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. ๊ฒฝ๋ถ๋Œ€ํ•™๊ต ์‹ ์†Œ์žฌ๊ณตํ•™๋ถ€ (Department of Materials Science and Metallurgical Engineering, Kyungpook National University, Daegu 41566, Republic of Korea)
  2. ๊ฒฝ๋ถ๋Œ€ํ•™๊ต ์œตํ•ฉ๋Œ€ํ•™์› (School of Industrial Technology Advances, Kyungpook National University, Daegu 41566, Republic of Korea)



polyvinylidene Fluoride (PVDF), polytetrafluoroethylene (PTFE), 1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU), micropore, mesopore

1. ์„œ ๋ก 

๋‹ค๊ณต์„ฑ ๊ตฌ์กฐ๋ฅผ ๊ฐ–๋Š” ํƒ„์†Œ ์†Œ์žฌ๋Š” ์ž‘์€ ๊ธฐ๊ณต์˜ ๋ฌผ์งˆ ํก์ฐฉ๋Šฅ๋ ฅ ๋•๋ถ„์— ์—๋„ˆ์ง€ ์ €์žฅ, ์ž…์ž ๋ฐ ์ด์˜จ ํ•„ํ„ฐ ๋“ฑ ๋‹ค์–‘ํ•œ ์‘์šฉ ๋ถ„์•ผ์—์„œ ๋„๋ฆฌ ์‚ฌ์šฉ๋˜๋Š” ์†Œ์žฌ์ด๋‹ค [1-5]. ์กด์žฌํ•˜๋Š” ๊ธฐ๊ณต์˜ ํฌ๊ธฐ์— ๋”ฐ๋ผ ํก์ฐฉ ๋˜๋Š” ๋ถ„๋ฆฌํ•˜๋Š” ๋ฌผ์งˆ์˜ ์ข…๋ฅ˜๊ฐ€ ๋‹ฌ๋ผ์ง€๋ฏ€๋กœ ๋‹ค๊ณต์„ฑ ํƒ„์†Œ์˜ ํ™œ์šฉ ๋ชฉ์ ์— ๋”ฐ๋ผ ๊ธฐ๊ณต ํฌ๊ธฐ์˜ ์ œ์–ด๋Š” ์ƒ๋‹นํžˆ ์ค‘์š”ํ•˜๋‹ค [1,6]. ์˜ˆ๋ฅผ๋“ค๋ฉด ๋ฏธ์„ธ๋จผ์ง€ ํก์ฐฉ์„ ์œ„ํ•œ ๋‹ค๊ณต์„ฑ ํƒ„์†Œํ•„ํ„ฐ๋Š” ๋ฏธ์„ธ๋จผ์ง€ ํฌ๊ธฐ์˜ ๊ธฐ๊ณต ํฌ๊ธฐ๋ฅผ ๊ฐ€์ ธ์•ผ ํ•œ๋‹ค. ๋”ฐ๋ผ์„œ, ๋‹ค๊ณต์„ฑ ํƒ„์†Œ๋ฅผ ํ•ฉ์„ฑํ•˜๊ณ ์ž ํ•˜๋Š” ๋Œ€๋ถ€๋ถ„์˜ ์—ฐ๊ตฌ๋“ค์˜ ์ฃผ์š”ํ•œ ๋ชฉํ‘œ๋Š” ๊ธฐ๊ณต ํฌ๊ธฐ๋ฅผ ์ œ์–ดํ•˜๋Š” ๊ฒƒ์ด์—ˆ์œผ๋ฉฐ ์ด๋ฅผ ์œ„ํ•ด ๋‹ค์–‘ํ•œ ํƒ„์†Œ ํ•ฉ์„ฑ๋ฒ•์„ ํ†ตํ•ด ๊ธฐ๊ณต ํฌ๊ธฐ๋ฅผ ์กฐ์ ˆํ•˜๊ณ ์ž ํ•˜๋Š” ์‹œ๋„๊ฐ€ ์ฃผ๋กœ ์ง„ํ–‰๋˜์—ˆ๋‹ค. ๋„๋ฆฌ ์‚ฌ์šฉ๋˜๋Š” ์ƒ์šฉ ๋‹ค๊ณต์„ฑ ํƒ„์†Œ ํ•ฉ์„ฑ๋ฒ•์ธ ๋ฌผ๋ฆฌ์  ๋˜๋Š” ํ™”ํ•™์  ํ™œ์„ฑํ™” ๋ฐฉ๋ฒ•์€ ๊ธฐ๊ณต์˜ ๊ตฌ์กฐ๋ฅผ ์ •๊ตํ•˜๊ฒŒ ์ œ์–ดํ•˜๊ธฐ ์–ด๋ ค์šด ๋ฌธ์ œ๊ฐ€ ์žˆ๋‹ค. ๋ฟ๋งŒ์•„๋‹ˆ๋ผ ์ฃผ๋กœ ์ž‘์€ ํฌ๊ธฐ์˜ ๋งˆ์ดํฌ๋กœ ๊ธฐ๊ณต์„ ์ƒ์„ฑ์‹œํ‚ค๋ฏ€๋กœ ๋ฉ”์กฐ ๊ธฐ๊ณต์„ ๊ฐ–๋Š” ๋‹ค๊ณต์„ฑ ํƒ„์†Œ๋ฅผ ํ•ฉ์„ฑํ•˜๊ธฐ๋Š” ์–ด๋ ต๋‹ค. ๋ณธ ์—ฐ๊ตฌ์—์„œ๋Š” ๋ฉ”์กฐ ๊ธฐ๊ณต์„ ๊ฐ–๋Š” ๋‹ค๊ณต์„ฑ ํƒ„์†Œ๋ฅผ ํ•ฉ์„ฑํ•˜๊ธฐ ์œ„ํ•ด Polyvinylidene Fluoride (PVDF) ํด๋ฆฌ๋จธ ์ „๊ตฌ์ฒด๋กœ๋ถ€ํ„ฐ ๋‹ค๊ณต์„ฑ ํƒ„์†Œ ํ•ฉ์„ฑ ๊ณต์ •์„ ๊ฐœ๋ฐœํ•˜๊ณ ์ž ํ•˜์˜€๋‹ค.

PVDF๋Š” ํƒ„์†Œ์˜ ์ฃผ ์‚ฌ์Šฌ(backbone)์— ๋‘ ๊ฐœ์˜ ๋ถˆ์†Œ(fluorine) ์›์†Œ์™€ ๋‘ ๊ฐœ์˜ ์ˆ˜์†Œ(hydrogen) ์›์†Œ๊ฐ€ ์ฐจ๋ก€๋กœ ์—ฐ๊ฒฐ๋œ ๊ตฌ์„ฑ์„ ๊ฐ–๊ณ  ์žˆ๋‹ค [7]. PVDF๋ฅผ ๋น„ํ™œ์„ฑ ๊ธฐ์ฒด ๋ถ„์œ„๊ธฐ์—์„œ ๊ณ ์˜จ ์—ด์ฒ˜๋ฆฌํ•˜๋ฉด ๋ถˆ์†Œ์™€ ์ˆ˜์†Œ์›์†Œ๊ฐ€ ๊ฒฐํ•ฉํ•˜์—ฌ HF ๊ธฐ์ฒด ํ˜•ํƒœ๋กœ ๋ฐฉ์ถœ๋˜๋Š” ๋™์‹œ์— ํƒ„์†Œ์›์†Œ๋“ค์€ ์œก๊ฐํ˜•์œผ๋กœ ๊ฒฐํ•ฉํ•˜์—ฌ ์ ์ธต ๊ตฌ์กฐ์˜ ๊ทธ๋ž˜ํ•€ ์ ์ธต ๊ตฌ์กฐ(graphene layered structure)๊ฐ€ ํ˜•์„ฑ๋œ๋‹ค. ์ด ๋•Œ ๋ถˆ์†Œ๊ฐ€ ๋น ์ ธ๋‚˜๊ฐ„ ์ž๋ฆฌ๋Š” ์ž‘์€ ํฌ๊ธฐ์˜ ๋งˆ์ดํฌ๋กœ ๊ธฐ๊ณต(์ง€๋ฆ„ < 2 nm)์„ ํ˜•์„ฑํ•˜๋ฏ€๋กœ ๋ฌด์ˆ˜ํžˆ ๋งŽ์€ ๋ฏธ์„ธ ๊ธฐ๊ณต์„ ๊ฐ–๋Š” ๋‹ค๊ณต์„ฑ ํƒ„์†Œ๊ฐ€ ํ•ฉ์„ฑ๋œ๋‹ค [8-10]. ํ•œํŽธ, ์•ž์„œ ์–ธ๊ธ‰ํ•˜์˜€๋˜ ๊ฒƒ์ฒ˜๋Ÿผ ํƒ„์†Œ ์ž…์ž์˜ ์‘์šฉ ๋ถ„์•ผ์— ๋”ฐ๋ผ ํฐ ์ž…์ž์˜ ํก์ฐฉ์„ ์œ„ํ•ด์„œ๋Š” ๋งˆ์ดํฌ๋กœ ๊ธฐ๊ณต๋ณด๋‹ค ํฐ ๋ฉ”์กฐ ๊ธฐ๊ณต์„ ๋ฐœ๋‹ฌ์‹œํ‚ฌ ํ•„์š”๊ฐ€ ์žˆ๋‹ค. ํŠนํžˆ 2 nm ์ด์ƒ์˜ ์ž…์ž์ œ๊ฑฐ๋ฅผ ์œ„ํ•ด์„œ๋Š” ๋งˆ์ดํฌ๋กœ ํฌ๊ธฐ์˜ ๊ธฐ๊ณต ์–‘์€ ์ ์œผ๋ฉด์„œ ๋ฉ”์กฐ ํฌ๊ธฐ(2 nm < ์ง€๋ฆ„ < 50 nm)์˜ ๊ธฐ๊ณต์„ ๋งŽ์ด ๋ณด์œ ํ•˜๋Š” ํƒ„์†Œ์˜ ํ•ฉ์„ฑ์ด ํ•„์š”ํ•˜๋‹ค [11].

