งˆ์˜ ์ „์œ„๋ฅผ ์˜๋ฏธํ•˜๋ฉฐ, Eeq์€ ํ™˜์›๋ฐ˜์‘์˜ ํ‰ํ˜•์ „์œ„๋ฅผ ์˜๋ฏธํ•œ๋‹ค. ๋˜ํ•œ Eeq๋Š” ์ด์˜จ๋†๋„์˜์กด์„ฑ์„ ๋‚˜ํƒ€๋‚ด๋Š” ์•„๋ž˜ ์‹ (6)๊ณผ ๊ฐ™์ด Nernst ๋ฐฉ์ •์‹์„ ํ†ตํ•ด ๊ณ„์‚ฐ๋  ์ˆ˜ ์žˆ๋‹ค.

(6)
E e q = E e q . r e f + R T z i F ln โก ( C i C i , r e f )

์Œ๊ทน ํ™œ์„ฑํ™” ๊ณผ์ „์••์ด ๋†’์„ ๊ฒฝ์šฐ, ๊ณผ์ „์••์— ๋”ฐ๋ฅธ ๋ฐ˜์‘์ „๋ฅ˜์™€ ํ™œ์„ฑํ™” ๊ณผ์ „์••์„ ๋†๋„ ์˜์กด์  Tafel ๋ฐฉ์ •์‹์„ ํ†ตํ•ด ์‹ (4)๋Š” ๋‹ค์Œ๊ณผ ๊ฐ™์ด ๋‚˜ํƒ€๋‚ผ ์ˆ˜ ์žˆ๋‹ค.

(7)
i l o c = โˆ’ i 0 ( C i C i , r e f ) a exp โก ( โˆ’ a z i F ฮท r e f R T )
(8)
ฮท r e f = ฯ• s โˆ’ ฯ• l โˆ’ E e q . ref

๋˜ํ•œ, ํŠธ๋ Œ์น˜ ํŒจํ„ด ๋‚ด๋ถ€์—์„œ ์ด์˜จ ์†Œ๋ชจ์™€ ํ•จ๊ป˜ ๋Œ€๋ฅ˜์˜ ์˜ํ–ฅ์ด ๋ฏธ์น˜์ง€ ์•Š๋Š” ๋ถ€๋ถ„์˜ ์ „๋ฅ˜๋ฐ€๋„๊ฐ€ ํ™•์‚ฐ์— ์˜ํ•ด ์ง€๋ฐฐ๋œ๋‹ค๊ณ  ๊ฐ€์ •ํ•˜๋ฉด, ๋ฐ˜์‘์ „๋ฅ˜๋ฅผ Fick's laws์„ ํ™œ์šฉํ•˜์—ฌ ๋‹ค์Œ๊ณผ ๊ฐ™์ด ๋‚˜ํƒ€๋‚ผ ์ˆ˜ ์žˆ๋‹ค[27].

(9)
i l o c = โˆ’ z i F D i โ‹… โˆ‡ C i

๊ทธ๋ฆผ 2์— ์œ ์‚ฐ์š”์†Œํ•ด์„์„ ์œ„ํ•ด ๊ตฌ์„ฑํ•œ ์š”์†Œ๋ง๊ณผ ๊ฒฝ๊ณ„์กฐ๊ฑด์„, ํ‘œ 3์—๋Š” ๊ณ„์‚ฐ์— ์‚ฌ์šฉ๋œ ๋„๊ธˆ ์ƒ์ˆ˜ ๋ฐ ๋ชจ๋ธ ์น˜์ˆ˜๋ฅผ ๋‚˜ํƒ€๋‚ด์—ˆ๋‹ค. ์œ ๋™ ๋ฐฉํ–ฅ์€ ๊ทธ๋ฆผ 1์—์„œ ์˜ค๋ฅธ์ชฝ์œผ๋กœ ์„ค์ •ํ•˜์˜€์œผ๋ฉฐ, ์œ ์ฒด์—ญํ•™์  ์ธต๋ฅ˜์˜ ๊ฒฝ๊ณ„์ธต ๋‘๊ป˜๋Š” ์‹œ๋ฃŒ ํ‘œ๋ฉด์—์„œ 0.1 mm ์ง€์  ๋†’์ด๋กœ ๊ฐ€์ •ํ•˜์˜€๋‹ค. ๊ฒฝ๊ณ„์ธต ์ง€์ ์˜ ์œ ์†์€ 0.1 m/sec๊ฐ€ ๋˜๋„๋ก ์„ค์ •ํ•˜์˜€๋‹ค. ๊ทธ๋ฆผ 1์—์„œ ์‹ค์„ ์œผ๋กœ ํ‘œํ˜„๋œ ์Œ๊ทน ํ‘œ๋ฉด์—์„œ์˜ ํ‰๊ท  ์ „๋ฅ˜๋ฐ€๋„๋Š” ๋„๊ธˆ์‹คํ—˜ ์กฐ๊ฑด๊ณผ ๋™์ผํ•˜๊ฒŒ 10, 30, 90 mA/cm2์ด๋ฉฐ, ๋„๊ธˆ์‹œ๊ฐ„ ๋˜ํ•œ ์‹คํ—˜์กฐ๊ฑด๊ณผ ๋™์ผํ•˜๊ฒŒ ๊ณ ๋ คํ•˜์˜€๋‹ค.

3. ๊ฒฐ๊ณผ ๋ฐ ๊ณ ์ฐฐ

์ฃผ Co ๋„๊ธˆ๊ณต์ • ์‹œ ๊ฐ๊ฐ 10, 30, 90 mA/cm2์˜ ์ „๋ฅ˜๋ฐ€๋„๋ฅผ ์ธ๊ฐ€ํ•˜์—ฌ ์ฆ์ฐฉ๋œ Co ๋„๊ธˆ์ธต๊ณผ ๊ธฐํŒ์˜ ๋‹จ๋ฉด์„ ์ฃผ์‚ฌ์ „์žํ˜„๋ฏธ๊ฒฝ์œผ๋กœ ๋ถ„์„ํ•œ ๊ฒฐ๊ณผ๋ฅผ ๊ทธ๋ฆผ 3์— ๋‚˜ํƒ€๋‚ด์—ˆ๋‹ค. ๋ชจ๋“  ์ „๋ฅ˜๋ฐ€๋„ ์กฐ๊ฑด์—์„œ ๊ธฐํŒ์˜ ํ‘œ๋ฉด์„ ์™„์ „ํžˆ ๋ฎ๋Š” ์—ฐ์†์ ์ธ Co ๋„๊ธˆ์ธต์ด ํ˜•์„ฑ๋˜์—ˆ์œผ๋ฉฐ, ์ •์ƒ์ ์œผ๋กœ ํ˜•์„ฑ๋œ ํŒจํ„ด ์ธก๋ฉด์˜ ๊ธฐํŒ-Co ๋„๊ธˆ์ธต ๊ฐ„ ๊ณ„๋ฉด์—์„œ ๋ฐ•๋ฆฌ ๋“ฑ์˜ ๊ฒฐํ•จ์€ ๊ด€์ฐฐ๋˜์ง€ ์•Š์•˜๋‹ค. ๊ทธ๋ฆผ 3์—์„œ, ํŒจํ„ด ์œ„์น˜์— ๋”ฐ๋ฅธ ๋„๊ธˆ์ธต์˜ ๋‘๊ป˜๊ฐ€ ์ „๋ฅ˜ ๋ฐ€๋„์— ์˜์กดํ•จ์„ ๊ด€์ฐฐํ•  ์ˆ˜ ์žˆ๋‹ค. ํŠนํžˆ, ์ „๋ฅ˜๋ฐ€๋„๊ฐ€ ์ฆ๊ฐ€ํ•จ์— ๋”ฐ๋ผ ๋„๊ธˆ์ธต์˜ ํŒจํ„ด ์ƒ๋‹จ๋ถ€์™€ ํ•˜๋‹จ๋ถ€์˜ ๋‘๊ป˜ ์ฐจ์ด๊ฐ€ ๋” ํฌ๊ฒŒ ๋‚˜ํƒ€๋‚ฌ๋‹ค. ๊ณ ๋ฐฐ์œจ SEM ์ด๋ฏธ์ง€๋กœ๋ถ€ํ„ฐ ๊ฐ ์ „๋ฅ˜๋ฐ€๋„ ์กฐ๊ฑด์—์„œ ํ˜•์„ฑ๋œ ๋„๊ธˆ์ธต์˜ ํŒจํ„ด ์ƒ ์œ„์น˜ ๋ณ„ ๋‘๊ป˜๋ฅผ 100 ฮผm ๊ฐ„๊ฒฉ์œผ๋กœ 5๋ฒˆ ์ธก์ •ํ•˜์˜€๊ณ , ๊ทธ ๊ฒฐ๊ณผ๋ฅผ ๊ทธ๋ฆผ 4์™€ ๊ฐ™์ด ํŒจํ„ด ์œ„์น˜-๋‘๊ป˜ ๊ทธ๋ž˜ํ”„๋กœ ํ‘œํ˜„ํ•˜์˜€๋‹ค.

๊ฐ ์ „๋ฅ˜๋ฐ€๋„์—์„œ ๋„๊ธˆ์ธต์˜ ํŒจํ„ด ์ƒ๋‹จ๋ถ€ (๊ทธ๋ฆผ 4(a)์—์„œ 1 ์œ„์น˜) ๋‘๊ป˜์— ๋Œ€ํ•œ ํ•˜๋‹จ๋ถ€ ์ขŒ์šฐ ๋ชจ์„œ๋ฆฌ (๊ทธ๋ฆผ 4(a)์˜ 3&7 ์œ„์น˜) ๋‘๊ป˜์˜ ๋น„์œจ์„ ๋น„๊ตํ•œ ๊ฒฐ๊ณผ, ์ „๋ฅ˜๋ฐ€๋„ 10 mA/cm2์—์„œ๋Š” ์•ฝ 75%, 30 mA/cm2์—์„œ๋Š” ์•ฝ 50%, 90 mA/cm2์—์„œ๋Š” ์•ฝ 20%๋กœ, ์ „๋ฅ˜๋ฐ€๋„๊ฐ€ ์ฆ๊ฐ€ํ• ์ˆ˜๋ก ์ƒ๋‹จ๋ถ€์™€ ํ•˜๋‹จ๋ถ€ ๋ชจ์„œ๋ฆฌ ๊ฐ„ ๋‘๊ป˜ ์ฐจ์ด๊ฐ€ ์ฆ๊ฐ€ํ•˜์˜€๋‹ค.

๋„๊ธˆ์ธต์˜ ์ „๋ฅ˜ ๋ฐ€๋„์— ๋”ฐ๋ฅธ ๊ตญ๋ถ€์ ์ธ ๋‘๊ป˜ ์ฐจ์ด๋ฅผ ์œ ๋ฐœํ•˜๋Š” ์ธ์ž๋ฅผ ๊ทœ๋ช…ํ•˜๊ธฐ ์œ„ํ•ด, ๊ฐ ์ „๋ฅ˜๋ฐ€๋„ ์กฐ๊ฑด์— ๋Œ€ํ•œ ๋„๊ธˆ์ธต์˜ ํŒจํ„ด ์ƒ๋‹จ๋ถ€ (๊ทธ๋ฆผ 4(a)์˜ 1 ์œ„์น˜) ํ‘œ๋ฉด์˜ ํ˜•์ƒ์„ ์ฃผ์‚ฌ์ „์žํ˜„๋ฏธ๊ฒฝ์„ ์ด์šฉํ•˜์—ฌ ๊ด€์ฐฐํ•˜์˜€๊ณ , ๊ทธ ๊ฒฐ๊ณผ๋ฅผ ๊ทธ๋ฆผ 5์— ๋‚˜ํƒ€๋‚ด์—ˆ๋‹ค.

10 mA/cm2์˜ ๋‚ฎ์€ ์ „๋ฅ˜๋ฐ€๋„ ์กฐ๊ฑด์—์„œ๋Š” ์ˆ˜ ฮผm ํฌ๊ธฐ์˜ ๊ฐ์ด ์ง€๊ณ  ์—ฐ์‹ ๋œ ์นจ์ƒ (acicular)์˜ ๊ฒฐ์ •๋“ค์ด ๊ด€์ฐฐ๋˜๊ณ , 30 mA/cm2์—์„œ๋„ ์—ญ์‹œ ๋‚ ์นด๋กญ๊ฒŒ ๊ฐ์ด ์กŒ์œผ๋‚˜ 10 mA/cm2์˜ ๊ฒฐ์ •๋“ค์— ๋น„ํ•˜๋ฉด ์—ฐ์‹ ๋˜์ง€ ์•Š์€ ์ž‘์€ ๊ฒฐ์ •๋“ค์„ ํ™•์ธํ•  ์ˆ˜ ์žˆ๋‹ค. ๋ฐ˜๋ฉด, 90 mA/cm2์—์„œ๋Š” ๊ฐ ์ง€์ง€ ์•Š๊ณ  ๋ญ‰ํˆญํ•œ ๊ฒฐ์ •๋ฆฝ๋“ค์ด ํด๋Ÿฌ์Šคํ„ฐ ํ˜•ํƒœ๋กœ ๋ญ‰์ณ ์žˆ๋Š” ๋ชจ์Šต์„ ๊ด€์ฐฐํ•  ์ˆ˜ ์žˆ๋‹ค. ์ด๋Ÿฌํ•œ ์ „๋ฅ˜๋ฐ€๋„ ์ฆ๊ฐ€์— ๋”ฐ๋ฅธ ์ˆ˜์ง€์ƒ์—์„œ ํด๋Ÿฌ์Šคํ„ฐ ํ˜•ํƒœ๋กœ์˜ Co ํ‘œ๋ฉด ํ˜•์ƒ์˜ ๋ณ€ํ™”๋Š” ์ด์ „ ์—ฐ๊ตฌ[31,32]์—์„œ๋„ ๋ณด๊ณ ๋œ ๋ฐ” ์žˆ๋Š”๋ฐ, ์ด๋Š” ์ „๋ฅ˜๋ฐ€๋„ ์ฆ๊ฐ€์— ๋”ฐ๋ผ ๊ธฐํŒ ๋˜๋Š” ๋„๊ธˆ์ธต ํ‘œ๋ฉด ์˜์—ญ์—์„œ์˜ ๊ณผ์ „์••์ด ์ฆ๊ฐ€ํ•˜๊ณ , ์ด๋กœ ์˜ํ•ด ๋„๊ธˆ์ธต ๊ฒฐ์ •๋ฆฝ์˜ ํ˜•์„ฑ ๋ฐ ์„ฑ์žฅ ๊ฑฐ๋™์ด ๋ณ€ํ™”ํ•˜๋Š” ๊ฒƒ์„ ๋ณด์—ฌ์ค€๋‹ค.

๊ทธ๋ฆผ 6์— X์„  ํšŒ์ ˆ ๋ถ„์„๊ธฐ์ˆ ์„ ์ด์šฉํ•˜์—ฌ ์ธก์ •๋œ ๊ฐ ๋„๊ธˆ์ธต์˜ ๊ด‘์—ญ์ ์ธ ๊ฒฐ์ • ํŠน์„ฑ์„ ๋‚˜ํƒ€๋‚ด์—ˆ๋‹ค. ์ด ๊ฒฐ๊ณผ๋ฅผ ํ†ตํ•ด, ์„ธ ์ „๋ฅ˜๋ฐ€๋„ ์กฐ๊ฑด์—์„œ ๋ชจ๋‘ HCP ๊ฒฐ์ •๊ตฌ์กฐ๋ฅผ ๊ฐ€์ง„ Co ๋„๊ธˆ์ธต์ด ํ˜•์„ฑ๋˜์—ˆ์œผ๋ฉฐ, FCC ๊ฒฐ์ •๊ตฌ์กฐ์— ์˜ํ•œ ํšŒ์ ˆ ๊ฐ•๋„(intensity)๋Š” ๋ฏธ๋ฏธํ•˜์˜€๋‹ค. ์ „๋ฅ˜๋ฐ€๋„ 10 mA/cm2์—์„œ ์ฆ์ฐฉ๋œ ๋„๊ธˆ์ธต์€ (1 1 -1 0) ๋ฉด์ด ๋„๊ธˆ์ธต ํ‘œ๋ฉด์— ์ˆ˜์ง์ธ ๋ฐฉํ–ฅ ๋˜๋Š” ๋„๊ธˆ์ธต ์„ฑ์žฅ๋ฐฉํ–ฅ์ธ ND์— ์ˆ˜์ง์ธ <1 1 -1 0> // ND ์„ฑ๋ถ„๊ณผ <1 0 -1 0> // ND ์„ฑ๋ถ„์˜ ํšŒ์ ˆ ๊ฐ•๋„๊ฐ€ ํฌ๋ฉฐ, ๊ทธ ์™ธ <1 1 -2 0> // ND์™€ <0 0 0 2> // ND ์„ฑ๋ถ„์˜ ๊ฐ•๋„๊ฐ€ ์ˆœ์„œ๋Œ€๋กœ ๋†’์•˜๋‹ค. ๋ฐ˜๋ฉด, 90 mA/cm2 ๋„๊ธˆ์ธต์€ <1 0 -1 0> // ND์ด ๊ฐ€์žฅ ๊ฐ•๋„๊ฐ€ ๋†’์€ ์„ฑ๋ถ„์ด๊ณ , <1 0 -1 1> // ND ๋ฐ <1 1 -2 0> // ND ์„ฑ๋ถ„ ์—ญ์‹œ ๊ฐ•๋„๊ฐ€ ๋†’์œผ๋‚˜, <0 0 0 2> // ND ์„ฑ๋ถ„์€, 10 mA/cm2 ๋„๊ธˆ์ธต๊ณผ ๋‹ฌ๋ฆฌ, ๋ฏธ์•ฝํ•˜์˜€๋‹ค. ํ•œํŽธ, 30 mA/cm2 ๋„๊ธˆ์ธต์—์„œ๋Š” <1 1 -2 0> // ND ์„ฑ๋ถ„์˜ ๊ฐ•๋„๊ฐ€ ๋†’์•˜๊ณ , 10 ๋ฐ 90 mA/cm2 ๋„๊ธˆ์ธต์—์„œ ์ฃผ์„ฑ๋ถ„์œผ๋กœ ๋‚˜ํƒ€๋‚œ <1 0 -1 0> // ND์™€ <1 0 -1 1> // ND ์„ฑ๋ถ„์˜ ๊ฐ•๋„๋Š” ์ƒ๋Œ€์ ์œผ๋กœ ๋‚ฎ์•˜๋‹ค. ์ด๋Ÿฌํ•œ, ์ „๋ฅ˜๋ฐ€๋„์— ๋”ฐ๋ฅธ ๋„๊ธˆ์ธต์˜ ๊ด‘์—ญ ๊ฒฐ์ •์„ฑ์˜ ์ฐจ์ด๋Š”, ๊ทธ๋ฆผ 5์—์„œ ๊ด€์ฐฐ๋˜๋Š” ํ‘œ๋ฉด ํ˜•์ƒ์˜ ์ฐจ์ด์™€ ๊ฐ™์ด, ์ „๋ฅ˜๋ฐ€๋„์— ๋”ฐ๋ผ ๋„๊ธˆ์ธต ๊ฒฐ์ •๋ฆฝ ํ˜•์„ฑ ๊ฑฐ๋™์ด ์ƒ์ดํ•จ์„ ์˜๋ฏธํ•œ๋‹ค.

์ „๋ฅ˜๋ฐ€๋„์— ๋”ฐ๋ฅธ ํŒจํ„ด ์œ„์น˜ ๋ณ„ ๋„๊ธˆ์ธต์˜ ๊ฒฐ์ •๋ฆฝ ํฌ๊ธฐ ๋ฐ ํ˜•์ƒ๊ณผ ๊ตญ๋ถ€์ ์ธ ์ง‘ํ•ฉ์กฐ์ง์˜ ์ฐจ์ด๋ฅผ ๋ถ„์„ํ•˜๊ธฐ ์œ„ํ•ด, EBSD ๊ธฐ์ˆ ์„ ์ด์šฉํ•œ ๊ฒฐ์ •๋ฐฉ์œ„ ์ง€๋„ (crystallographic orientation map)๋ฅผ ์ธก์ •ํ•˜์˜€๊ณ , ๊ทธ ๊ฒฐ๊ณผ๋ฅผ ๊ทธ๋ฆผ 7์— ๋‚˜ํƒ€๋‚ด์—ˆ๋‹ค.