PVDF ์ „๊ตฌ์ฒด์˜ ์—ด๋ถ„ํ•ด์‹œ ๋งˆ์ดํฌ๋กœ ๊ธฐ๊ณต์˜ ์ƒ์„ฑ์„ ์–ต์ œํ•˜๊ธฐ ์œ„ํ•˜์—ฌ 1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU) ์šฉ๋งค๋ฅผ ์ด์šฉํ•˜์—ฌ PVDF ์ „๊ตฌ์ฒด๋ฅผ ํƒˆ๋ถˆํ™”์‹œํ‚จ ํ›„ ํƒ„์†Œ๋ฅผ ํ•ฉ์„ฑํ•˜๊ณ ์ž ํ•˜์˜€๋‹ค [12]. ํ•œํŽธ, ๋‹ค๊ณต์„ฑ ํƒ„์†Œ๊ฐ€ ๊ฐ–๋Š” ๋น„ํ‘œ๋ฉด์ ์€ ํƒ„์†Œ ์†Œ์žฌ์˜ ๋ฏธ์„ธ ์ž…์ž๋ฅผ ํก์ฐฉํ•  ์ˆ˜ ์žˆ๋Š” ๋Šฅ๋ ฅ ์ฆ‰, ์ž…์ž ํก์ฐฉ ์šฉ๋Ÿ‰์— ๋น„๋ก€ํ•˜๋Š”๋ฐ ํƒˆ๋ถˆํ™”์— ์˜ํ•œ ๋ฏธ์„ธ๊ธฐ๊ณต์˜ ๊ฐ์†Œ๋Š” ํƒ„์†Œ์˜ ํก์ฐฉ ์šฉ๋Ÿ‰์„ ๊ฐ์†Œ์‹œํ‚ฌ ์ˆ˜ ์žˆ๋‹ค. ๋”ฐ๋ผ์„œ ์ž…์ž ํก์ฐฉ ์šฉ๋Ÿ‰์˜ ํ–ฅ์ƒ์„ ์œ„ํ•ด์„œ๋Š” ๋ฉ”์กฐ ๊ธฐ๊ณต์„ ์ถฉ๋ถ„ํžˆ ํ˜•์„ฑ์‹œํ‚ฌ ํ•„์š”๊ฐ€ ์žˆ๋‹ค. ๋ฉ”์กฐ ๊ธฐ๊ณต์„ ํ˜•์„ฑํ•˜๋Š” ์ผ๋ฐ˜์ ์ธ ๋ฐฉ๋ฒ•์€ ํ…œํ”Œ๋ ˆ์ดํŒ…(templating), ์กธ-๊ฒ”๋ฒ•(sol-gel method)์— ์˜ํ•œ ๊ธฐ๊ณต ํ˜•์„ฑ, ํด๋ฆฌ๋จธ ๋ธ”๋ Œ๋”ฉ(blending) ๋ฐฉ๋ฒ• ๋“ฑ ๋‹ค์–‘ํ•˜๋‹ค. ์ด๋Ÿฌํ•œ ์ „๋žต ์ค‘ ๊ฐ„ํŽธํ•˜๊ณ  ์†์‰ฌ์šด ๋ฐฉ๋ฒ•์œผ๋กœ ์—ด์  ์•ˆ์ •์„ฑ์ด ๋‹ค๋ฅธ ๋‘ ์ „๊ตฌ์ฒด๋ฅผ ๋ธ”๋ Œ๋”ฉํ•˜์—ฌ ํƒ„ํ™”ํ•˜๋ฉด ์—ด์  ์•ˆ์ •์„ฑ์ด ๋†’์€ ์ „๊ตฌ์ฒด๋Š” ํƒ„ํ™”ํ•˜๊ณ  ์ƒ๋Œ€์ ์œผ๋กœ ๋‚ฎ์€ ์—ด ์•ˆ์ •์„ฑ์„ ๊ฐ–๋Š” ์ „๊ตฌ์ฒด๋Š” ์‚ฌ๋ผ์ ธ์„œ ๊ธฐ๊ณต์„ ํ˜•์„ฑํ•  ์ˆ˜ ์žˆ๋‹ค [13-17]. ์ „๊ตฌ์ฒด๋กœ ์‚ฌ์šฉํ•œ PVDF๋Š” ์—ด์  ์•ˆ์ •์„ฑ์ด ๋†’์€ ๋ฌผ์งˆ์ด๋ฏ€๋กœ ๋‚ฎ์€ ์—ด์•ˆ์ •์„ฑ์„ ๊ฐ–๋Š” ์ „๊ตฌ์ฒด๋ฅผ ํ˜ผํ•ฉํ•˜์—ฌ ํƒ„ํ™”์‹œ์ผœ ๊ธฐ๊ณต์„ ์ƒ์„ฑ์‹œํ‚ค๋Š” ๋ธ”๋ Œ๋”ฉ ๋ฐฉ๋ฒ•์œผ๋กœ ๋ฉ”์กฐ๊ธฐ๊ณต์„ ํ˜•์„ฑํ•˜๊ณ ์ž ํ•˜์˜€๋‹ค. ๋”ฐ๋ผ์„œ, PVDF๋ณด๋‹ค ๋‚ฎ์€ ์—ด์  ์•ˆ์ •์„ฑ์„ ๊ฐ€์ง€๋ฉฐ PVDF์™€ ๋น„์Šทํ•œ ํ™”ํ•™ ๊ตฌ์กฐ๋ฅผ ๊ฐ–๋Š” PTFE๋ฅผ ๋ธ”๋ Œ๋”ฉ ๋ฌผ์งˆ๋กœ ํ™œ์šฉํ•˜๊ณ ์ž ํ•˜์˜€๋‹ค. ํŠนํžˆ PTFE๋Š” 480 ยฐC ์ •๋„์˜ ์˜จ๋„์—์„œ๋ถ€ํ„ฐ ๋ถ„ํ•ด๋˜๊ธฐ ์‹œ์ž‘ํ•˜์—ฌ 600 ยฐC์˜ ์˜จ๋„์—์„œ ๊ฑฐ์˜ ์™„์ „ํ•˜๊ฒŒ ๋ถ„ํ•ด๋˜์–ด ์‚ฌ๋ผ์ง„๋‹ค [18].

๋ณธ ์—ฐ๊ตฌ์—์„œ๋Š” ๋น„๊ต์  ํฐ ํฌ๊ธฐ์˜ ์ž…์ž๋ฅผ ๋ถ„๋ฆฌ ๋˜๋Š” ์ œ๊ฑฐํ•˜๊ธฐ ์œ„ํ•œ ํƒ„์†Œ ์†Œ์žฌ๋ฅผ ํ•ฉ์„ฑํ•˜๊ธฐ ์œ„ํ•˜์—ฌ ๋‹จ์ˆœํ•œ ์—ด์ฒ˜๋ฆฌ๋กœ๋งŒ ๋†’์€ ๋น„ํ‘œ๋ฉด์ ์„ ํ˜•์„ฑํ•˜๋Š” PVDF๋ฅผ ์ „๊ตฌ์ฒด๋กœ ์‚ฌ์šฉํ•˜์—ฌ ํƒ„์†Œ๋ฅผ ํ•ฉ์„ฑํ•˜๊ณ ์ž ํ•˜์˜€๋‹ค. ํŠนํžˆ PVDF๋ฅผ ํƒˆ๋ถˆํ™” ์‹œ์ผœ ๋งˆ์ดํฌ๋กœ ๊ธฐ๊ณต ์ƒ์„ฑ์„ ์–ต์ œํ•˜๊ณ ์ž ํ•˜์˜€๋‹ค. ๋งˆ์ดํฌ๋กœ ๊ธฐ๊ณต ๊ฐ์†Œ์— ์˜ํ•œ ๋น„ํ‘œ๋ฉด์  ๊ฐ์†Œ๋ฅผ ์ƒ์‡„์‹œํ‚ค๋Š” ๋™์‹œ์— ํฐ ์ž…์ž์˜ ๋ถ„๋ฆฌ ๋ฐ ์ œ๊ฑฐ๋ฅผ ์œ„ํ•˜์—ฌ ๋ฉ”์กฐ ๊ธฐ๊ณต์„ ๊ฐ–๋Š” ํ•œ ๋‹ค๊ณต์„ฑ ํƒ„์†Œ๋ฅผ ํ˜•์„ฑํ•˜๊ณ ์ž ํ•˜์˜€๋‹ค. ํ•ฉ์„ฑ๋œ ๋‹ค๊ณต์„ฑ ํƒ„์†Œ๋ฅผ ์ˆ˜์šฉ์•ก๋‚ด ๋ถˆ์ˆœ๋ฌผ ์ž…์ž ์ œ๊ฑฐ์— ํ™œ์šฉํ•˜๊ธฐ ์œ„ํ•˜์—ฌ ํ•ฉ์„ฑ๋œ ํƒ„์†Œ์˜ ์ –์Œ์„ฑ์„ ๋ถ„์„ํ•˜์˜€์œผ๋ฉฐ ํก์ฐฉ ์„ฑ๋Šฅ์˜ ๋ถ„์„์„ ์œ„ํ•ด์„œ ์ „๊ธฐํ™”ํ•™์  ๋ฐฉ๋ฒ•์„ ์‚ฌ์šฉํ•˜์—ฌ ํก์ฐฉ ์šฉ๋Ÿ‰๊ณผ ๋ฉ”์กฐ ๊ธฐ๊ณต์˜ ๋ฐœ๋‹ฌ์„ ๋ถ„์„ํ•˜์˜€๋‹ค.

2. ์‹คํ—˜ ๋ฐฉ๋ฒ•

2.1 Materials

ํƒ„์†Œ ํ•ฉ์„ฑ์„ ์œ„ํ•œ ์ „๊ตฌ๋ฌผ์งˆ์ธ Polyvinylidene fluoride(PVDF)๋Š” Fisher Scientific Korea Ltd.์—์„œ ๊ตฌ์ž…ํ•˜์˜€์œผ๋ฉฐ Polytetrafluoroethylene (PTFE; ์ž…์ž ์ง€๋ฆ„ 1 ฮผm)๋Š” Sigma Aldrich Inc.์—์„œ ๊ตฌ์ž…ํ•˜์˜€๋‹ค. ํด๋ฆฌ๋จธ ๊ธฐ๋ฐ˜์˜ ์ „๊ตฌ์ฒด๋ฅผ ์šฉํ•ด์‹œํ‚ค๊ธฐ ์œ„ํ•˜์—ฌ Dimethylformamide(DMF)์™€ ํƒˆ๋ถˆํ™” ์ฒ˜๋ฆฌ๋ฅผ ์œ„ํ•œ ์šฉ๋งค๋กœ 1,8-Diazabicyclo(5.4.0)undec-7-ene(DBU)๋Š” Samchun chemicals์—์„œ ๊ตฌ๋งคํ•˜์˜€๋‹ค. ํ•ฉ์„ฑ ์ค‘์— ์‚ฌ์šฉํ•œ ์—ํƒ„์˜ฌ์€ Duksan pure chemicals์—์„œ ๊ตฌ๋งคํ•˜์˜€๋‹ค. ๋ชจ๋“  ํ™”ํ•™ ๋ฌผ์งˆ์€ ์ƒ์—…์ ์œผ๋กœ ๊ตฌ๋งค๋˜์—ˆ์œผ๋ฉฐ ์ถ”๊ฐ€์ ์ธ ์ •์ œ๊ณผ์ • ์—†์ด ํ™œ์šฉ๋˜์—ˆ๋‹ค.