์ธก์ •๋œ ๋„๊ธˆ์ธต์˜ ํŒจํ„ด ์ƒ ์œ„์น˜๋Š” ํŒจํ„ด ์ƒ๋‹จ๋ถ€์™€ ํ•˜๋‹จ๋ถ€ ๋ชจ์„œ๋ฆฌ ๊ทผ๋ฐฉ์œผ๋กœ ๊ทธ๋ฆผ 4(a)์˜ 1 ๋ฐ 4 ์œ„์น˜์— ํ•ด๋‹นํ•œ๋‹ค. ๊ฒฐ์ •๋ฐฉ์œ„ ์ง€๋„ ์ƒ์˜ ๊ฐ ์ƒ‰์€ ๋„๊ธˆ์ธต ํ‘œ๋ฉด์— ์ˆ˜์ง์ธ ๋ฐฉํ–ฅ ๋˜๋Š” ๋„๊ธˆ์ธต ์„ฑ์žฅ๋ฐฉํ–ฅ์ธ ND์— ํ‰ํ–‰ํ•œ ๊ฒฐ์ •๋ฐฉ์œ„๋ฅผ ๋‚˜ํƒ€๋‚ด๋Š” ๋ฐ, ์˜ˆ๋ฅผ ๋“ค์–ด, ๋นจ๊ฐ„์ƒ‰, ํŒŒ๋ž€์ƒ‰, ์ดˆ๋ก์ƒ‰์€ ๊ฐ๊ฐ <0 0 0 1>, <1 0 -1 0>, <2 -1 -1 0> ๊ฒฐ์ •๋ฐฉ์œ„๋ฅผ ํ‘œํ˜„ํ•œ๋‹ค. ์ „๋ฅ˜๋ฐ€๋„ 10 mA/cm2์—์„œ ์ฆ์ฐฉ๋œ Co ๋„๊ธˆ์ธต์˜ ํŒจํ„ด ์ƒ๋‹จ๋ถ€๋Š” ๋„๊ธˆ ์ดˆ๊ธฐ์— ND ๋ฐฉํ–ฅ์œผ๋กœ ๊ธธ๊ฒŒ ์„ฑ์žฅํ•œ ์กฐ๋Œ€ํ•œ ์ˆ˜์ง€์ƒ ๊ฒฐ์ •๋ฆฝ๋“ค์ด, ๋„๊ธˆ ํ›„๊ธฐ์—๋Š” ๋„๊ธˆ ์ดˆ๊ธฐ๋ถ€ํ„ฐ ์„ฑ์žฅํ•ด ์˜ค๊ณ  ์žˆ๋Š” ํฐ ์ˆ˜์ง€์ƒ ๊ฒฐ์ •๋ฆฝ๋“ค๊ณผ ํ•จ๊ป˜ ๋“ฑ์ถ•์ƒ์˜ ๋ฏธ์„ธํ•œ ๊ฒฐ์ •๋ฆฝ๋“ค์ด ๊ณต์กดํ•˜๋Š” ๊ฒฐ์ •๋ฆฝ ๊ตฌ์กฐ๋กœ ๊ตฌ์„ฑ๋˜๋ฉฐ, ํŒจํ„ด ํ•˜๋‹จ๋ถ€์—์„œ๋„ ์ƒ๋‹จ๋ถ€์™€ ์œ ์‚ฌํ•œ ๊ฒฐ์ •๋ฆฝ ๊ตฌ์กฐ๊ฐ€ ๊ด€์ฐฐ๋œ๋‹ค. 90 mA/cm2 ์กฐ๊ฑด์˜ ๋„๊ธˆ์ธต์—์„œ๋Š”, ํŒจํ„ด ์ƒ๋‹จ๋ถ€์—์„œ ๋„๊ธˆ ์ดˆ๊ธฐ์—๋Š” ์—ฐ์‹ ๋œ ๋ฏธ์„ธํ•œ ๊ฒฐ์ •๋ฆฝ๋“ค์ด ์„ฑ์žฅํ•˜๋‹ค๊ฐ€ ๋„๊ธˆ ํ›„๋ฐ˜๊ธฐ์—๋Š” ์ƒ๋Œ€์ ์œผ๋กœ ํฌ๊ธฐ๊ฐ€ ํฐ ๋“ฑ์ถ•์ƒ์— ๊ฐ€๊นŒ์šด ๊ฒฐ์ •๋ฆฝ๋“ค์ด ์„ฑ์žฅํ•œ ๋šœ๋ ทํ•œ 2์ธต ๊ตฌ์กฐ๊ฐ€ ๋ฐœ๋‹ฌํ•˜๋Š” ๋ฐ˜๋ฉด, ํŒจํ„ด ํ•˜๋‹จ๋ถ€์—์„œ๋Š” ์ƒ๋‹จ๋ถ€์˜ ๋„๊ธˆ ์ดˆ๊ธฐ ๊ฒฐ์ •๋ฆฝ ๊ตฌ์กฐ์™€ ์œ ์‚ฌํ•œ ๊ฒฐ์ •๋ฆฝ๋“ค์ด ๊ด€์ฐฐ๋œ๋‹ค. 30 mA/cm2์˜ ์ „๋ฅ˜๋ฐ€๋„ ์กฐ๊ฑด์—์„œ๋Š”, ํŒจํ„ด ์ƒ๋‹จ๋ถ€ ๋ฐ ํ•˜๋‹จ๋ถ€ ๊ฒฐ์ •๋ฆฝ ๊ตฌ์กฐ๊ฐ€ 10 ๋ฐ 90 mA/cm2์˜ ์ „๋ฅ˜๋ฐ€๋„์—์„œ ๊ด€์ฐฐ๋˜๋Š” ๋‘ ๊ฒฐ์ •๋ฆฝ ๊ตฌ์กฐ๊ฐ€ ํ˜ผ์žฌ๋œ ๋ชจ์Šต์„ ๋ณด์—ฌ์ค€๋‹ค.

๊ทธ๋ฆผ 8์€ ์ธก์ •๋œ ๊ฒฐ์ •๋ฐฉ์œ„ ์ง€๋„๋กœ๋ถ€ํ„ฐ ๊ณ„์‚ฐ๋œ ๊ฐ ๋„๊ธˆ์ธต์˜ ์œ„์น˜ ๋ณ„ ๊ฒฐ์ •๋ฆฝ ํฌ๊ธฐ ์ง€๋„ ๋ฐ ๋ถ„ํฌ๋ฅผ ๋ณด์—ฌ์ค€๋‹ค. ์„ธ Co ๋„๊ธˆ์ธต์˜ ๊ฒฐ์ •๋ฆฝ ํฌ๊ธฐ๋Š” ๋Œ€์ฒด๋กœ ์•ฝ 2 ฮผm์˜€์œผ๋ฉฐ, ํŒจํ„ด ์ƒ๋‹จ๋ถ€์— ๋น„ํ•ด ํ•˜๋‹จ๋ถ€์—์„œ ํฌ๊ธฐ๊ฐ€ ๋‹ค์†Œ ์ž‘์€ ๊ฒฝํ–ฅ์ด ์žˆ์—ˆ๋‹ค. 10 ๋ฐ 30 mA/cm2์˜ ์ „๋ฅ˜๋ฐ€๋„์—์„œ ์ฆ์ฐฉ๋œ ๋„๊ธˆ์ธต์— ๋น„ํ•ด, 90 mA/cm2 ๋„๊ธˆ์ธต์—์„œ ํŒจํ„ด ์ƒ๋‹จ๋ถ€-ํ•˜๋‹จ๋ถ€ ๊ฐ„ ๊ฒฐ์ •๋ฆฝ ํฌ๊ธฐ์˜ ์ฐจ์ด๊ฐ€ ์ƒ๋Œ€์ ์œผ๋กœ ์ปธ๋Š”๋ฐ, ์ด๋Š” 10 ๋ฐ 30 mA/cm2์˜ ์ƒ๋Œ€์ ์œผ๋กœ ์ž‘์€ ์ „๋ฅ˜๋ฐ€๋„์—์„œ๋Š” ๋Œ€์ฒด๋กœ ํ•˜๋‚˜์˜ ๊ฒฐ์ •๋ฆฝ ์„ฑ์žฅ ๋ฉ”์ปค๋‹ˆ์ฆ˜์œผ๋กœ ๋„๊ธˆ์ธต ๊ฒฐ์ •๋ฆฝ์ด ์„ฑ์žฅํ•˜๋Š” ๋ฐ˜๋ฉด, 90 mA/cm2์˜ ๋†’์€ ์ „๋ฅ˜๋ฐ€๋„์—์„œ๋Š” ๋„๊ธˆ ์ดˆ๊ธฐ-ํ›„๊ธฐ ๋ฐ ํŒจํ„ด ์ƒ๋‹จ๋ถ€-ํ•˜๋‹จ๋ถ€ ๊ฐ„ ์ƒ์ดํ•œ ๊ฒฐ์ •๋ฆฝ ์„ฑ์žฅ ๋ฉ”์ปค๋‹ˆ์ฆ˜์„ ํ†ตํ•ด ๋„๊ธˆ์ธต์ด ํ˜•์„ฑ๋˜์—ˆ์Œ์„ ์˜๋ฏธํ•œ๋‹ค.

๊ทธ๋ฆผ 7์˜ ๊ฒฐ์ •๋ฐฉ์œ„ ์ง€๋„๋กœ๋ถ€ํ„ฐ ์ถ”์ถœํ•œ ์—ญ๊ทน์ ๋„ (inverse pole figure)๋ฅผ ํ†ตํ•ด ์ „๋ฅ˜๋ฐ€๋„ ๋ณ„๋กœ ํŒจํ„ด ์ƒ๋‹จ๋ถ€ ๋ฐ ํ•˜๋‹จ๋ถ€์˜ ๊ตญ๋ถ€์  ์ง‘ํ•ฉ์กฐ์ง์˜ ์ฐจ์ด๋ฅผ ๋ถ„์„ํ•˜์—ฌ ๊ทธ๋ฆผ 9์—์„œ ์ •๋ฆฌํ•˜์˜€๋‹ค.

10 mA/cm2์˜ ์ „๋ฅ˜๋ฐ€๋„ ์‹œ, ํŒจํ„ด ์ƒ๋‹จ๋ถ€์— <1 0 -1 0>์—์„œ <2 -1 -1 0>๊นŒ์ง€ ๊ฑธ์ณ ๋ถ„ํฌํ•˜๋Š” ๊ฒฐ์ •๋ฐฉ์œ„๊ฐ€ ND์— ํ‰ํ–‰ํ•œ ์ง‘ํ•ฉ์กฐ์ง์ด ๋ฐœ๋‹ฌํ•˜๋ฉฐ, ํ•˜๋‹จ๋ถ€์—๋„ ์„ฑ๋ถ„ ๋ฐ ๊ฐ•๋„๊ฐ€ ์œ ์‚ฌํ•œ ์ง‘ํ•ฉ์กฐ์ง์ด ๊ด€์ฐฐ๋œ๋‹ค. 30 mA/cm2 ์กฐ๊ฑด์—์„œ๋Š”, ํŒจํ„ด ์ƒ๋‹จ๋ถ€-ํ•˜๋‹จ๋ถ€ ๋ชจ๋‘ ์ฃผ์„ฑ๋ถ„์ด <2 -1 -1 0> // ND์ด๊ณ  ๋ถ€์„ฑ๋ถ„์ด <1 0 -1 0> // ND์ธ ์ง‘ํ•ฉ์กฐ์ง์ด ๋ฐœ๋‹ฌํ•œ๋‹ค. ๋ฐ˜๋ฉด, 90 mA/cm2์˜ ์ „๋ฅ˜๋ฐ€๋„์—์„œ ์ฆ์ฐฉ๋œ ๋„๊ธˆ์ธต์—์„œ๋Š” ํŒจํ„ด ์ƒ๋‹จ๋ถ€-ํ•˜๋‹จ๋ถ€ ๊ฐ„ ์ง‘ํ•ฉ์กฐ์ง์ด ์ƒ์ดํ•˜๋ฉฐ, ํŠนํžˆ ํ•˜๋‹จ๋ถ€์— <2 -1 -1 0> // ND ์ง‘ํ•ฉ์กฐ์ง์ด ๊ฐ•ํ•˜๊ฒŒ ๋ฐœ๋‹ฌํ•˜๋Š” ๊ฒƒ์„ ์•Œ ์ˆ˜ ์žˆ๋‹ค.

ํŒจํ„ด ์œ„์น˜ ๋ณ„ ์ง‘ํ•ฉ์กฐ์ง ์œ ์˜์ฐจ์™€ ํ•จ๊ป˜, ์ „๋ฅ˜๋ฐ€๋„ ๋ณ„ ๋„๊ธˆ ์ดˆ๊ธฐ์™€ ํ›„๊ธฐ์— ๋ฐœ๋‹ฌํ•˜๋Š” ์ง‘ํ•ฉ์กฐ์ง์˜ ์ฐจ์ด๋ฅผ ํ™•์ธํ•˜๊ธฐ ์œ„ํ•ด, ํŒจํ„ด ์ƒ๋‹จ๋ถ€์—์„œ ๋„๊ธˆ ์ดˆ๊ธฐ์— ์„ฑ์žฅํ•œ ํ•˜๋ถ€ ํ‘œ๋ฉด์—์„œ ๋‘๊ป˜ 20 ฮผm ์ง€์ ๊นŒ์ง€์˜ ์˜์—ญ๊ณผ ๋„๊ธˆ ํ›„๊ธฐ์— ์ฆ์ฐฉ๋œ ๋‘๊ป˜ 20 ฮผm ์ง€์ ์—์„œ ์ƒ๋ถ€ ํ‘œ๋ฉด๊นŒ์ง€์˜ ์˜์—ญ์—์„œ์˜ ์ง‘ํ•ฉ์กฐ์ง์„ ๊ทธ๋ฆผ 10๊ณผ ๊ฐ™์ด ๋น„๊ตํ•˜์˜€๋‹ค.