2.2 Carbon synthesis

ํƒ„์†Œ ์ „๊ตฌ์ฒด์ธ PVDF (2 g)์™€ ๋ฉ”์กฐ ๊ธฐ๊ณต ํ˜•์„ฑ์„ ์œ„ํ•œ PTFE (2 g)๋ฅผ ์šฉํ•ดํ•˜๊ธฐ ์œ„ํ•˜์—ฌ DMF ์šฉ๋งค(100 ml)๋ฅผ ์‚ฌ์šฉํ•˜์˜€๋‹ค. ๋‘ ๊ฐ€์ง€ ํด๋ฆฌ๋จธ๊ฐ€ ์™„์ „ํžˆ ์šฉํ•ด๋œ ์šฉ์•ก์— DBU์šฉ๋งค๋ฅผ ์ถ”๊ฐ€๋กœ ์ฒจ๊ฐ€ํ•˜์—ฌ ํƒˆ๋ถˆํ™” ๊ณต์ •์„ ์ง„ํ–‰ํ•˜์˜€๋‹ค. ์ „๊ตฌ์ฒด์ธ PVDF๋กœ๋ถ€ํ„ฐ ๋ถˆ์†Œ์˜ ์ œ๊ฑฐ ์–‘์„ ์กฐ์ ˆํ•˜๊ธฐ ์œ„ํ•˜์—ฌ ์ฒจ๊ฐ€ํ•˜๋Š” DBU์˜ ์–‘์„ ์กฐ์ ˆํ•˜์˜€๋‹ค. DBU์™€ PVDF์˜ ๋น„์œจ์„ DBU/vinylidene fluoride unit = 1, 5, 10, 20์˜ 4๊ฐ€์ง€ ๋น„์œจ๋กœ ์กฐ์ ˆํ•˜์˜€๋‹ค. ์šฉ์•ก๋‚ด์—์„œ ๋‘ ๊ฐ€์ง€ ํด๋ฆฌ๋จธ์™€ DBU์šฉ๋งค๊ฐ€ ์ž˜ ํ˜ผํ•ฉ๋˜๊ฒŒ ํ•˜๊ธฐ ์œ„ํ•ด ์—ํƒ„์˜ฌ 11 ml๋ฅผ ์ถ”๊ฐ€๋กœ ์ฒจ๊ฐ€ํ•˜์˜€๋‹ค. ๋”ฐ๋ผ์„œ, ์šฉ์•ก๋‚ด์—์„œ ์—ํƒ„์˜ฌ(11 ml)๊ณผ DMF(100 ml)์˜ ๋น„์œจ์€ ์•ฝ 1:9๋กœ ์กฐ์ ˆ๋˜์—ˆ๋‹ค. ์ฒจ๊ฐ€ ํ›„ ์œ ๋ฆฌ๋ง‰๋Œ€๋ฅผ ์‚ฌ์šฉํ•˜์—ฌ ํด๋ฆฌ๋จธ ์ „๊ตฌ์ฒด๊ฐ€ ์šฉ๋งค์— ์™„์ „ํžˆ ์šฉํ•ด๋˜๋„๋ก ์ถฉ๋ถ„ํžˆ ์ €์–ด์ค€ ํ›„ 70 ยฐC์˜ ์˜จ๋„์—์„œ 24 h ๋™์•ˆ ์œ ์ง€ํ•˜๋ฉฐ ํƒˆ๋ถˆํ™”๊ณผ์ •์„ ์ˆ˜ํ–‰ํ•˜์˜€๋‹ค. ํƒˆ๋ถˆํ™”๊ฐ€ ์™„๋ฃŒ๋œ ํ›„ DMF์™€ DBU๋ฅผ ์ œ๊ฑฐํ•˜๊ธฐ ์œ„ํ•ด ์ง„๊ณต ์—ฌ๊ณผ์žฅ์น˜(vacuum filtration)๋ฅผ ํ™œ์šฉํ•˜์—ฌ ์—ํƒ„์˜ฌ๋กœ ์—ฌ๋Ÿฌ ๋ฒˆ ์„ธ์ฒ™๊ณผ ๋™์‹œ์— ์—ฌ๊ณผ์‹œ์ผœ ์ฃผ์—ˆ๋‹ค. ์—ฌ๊ณผ๋œ ๋ฌผ์งˆ์€ ์ƒ์˜จ(25ยฑ2 ยฐC)์—์„œ 24 h๋™์•ˆ ์ž์—ฐ ๊ฑด์กฐํ•˜์—ฌ ์ค€๋น„๋˜์—ˆ๋‹ค. ๊ฑด์กฐ๋œ ๋ฌผ์งˆ์€ tube furnace๋‚ด์—์„œ ๋ถ„๋‹น 5 ยฐC์˜ ์Šน์˜จ ์†๋„์กฐ๊ฑด์—์„œ ์—ด์„ ๊ฐ€ํ•˜์—ฌ 900 ยฐC์—์„œ 2์‹œ๊ฐ„ ๋™์•ˆ ์งˆ์†Œ๋ถ„์œ„๊ธฐ(flow rate: 300 cm3 min-1)์—์„œ ์—ด์ฒ˜๋ฆฌํ•˜์—ฌ ํƒ„์†Œ๋ฅผ ํ•ฉ์„ฑํ•˜์˜€๋‹ค. ํ•ฉ์„ฑ๋œ ํƒ„์†Œ๋Š” DBU์˜ ๋น„์œจ์— ๋”ฐ๋ผ์„œ xDBU(x: DBU/vinylidene fluoride unit)๋ผ๊ณ  ๋ช…๋ช…๋˜์—ˆ๋‹ค. ์˜ˆ๋ฅผ ๋“ค์–ด 5DBU ์ƒ˜ํ”Œ์€ PVDF 2 g๊ณผ PTFE 2 g์˜ ์šฉ์งˆ๊ณผ DBU/vinylidene fluoride = 5์˜ ๋น„์œจ๋กœ DBU์šฉ๋งค๊ฐ€ ์‚ฌ์šฉ๋œ ์šฉ์•ก์œผ๋กœ๋ถ€ํ„ฐ ํ•ฉ์„ฑ๋œ ๋‹ค๊ณต์„ฑ ํƒ„์†Œ๋ฅผ ์˜๋ฏธํ•œ๋‹ค.

2.3 Material Characterization

์ œ์กฐ๋œ ํƒ„์†Œ์˜ ํ˜•์ƒํ•™์  ํŠน์„ฑ ๋ถ„์„์„ ์œ„ํ•ด ์ „๊ณ„ ๋ฐฉ์ถœ ์ฃผ์‚ฌ ์ „์ž ํ˜„๋ฏธ๊ฒฝ(FE-SEM) (SU9220, Hitachi, Japan)์„ ์‚ฌ์šฉํ•˜์—ฌ ๋ถ„์„ํ•˜์˜€์œผ๋ฉฐ, 5 kV ๊ฐ€์† ์ „์•• ๋ฐ 10 mm ์ž‘๋™ ๊ฑฐ๋ฆฌ์—์„œ ํƒ„์†Œ ์ƒ˜ํ”Œ์˜ ํ‘œ๋ฉด ๊ตฌ์กฐ๋ฅผ ๊ด€์ฐฐํ•˜์˜€๋‹ค. FE-SEM์žฅ๋น„์— ๊ฒฐํ•ฉ๋œ Energy Dispersive Spectroscopy (EDS) (X-max n80, Horiba, Japan) ์žฅ๋น„๋ฅผ ์ด์šฉํ•˜์—ฌ ํ•ฉ์„ฑ๋œ ํƒ„์†Œ์˜ ํ™”ํ•™์  ์„ฑ๋ถ„ ๋ถ„์„์„ ์‹ค์‹œํ•˜์˜€๋‹ค.

ํƒ„์†Œ์— ์กด์žฌํ•˜๋Š” ํ‰๊ท  ๊ธฐ๊ณต ํฌ๊ธฐ, ๊ธฐ๊ณต ๋ถ„ํฌ ๋ฐ ๋น„ํ‘œ๋ฉด์ ์„ ์ธก์ •ํ•˜๊ธฐ ์œ„ํ•˜์—ฌ ์งˆ์†Œ ํก์ฐฉ๊ฐ€์Šค๋ฅผ ์ด์šฉํ•˜์—ฌ Gas sorption analyzer๋ฅผ ์ด์šฉํ•˜์˜€๊ณ , ๋น„ํ‘œ๋ฉด์ ์€ ์ธก์ •๋œ ๋“ฑ์˜จ ํก์ฐฉ๊ณก์„ ์„ multi-point Brunauer-Emmett-Teller (BET)์ด๋ก ์„ ๋ฐ”ํƒ•์œผ๋กœ ๊ณ„์‚ฐํ•˜์˜€๋‹ค. ์–ป์–ด์ง„ ๋“ฑ์˜จ ํก์ฐฉ ๊ณก์„ ์œผ๋กœ๋ถ€ํ„ฐ quenched solid density functional theory (QSDFT) ๋ฐฉ๋ฒ•์„ ์‚ฌ์šฉํ•˜์—ฌ ๊ธฐ๊ณต ๋ถ„ํฌ๋„ ๊ณก์„ ์„ ๋‚˜ํƒ€๋‚ด์—ˆ๋‹ค.

ํ•ฉ์„ฑ๋œ ํƒ„์†Œ์˜ ๋ชจ๋“  ์ „๊ธฐ ํ™”ํ•™์  ๋ถ„์„์€ ์ „์œ„์ฐจ๊ณ„(VMP3, Bio-Logic Science lns, France)๋ฅผ ์‚ฌ์šฉํ•˜์—ฌ ๋‹ค์Œ์˜ ์กฐ๊ฑด์—์„œ ์ „๊ทน์„ ์ œ์ž‘ํ•œ ํ›„ ๋ถ„์„ํ•˜์˜€๋‹ค. ํ•ฉ์„ฑ๋œ ํƒ„์†Œ, PTFE, Acetylene black์„ 85:10:5์˜ ์งˆ๋Ÿ‰๋น„๋กœ ๋งˆ๋…ธ์œ ๋ฐœ(agate mortar)๊ณผ ๋งˆ๋…ธ์œ ๋ด‰(agate pestle)์„ ์ด์šฉํ•˜์—ฌ ๋ฌผ๋ฆฌ์ ์œผ๋กœ ์„ž์–ด ํ˜ผํ•ฉํ•˜์˜€๋‹ค. ์ œ์กฐ๋œ ํ˜ผํ•ฉ๋ฌผ์€ ๋‹ˆ์ผˆ ๋ฉ”์‰ฌ ๊ธฐํŒ์œ„์— ์œ ์••ํ”„๋ ˆ์Šค(hydraulic press; 200 Mpa)๋ฅผ ์‚ฌ์šฉํ•˜์—ฌ ์••์ฐฉํ•˜์—ฌ ์ „๊ทน์„ ์ œ์กฐํ•˜์˜€๋‹ค. ์ „๊ทน ๋ฌผ์งˆ์˜ ์ „๊ธฐํ™”ํ•™์  ํŠน์„ฑ์€ ๋น„์ปคํ˜•ํƒœ์˜ ์‚ผ ์ „๊ทน ์…€(three-electrode cell)์„ ๊ตฌ์„ฑํ•˜์—ฌ ๋ฐ˜์ชฝ ์ „์ง€ ๊ตฌ์„ฑ์œผ๋กœ ์ธก์ • ๋ฐ ๋ถ„์„ํ•˜์˜€์œผ๋ฉฐ ์‚ฌ์šฉ๋œ ์ „ํ•ด์งˆ์€ 0.5M Na2SO4์„ ์‚ฌ์šฉํ•˜์˜€๋‹ค. ํ˜ผํ•ฉ๋œ ํƒ„์†Œ ์ „๊ทน์€ ์ž‘๋™์ „๊ทน(working electrode)์œผ๋กœ ์‚ฌ์šฉํ•˜์˜€๋‹ค. ์ƒ๋Œ€ ์ „๊ทน(counter electrode)์œผ๋กœ ๋ฐฑ๊ธˆ ์„ ์„ ์‚ฌ์šฉํ•˜์˜€๊ณ  ์ฐธ์กฐ ์ „๊ทน(reference electrode)์œผ๋กœ saturated calomel electrode(-0.241 V vs. Normal hydrogen electrode(NHE))๋ฅผ ์‚ฌ์šฉํ•˜์˜€๋‹ค.