๊ทธ ๊ฒฐ๊ณผ, ์ „๋ฅ˜๋ฐ€๋„๊ฐ€ 10 ๋ฐ 30 mA/cm2 ์‹œ ์ฆ์ฐฉ๋œ ๋„๊ธˆ์ธต์˜ ํŒจํ„ด ์ƒ๋‹จ๋ถ€์—์„œ๋Š” ๋„๊ธˆ ์ดˆ๊ธฐ-ํ›„๊ธฐ ๊ฐ„ ์ง‘ํ•ฉ์กฐ์ง์˜ ์ฐจ์ด๊ฐ€ ํฌ์ง€ ์•Š์œผ๋‚˜, 90 mA/cm2 ๋„๊ธˆ์ธต์—์„œ๋Š” ๋šœ๋ ทํ•œ ๋„๊ธˆ ์ดˆ๊ธฐ-ํ›„๊ธฐ ๊ฐ„ ์ง‘ํ•ฉ์กฐ์ง ์ฐจ์ด๋ฅผ ๊ด€์ฐฐํ•  ์ˆ˜ ์žˆ๋‹ค.

๊ทธ๋ฆผ 7~10์„ ํ†ตํ•ด ํ™•์ธํ•œ ์ „๋ฅ˜๋ฐ€๋„ ๋ณ„ ๊ฒฐ์ •๋ฆฝ ํฌ๊ธฐ ๋ฐ ํ˜•์ƒ๊ณผ ์ง‘ํ•ฉ์กฐ์ง์˜ ์ฐจ์ด๋ฅผ ํ†ตํ•ด, 1์ฐจ์ ์œผ๋กœ ์ „๋ฅ˜๋ฐ€๋„์— ์˜ํ•ด ๊ฒฐ์ •๋˜๋Š” ๊ธฐํŒ ๋˜๋Š” ๋„๊ธˆ์ธต ํ‘œ๋ฉด (์ฆ‰, ์ „๊ทน)๊ณผ ๋„๊ธˆ ์šฉ์•ก ๊ฐ„์— ์ธ๊ฐ€๋˜๋Š” ๊ณผ์ „์••์˜ ํฌ๊ธฐ์— ๋”ฐ๋ฅธ ๊ฒฐ์ •๋ฆฝ ์„ฑ์žฅ ๋ฉ”์ปค๋‹ˆ์ฆ˜์„ ์ถ”์ •ํ•ด ๋ณผ ์ˆ˜ ์žˆ๋‹ค. 10 mA/cm2์™€ ๊ฐ™์ด ์ „๋ฅ˜๋ฐ€๋„๊ฐ€ ์ž‘์„ ๊ฒฝ์šฐ, Co ์ด์˜จ์˜ ํ™˜์› ๋ฐ˜์‘์˜ ์†๋„๊ฐ€ ์ž‘์•„ ๋„๊ธˆ์ธต ํ˜•์„ฑ์ด ํ•ต์ƒ์„ฑ๊ณผ ํ•จ๊ป˜ <1 0 -1 0>์—์„œ <2 -1 -1 0>์— ๊ฑธ์นœ ๊ฒฐ์ •๋ฐฉ์œ„๊ฐ€ ND์— ํ‰ํ–‰ํ•œ ์ง‘ํ•ฉ์กฐ์ง์„ ๊ฐ€์ง€๋Š” ํŠน์ • ๊ฒฐ์ •๋ฆฝ๋“ค์˜ ์šฐ์„ ์ ์ธ ์„ฑ์žฅ์ด ๋™๋ฐ˜ํ•˜์—ฌ ๋ฏธ์„ธํ•œ ๊ฒฐ์ •๋ฆฝ๋“ค๊ณผ ์กฐ๋Œ€ํ•œ ์ˆ˜์ง€์ƒ ๊ฒฐ์ •๋ฆฝ๋“ค์ด ๊ณต์กดํ•˜๋Š” ๊ฒƒ์œผ๋กœ ํŒ๋‹จํ•  ์ˆ˜ ์žˆ๋‹ค. ์ด๋Š” ๊ทธ๋ฆผ 8์˜ ๊ฒฐ์ •๋ฆฝ ํฌ๊ธฐ โ€“ ๋ฉด์  ๋ถ„์œจ ๋ถ„ํฌ ๊ทธ๋ž˜ํ”„์—์„œ ๊ฒฐ์ •๋ฆฝ ํฌ๊ธฐ๊ฐ€ ๋„“์€ ๋ฒ”์œ„๋กœ ๋ถ„ํฌํ•˜๋Š” ๊ฒƒ์œผ๋กœ ์œ ์ถ”ํ•  ์ˆ˜ ์žˆ๋‹ค. ๋ฐ˜๋ฉด, ์ „๋ฅ˜๋ฐ€๋„๊ฐ€ 90 mA/cm2๋กœ ํด ๊ฒฝ์šฐ, ๋„๊ธˆ ์†๋„์˜ ์ฆ๊ฐ€๋กœ ์ธํ•ด ํŠน์ •ํ•œ ๊ฒฐ์ •๋ฆฝ๋“ค์˜ ์„ฑ์žฅ๋ณด๋‹ค๋Š” ๋‹ค์ˆ˜์˜ <2 -1 -1 0> // ND ์ง‘ํ•ฉ์กฐ์ง์„ ๊ฐ€์ง€๋Š” ํ•ต๋“ค์˜ ์ƒ์„ฑ๊ณผ ์ด๋“ค์˜ ๊ฒฝ์Ÿ ์„ฑ์žฅ์œผ๋กœ ์ธํ•ด ์ƒ๋Œ€์ ์œผ๋กœ ๋” ๋ฏธ์„ธํ•œ ๊ฒฐ์ •๋ฆฝ ๊ตฌ์กฐ๋ฅผ ํ˜•์„ฑํ•˜๊ฒŒ ๋˜๋Š” ๊ฒƒ์œผ๋กœ ์ถ”์ •ํ•  ์ˆ˜ ์žˆ๋‹ค.

ํ•œํŽธ, ์ „๋ฅ˜๋ฐ€๋„๊ฐ€ 90 mA/cm2๋กœ ํด ๋•Œ ํŒจํ„ด ์ƒ๋‹จ๋ถ€์—์„œ ๋„๊ธˆ ์ดˆ๊ธฐ์— ์ฆ์ฐฉ๋œ Co ๋„๊ธˆ์ธต๊ณผ ๋„๊ธˆ ํ›„๊ธฐ ๋„๊ธˆ์ธต ๊ฐ„ ์ƒ์ดํ•œ ์ง‘ํ•ฉ์กฐ์ง์ด ๋ฐœ๋‹ฌํ•˜๋Š” ๋ชจ์Šต (Fig 10(c))์€ ๋„๊ธˆ ์ค‘ ์ฆ์ฐฉ ๊ฑฐ๋™์˜ ๋ณ€ํ™”๊ฐ€ ๋ฐœ์ƒํ–ˆ์Œ์„ ์˜๋ฏธํ•œ๋‹ค. Co ๋„๊ธˆ ์‹œ ์Œ๊ทน์—์„œ๋Š” Co ์ด์˜จ์˜ ํ™˜์›์— ์˜ํ•œ ๋„๊ธˆ์ธต ํ˜•์„ฑ๊ณผ ํ•จ๊ป˜ ์ˆ˜์†Œ ์ด์˜จ์˜ ํ™˜์›์— ์˜ํ•œ ์ˆ˜์†Œ ๋ฒ„๋ธ”์˜ ๋ฐœ์ƒ์ด ๋™์‹œ์— ์ผ์–ด๋‚˜๋Š” ๋ฐ, ์ด ๋•Œ ์ˆ˜์†Œ ์ด์˜จ์˜ ํ™˜์› ์†๋„๊ฐ€ Co ์ด์˜จ์˜ ํ™˜์› ์†๋„๋ณด๋‹ค ๋” ๋น ๋ฅด๋‹ค๊ณ  ์•Œ๋ ค์ ธ ์žˆ๋‹ค[33]. ๋ณธ ์—ฐ๊ตฌ์—์„œ 10 mA/cm2์˜ ๋‚ฎ์€ ์ „๋ฅ˜๋ฐ€๋„์—์„œ๋Š” ์ˆ˜์†Œ ๋ฐœ์ƒ ๋ฐ ๋„๊ธˆ์ธต ํ˜•์„ฑ์˜ ์†๋„๊ฐ€ ์ž‘์•„ ๋„๊ธˆ ์ค‘ ์ˆ˜์†Œ ๋ฐœ์ƒ์ด ๋„๊ธˆ์ธต ํ˜•์„ฑ์— ๋ฏธ์น˜๋Š” ์˜ํ–ฅ๋ ฅ์ด ์ƒ๋Œ€์ ์œผ๋กœ ์ž‘์•„ ๋„๊ธˆ ์‹œ๊ฐ„์— ๋”ฐ๋ฅธ ๋ฏธ์„ธ์กฐ์ง ๋ฐ ์ง‘ํ•ฉ์กฐ์ง์ด ๋Œ€์ฒด๋กœ ๊ท ์ผํ•˜๊ฒŒ ๋ฐœ๋‹ฌํ•˜๋Š” ๋ฐ˜๋ฉด, ์ˆ˜์†Œ ๋ฐœ์ƒ๊ณผ ๋„๊ธˆ์ธต ํ˜•์„ฑ์ด ๊ธ‰๊ฒฉํ•˜๊ฒŒ ์ผ์–ด๋‚˜๋Š” 90 mA/cm2์—์„œ๋Š” ๋„๊ธˆ ์ดˆ๊ธฐ ์ˆ˜์†Œ ๋ฐœ์ƒ์˜ ์˜ํ–ฅ์ด ์ปค ์—ด์—ญํ•™์  ์•ˆ์ • ์ƒํƒœ์—์„œ ๋ฒ—์–ด๋‚œ ๋„๊ธˆ์ธต, ์ฆ‰ ํ‘œ๋ฉด์—๋„ˆ์ง€๊ฐ€ ์ƒ๋Œ€์ ์œผ๋กœ ํฐ <2 -1 -1 0> // ND ์ง‘ํ•ฉ์กฐ์ง์„ ๊ฐ€์ง€๋Š” ๋„๊ธˆ์ธต์ด ์ฃผ๋„์ ์œผ๋กœ ํ˜•์„ฑ๋˜๊ณ , ์‹œ๊ฐ„์ด ์ง€๋‚จ์— ๋”ฐ๋ผ ์ˆ˜์†Œ ๋ฐœ์ƒ๊ณผ ๋„๊ธˆ์ธต ํ˜•์„ฑ ๊ฐ„์˜ ๊ท ํ˜•์ด ์ด๋ฃจ์–ด์ ธ ์ƒ๋Œ€์ ์œผ๋กœ ํ‘œ๋ฉด์—๋„ˆ์ง€๊ฐ€ ์ž‘์€ <1 0 -1 0> // ND ์ง‘ํ•ฉ์กฐ์ง์ด ๋‹ค์†Œ ์šฐ์„ธํ•˜๊ฒŒ ๋ฐœ๋‹ฌํ•˜๋Š” ๊ฒƒ์œผ๋กœ ์ถ”์ •ํ•œ๋‹ค. ๊ณผ๊ฑฐ Co ๋„๊ธˆ์ธต์˜ ์ง‘ํ•ฉ์กฐ์ง์— ๋Œ€ํ•œ ์—ฐ๊ตฌ๋“ค์€ ๋Œ€๋ถ€๋ถ„ X์„  ํšŒ์ ˆ ๋ฐฉ๋ฒ•์„ ์ด์šฉํ•˜์—ฌ ์ธก์ •๋œ ๋„๊ธˆ์ธต ์„ฑ์žฅ ๋ฐฉํ–ฅ์— ์ˆ˜์งํ•œ ๋ฉด์˜ ์ •๋ณด์— ์˜์กดํ•˜๊ณ  ์žˆ์–ด ๋‘๊ป˜ ๋ฐฉํ–ฅ์œผ๋กœ์˜ ์ง‘ํ•ฉ์กฐ์ง ๋ณ€ํ™”๋ฅผ ๋ณด๊ณ ํ•œ ์—ฐ๊ตฌ๋Š” ๋ฏธ๋ฏธํ•œ ์‹ค์ •์œผ๋กœ[34], ๋ณธ ์—ฐ๊ตฌ์—์„œ ๋†’์€ ์ „๋ฅ˜๋ฐ€๋„ ์กฐ๊ฑด์— ๊ด€์ฐฐ๋œ ๋„๊ธˆ์ธต ํ˜•์„ฑ ๊ฑฐ๋™ ๋ฐ ์ง‘ํ•ฉ์กฐ์ง์˜ ๋ณ€ํ™”์— ๋Œ€ํ•œ ์ •ํ™•ํ•œ ์›์ธ์€ ํ–ฅํ›„ ์ถ”๊ฐ€ ์—ฐ๊ตฌ๋ฅผ ํ†ตํ•ด ๊ทœ๋ช…ํ•  ์ˆ˜ ์žˆ์„ ๊ฒƒ์ด๋‹ค.