์ „๊ทน/์ „ํ•ด์งˆ ๊ณ„๋ฉด์—์„œ์˜ ๋ฐ˜์‘์„ ๋ถ„์„ํ•˜๊ธฐ ์œ„ํ•˜์—ฌ ์ž„ํ”ผ๋˜์Šค ๋ถ„์„์„ ์‚ฌ์šฉํ•˜์˜€๊ณ  0.1 Hz-1000 kHz ์ฃผํŒŒ์ˆ˜ ๋ฒ”์œ„์—์„œ 5mV ์ง„ํญ์„ ๊ฐ–๋Š” ์‚ฌ์ธ ํŒŒํ˜•์„ ๊ฐ€ํ•˜์—ฌ 0 V์˜ ์กฐ๊ฑด์—์„œ ์ˆ˜ํ–‰ํ•˜์˜€๋‹ค [19]. ์ œ์กฐ๋œ ํƒ„์†Œ์˜ ๋น„ ์ „๊ธฐ์šฉ๋Ÿ‰(specific capacitance)๊ณผ ์ „๊ธฐํ™”ํ•™์  ๊ฑฐ๋™์˜ ๋ณ€ํ™”๋Š” cyclic voltammetry(CV) ๋ฐฉ๋ฒ•์„ ์ด์šฉํ•˜์—ฌ ๋ถ„์„ํ•˜์˜€์œผ๋ฉฐ ์ฃผ์‚ฌ ์†๋„(scan rate)๋ฅผ 50, 20, 10, 5 mV s-1๋กœ ๋ณ€ํ™”ํ•˜๋ฉฐ ์ „๊ธฐํ™”ํ•™ ๋ฐ˜์‘์˜ ๋ณ€ํ™”๋ฅผ ๊ด€์ฐฐํ•˜์˜€๋‹ค. ๋น„ ์ „๊ธฐ์šฉ๋Ÿ‰์€ 5 mV s-1์˜ ๋А๋ฆฐ ์ฃผ์‚ฌ ์†๋„์—์„œ ์ธก์ •๋œ voltammogram์œผ๋กœ๋ถ€ํ„ฐ ์–ป์–ด์ง„ ๊ฐ’์œผ๋กœ ๊ณ„์‚ฐํ•˜์˜€๋‹ค. ์ฃผ์‚ฌ์†๋„์— ๋”ฐ๋ฅธ ๋น„ ์ „๊ธฐ์šฉ๋Ÿ‰์˜ ๋ณ€ํ™”๋Š” 5 mV s-1์—์„œ ๊ณ„์‚ฐ๋œ ๋น„ ์ „๊ธฐ์šฉ๋Ÿ‰ ๊ฐ’์„ ๊ธฐ์ค€์œผ๋กœ ๋‹ค๋ฅธ ์ฃผ์‚ฌ ์†๋„์—์„œ ์ธก์ •๋œ ๋น„์ „๊ธฐ์šฉ๋Ÿ‰ ๊ฐ’์˜ ๋น„๋ฅผ ๋ฐฑ๋ถ„์œจ๋กœ ๋‚˜ํƒ€๋‚ด์–ด ๋ถ„์„ํ•˜์˜€๋‹ค.

3. ๊ฒฐ๊ณผ ๋ฐ ๊ณ ์ฐฐ

๊ทธ๋ฆผ 1์€ PVDF ์ „๊ตฌ์ฒด์˜ ์—ด์ฒ˜๋ฆฌ๋กœ ํ•ฉ์„ฑํ•œ ํƒ„์†Œ(PVDF-only)๋ฅผ ์งˆ์†Œ ํก์ฐฉ๋ฒ•์„ ์ด์šฉํ•˜์—ฌ ๊ธฐ๊ณต ํฌ๊ธฐ ๋ณ„ ๋ถ„ํฌ๋ฅผ ๋ถ„์„ํ•œ ๊ฒฐ๊ณผ์ด๋‹ค. 2 nm๋ณด๋‹ค ์ž‘์€ ํฌ๊ธฐ์˜ ๋งˆ์ดํฌ๋กœ ๊ธฐ๊ณต์ด ๋ฉ”์กฐ ํฌ๊ธฐ์˜ ๊ธฐ๊ณต์— ๋น„ํ•ด ์ƒ๋‹นํžˆ ๋งŽ์ด ํ˜•์„ฑ๋œ ๊ฒƒ์„ ํ™•์ธํ•  ์ˆ˜ ์žˆ๋‹ค. PVDF์˜ ์—ด์ฒ˜๋ฆฌ๋กœ ํ•ฉ์„ฑ๋œ ๋‹ค๊ณต์„ฑ ํƒ„์†Œ์— ํ˜•์„ฑ๋œ ์ž‘์€ ๋งˆ์ดํฌ๋กœ ๊ธฐ๊ณต์€ PVDF์˜ ๋ถˆ์†Œ์›์ž์™€ ์ˆ˜์†Œ์›์ž๊ฐ€ ๊ณ ์˜จ ์—ด์ฒ˜๋ฆฌ์‹œ HF๋กœ ๋ฐœ์ƒํ•˜์—ฌ ์ œ๊ฑฐ๋œ ๋ถˆ์†Œ ์ž๋ฆฌ๋กœ๋ถ€ํ„ฐ ํ˜•์„ฑ๋œ๋‹ค. ์ž‘์€ ๋ฏธ์„ธ๊ธฐ๊ณต์€ ๋น„ํ‘œ๋ฉด์ ์„ ํ–ฅ์ƒ์‹œํ‚ค๊ณ  ๋‚˜๋…ธ ๋‹จ์œ„์˜ ํก์ฐฉ์งˆ(adsorbate)์˜ ํก์ฐฉ ๋ฐ ๋ถ„๋ฆฌ๋ฅผ ๊ฐ€๋Šฅํ•˜๊ฒŒ ํ•˜๋ฏ€๋กœ ๋‹ค์–‘ํ•œ ๋ถ„์•ผ์—์„œ ํ™œ์šฉ๋  ์ˆ˜ ์žˆ๋‹ค. ํ•˜์ง€๋งŒ, ์‘์šฉ๋ถ„์•ผ์— ๋”ฐ๋ผ์„œ ํฐ ํฌ๊ธฐ์˜ ๊ธฐ๊ณต์„ ๊ฐ–๋Š” ๋‹ค๊ณต์„ฑ ํƒ„์†Œ๋ฅผ ํ•„์š”๋กœ ํ•˜๊ธฐ๋„ ํ•œ๋‹ค. ์˜ˆ๋ฅผ๋“ค๋ฉด, ํฐ ํฌ๊ธฐ ์ž…์ž์˜ ํก์ฐฉ ๋˜๋Š” ๋ถ„๋ฆฌ๋ฅผ ํ•„์š”๋กœ ํ•˜๋Š” ํ•„ํ„ฐ์†Œ์žฌ์˜ ๊ฒฝ์šฐ์—๋Š” ๋ฉ”์กฐ ๊ธฐ๊ณต(2 nm <์ง€๋ฆ„ < 50 nm)์„ ๊ฐ–๋Š” ๋‹ค๊ณต์„ฑ ๊ตฌ์กฐ๊ฐ€ ํ•„์š”ํ•˜๋‹ค [20]. ๋”ฐ๋ผ์„œ, ๋ณธ ์—ฐ๊ตฌ์—์„œ๋Š” ํฐ ์ž…์ž์˜ ํก์ฐฉ ๋˜๋Š” ๋ถ„๋ฆฌ๋ฅผ ์œ„ํ•œ ๋‹ค๊ณต์„ฑ ํƒ„์†Œ ํ•ฉ์„ฑ์„ ์œ„ํ•ด ํฐ ์ž…์ž ํก์ฐฉ์— ๋ถˆ๋ฆฌํ•œ ๋งˆ์ดํฌ๋กœ ๊ธฐ๊ณต์˜ ํ˜•์„ฑ์„ ์–ต์ œํ•˜๊ณ ์ž ํ•˜์˜€๋‹ค. PVDF๋‚ด ๋ถˆ์†Œ์›์†Œ ์ œ๊ฑฐ ์ฆ‰, ํƒˆ๋ถˆํ™” ๊ณต์ •์„ ํ†ตํ•˜์—ฌ ๋งˆ์ดํฌ๋กœ ๊ธฐ๊ณต ํ˜•์„ฑ ๋ฐ˜์‘์„ ์–ต์ œํ•˜๊ณ ์ž ํ•˜์˜€๋‹ค.

PVDF์˜ ํƒˆ๋ถˆํ™” ๊ณต์ •์€ DBU์šฉ๋งค๋ฅผ ์ด์šฉํ•˜์˜€๋‹ค. ๋จผ์ €, PVDF์ „๊ตฌ์ฒด๋ฅผ DMF(100 ml)์™€ ์—ํƒ„์˜ฌ(11 ml) ํ˜ผํ•ฉ์šฉ๋งค์— ๋„ฃ์–ด ์œ ๋ฆฌ๋ง‰๋Œ€๋ฅผ ์‚ฌ์šฉํ•˜์—ฌ ํด๋ฆฌ๋จธ ์ „๊ตฌ์ฒด๊ฐ€ ํ˜ผํ•ฉ์šฉ๋งค์— ์ถฉ๋ถ„ํžˆ ์šฉํ•ด๋  ์ˆ˜ ์žˆ๋„๋ก ์ €์–ด์ฃผ์—ˆ๋‹ค. ์ด๋•Œ ๋ถˆ์†Œ์›์†Œ๋ฅผ ์ถฉ๋ถ„ํžˆ ์ œ๊ฑฐํ•˜๊ธฐ ์œ„ํ•˜์—ฌ ์ถฉ๋ถ„ํ•œ ์–‘์˜ DBU๋ฅผ ์‚ฌ์šฉํ•˜์˜€๋‹ค(DBU/vinylidene fluoride unit = 10). ํ˜ผํ•ฉ๋œ ์šฉ์•ก์œผ๋กœ๋ถ€ํ„ฐ ํƒ„์†Œ์˜ ํ•ฉ์„ฑ์€ ์‹คํ—˜ ๋ฐฉ๋ฒ•์— ์–ธ๊ธ‰๋œ ์ ˆ์ฐจ๋ฅผ ๋”ฐ๋ผ ์ˆ˜ํ–‰๋˜์—ˆ์œผ๋ฉฐ ์ด๋ ‡๊ฒŒ ํ•ฉ์„ฑ๋œ ํƒ„์†Œ๋Š” PVDF-10DBU๋กœ ๋ช…๋ช…๋˜์—ˆ๋‹ค. ํ•ฉ์„ฑ๋œ ํƒ„์†Œ์— ๋Œ€ํ•ด ์ธก์ •ํ•œ ๊ธฐ๊ณต ๊ตฌ์กฐ๋Š” ๋งˆ์ดํฌ๋กœ ๊ธฐ๊ณต์ด ๊ฑฐ์˜ ์กด์žฌํ•˜์ง€ ์•Š์œผ๋ฉฐ 3-20 nm ํฌ๊ธฐ์˜ ๋ฉ”์กฐ๊ธฐ๊ณต์„ ๊ฐ–๋Š” ๋‹ค๊ณต์„ฑ ํƒ„์†Œ๊ฐ€ ํ•ฉ์„ฑ๋˜์—ˆ๋‹ค (๊ทธ๋ฆผ 1(a)). PVDF๋‚ด ๋ฐฑ๋ณธ(backbone)์— ์žˆ๋Š” ํƒ„์†Œ์›์ž๋“ค์€ ์—ด์ฒ˜๋ฆฌ์‹œ ์‘์ง‘ํ•˜์—ฌ ๊ทธ๋ž˜ํ•€ ์ ์ธต ๊ตฌ์กฐ์˜ ํƒ„์†Œ ์ž…์ž๋ฅผ ํ˜•์„ฑํ•˜๋Š”๋ฐ ํƒ„์†Œ์ž…์ž ์‚ฌ์ด์˜ ๊ณต๊ฐ„์€ ํฐ ํฌ๊ธฐ์˜ ๋ฉ”์กฐ๊ธฐ๊ณต์„ ํ˜•์„ฑํ•˜๋Š” ๊ฒƒ์œผ๋กœ ์ƒ๊ฐ๋œ๋‹ค. ๊ธฐ๊ณต ๊ตฌ์กฐ์˜ ๋ถ„์„๊ณผ ํ•จ๊ป˜ ํ•ฉ์„ฑ๋œ ํƒ„์†Œ๋“ค์— ๋Œ€ํ•œ ๋น„ํ‘œ๋ฉด์  ๋ถ„์„๊ฒฐ๊ณผ PVDF-only์™€ PVDF-10DBU ์ƒ˜ํ”Œ์€ ๊ฐ๊ฐ 971 m2 g-1๊ณผ 93 m2 g-1์„ ๋‚˜ํƒ€๋‚ด์—ˆ๋‹ค (ํ‘œ 1). DBU๋ฅผ ์ด์šฉํ•˜์—ฌ ํƒˆ๋ถˆํ™”๋œ ์ „๊ตฌ์ฒด๋กœ๋ถ€ํ„ฐ ํ•ฉ์„ฑ๋œ PVDF-10DBU์ƒ˜ํ”Œ์˜ ๊ฒฝ์šฐ ๋งˆ์ดํฌ๋กœ ๊ธฐ๊ณต์˜ ํ˜•์„ฑ์ด ์–ต์ œ๋˜๊ณ  ๋˜ํ•œ ๋ฉ”์กฐ ๊ธฐ๊ณต๋Ÿ‰๋„ ๊ฐ์†Œํ•˜์—ฌ ๋น„ํ‘œ๋ฉด์ ์ด ์ƒ๋‹นํžˆ ๋‚ฎ์•„์ง„ ๊ฒƒ์œผ๋กœ ๊ฐ„์ฃผ๋œ๋‹ค.