ํŒจํ„ด ์œ„์น˜์— ๋”ฐ๋ฅธ ๋„๊ธˆ ์šฉ์•ก์˜ ์œ ๋™ ๊ฑฐ๋™์˜ ์ฐจ์ด์™€ ๊ทธ๋กœ ์ธํ•œ ๋„๊ธˆ ๊ณผ์ „์•• ์ฐจ์ด๊ฐ€ ๋„๊ธˆ์ธต ์„ฑ์žฅ ๊ฑฐ๋™์— ์ค‘์š”ํ•œ ์˜ํ–ฅ์„ ๋ฏธ์น  ๊ฒƒ์œผ๋กœ ํŒ๋‹จํ•˜์—ฌ, ์‹คํ—˜์— ์‚ฌ์šฉ๋œ ๊ธฐํŒ ํŒจํ„ด๊ณผ ๋™์ผํ•œ ๊ตฌ์กฐ์— ๋Œ€ํ•ด ๋„๊ธˆ ์‹œ ๊ต๋ฐ˜์— ์˜ํ•ด ๋ฐœ์ƒํ•˜๋Š” ๋„๊ธˆ ์šฉ์•ก์˜ ์œ ๋™๊ณผ ๊ณผ์ „์••์— ์˜ํ•œ ๋ฐ˜์‘ ์ „๋ฅ˜๋ฐ€๋„์˜ ์˜ํ–ฅ์„ ๋™์‹œ์— ๊ณ ๋ คํ•˜์—ฌ ํŒจํ„ด ์œ„์น˜ ๋ณ„ Co ์ด์˜จ ๋†๋„์™€ ๋„๊ธˆ์ธต ์„ฑ์žฅ ์†๋„๋ฅผ ์‹œ๋ฎฌ๋ ˆ์ด์…˜ ํ•˜์˜€๋‹ค.

๊ทธ๋ฆผ 11์— ๋‚˜ํƒ€๋‚ธ ๊ณ„์‚ฐ๋œ ๋„๊ธˆ ์šฉ์•ก ๋‚ด ์œ ๋™ ์†๋„ ๋ถ„ํฌ๋ฅผ ํ†ตํ•ด, ํŒจํ„ด ์ƒ๋‹จ๋ถ€ ํ‘œ๋ฉด์—๋Š” ์œ ๋™์ด ์ธต๋ฅ˜์˜ ํ˜•ํƒœ๋ฅผ ์œ ์ง€ํ•˜๋ฉฐ ํ‘œ๋ฉด์— ๊ฐ€๊นŒ์›Œ์งˆ์ˆ˜๋ก ์œ ๋™ ์†๋„๊ฐ€ ๊ฐ์†Œํ•˜๋Š” ๋ชจ์Šต์„ ๊ด€์ฐฐํ•  ์ˆ˜ ์žˆ๋‹ค. ํŠธ๋ Œ์น˜ ํŒจํ„ด ๋‚ด๋ถ€์—๋Š” ์™€๋ฅ˜๊ฐ€ ํ˜•์„ฑ๋˜๋Š”๋ฐ, ์ด ์™€๋ฅ˜์˜ ์ค‘์‹ฌ์œผ๋กœ๋ถ€ํ„ฐ ํŒจํ„ด ํ•˜๋‹จ๋ถ€์—๋Š” ์œ ๋™์˜ ๋ฐฉํ–ฅ์ด ๋ฐ˜์ „๋˜๊ณ  ํ•˜๋‹จ๋ถ€ ํ‘œ๋ฉด์— ๊ฐ€๊นŒ์›Œ์งˆ์ˆ˜๋ก ์œ ๋™ ์†๋„๊ฐ€ ๊ธ‰๊ฒฉํžˆ ๊ฐ์†Œํ•˜๋Š” ์–‘์ƒ์ด ๋‚˜ํƒ€๋‚ฌ๋‹ค. ๊ทธ ๊ฒฐ๊ณผ, ํŒจํ„ด ํ•˜๋‹จ๋ถ€, ํŠนํžˆ ํ•˜๋‹จ๋ถ€ ๋ชจ์„œ๋ฆฌ์—์„œ๋Š” ์ƒ๋‹จ๋ถ€์— ๋น„ํ•ด ์œ ๋™ ์†๋„๊ฐ€ ๋ฌด์‹œํ•  ์ˆ˜ ์žˆ์„ ์ •๋„๋กœ ์ž‘๋‹ค. ๊ณ„์‚ฐ๋œ Co ์ด์˜จ ๋†๋„๋Š” ํŒจํ„ด ์ƒ๋‹จ๋ถ€ ํ‘œ๋ฉด์— ๋น„ํ•ด ํ•˜๋‹จ๋ถ€ ํ‘œ๋ฉด์—์„œ ๋‚ฎ๊ณ , ํŠนํžˆ ํ•˜๋‹จ๋ถ€ ๋ชจ์„œ๋ฆฌ์—์„œ ๋†๋„๊ฐ€ ๊ฐ€์žฅ ๋‚ฎ๋‹ค. ๋˜ํ•œ, ์ „๋ฅ˜๋ฐ€๋„๊ฐ€ ์ฆ๊ฐ€ํ•จ์— ๋”ฐ๋ผ ์ƒ๋‹จ๋ถ€์™€ ํ•˜๋‹จ๋ถ€ ๋ชจ์„œ๋ฆฌ ๊ฐ„ Co ์ด์˜จ ๋†๋„์˜ ์ฐจ์ด ์—ญ์‹œ ์ฆ๊ฐ€ํ•˜์˜€๋‹ค.

๊ณ„์‚ฐ๋œ Co ์ด์˜จ ๋†๋„์˜ ๋ถ„ํฌ (๊ทธ๋ฆผ 11)๋Š” ๋„๊ธˆ ์šฉ์•ก ๋‚ด ์ด์˜จ์ด ํ™˜์› ๋ฐ˜์‘์„ ์œ„ํ•ด ์šฉ์•ก-๊ธฐํŒ (๋˜๋Š” ๋„๊ธˆ์ธต) ๊ณ„๋ฉด์œผ๋กœ ๋„๋‹ฌํ•˜๊ธฐ ์œ„ํ•œ ์œ ๋™ ๋ฐ ํ™•์‚ฐ ๊ณผ์ •์ด ํŒจํ„ด ์œ„์น˜์— ๋”ฐ๋ผ ์ƒ์ดํ•จ์„ ๋ณด์—ฌ์ค€๋‹ค. ๊ธฐํŒ ๋˜๋Š” ๋„๊ธˆ์ธต ํ‘œ๋ฉด์—์„œ ํ™˜์› ๋ฐ˜์‘์ด ์ผ์–ด๋‚  ๋•Œ ๊ทธ ๊ทผ์ฒ˜์—๋Š” ํ™˜์›๋˜๋Š” ์ด์˜จ์— ์˜ํ•œ ์ด์˜จ ๊ณ ๊ฐˆ์ธต์ด ํ˜•์„ฑ๋˜๋Š”๋ฐ, ์šฉ์•ก ๋‚ด ์ด์˜จ์ด ์ด์˜จ ๊ณ ๊ฐˆ์ธต์„ ํ†ต๊ณผํ•˜์—ฌ ํ‘œ๋ฉด์— ๋„๋‹ฌํ•˜๋Š” ์†๋„๋Š” ์šฉ์•ก์˜ ๊ต๋ฐ˜์— ์˜ํ•œ ์œ ๋™๊ณผ ์ด์˜จ์˜ ํ™•์‚ฐ์— ์˜ํ•ด ์ œ์–ด๋œ๋‹ค. ๋ณธ ์—ฐ๊ตฌ์—์„œ๋Š” ํŒจํ„ด ์ƒ๋‹จ๋ถ€์—์„œ ์œ ๋™ ์†๋„๊ฐ€ ํฌ๊ธฐ ๋•Œ๋ฌธ์— ์ด์˜จ ๊ณ ๊ฐˆ์ธต์˜ ์˜ํ–ฅ์ด ๋ฏธ๋ฏธํ•˜์—ฌ, ์šฉ์•ก ๋‚ด ์ด์˜จ๋“ค์ด ์ฆ‰์‹œ ๊ณ„๋ฉด์— ๋„๋‹ฌํ•  ์ˆ˜ ์žˆ์–ด ๋„๊ธˆ์ธต์ด ๋น ๋ฅด๊ฒŒ ์„ฑ์žฅํ•  ์ˆ˜ ์žˆ์—ˆ๋‹ค. ๋ฐ˜๋ฉด, ํŒจํ„ด ํ•˜๋‹จ๋ถ€์—์„œ๋Š” ์œ ๋™์ด ๋ฏธ์•ฝํ•˜์—ฌ ๊ณ ๊ฐˆ์ธต์˜ ๋‘๊ป˜๊ฐ€ ์ƒ๋Œ€์ ์œผ๋กœ ์ปค์ง€๊ณ , ์ด์˜จ์€ ํ™•์‚ฐ์„ ํ†ตํ•ด ์ด๋™ํ•ด์•ผ ํ•˜๋ฏ€๋กœ ๋„๊ธˆ์ธต ์„ฑ์žฅ์ด ๋А๋ฆฌ๊ฒŒ ์ง„ํ–‰๋œ๋‹ค. ํŠนํžˆ, ํŒจํ„ด ํ•˜๋‹จ๋ถ€ ๋ชจ์„œ๋ฆฌ์—์„œ๋Š” ์œ ๋™ ์†๋„๊ฐ€ ๋งค์šฐ ์ž‘๊ณ  ํ™˜์› ๋ฐ˜์‘์ด ์ธก๋ฒฝ๊ณผ ๋ฐ”๋‹ฅ๋ฒฝ์—์„œ ๋™์‹œ์— ์ผ์–ด๋‚˜๋ฉด์„œ ์†Œ๋ชจ๋˜๋Š” ์ด์˜จ์˜ ์ˆ˜๊ฐ€ ๊ฐ€์žฅ ๋งŽ์œผ๋ฏ€๋กœ ์ด ์˜์—ญ์—์„œ์˜ ์ด์˜จ ๋†๋„๊ฐ€ ๊ฐ€์žฅ ๋‚ฎ๊ฒŒ ๋จ์„ ์œ ์ถ”ํ•  ์žˆ๋‹ค. ํ•œํŽธ, ์ „๋ฅ˜๋ฐ€๋„์˜ ์ฆ๊ฐ€๋กœ ์ธํ•œ ํ™˜์› ๋ฐ˜์‘ ์†๋„์˜ ์ฆ๊ฐ€์™€ ์ด์— ์˜ํ•œ ์ด์˜จ ๊ณ ๊ฐˆ์ธต ๋‘๊ป˜์˜ ์ฆ๊ฐ€๋Š” ๋„๊ธˆ์ธต ์„ฑ์žฅ ๊ฑฐ๋™์˜ ์ฐจ์ด๋ฅผ ์œ ๋ฐœํ•  ๊ฒƒ์ด๋ฉฐ, ์ด๋Š” 90 mA/cm2์˜ ๋†’์€ ์ „๋ฅ˜๋ฐ€๋„์—์„œ ์ฆ์ฐฉ๋œ ๋„๊ธˆ์ธต์ด 10 mA/cm2 ๋„๊ธˆ์ธต๊ณผ ๋น„๊ตํ•˜์—ฌ ์ƒ์ดํ•œ ๊ฒฐ์ •๋ฆฝ ๊ตฌ์กฐ ๋ฐ ์ง‘ํ•ฉ์กฐ์ง์ด ๋ฐœ๋‹ฌํ•œ ์ด์œ ๋ฅผ ์„ค๋ช…ํ•œ๋‹ค.