๋‘ ๊ฐ€์ง€ ํ•ฉ์„ฑ๋œ ๋‹ค๊ณต์„ฑ ํƒ„์†Œ์˜ ๊ธฐ๊ณต ๊ตฌ์กฐ๋ฅผ cyclic voltammetry๋ฅผ ์ด์šฉํ•˜์—ฌ ์ „๊ธฐํ™”ํ•™ ์ธก์ •๋ฒ•์œผ๋กœ ๋ถ„์„ํ•˜์˜€๋‹ค(๊ทธ๋ฆผ 1(b)). ๋‹ค๊ณต์„ฑ ํƒ„์†Œ๋กœ ์ œ์ž‘๋œ ์ „๊ทน์„ ์ „ํ•ด์งˆ์— ๋‹ด๊ทผ ํ›„ ์ผ์ •ํ•œ ์ „์•• ํฌํ…์…œ ๊ตฌ๊ฐ„์—์„œ ์ผ์ •ํ•œ ์†๋„๋กœ ํฌํ…์…œ์„ ์ฆ๊ฐ€์‹œํ‚ค๋ฉด ์ „ํ•ด์งˆ๋‚ด ์กด์žฌํ•˜๋Š” ์ด์˜จ๋“ค์ด ์ „๊ทน์— ํก์ฐฉํ•˜๋ฉฐ ์ „๋ฅ˜๊ฐ€ ํ๋ฅด๊ฒŒ ๋˜๋Š”๋ฐ, ์ด๋•Œ ์ธก์ •๋˜๋Š” ์ „๋ฅ˜๊ฐ’์€ ์ „ํ•ด์งˆ ์ด์˜จ๋“ค์ด ํƒ„์†Œ ์ „๊ทน์— ํก์ฐฉ๋˜๋Š” ์–‘์— ๋น„๋ก€ํ•œ๋‹ค. ์ฆ‰, ์ธก์ •๋œ voltammogram๊ณก์„ ์—์„œ ๊ณ„์‚ฐ๋œ ๋น„ ์ „๊ธฐ์šฉ๋Ÿ‰ ๊ฐ’์€ ํƒ„์†Œ ์ „๊ทน์— ํก์ฐฉ๋œ ์ด์˜จ ํก์ฐฉ๋Ÿ‰์— ๋น„๋ก€ํ•œ๋‹ค. ๋”ฐ๋ผ์„œ voltammetry ์‹คํ—˜์œผ๋กœ๋ถ€ํ„ฐ ํƒ„์†Œ ์ „๊ทน์˜ ์ „ํ•ด์งˆ ์šฉ์•ก๋‚ด ์กด์žฌํ•˜๋Š” Na+(0.358 nm), SO42-(0.379 nm) ์ด์˜จ ํก์ฐฉ ๋Šฅ๋ ฅ์„ ์ •๋Ÿ‰์ ์œผ๋กœ ๊ณ„์‚ฐํ•  ์ˆ˜ ์žˆ๋‹ค [21]. ํ‘œ 1์—์„œ ๋ณด์ด๋Š” ๊ฒƒ์ฒ˜๋Ÿผ PVDF-10DBU์ƒ˜ํ”Œ๋กœ๋ถ€ํ„ฐ ๊ณ„์‚ฐ๋œ ๋น„์ „๊ธฐ์šฉ๋Ÿ‰ 2.8 F g-1์€ PVDF0nly์˜ 78.4 F g-1์— ์ƒ๋‹นํžˆ ๋‚ฎ์€ ๊ฐ’์„ ๋ณด์—ฌ์ค€๋‹ค. ์ฆ‰, ๋งˆ์ดํฌ๋กœ ํฌ๊ธฐ์˜ ๊ธฐ๊ณต์ด ๊ฑฐ์˜ ์‚ฌ๋ผ์ง€๊ณ  ๋ฉ”์กฐ ๊ธฐ๊ณต์œผ๋กœ๋งŒ ๊ตฌ์„ฑ๋œ ๋‹ค๊ณต์„ฑ ํƒ„์†Œ๋Š” ๋‚˜๋…ธ ํฌ๊ธฐ์˜ ์ด์˜จ ํก์ฐฉ ๋Šฅ๋ ฅ์ด ์ƒ๋‹นํžˆ ๋‚ฎ๋‹ค๋Š” ๊ฒƒ์„ voltammogram ๊ฒฐ๊ณผ๋กœ๋ถ€ํ„ฐ ์•Œ ์ˆ˜ ์žˆ๋‹ค. ๋”ฐ๋ผ์„œ PVDF-10DBU์ƒ˜ํ”Œ์˜ ๊ฒฝ์šฐ PVDF-only์ƒ˜ํ”Œ์— ๋น„ํ•˜์—ฌ ๋น„๋ก ๋ฉ”์กฐ๊ธฐ๊ณต์˜ ๋น„์œจ์€ ์ฆ๊ฐ€ํ•˜์˜€์œผ๋‚˜ ์ ˆ๋Œ€์ ์ธ ๊ธฐ๊ณต๋Ÿ‰ ๊ฐ์†Œ๋กœ ์ธํ•œ ํ‘œ๋ฉด์ ์˜ ๊ฐ์†Œ๋กœ ์ธํ•˜์—ฌ ์ด์˜จ ํก์ฐฉ๋Ÿ‰์ด ๊ฐ์†Œํ•œ ๊ฒƒ์œผ๋กœ ์ƒ๊ฐ๋œ๋‹ค.

๋‹ค๊ณต์„ฑ ํƒ„์†Œ์— ์กด์žฌํ•˜๋Š” ๊ธฐ๊ณต์˜ ํ‰๊ท  ํฌ๊ธฐ๊ฐ€ ์ฆ๊ฐ€ํ•˜๋ฉด ์ „ํ•ด์งˆ ์ด์˜จ์˜ ์ „๊ทน ํ‘œ๋ฉด์œผ๋กœ ํก์ฐฉ์ด ์šฉ์ดํ•˜๊ฒŒ ๋œ๋‹ค. ๋”ฐ๋ผ์„œ ๋†’์€ ์ฃผ์‚ฌ ์†๋„์˜ voltammetry์—์„œ๋„ ๋†’์€ ๋น„ ์ „๊ธฐ์šฉ๋Ÿ‰์„ ๋‚˜ํƒ€๋‚ผ ๊ฒƒ์œผ๋กœ ๊ธฐ๋Œ€๋œ๋‹ค. ํ•˜์ง€๋งŒ, ๊ทธ๋ฆผ 1(b)์˜ ์‚ฝ๋„๋ฅผ ์‚ดํŽด๋ณด๋ฉด ๋ฉ”์กฐ ๊ธฐ๊ณต์˜ ๋น„์œจ์ด ๋†’์€ PVDF-10DBU์ƒ˜ํ”Œ์˜ ์šฉ๋Ÿ‰ ๋ณด์กด์œจ์ด ์˜คํžˆ๋ ค ๋” ๋‚ฎ์€ ๊ฒƒ์„ ๋ณผ ์ˆ˜ ์žˆ๋‹ค. ๋‚ฎ์€ ์šฉ๋Ÿ‰ ๋ณด์กด์œจ์˜ ์ด์œ ๋Š” ๋น„๋ก ๋ฉ”์กฐ๊ธฐ๊ณต์˜ ๋น„์œจ์€ ๋†’์•„์กŒ์œผ๋‚˜ ํƒˆ๋ถˆํ™”์— ์˜ํ•ด์„œ ๋งˆ์ดํฌ๋กœ ๊ธฐ๊ณต ์ƒ์„ฑ ์–ต์ œ์™€ ํ•จ๊ป˜ ๋ฉ”์กฐ ๊ธฐ๊ณต ๋˜ํ•œ ๊ฐ์†Œํ•˜์—ฌ ์ด์˜จ์˜ ์ด๋™์ด PVDF-only์— ๋น„ํ•ด์„œ ์˜คํžˆ๋ ค ๋” ๊ฐ์†Œํ•˜์˜€๊ธฐ ๋•Œ๋ฌธ์œผ๋กœ ์ƒ๊ฐ๋œ๋‹ค. ๋”ฐ๋ผ์„œ ๋ฉ”์กฐ๊ธฐ๊ณต์˜ ๋น„์œจ๊ณผ ํ•จ๊ป˜ ๋ฉ”์กฐ๊ธฐ๊ณต์˜ ์ ˆ๋Œ€๋Ÿ‰์„ ์ฆ๊ฐ€์‹œํ‚ค๊ธฐ ์œ„ํ•˜์—ฌ PVDF์™€ ํ•จ๊ป˜ PTFE๋ฅผ ์ „๊ตฌ์ฒด๋กœ ์‚ฌ์šฉํ•˜์—ฌ ํƒ„์†Œ๋ฅผ ํ•ฉ์„ฑํ•˜๊ณ ์ž ํ•˜์˜€๋‹ค. (C2F4)n์˜ ํ™”ํ•™์‹์„ ๊ฐ–๋Š” PTFE๋Š” ์—ด์ฒ˜๋ฆฌ์‹œ ๋ถˆ์†Œ์›์†Œ๊ฐ€ ํƒ„์†Œ์›์†Œ์™€ ํ•จ๊ป˜ C2F4์˜ ๊ธฐ์ฒด์ƒ์œผ๋กœ 99.97% ์ด์ƒ์ด ์ œ๊ฑฐ๊ฐ€ ๋˜๋ฉฐ PVDF์™€ ํ•จ๊ป˜ ํ˜ผํ•ฉํ•˜์—ฌ ํƒ„ํ™”์‹œํ‚ค๋ฉด PTFE๊ฐ€ ์ฐจ์ง€ํ•œ ๊ณต๊ฐ„์ด ๋ฉ”์กฐ ๊ธฐ๊ณต์œผ๋กœ ํ˜•์„ฑํ•œ๋‹ค [18,20]. ๊ฒŒ๋‹ค๊ฐ€ PTFE๋Š” PVDF์™€ ์œ ์‚ฌํ•œ ํ™”ํ•™ ๊ตฌ์กฐ์˜ ๊ฐ€์ง€๋ฉฐ, PVDF์™€ ๋‹ฌ๋ฆฌ DBU์— ์˜ํ•œ ํƒˆ๋ถˆํ™”๊ฐ€ ์ผ์–ด๋‚˜์ง€ ์•Š์œผ๋ฏ€๋กœ ๋ฉ”์กฐ ๊ธฐ๊ณต ํ˜•์„ฑ์— ๊ธฐ์—ฌ๋ฅผ ํ•  ์ˆ˜ ์žˆ์„ ๊ฒƒ์œผ๋กœ ๊ธฐ๋Œ€๋œ๋‹ค. ์ดํ›„ ๋…ผ์˜๋˜๋Š” ํƒ„์†Œ ์ƒ˜ํ”Œ๋“ค์€ ๋ชจ๋‘ PVDF์™€ PTFE์˜ ํ˜ผํ•ฉ์ „๊ตฌ์ฒด๋กœ๋ถ€ํ„ฐ ํ•ฉ์„ฑ๋˜์—ˆ๋‹ค.