์‹œ๋ฎฌ๋ ˆ์ด์…˜์„ ํ†ตํ•ด ๊ณ„์‚ฐ๋œ ์œ ๋™ ์†๋„์™€ ์ด์˜จ ๋†๋„์˜ ํŒจํ„ด ์œ„์น˜์— ๋”ฐ๋ฅธ ์ฐจ์ด์˜ ๊ฒฐ๊ณผ๋กœ ์–ป์–ด์ง€๋Š” ๋„๊ธˆ์ธต์˜ ํŒจํ„ด ์œ„์น˜ ๋ณ„ ๋‘๊ป˜๋ฅผ, ๊ทธ๋ฆผ 12์—์„œ ๋‚˜ํƒ€๋‚ธ ๊ฒƒ๊ณผ ๊ฐ™์ด, ์‹คํ—˜์„ ํ†ตํ•ด ์ธก์ •๋œ ๋‘๊ป˜์™€ ๋น„๊ตํ•˜์˜€๋‹ค.

๋‚ฎ์€ ์ „๋ฅ˜๋ฐ€๋„ (10 & 30 mA/cm2)์—์„œ๋Š” ์‹คํ—˜๊ณผ ์‹œ๋ฎฌ๋ ˆ์ด์…˜ ๊ฐ„ ๋„๊ธˆ์ธต์˜ ๊ตญ๋ถ€์  ๋‘๊ป˜ ๊ฒฝํ–ฅ์ด ์ž‘์€ ์˜ค์ฐจ๋ฅผ ๊ฐ€์ง€๋ฉด์„œ ์œ ์‚ฌํ•œ ๋ฐ˜๋ฉด, ๋†’์€ ์ „๋ฅ˜๋ฐ€๋„ (90 mA/cm2)์—์„œ๋Š” ๋‘ ๊ฐ’ ๊ฐ„์— ๋‹ค์†Œ ํฐ ์ฐจ์ด๊ฐ€ ๊ด€์ฐฐ๋œ๋‹ค. ์ด๋Š” 90 mA/cm2 ๋„๊ธˆ์ธต์˜ ํ˜•์„ฑ ์‹œ ๋†’์€ ์ „๋ฅ˜๋ฐ€๋„์—์„œ๋Š” ์œ ๋™๊ณผ ๊ณผ์ „์•• ์™ธ์— ๋˜ ๋‹ค๋ฅธ ๋„๊ธˆ ์ธ์ž๊ฐ€ ํŒจํ„ด ์œ„์น˜ ๋ณ„ ์ด์˜จ ๋†๋„์— ์˜ํ–ฅ์„ ๋ผ์น  ์ˆ˜ ์žˆ์Œ์„ ์˜๋ฏธํ•˜๋ฉฐ, ์•ž์„œ ์ด ์ „๋ฅ˜๋ฐ€๋„ ์กฐ๊ฑด์˜ ๋„๊ธˆ์ธต์—์„œ ๊ด€์ฐฐ๋œ ํŒจํ„ด ์ƒ๋‹จ๋ถ€์˜ ๋„๊ธˆ ์ดˆ๊ธฐ-ํ›„๊ธฐ ๊ฐ„ ๋ฐ ํŒจํ„ด ์ƒ๋‹จ๋ถ€-ํ•˜๋‹จ๋ถ€ ๊ฐ„ ์ƒ์ดํ•˜๊ฒŒ ๋ฐœ๋‹ฌํ•œ ๊ฒฐ์ •๋ฆฝ ๊ตฌ์กฐ/์ง‘ํ•ฉ์กฐ์ง๊ณผ๋„ ์—ฐ๊ด€๋˜์–ด ์žˆ๋Š” ๊ฒƒ์œผ๋กœ ์ถ”์ •๋œ๋‹ค. ๋˜ํ•œ, ์ด ์ธ์ž๋Š” ์œ ๋™ ์†๋„๊ฐ€ ํฐ ํŒจํ„ด ์ƒ๋‹จ๋ถ€๋ณด๋‹ค๋Š” ์œ ๋™ ์†๋„๊ฐ€ ์ž‘์€ ํ•˜๋‹จ๋ถ€, ํŠนํžˆ ํ•˜๋‹จ๋ถ€ ๋ชจ์„œ๋ฆฌ ์˜์—ญ์—์„œ ํฐ ์˜ํ–ฅ์„ ๋ผ์นจ์„ ์•Œ ์ˆ˜ ์žˆ๋‹ค.

Co ๋„๊ธˆ ์‹œ ์ด์˜จ์˜ ํ™˜์› ๋ฐ˜์‘ (Co2+ (aq)+ 2e- โ†’ Co (s))์˜ ํ‘œ์ค€ ํ™˜์› ์ „์œ„ (standard reduction potential)๊ฐ€ -0.277VSHE๋กœ ๋‚ฎ์•„ ์ˆ˜์†Œ ๋ฐœ์ƒ์ด Co ๋„๊ธˆ์ธต ์„ฑ์žฅ ๊ฑฐ๋™์— ์˜ํ–ฅ์„ ๋ฏธ์น  ๊ฒƒ์œผ๋กœ ํŒ๋‹จํ•˜์˜€๋‹ค. ์ด์— ํ‘œ์ค€ ํ™˜์› ์ „์œ„๊ฐ€ 0.337 VSHE๋กœ ๋†’์•„ ์ˆ˜์†Œ ๋ฐœ์ƒ์ด ์–ต์ œ๋˜๋Š” Cu ๋„๊ธˆ์„ Co ๋„๊ธˆ๊ณผ ๋™์ผํ•œ ํŒจํ„ด ๊ธฐํŒ์— ๋Œ€ํ•ด ๋™์ผํ•œ ๋ฐฉ๋ฒ•์œผ๋กœ ์‹คํ—˜๊ณผ ์‹œ๋ฎฌ๋ ˆ์ด์…˜์„ ์‹ค์‹œํ•˜์˜€๋‹ค. ๊ทธ ๊ฒฐ๊ณผ, ๊ทธ๋ฆผ 13์— ๋‚˜ํƒ€๋‚ธ ๊ฒƒ๊ณผ ๊ฐ™์ด, 90 mA/cm2์˜ ๋†’์€ ์ „๋ฅ˜๋ฐ€๋„์—์„œ๋„ Cu ๋„๊ธˆ์ธต ๋‘๊ป˜์˜ ํŒจํ„ด ์œ„์น˜ ๋ณ„ ์‹คํ—˜ ๋ฐ ์‹œ๋ฎฌ๋ ˆ์ด์…˜ ๊ฒฐ๊ณผ ๊ฐ„ ์ฐจ์ด๊ฐ€ Co ๋„๊ธˆ์ธต์— ๋น„ํ•ด ๋งค์šฐ ์ž‘์€ ๊ฒƒ์„ ํ™•์ธํ•  ์ˆ˜ ์žˆ๋‹ค.

์ด๋ฅผ ํ†ตํ•ด, ๋†’์€ ์ „๋ฅ˜๋ฐ€๋„ ์กฐ๊ฑด์˜ Co ๋„๊ธˆ ์‹œ์—๋Š” ๋„๊ธˆ ์ธต์˜ ์„ฑ์žฅ ๊ฑฐ๋™์ด ์ˆ˜์†Œ ๋ฐœ์ƒ์˜ ์˜ํ–ฅ์„ ๋ฐ›์œผ๋ฉฐ, ์ด๋กœ ์ธํ•ด ํŒจํ„ด ์ƒ๋‹จ๋ถ€-ํ•˜๋‹จ๋ถ€ ๋ฐ ๋„๊ธˆ ์ดˆ๊ธฐ-ํ›„๊ธฐ ๊ฐ„ ์ƒ์ดํ•œ ๊ฒฐ์ •๋ฆฝ ๊ตฌ์กฐ/์ง‘ํ•ฉ์กฐ์ง์ด ๋ฐœ๋‹ฌํ•˜๋Š” ๊ฒƒ์œผ๋กœ ์œ ์ถ”ํ•  ์ˆ˜ ์žˆ๋‹ค.

Co ๋„๊ธˆ์ธต์ด ์ ์šฉ๋œ ์—ฐ๊ฒฐ์žฌ์˜ ์ „๊ธฐ์  ์„ฑ๋Šฅ ํ‰๊ฐ€๋กœ์„œ, ๋ณธ ์—ฐ๊ตฌ์˜ Co ์ŠคํŠธ๋ผ์ดํฌ โ€“ Co ์ฃผ ๋„๊ธˆ ๊ณต์ •๊ณผ Ni ์ŠคํŠธ๋ผ์ดํฌ โ€“ Co ์ฃผ ๋„๊ธˆ ๊ณต์ •์ด ์ ์šฉ๋œ ๋‘ ํ‰ํŒ ์‹œ๋ฃŒ์˜ 800 ยฐC ์—ด์ฒ˜๋ฆฌ ์‹œ ์‹œ๊ฐ„์— ๋”ฐ๋ฅธ ๋ฉด์ €ํ•ญ (ASR)์˜ ๋ณ€ํ™”๋ฅผ ์ธก์ •ํ•˜์˜€๊ณ , ๊ทธ ๊ฒฐ๊ณผ๋ฅผ ๊ทธ๋ฆผ 14์— ๋‚˜ํƒ€๋‚ด์—ˆ๋‹ค.

์—ด์ฒ˜๋ฆฌ ์ดˆ๊ธฐ (100 & 300 h)์—๋Š” Co ์ŠคํŠธ๋ผ์ดํฌ โ€“ Co ์ฃผ ๋„๊ธˆ ๊ณต์ •์ด ์ ์šฉ๋œ ์‹œ๋ฃŒ์˜ ๋ฉด์ €ํ•ญ์ด Ni ์ŠคํŠธ๋ผ์ดํฌ โ€“ Co ์ฃผ ๋„๊ธˆ ๊ณต์ •์ด ์ ์šฉ๋œ ์‹œ๋ฃŒ์— ๋น„ํ•ด ๋‹ค์†Œ ๋†’์œผ๋‚˜, 500 h ํ›„์—๋Š” Co ์ŠคํŠธ๋ผ์ดํฌ โ€“ Co ์ฃผ ๋„๊ธˆ ๊ณต์ •์ด ๋” ๋‚ฎ์€ ASR์„ ๋ณด์˜€๋Š”๋ฐ, ์ด๋Š” Co ์ŠคํŠธ๋ผ์ดํฌ โ€“ Co ์ฃผ ๋„๊ธˆ ๊ณต์ •์„ ํ†ตํ•ด ์žฅ์‹œ๊ฐ„ ๊ณ ์˜จ ์•ˆ์ •์„ฑ ๋˜๋Š” Cr ํœ˜๋ฐœ ๋ฐฉ์ง€ ์„ฑ๋Šฅ์ด ๋” ์šฐ์ˆ˜ํ•œ ์—ฐ๊ฒฐ์žฌ์˜ ์ œ์กฐ๊ฐ€ ๊ฐ€๋Šฅํ•จ์„ ์˜๋ฏธํ•œ๋‹ค. ํ–ฅํ›„ Co ๋„๊ธˆ์ธต์˜ ๊ณ ์˜จ ๊ฑฐ๋™์— ๋Œ€ํ•œ ์ถ”๊ฐ€ ์—ฐ๊ตฌ๋ฅผ ํ†ตํ•ด ๊ณ ์˜จ์—์„œ์˜ Cr ํœ˜๋ฐœ ๋˜๋Š” ASR ์ฆ๊ฐ€๋ฅผ ํš๊ธฐ์ ์œผ๋กœ ๋ฐฉ์ง€ํ•˜๋Š” ๊ธฐ์ˆ ์ด ๊ฐœ๋ฐœ๋  ์ˆ˜ ์žˆ์„ ๊ฒƒ์œผ๋กœ ๊ธฐ๋Œ€ํ•œ๋‹ค.

4. ๊ฒฐ ๋ก 

์ €์˜จ SOFC์šฉ ํŽ˜๋ผ์ดํŠธ๊ณ„ ์Šคํ…์ธ๋ฆฌ์Šค๊ฐ• ์—ฐ๊ฒฐ์žฌ ํ‘œ๋ฉด์— ๊ณ„๋ฉด ๋ฐ€์ฐฉ๋ ฅ๊ณผ ๋‘๊ป˜ ๊ท ์ผ๋„๊ฐ€ ์šฐ์ˆ˜ํ•œ Co ์ „๊ธฐ๋„๊ธˆ ๊ธฐ์ˆ ์„ ๊ฐœ๋ฐœํ•˜๊ธฐ ์œ„ํ•ด, ์ŠคํŠธ๋ผ์ดํฌ + ์ฃผ ๋„๊ธˆ ๊ณต์ •์˜ ๋‘ ๋‹จ๊ณ„ ๋„๊ธˆ ๊ณต์ •๊ธฐ์ˆ ์„ ๊ฐœ๋ฐœํ•˜์˜€๋‹ค. ์ด๋ฅผ ์ด์šฉํ•˜์—ฌ ์ฃผ ๋„๊ธˆ ๊ณต์ • ์‹œ ์ธ๊ฐ€๋˜๋Š” ์ „๋ฅ˜๋ฐ€๋„์— ๋”ฐ๋ฅธ ์—ฐ๊ฒฐ์žฌ ํŒจํ„ด ์œ„์น˜ ๋ณ„ ๋„๊ธˆ์ธต ๋‘๊ป˜์™€ ๋ฏธ์„ธ์กฐ์ง์„ ๋ถ„์„ํ•˜๊ณ , ์œ ํ•œ์š”์†Œ๋ฒ• ๊ธฐ๋ฐ˜ ๋„๊ธˆ ์‹œ๋ฎฌ๋ ˆ์ด์…˜์„ ์‹ค์‹œํ•˜์—ฌ ๋‹ค์Œ๊ณผ ๊ฐ™์€ ๊ฒฐ๋ก ์„ ๋„์ถœํ•˜์˜€๋‹ค.

1) ํŽ˜๋ผ์ดํŠธ๊ณ„ ์Šคํ…Œ์ธ๋ฆฌ์Šค๊ฐ• ๊ธฐํŒ๊ณผ Co ๋„๊ธˆ์ธต ๊ฐ„์˜ ๊ณ„๋ฉด ๋ฐ€์ฐฉ๋ ฅ์„ ํ–ฅ์ƒ์‹œํ‚ค๊ธฐ ์œ„ํ•œ Co ์ด์˜จ์ด ํฌํ•จ๋œ ๋„๊ธˆ ์šฉ์•ก์— ๊ธฐ๋ฐ˜ํ•œ ์ŠคํŠธ๋ผ์ดํฌ ๊ณต์ •์„ ๊ฐœ๋ฐœํ•˜์˜€๋‹ค.

2) ํŒจํ„ด ์œ„์น˜์— ๋”ฐ๋ผ ๋„๊ธˆ์ธต ๋‘๊ป˜์˜ ๋ถˆ๊ท ์ผ์„ฑ์ด ํ™•์ธ๋˜์—ˆ์œผ๋ฉฐ, ํŒจํ„ด ์ƒ๋‹จ๋ถ€์—์„œ ๋‘๊ป๊ณ  ํ•˜๋‹จ๋ถ€์—์„œ ์–‡์•˜๋‹ค. ํŠนํžˆ ํŒจํ„ด ํ•˜๋‹จ๋ถ€ ๋ชจ์„œ๋ฆฌ์—์„œ ๋„๊ธˆ์ธต์˜ ๋‘๊ป˜๊ฐ€ ๊ฐ€์žฅ ์ž‘์•˜์œผ๋ฉฐ, ์ด๋Ÿฌํ•œ ํŒจํ„ด ์œ„์น˜ ๋ณ„ ๋„๊ธˆ์ธต ๋‘๊ป˜์˜ ๋ถˆ๊ท ์ผ์„ฑ์€ ์ „๋ฅ˜๋ฐ€๋„๊ฐ€ ์ฆ๊ฐ€ํ• ์ˆ˜๋ก ์‹ฌํ™”๋˜์—ˆ๋‹ค.

3) ์ „๋ฅ˜๋ฐ€๋„์— ๋”ฐ๋ฅธ ๋„๊ธˆ์ธต์˜ ๊ฒฐ์ •๋ฆฝ ํ˜•์ƒ ๋ฐ ํฌ๊ธฐ์™€ ์ง‘ํ•ฉ์กฐ์ง์„ ๋ถ„์„ํ•œ ๊ฒฐ๊ณผ, ๋‚ฎ์€ ์ „๋ฅ˜๋ฐ€๋„ (10 mA/cm2)์—์„œ ์ฆ์ฐฉ๋œ ๋„๊ธˆ์ธต์€ ๋Œ€์ฒด๋กœ <1 0 -1 0> ~ <2 -1 -1 0> // ND ์ง‘ํ•ฉ์กฐ์ง์„ ๊ฐ€์ง€๋Š” ๊ธธ๊ฒŒ ์—ฐ์‹ ๋œ ์กฐ๋Œ€ํ•œ ์ˆ˜์ง€์ƒ ๊ฒฐ์ •๋ฆฝ๋“ค์ด ํ˜•์„ฑ๋˜์—ˆ์œผ๋ฉฐ, ํŒจํ„ด ์ƒ๋‹จ๋ถ€์™€ ํ•˜๋‹จ๋ถ€ ๊ฐ„ ๋ฏธ์„ธ์กฐ์ง/์ง‘ํ•ฉ์กฐ์ง์˜ ์ฐจ์ด๊ฐ€ ๋ฏธ๋ฏธํ–ˆ๋‹ค. ๋ฐ˜๋ฉด, ๋†’์€ ์ „๋ฅ˜๋ฐ€๋„ (90 mA/cm2) ์กฐ๊ฑด์—์„œ๋Š” ํŒจํ„ด ์ƒ๋‹จ๋ถ€์—์„œ ์ดˆ๊ธฐ์—๋Š” ๋ฏธ์„ธํ•œ <2 -1 -1 0> // ND ์ง‘ํ•ฉ์กฐ์ง์˜ ๊ฒฐ์ •๋ฆฝ๋“ค์ด ์„ฑ์žฅํ•˜๊ณ , ํ›„๊ธฐ์—๋Š” ์ƒ๋Œ€์ ์œผ๋กœ ํฌ๊ธฐ๊ฐ€ ํฐ ๋“ฑ์ถ•์ƒ์˜ <1 0 -1 0> // ND ์ง‘ํ•ฉ์กฐ์ง์„ ๊ฐ€์ง€๋Š” ๊ฒฐ์ •๋ฆฝ๋“ค์ด ์„ฑ์žฅํ•˜์—ฌ ๋šœ๋ ท์ด ๊ตฌ๋ถ„๋˜๋Š” 2์ธต์˜ ๋ฏธ์„ธ์กฐ์ง/์ง‘ํ•ฉ์กฐ์ง์ด ๋ฐœ๋‹ฌํ•˜์˜€๊ณ , ํŒจํ„ด ํ•˜๋‹จ๋ถ€์—๋Š” ์ƒ๋‹จ๋ถ€์˜ ์ดˆ๊ธฐ ๋ฏธ์„ธ์กฐ์ง/์ง‘ํ•ฉ์กฐ์ง์ด ๊ด€์ฐฐ๋˜์—ˆ๋‹ค.

4) ์œ ํ•œ์š”์†Œ๋ฒ• ๊ธฐ๋ฐ˜ ์‹œ๋ฎฌ๋ ˆ์ด์…˜์„ ํ†ตํ•ด, ์‹คํ—˜์—์„œ ๊ด€์ฐฐ๋œ ๋„๊ธˆ์ธต ๋‘๊ป˜์˜ ํŒจํ„ด ์œ„์น˜ ๋ณ„ ์ฐจ์ด๋ฅผ ์šฉ์•ก ๋‚ด Co ์ด์˜จ์˜ ์œ ๋™๊ณผ ํ™•์‚ฐ์— ์˜ํ•œ ์ด๋™์˜ ํŒจํ„ด ์œ„์น˜ ๋ณ„ ์˜ํ–ฅ์„ฑ ์ฐจ์ด๋กœ ์„ค๋ช…ํ•  ์ˆ˜ ์žˆ์—ˆ๋‹ค. ํŒจํ„ด ์ƒ๋‹จ๋ถ€์—์„œ๋Š” ํฐ ์œ ๋™ ์†๋„๋กœ ์ธํ•ด ์ด์˜จ ๊ณ ๊ฐˆ์ธต์˜ ์˜ํ–ฅ์ด ๋ฏธ์•ฝํ•˜์—ฌ ๋„๊ธˆ์ธต์ด ๋น ๋ฅด๊ฒŒ ์„ฑ์žฅํ•  ์ˆ˜ ์žˆ๋Š” ๋ฐ˜๋ฉด, ํŒจํ„ด ํ•˜๋‹จ๋ถ€์—์„œ๋Š” ์œ ๋™์ด ๋ฏธ์•ฝํ•˜๊ณ  ์ด์˜จ ๊ณ ๊ฐˆ์ธต์˜ ๋‘๊ป˜๊ฐ€ ์ƒ๋Œ€์ ์œผ๋กœ ์ปค ํ™•์‚ฐ์— ์˜ํ•œ ์ด์˜จ์˜ ์ด๋™์— ์˜ํ•ด ์ œ์–ด๋˜์–ด ๋„๊ธˆ์ธต์˜ ์„ฑ์žฅ์ด ๋А๋ฆฌ๊ฒŒ ๋œ๋‹ค. ๋˜ํ•œ, ์ „๋ฅ˜๋ฐ€๋„์˜ ์ฆ๊ฐ€์— ๋”ฐ๋ฅธ ํ™˜์› ๋ฐ˜์‘ ์†๋„์˜ ์ฆ๊ฐ€ ๋ฐ ์ด์— ๋”ฐ๋ฅธ ์ด์˜จ ๊ณ ๊ฐˆ์ธต ๋‘๊ป˜์˜ ์ฆ๊ฐ€๊ฐ€ ํŒจํ„ด ์œ„์น˜์— ๋”ฐ๋ฅธ ๋„๊ธˆ์ธต์˜ ๋ฏธ์„ธ์กฐ์ง/์ง‘ํ•ฉ์กฐ์ง์ด ์ƒ์ดํ•˜๊ฒŒ ๋ฐœ๋‹ฌํ•  ์ˆ˜ ์žˆ์Œ์„ ์œ ์ถ”ํ•  ์ˆ˜ ์žˆ์—ˆ๋‹ค.