PVDF์™€ ํ•จ๊ป˜ PTFE๋ฅผ ํ˜ผํ•ฉํ•œ ์ „๊ตฌ์ฒด๋ฅผ DBU ์šฉ๋งค๋ฅผ ์ด์šฉํ•˜์—ฌ ํƒˆ๋ถˆํ™” ํ•œ ํ›„ ์—ด์ฒ˜๋ฆฌ ๊ณต์ •์„ ํ†ตํ•˜์—ฌ ํ•ฉ์„ฑ๋œ ํƒ„์†Œ์˜ ํ‘œ๋ฉด ํ˜•์ƒ์„ ์ „์ž ์ฃผ์‚ฌ ํ˜„๋ฏธ๊ฒฝ(FE-SEM)์„ ์‚ฌ์šฉํ•˜์—ฌ ์ธก์ •ํ•˜์˜€๋‹ค (๊ทธ๋ฆผ 2). ๋‹ค์–‘ํ•œ ์–‘์˜ DBU์šฉ๋งค๋ฅผ ์‚ฌ์šฉํ•˜์—ฌ ํƒˆ๋ถˆํ™”์˜ ์ •๋„๋ฅผ ๋‹ฌ๋ฆฌํ•˜์—ฌ 4๊ฐ€์ง€ ์ข…๋ฅ˜์˜ ์ƒ˜ํ”Œ์ด ํ•ฉ์„ฑ๋˜์—ˆ๋‹ค. ํ•ฉ์„ฑ๋œ ํƒ„์†Œ์˜ ์›์ž ์กฐ์„ฑ ๋น„์œจ์€ EDS๋ถ„์„์„ ํ†ตํ•˜์—ฌ ์ธก์ •ํ•˜์˜€์œผ๋ฉฐ ์‚ฐ์†Œ(O)์ด์™ธ์˜ ๋‹ค๋ฅธ ๋ถˆ์ˆœ๋ฌผ์€ ์กด์žฌํ•˜์ง€ ์•Š๋Š” ๊ฒƒ์ด ํ™•์ธ๋˜์—ˆ๋‹ค (ํ‘œ 2). ๋‹ค๋งŒ, ์ˆ˜์†Œ ์›์†Œ๋Š” EDS๋ถ„์„์— ์˜ํ•ด ์ธก์ •๋˜์ง€ ์•Š์œผ๋ฏ€๋กœ XPS๋ฅผ ์ด์šฉํ•˜์—ฌ ์ˆ˜์†Œ์›์†Œ์™€์˜ ๊ฒฐํ•ฉ์€ ๋ถ„์„๋˜์—ˆ๋‹ค [22]. 1DBU์ƒ˜ํ”Œ์˜ ๊ฒฝ์šฐ ํƒ„์†Œ ํ‘œ๋ฉด์ด ์ƒ๋‹นํžˆ ๋งค๋ˆํ•œ ๊ฒƒ์„ ํ™•์ธํ•  ์ˆ˜ ์žˆ๋‹ค. ๋งค๋ˆํ•œ ํ‘œ๋ฉด์œผ๋กœ ๊ด€์ธก๋˜๋Š” ์ด์œ ๋Š” ํ‘œ๋ฉด์— ์ƒ์„ฑ๋œ ๊ธฐ๊ณต์˜ ํฌ๊ธฐ๊ฐ€ ์ƒ๋‹นํžˆ ์ž‘๊ธฐ ๋•Œ๋ฌธ์— ๋‚ฎ์€ ํ•ด์ƒ๋„๋ฅผ ๊ฐ–๊ณ  ์žˆ๋Š” SEM ์‚ฌ์ง„์—์„œ๋Š” ๋‹ค๊ณต์„ฑ์˜ ๊ตฌ์กฐ๊ฐ€ ๊ด€์ธก๋˜๊ธฐ ์–ด๋ ต๊ธฐ ๋•Œ๋ฌธ์œผ๋กœ ์ƒ๊ฐ๋œ๋‹ค [20]. ๊ทธ์— ๋ฐ˜ํ•˜์—ฌ ๋งŽ์€ DBU์–‘๋ฅผ ์‚ฌ์šฉํ•˜์—ฌ ํƒˆ๋ถˆํ™”๋œ ์ „๊ตฌ์ฒด๋กœ๋ถ€ํ„ฐ ํ•ฉ์„ฑ๋œ ํƒ„์†Œ์˜ ๊ฒฝ์šฐ์—๋Š” ๊ฑฐ์นœ ํ‘œ๋ฉด์ด SEM ์‚ฌ์ง„์—์„œ ๊ด€์ฐฐ๋œ๋‹ค. ์ด๋Š” DBU์ฒจ๊ฐ€์— ๋”ฐ๋ผ ํฐ ํฌ๊ธฐ์˜ ๊ธฐ๊ณต์ด ํ‘œ๋ฉด์— ๋งŽ์ด ์ƒ์„ฑ๋˜์—ˆ๋‹ค๊ณ  ์ƒ๊ฐํ•  ์ˆ˜ ์žˆ๋‹ค. ๋˜ํ•œ DBU์ฒจ๊ฐ€๋Ÿ‰์„ ๋Š˜๋ ค ํ•ฉ์„ฑ๋œ ํƒ„์†Œ์˜ ๊ฒฝ์šฐ ์‚ฐ์†Œ์˜ ๋น„์œจ์ด ์ฆ๊ฐ€ํ•œ ๊ฒƒ์„ ๋ณผ ์ˆ˜ ์žˆ๋‹ค(ํ‘œ 2). ๋”ฐ๋ผ์„œ ์‚ฐ์†Œ ๋น„์œจ์˜ ์ฆ๊ฐ€์— ๋”ฐ๋ผ ์‚ฐ์†Œ๋ฅผ ํฌํ•จํ•œ ํ‘œ๋ฉด ์ž‘์šฉ๊ธฐ๊ฐ€ ์ ์ฐจ ์ฆ๊ฐ€ํ•  ๊ฒƒ์œผ๋กœ ์ƒ๊ฐ๋œ๋‹ค. DBU์–‘์— ๋”ฐ๋ผ ์ƒ์„ฑ๋˜๋Š” ์ž‘์šฉ๊ธฐ์˜ ๋ณ€ํ™”๋Š” ํ›„์— ๋ถ„์„๋˜์—ˆ๋‹ค.

์ „๊ตฌ์ฒด ์šฉ์•ก ๋‚ด ์ฒจ๊ฐ€๋˜๋Š” DBU์–‘์„ ๋‹ฌ๋ฆฌํ•˜์—ฌ ํ•ฉ์„ฑ๋œ ํƒ„์†Œ์˜ ๊ธฐ๊ณต ๊ตฌ์กฐ๋ฅผ ์ •๋Ÿ‰์ ์œผ๋กœ ๋ถ„์„ํ•˜๊ธฐ ์œ„ํ•˜์—ฌ ์งˆ์†Œ ํก์ฐฉ๋ฒ•์„ ์‚ฌ์šฉํ•˜์—ฌ ์–ป์–ด์ง„ ๋“ฑ์˜จ ํก์ฐฉ๊ณก์„ ๊ณผ ์ด๋กœ๋ถ€ํ„ฐ ๊ณ„์‚ฐ๋œ ๊ธฐ๊ณต ํฌ๊ธฐ ๋ณ„ ๋ถ„ํฌ๋„๋ฅผ ๊ทธ๋ฆผ 3์— ๋‚˜ํƒ€๋‚ด์—ˆ๋‹ค. PVDF์™€ ํ•จ๊ป˜ PTFE๋ฅผ ์ฒจ๊ฐ€ํ•œ ์ „๊ตฌ์ฒด์— DBU์˜ ์ฒจ๊ฐ€๋Ÿ‰์„ DBU/vinylidene fluoride unit = 1๋กœ ํ•˜์—ฌ ํ•ฉ์„ฑ๋œ ํƒ„์†Œ(1DBU)์˜ ๊ฒฝ์šฐ ๋“ฑ์˜จ ํก์ฐฉ๊ณก์„ ์—์„œ ์ƒ๋Œ€์••๋ ฅ(P/P0) 0.1์—์„œ ๊ฐ€์žฅ ๋†’์€ ์งˆ์†Œ ํก์ฐฉ๋Ÿ‰์„ ๋ณด์˜€๋‹ค. ์ด๋Š” ๋งˆ์ดํฌ๋กœ ๊ธฐ๊ณต์—์„œ์˜ ์งˆ์†Œ ํก์ฐฉ๋Ÿ‰์„ ์˜๋ฏธํ•˜๋Š” ๊ฒƒ์œผ๋กœ ํ•ฉ์„ฑ๋œ ํƒ„์†Œ๋Š” ์ƒ๋‹นํ•œ ์–‘์˜ ๋งˆ์ดํฌ๋กœ ๊ธฐ๊ณต์„ ๊ฐ€์ง„ ๊ฒƒ์œผ๋กœ ์ƒ๊ฐ๋˜๋ฉฐ ๋”ฐ๋ผ์„œ ๋†’์€ ๋น„ํ‘œ๋ฉด์ ์„ ๊ฐ€์งˆ ๊ฒƒ์ด๋‹ค. ์ƒ๋Œ€์••๋ ฅ 0.3์ดํ•˜์˜ ๊ตฌ๊ฐ„์— ๋Œ€ํ•œ ํก์ฐฉ ๊ณก์„ ์œผ๋กœ๋ถ€ํ„ฐ ๊ณ„์‚ฐ๋œ ๋น„ํ‘œ๋ฉด์ ์€ 1,357 m2 g-1์˜ ๋†’์€ ๋น„ํ‘œ๋ฉด์ ์„ ๋ณด์—ฌ์ฃผ์—ˆ๋‹ค. ๋˜ํ•œ ๋ชจ๋“  ์ƒ˜ํ”Œ์˜ ๋“ฑ์˜จ ํก์ฐฉ ๊ณก์„ ์—์„œ ํก์ฐฉ๊ณผ ํƒˆ์ฐฉ ๊ณก์„  ์‚ฌ์ด์˜ ์ด๋ ฅ๊ณก์„ (hysteresis loop)์ด ํ™•์ธ๋œ๋‹ค. ์ด๋Š” ๋ฉ”์กฐ ๊ธฐ๊ณต๋‚ด๋ถ€๋กœ ์งˆ์†Œ ๊ธฐ์ฒด์˜ ํก์ฐฉ๊ณผ ํƒˆ์ฐฉ ๋ฉ”์ปค๋‹ˆ์ฆ˜์ด ์ฐจ์ด๊ฐ€ ๋•Œ๋ฌธ์— ๋‚˜ํƒ€๋‚˜๋Š” ๊ฒƒ์œผ๋กœ ํ•ฉ์„ฑ๋œ ๋‹ค๊ณต์„ฑ ํƒ„์†Œ๋Š” ๋ฉ”์กฐ๊ธฐ๊ณต์„ ๊ฐ–๋Š” ๊ฒƒ์„ ์•Œ ์ˆ˜ ์žˆ๋‹ค [23].

DBU ์‚ฌ์šฉ๋Ÿ‰์„ ์ฆ๊ฐ€ํ•˜์—ฌ ํ•ฉ์„ฑ๋œ ํƒ„์†Œ์˜ ๊ฒฝ์šฐ ์ƒ๋Œ€๊ธฐ์•• 0.1์—์„œ์˜ ์งˆ์†Œ ํก์ฐฉ๋Ÿ‰์ด ์ ์ฐจ ๋‚ฎ์•„์ง€๋Š”๋ฐ ์ด๋Š” ๋งˆ์ดํฌ๋กœ ๊ธฐ๊ณต์˜ ์ƒ์„ฑ๋Ÿ‰์ด ์ค„์–ด๋“  ๊ฒƒ์„ ์˜๋ฏธํ•œ๋‹ค (๊ทธ๋ฆผ 3(a)). ๋งˆ์ดํฌ๋กœ ๊ธฐ๊ณต์˜ ์ƒ์„ฑ๋Ÿ‰ ๊ฐ์†Œ๋Š” ์ „๊ตฌ์ฒด๋‚ด DBU์–‘ ์ฆ๊ฐ€์— ๋”ฐ๋ผ ํƒˆ๋ถˆํ™”๊ฐ€ ๋” ์šฉ์ดํ•˜๊ฒŒ ์ง„ํ–‰๋˜์–ด ์—ด์ฒ˜๋ฆฌ์‹œ ๋ถˆ์†Œ์›์†Œ์ œ๊ฑฐ์— ์˜ํ•œ ๋งˆ์ดํฌ๋กœ ๊ธฐ๊ณต ์ƒ์„ฑ์ด ์ค„์–ด๋“ค์—ˆ๊ธฐ ๋•Œ๋ฌธ์œผ๋กœ ์ƒ๊ฐ๋œ๋‹ค. ๋งˆ์ดํฌ๋กœ ๊ธฐ๊ณต์˜ ๊ฐ์†Œ๋Š” ๊ธฐ๊ณต ํฌ๊ธฐ ๋ณ„ ๋ถ„ํฌ๋„์—์„œ๋„ ์ง๊ด€์ ์œผ๋กœ ํ™•์ธ๋˜๋ฉฐ DBU/vinylidene fluoride unit ๋น„์œจ์ด 5์ด์ƒ์ธ ์ƒ˜ํ”Œ๋“ค ๋ชจ๋‘ ๊ฑฐ์˜ ๋ฉ”์กฐ ๊ธฐ๊ณต์œผ๋กœ๋งŒ ๊ตฌ์„ฑ๋˜์–ด ์žˆ๋Š” ๊ฒƒ์ด ํ™•์ธ๋œ๋‹ค (๊ทธ๋ฆผ 3(b), ํ‘œ 3). ํ‰๊ท  ๊ธฐ๊ณต ํฌ๊ธฐ์˜ ์ฆ๊ฐ€๋Š” ํ•ฉ์„ฑ๋œ ํƒ„์†Œ์˜ ๋น„ํ‘œ๋ฉด์ ์„ ๊ฐ์†Œ์‹œํ‚ค๋ฉฐ DBU์™€ vinylidene fluoride unit์‚ฌ์ด์˜ ๋น„์œจ์ด 10๊ณผ 20์ธ ์ „๊ตฌ์ฒด์—์„œ ํ•ฉ์„ฑ๋œ 10DBU์ƒ˜ํ”Œ๊ณผ 20DBU์ƒ˜ํ”Œ์€ 450.4 m2 g-1์™€ 481.8 m2 g-1์˜ ๋‚ฎ์€ ๋น„ํ‘œ๋ฉด์ ์„ ๋ณด์—ฌ์ค€๋‹ค.

ํƒ„์†Œ๋‚ด ์กด์žฌํ•˜๋Š” ํŠน์ • ํ‘œ๋ฉด ์ž‘์šฉ๊ธฐ๋Š” ์ˆœ์ˆ˜ํ•œ ํƒ„์†Œ์˜ ์†Œ์ˆ˜์„ฑ์„ ๋ณ€ํ™”์‹œํ‚ฌ ์ˆ˜ ์žˆ๋‹ค [24]. ํŠนํžˆ ํŽ˜๋†€(โ€“OH) ์ž‘์šฉ๊ธฐ์™€ ์นด๋ฅด๋ณต์‹ค์‚ฐ(โ€“COOH) ์ž‘์šฉ๊ธฐ๋Š” ํƒ„์†Œ๊ตฌ์กฐ๋‚ด์— ์ˆ˜์†Œ์ด์˜จ๊ณผ ๊ฒฐํ•ฉ์„ ํ•˜๊ณ  ์žˆ๋Š” ๊ตฌ์กฐ๋กœ ๊ทน์„ฑ์˜ ์„ฑ์งˆ์„ ๋ณด์œ ํ•˜๊ณ  ์žˆ๊ธฐ ๋•Œ๋ฌธ์— ๋ฌผ๊ณผ์˜ ์นœ์ˆ˜์„ฑ์ด ์ข‹์€ ์ž‘์šฉ๊ธฐ์ด๋‹ค [25,26]. ๋”ฐ๋ผ์„œ ํƒ„์†Œํ•ฉ์„ฑ ์‹œ ์ด๋Ÿฌํ•œ ์ž‘์šฉ๊ธฐ์˜ ํ˜•์„ฑ ๋น„์œจ์ด ๋†’์œผ๋ฉด ํƒ„์†Œ๋Š” ์นœ์ˆ˜์„ฑ์„ ๋„๊ฒŒ ๋œ๋‹ค. ํ•ฉ์„ฑ๋œ ํƒ„์†Œ์— ์ƒ์„ฑ๋œ ์—ฌ๋Ÿฌ๊ฐ€์ง€ ์ž‘์šฉ๊ธฐ๋ฅผ ๋ถ„์„ํ•˜๊ธฐ ์œ„ํ•˜์—ฌ XPS ๊ณ ํ•ด์ƒ๋„ ์Šค์บ”์„ ์ด์šฉํ•˜์—ฌ C์™€ ๊ฒฐํ•ฉ๋œ ์—ฌ๋Ÿฌ๊ฐ€์ง€ ์ž‘์šฉ๊ธฐ๋ฅผ ๋ถ„์„ํ•˜์—ฌ ๊ทธ๋ฆผ 4์™€ ํ‘œ 4์— ๋‚˜ํƒ€๋‚ด์—ˆ๋‹ค. ๊ณ ํ•ด์ƒ๋„ ์Šค์บ”์—์„œ ํƒ„์†Œ 1s ์ŠคํŽ™ํŠธ๋Ÿผ์€ Cโ€“C (284.3 eV ยฑ 0.1 eV), Cโ€“OH (285.6 eV), C=O (287.5 eV), ๊ทธ๋ฆฌ๊ณ  โ€“COOH (288.9 eV)์˜ 4๊ฐœ์˜ ์ž‘์šฉ๊ธฐ์— ๋Œ€ํ•œ ํ”ผํฌ๋กœ ๋ถ„๋ฆฌํ•  ์ˆ˜ ์žˆ๋‹ค. ์ „๊ตฌ์ฒด๋‚ด DBU ์–‘ ์ฆ๊ฐ€์— ๋”ฐ๋ผ ํŽ˜๋†€๊ณผ ์นด๋ฅด๋ณต์‹ค์‚ฐ ์ž‘์šฉ๊ธฐ์˜ ๋น„์œจ์ด ์ ์ฐจ ๊ฐ์†Œํ•˜๋Š” ๊ฒƒ์„ ๋ณผ ์ˆ˜ ์žˆ๋‹ค. DBU ์‚ฌ์šฉ๋Ÿ‰์ด ์ฆ๊ฐ€ํ• ์ˆ˜๋ก DMF ๋˜๋Š” ์—ํƒ„์˜ฌ์— ๊ฒฐํ•ฉ๋˜์–ด ์žˆ๋Š” ์ˆ˜์†Œ์›์ž๊ฐ€ ํƒ„์†Œ ์›์†Œ์™€ ๊ฒฐํ•ฉํ•˜์—ฌ ์นœ์ˆ˜์„ฑ ์ž‘์šฉ๊ธฐ์˜ ์ƒ์„ฑ์„ ๋ฐฉํ•ดํ•˜๋Š” ๊ฒƒ์œผ๋กœ ์ถ”์ธก๋œ๋‹ค. ๋”ฐ๋ผ์„œ ์ „๊ตฌ์ฒด์— DBU ์‚ฌ์šฉ๋Ÿ‰์„ ๋Š˜๋ ค ํƒˆ๋ถˆํ™”๋ฅผ ๋งŽ์ด ์‹œํ‚จ ํƒ„์†Œ์ผ์ˆ˜๋ก ์นœ์ˆ˜์„ฑ์ด ๊ฐ์†Œํ•  ๊ฒƒ์œผ๋กœ ์˜ˆ์ƒ๋œ๋‹ค.