5) ํ‘œ์ค€ ํ™˜์› ์ „์œ„๊ฐ€ -0.277 VSHE๋กœ ๋‚ฎ์€ Co ๋„๊ธˆ ๋Œ€๋น„, ์ƒ๋Œ€์ ์œผ๋กœ ๋†’์€ ํ‘œ์ค€ ํ™˜์› ์ „์œ„ (0.337 V)๋กœ ์ธํ•ด ์ˆ˜์†Œ ๋ฐœ์ƒ์ด ์–ต์ œ๋˜๋Š” Cu ๋„๊ธˆ์— ๋Œ€ํ•ด ๋™์ผํ•œ ๋ฐฉ๋ฒ•์˜ ์‹คํ—˜๊ณผ ์‹œ๋ฎฌ๋ ˆ์ด์…˜์„ ์‹ค์‹œํ•œ ๊ฒฐ๊ณผ, ๋†’์€ ์ „๋ฅ˜๋ฐ€๋„ ์กฐ๊ฑด์—์„œ ์‹คํ—˜-์‹œ๋ฎฌ๋ ˆ์ด์…˜ ๊ฐ„ ๋„๊ธˆ์ธต ๋‘๊ป˜ ์ฐจ์ด๋ฅผ ๋ณด์˜€๋˜ Co ๋„๊ธˆ์— ๋น„ํ•ด Cu ๋„๊ธˆ์ธต์—์„œ๋Š” ๊ทธ ์ฐจ์ด๊ฐ€ ๋ฏธ์•ฝํ•˜์˜€๋‹ค. ์ด๋ฅผ ํ†ตํ•ด, ๋†’์€ ์ „๋ฅ˜๋ฐ€๋„ ์กฐ๊ฑด์˜ Co ๋„๊ธˆ ์‹œ ๋„๊ธˆ์ธต์˜ ์„ฑ์žฅ ๊ฑฐ๋™์˜ ํ•ด์„์— ์ˆ˜์†Œ ๋ฐœ์ƒ์˜ ์˜ํ–ฅ์„ ๊ณ ๋ คํ•ด์•ผ ํ•จ์„ ์•Œ ์ˆ˜ ์žˆ์—ˆ๋‹ค.

Notes

[1] ๊ฐ์‚ฌ์˜ ๊ธ€

์ด ์„ฑ๊ณผ๋Š” ์ •๋ถ€(๊ณผํ•™๊ธฐ์ˆ ์ •๋ณดํ†ต์‹ ๋ถ€)์˜ ์žฌ์›์œผ๋กœ ํ•œ๊ตญ์—ฐ๊ตฌ์žฌ๋‹จ์˜ ์ง€์›์„ ๋ฐ›์•„ ์ˆ˜ํ–‰๋œ ์—ฐ๊ตฌ์ž„ (No. RS-2021-NR057526(2021M3H4A6A01041234)). ๋˜ํ•œ, ์ด ์—ฐ๊ตฌ๋Š”2021๋…„๋„ ์‚ฐ์—…ํ†ต์ƒ์ž์›๋ถ€ ๋ฐ ์‚ฐ์—…๊ธฐ์ˆ ํ‰๊ฐ€๊ด€๋ฆฌ์›(KEIT) ์—ฐ๊ตฌ๋น„ ์ง€์›์— ์˜ํ•œ ์—ฐ๊ตฌ์ž„(โ€˜20015767โ€™). ๋์œผ๋กœ, SOFC ์—ฐ ๊ฒฐ์žฌ์— ๋Œ€ํ•œ ์กฐ์–ธ๊ณผ ASR ์ธก์ •์— ์•„๋‚Œ์—†๋Š” ๋„์›€์„ ์ฃผ์‹ KIST ๊น€๋™์ต ๋ฐ•์‚ฌ๋‹˜๊ณผ ๊ณ ์œค์„ ๋ฐ•์‚ฌ๋‹˜๊ป˜ ๊ฐ์‚ฌ๋“œ๋ฆฝ๋‹ˆ๋‹ค.

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Figures and Tables

Fig. 1.

Schematic drawing of trench-type pattern formed on 430 ferritic stainless-steel substrate before Co electrodeposition.

../../Resources/kim/KJMM.2025.63/kjmm-2025-63-7-494f1.jpg
Fig. 2.

Mesh and boundary conditions used for finite element method-based simulation of Co electrodeposition on trench pattern. The bold solid line along the lower part of the model indicates the surface where electrodeposition takes place.

../../Resources/kim/KJMM.2025.63/kjmm-2025-63-7-494f2.jpg
Fig. 3.

Cross-sectional SEM images of Co coatings (left) and substrate/Co coating interfaces at the pattern side wall (right) deposited on patterned substrate at current density of (a) 10, (b) 30, and (c) 90 mA/cm2.

../../Resources/kim/KJMM.2025.63/kjmm-2025-63-7-494f3.jpg
Fig. 4.

(a) Schematic diagram showing positions on trench pattern where Co coating thickness was measured, and (b) graph showing coating thickness according to position on the pattern.

../../Resources/kim/KJMM.2025.63/kjmm-2025-63-7-494f4.jpg
Fig. 5.

Top-view SEM images showing surface morphology of Co coating deposited at current density of (a) 10, (b) 30, and (c) 90 mA/cm2.

../../Resources/kim/KJMM.2025.63/kjmm-2025-63-7-494f5.jpg
Fig. 6.

Global textures of Co coatings fabricated at current density of 10, 30, and 90 mA/cm2, measured using XRD technique.

../../Resources/kim/KJMM.2025.63/kjmm-2025-63-7-494f6.jpg
Fig. 7.

Cross-sectional crystallographic orientation maps at pattern top (position 1 on Fig. 4(a)) and bottom (position 4 on Fig. 4(a)) of Co coatings fabricated at current density of (a) 10, (b) 30, and (c) 90 mA/cm2, measured using EBSD technique. Each color on the maps indicates a specific crystal orientation parallel to ND.

../../Resources/kim/KJMM.2025.63/kjmm-2025-63-7-494f7.jpg
Fig. 8.

Cross-sectional grain size maps and distributions at pattern top (position 1 on Fig. 4(a)) and bottom (position 4 on Fig. 4(a)) of Co coatings fabricated at current density of (a) 10, (b) 30, and (c) 90 mA/cm2, obtained from the crystallographic orientation maps in Fig. 7.

../../Resources/kim/KJMM.2025.63/kjmm-2025-63-7-494f8.jpg
Fig. 9.

Local textures at pattern top and bottom of Co coatings fabricated at current density of (a) 10, (b) 30, and (c) 90 mA/cm2, extracted from the crystallographic orientation maps in Fig. 7.

../../Resources/kim/KJMM.2025.63/kjmm-2025-63-7-494f9.jpg
Fig. 10.

Local textures of lower region from bottom surface to 20 ยตm and upper region from 20 ยตm to top surface at pattern top of Co coatings fabricated at current density of (a) 10, (b) 30, and (c) 90 mA/cm2, extracted from the crystallographic orientation maps in Fig. 7.

../../Resources/kim/KJMM.2025.63/kjmm-2025-63-7-494f10.jpg
Fig. 11.

Distribution of flow rate/direction and Co ion concentration near deposit surface during electrodeposition at current density of (a) 10, (b) 30, and (c) 90 mA/cmยฒ, calculated using finite element method. The distribution of flow rate and direction are expressed by arrows, and the length and grey intensities of the arrows indicate the magnitude of the rate as shown in the legend on the left side of the figure.

../../Resources/kim/KJMM.2025.63/kjmm-2025-63-7-494f11.jpg
Fig. 12.

Comparison of simulated local thicknesses with experimentally measured ones of Co coatings deposited at current density of (a) 10, (b) 30, and (c) 90 mA/cmยฒ. โ€œPosition on patternโ€ as the horizontal axis and โ€œStep coverageโ€ as the vertical axis in the graphs indicate the positions on the substrate pattern shown in Fig. 4(a) and the ratio of the thickness at each position to one at the upper region of the pattern, respectively.

../../Resources/kim/KJMM.2025.63/kjmm-2025-63-7-494f12.jpg
Fig. 13.

Comparison of simulated local thicknesses with experimentally measured ones of Cu coatings deposited at current density of (a) 10, (b) 30, and (c) 90 mA/cmยฒ. โ€œPosition on patternโ€ as the horizontal axis and โ€œStep coverageโ€ as the vertical axis in the graphs indicate the positions on the substrate pattern shown in Fig. 4(a) and the ratio of the thickness at each position to one at the upper region of the pattern, respectively.

../../Resources/kim/KJMM.2025.63/kjmm-2025-63-7-494f13.jpg
Fig. 14.

Change in area specific resistance (ASR) over time during heat treatment at 800 ยฐC of blanket specimens fabricated through Co strike โ€“ Co main deposition and Ni strike โ€“ Co main deposition processes.

../../Resources/kim/KJMM.2025.63/kjmm-2025-63-7-494f14.jpg
Table 1.

Chemical ingredients of solutions for strike and main Co electrodeposition processes

Chemical species Strike electroplating Electroplating
CoCl2ยท6H2O 0.42 M 0.42 M
H3BO3 - 0.57 M
HCl 1.20 M -
Table 2.

Electrode material and process conditions for Co electrodeposition.

Items[unit] Conditions
Anode material Pt mesh
Agitation (rotating stirrer) [rpm] 200
Temperature [ยฐC] 25
Strike electroplating current density [mA/cm2] 300
Electroplating current density [mA/cm2] 10, 30 or 90
Target thickness [ฮผm] 82
Table 3.

Parameters and their values for simulations of Co electrodeposition

Parameter [unit] Symbol Value Reference
Ionic charge, Co zCo2+ 2 -
Molar volume, Co [m3/mol] โ„ฆ 6.67 ร— 10-6 -
Bulk concentration, Co [mol/m3] CโˆžCo2+ 420 -
Diffusion coefficient, Co [m2/s] DCo2+ 7.32 ร— 10-10 [28]
Transfer coefficient a 0.5 [29]
Electrolyte conductivity [S/m] ฯƒ 15.6 [29]
Exchange current density [A/m2] i0 20 [29]
Boundary layer thickness [mm] ฮด 0.1 [30]
Trench pattern width [mm] w 2 -
Trench pattern height [mm] h 1 -
Temperature [K] T 298 -