๊ทธ๋ฆผ 5๋Š” ํ‘œ๋ฉด ์ž‘์šฉ๊ธฐ ์–‘์— ๋”ฐ๋ฅธ ์นœ์ˆ˜์„ฑ์˜ ๋ณ€ํ™”๋ฅผ ์‚ดํ”ผ๊ธฐ ์œ„ํ•˜์—ฌ ์ˆ˜ํ–‰ํ•œ ์ ‘์ด‰๊ฐ ์‹คํ—˜ ๊ฒฐ๊ณผ๋ฅผ ๋ณด์—ฌ์ค€๋‹ค. ํ•ฉ์„ฑ๋œ ํƒ„์†Œ๊ฐ€ ์ˆ˜์šฉ์•ก๋‚ด ๋ถˆ์ˆœ๋ฌผ ํก์ฐฉ ๋ฐ ํ•„ํ„ฐ ์†Œ์žฌ๋กœ ํ™œ์šฉ๋˜๊ธฐ ์œ„ํ•ด์„œ๋Š” ์ˆ˜์šฉ์•ก๊ณผ์˜ ์ –์Œ์„ฑ์ด ์ข‹์•„์•ผ ํ•œ๋‹ค [27,28]. ๋”ฐ๋ผ์„œ ์นœ์ˆ˜์„ฑ์€ ํ•ฉ์„ฑ๋œ ํƒ„์†Œ๊ฐ€ ๊ฐ€์ ธ์•ผํ•  ์ค‘์š”ํ•œ ๋ฌผ์„ฑ์œผ๋กœ ๊ฐ„์ฃผ๋  ์ˆ˜ ์žˆ๋‹ค. ํ•ฉ์„ฑ๋œ ํƒ„์†Œ์˜ ์นœ์ˆ˜์„ฑ์„ sessile ๋ฐฉ๋ฒ•์œผ๋กœ ๋–จ์–ด๋œจ๋ฆฐ ๋ฌผ๋ฐฉ์šธ์ด 60์ดˆ ๋™์•ˆ ํŽ ๋ › ํ˜•ํƒœ์˜ ์ƒ˜ํ”Œ์— ํก์ˆ˜๋˜๋Š” ์†๋„๋ฅผ ์ธก์ •ํ•˜์˜€๋‹ค. ์ „๊ตฌ์ฒด ์šฉ์•ก์— ์‚ฌ์šฉ๋œ DBU ์–‘์ด ์ฆ๊ฐ€ํ• ์ˆ˜๋ก ์ดˆ๊ธฐ(1์ดˆ) ์ ‘์ด‰๊ฐ์ด ์ฆ๊ฐ€ํ•˜๋ฉฐ ๋˜ํ•œ ์‹œ๊ฐ„์— ๋”ฐ๋ผ ์ ‘์ด‰๊ฐ์ด ๊ฑฐ์˜ ์ค„์–ด๋“ค์ง€ ์•Š๋Š”๋‹ค๋Š” ๊ฒƒ์„ ์•Œ ์ˆ˜ ์žˆ๋‹ค. ์ด๋Ÿฌํ•œ ์‹คํ—˜ ๊ฒฐ๊ณผ๋Š” ์•ž์˜ XPS๋ถ„์„์—์„œ ํ™•์ธ๋˜์—ˆ๋˜ ๊ฒƒ์ฒ˜๋Ÿผ ํ•ฉ์„ฑ๋œ ํƒ„์†Œํ‘œ๋ฉด์— ํ˜•์„ฑ๋œ ํŽ˜๋†€๊ณผ ์นด๋ฅด๋ณต์‹ค์‚ฐ ์ž‘์šฉ๊ธฐ ์–‘๊ณผ ๊ด€๊ณ„์žˆ๋‹ค. ์ฆ‰, DBU๋ฅผ ์ ๊ฒŒ ์‚ฌ์šฉํ•˜์—ฌ ํ•ฉ์„ฑ๋œ ํƒ„์†Œ์— ๋น„ํ•˜์—ฌ DBU๋ฅผ ๋งŽ์ด ์‚ฌ์šฉํ•˜์—ฌ ์ œ์กฐํ•œ ํƒ„์†Œ์˜ ๊ฒฝ์šฐ์—๋Š” ์นœ์ˆ˜์„ฑ ์ž‘์šฉ๊ธฐ์ธ ํŽ˜๋†€๊ณผ ์นด๋ฅด๋ณต์‹ค์‚ฐ ์ž‘์šฉ๊ธฐ์˜ ๋น„์œจ์ด ์ค„์–ด๋“ค์—ˆ๊ธฐ ๋•Œ๋ฌธ์ด๋‹ค.

ํ•ฉ์„ฑ๋œ ํƒ„์†Œ์˜ ๊ฒฐ์ •๊ตฌ์กฐ๋ฅผ ๋ถ„์„ํ•˜๊ธฐ ์œ„ํ•˜์—ฌ ์ธก์ •ํ•œ Raman ์‹คํ—˜ ๊ฒฐ๊ณผ๋ฅผ ๊ทธ๋ฆผ 6์— ๋‚˜ํƒ€๋‚ด์—ˆ๋‹ค. DBU์˜ ์–‘ ์ฆ๊ฐ€์— ๋”ฐ๋ผ D ๋ฐด๋“œ๊ฐ’์ด ์ ์ฐจ ์˜ค๋ฅธ์ชฝ์œผ๋กœ ์ด๋™ํ•˜๋Š” ๊ฒƒ์„ ์‚ดํŽด๋ณผ ์ˆ˜ ์žˆ๋‹ค. D ๋ฐด๋“œ์˜ ์˜ค๋ฅธ์ชฝ์œผ๋กœ์˜ ์ด๋™์€ ํƒ„์†Œ๋ฅผ ๊ตฌ์„ฑํ•˜๋Š” ๊ทธ๋ž˜ํ•€ ๋„๋ฉ”์ธ์˜ ํ‰๊ท  ํฌ๊ธฐ๊ฐ€ ์ ์ฐจ ์ปค์ง€๋Š” ๊ฒƒ์„ ์˜๋ฏธํ•œ๋‹ค [12]. D ๋ฐด๋“œ์˜ ์˜ค๋ฅธ์ชฝ ์ด๋™๊ณผ ํ•จ๊ป˜ ID/IG ๊ฐ’์ด DBU์ฆ๊ฐ€์™€ ํ•จ๊ป˜ ์ ์ฐจ ์ฆ๊ฐ€ํ•˜๋Š” ๊ฒƒ์„ ๋ณผ ์ˆ˜ ์žˆ๋‹ค (ํ‘œ 5). ID/IG ๊ฐ’์€ ๊ทธ๋ž˜ํ•€๋“ค์˜ ์ ์ธต์œผ๋กœ ์ด๋ฃจ์–ด์ง„ ๊ทธ๋ž˜ํ•€ ๋„๋ฉ”์ธ๋‚ด์—์„œ ๊ฒฐํ•จ์˜ ์ƒ๋Œ€์ ์ธ ์ˆ˜์™€ ๋น„๋ก€ํ•˜๋Š” ์ •๋Ÿ‰์ ์ธ ๊ด€๊ณ„๋ฅผ ๊ฐ–๊ณ  ์žˆ๋‹ค. ์ฆ‰, DBU ์–‘์„ ๋Š˜๋ ค์„œ ํ•ฉ์„ฑ๋œ ํƒ„์†Œ์˜ ๊ฒฝ์šฐ์—๋Š” ๊ฒฐํ•จ์˜ ์ˆ˜๊ฐ€ ๋งŽ๋‹ค๋Š” ๊ฒƒ์„ ์˜๋ฏธํ•˜๋Š”๋ฐ ์ด๋Ÿฌํ•œ ๊ฒฐ๊ณผ๋Š” ๊ธฐ๊ณต ๋ถ„ํฌ๋ถ„์„์—์„œ ํ™•์ธํ•˜์˜€๋˜ ๊ฒƒ์ฒ˜๋Ÿผ ๋ฉ”์กฐํฌ๊ธฐ์˜ ๊ธฐ๊ณต์ด ์ ์ฐจ ๋งŽ์•„์กŒ๊ธฐ ๋•Œ๋ฌธ์œผ๋กœ ์ƒ๊ฐํ•  ์ˆ˜ ์žˆ๋‹ค [29]. Raman ๋ถ„์„ ๊ฒฐ๊ณผ๋Š” ๊ธฐ๊ณต ๋ถ„์„ ๊ฒฐ๊ณผ์™€ ํ•จ๊ป˜ ์ „๊ตฌ์ฒด๋‚ด ์‚ฌ์šฉ๋˜๋Š” DBU์–‘์ด ๊ธฐ๊ณต์ƒ์„ฑ๋Ÿ‰์— ์ง์ ‘์ ์ธ ์˜ํ–ฅ์„ ๋ฏธ์นœ๋‹ค๋Š” ๊ฒƒ์„ ์ž˜ ๋ณด์—ฌ์ค€๋‹ค.

DBU์–‘์„ ๋‹ฌ๋ฆฌํ•˜์—ฌ ํ•ฉ์„ฑ๋œ ํƒ„์†Œ์˜ ์ˆ˜์šฉ์•ก๋‚ด ์ด์˜จ ํก์ฐฉ ์šฉ๋Ÿ‰์€ Na2SO4 ์ „ํ•ด์งˆ์„ ์‚ฌ์šฉํ•˜์—ฌ cyclic voltammetry ๋ฐฉ๋ฒ•์œผ๋กœ ๋น„ ์ „๊ธฐ์šฉ๋Ÿ‰์œผ๋กœ ํ™•์ธํ•˜์˜€์œผ๋ฉฐ ํƒ„์†Œ๋‚ด ๋ฉ”์กฐ๊ธฐ๊ณต์˜ ์ƒ์„ฑ๋น„์œจ์€ ์œจ์† ํŠน์„ฑ ๋ถ„์„์„ ํ†ตํ•˜์—ฌ ํ™•์ธํ•˜์˜€๋‹ค (๊ทธ๋ฆผ 7). ๊ทธ๋ฆผ 7(a)๋Š” PVDF์˜ ์ง์ ‘์ ์ธ ์—ด๋ถ„ํ•ด๋กœ๋ถ€ํ„ฐ ํ•ฉ์„ฑ๋œ PVDF-only ํƒ„์†Œ ์ƒ˜ํ”Œ์— ๋น„ํ•˜์—ฌ PVDF์™€ PTFE์˜ ํ˜ผํ•ฉ ์ „๊ตฌ์ฒด๋ฅผ DBU๋กœ์จ ํƒˆ๋ถˆํ™”ํ•˜์—ฌ ํ•ฉ์„ฑ๋œ ํƒ„์†Œ๋“ค์€ ๋” ๋‚ฎ์€ ๋น„ ์ „๊ธฐ์šฉ๋Ÿ‰ ๊ฒฐ๊ณผ๋ฅผ ๋ณด์—ฌ์ค€๋‹ค. ๋‚ฎ์€ ๋น„ ์ „๊ธฐ์šฉ๋Ÿ‰์€ ์ „ํ•ด์งˆ ๋‚ด Na+์ด์˜จ๊ณผ SO42-์ด์˜จ์— ๋Œ€ํ•ด ๋‚ฎ์€ ํก์ฐฉํŠน์„ฑ์„ ๋ณด์—ฌ์ฃผ๋Š” ๊ฒƒ์œผ๋กœ ๋น„ ์ „๊ธฐ์šฉ๋Ÿ‰ ์ธก์ • ๊ฒฐ๊ณผ๋กœ๋ถ€ํ„ฐ DBU์˜ ์–‘์„ ๋Š˜๋ ค์„œ ํƒˆ๋ถˆํ™” ํ•œ ํ›„ ํ•ฉ์„ฑ๋œ ํƒ„์†Œ ์ „๊ทน์ผ์ˆ˜๋ก ์ด์˜จ ํก์ฐฉ์šฉ๋Ÿ‰์ด ๋” ๋‚ฎ์•„์ง„๋‹ค๋Š” ๊ฒƒ์„ ์•Œ ์ˆ˜ ์žˆ๋‹ค. ํ•œํŽธ, DBU ์ฒจ๊ฐ€๋Ÿ‰์ด ์ฆ๊ฐ€ํ•˜์—ฌ ํ•ฉ์„ฑ๋œ ๋‹ค๊ณต์„ฑ ํƒ„์†Œ์ผ์ˆ˜๋ก ์œจ์† ํŠน์„ฑ์€ ์ ์ฐจ ์ฆ๊ฐ€ํ•˜๋‹ค๊ฐ€ DBU/vinylidene fluoride unit ๋น„์œจ์ด 5์ด์ƒ์ธ ์ƒ˜ํ”Œ๋“ค์€ ๊ฑฐ์˜ ๋น„์Šทํ•œ ์œจ์† ํŠน์„ฑ์„ ๋ณด์—ฌ์ค€๋‹ค (๊ทธ๋ฆผ 7(b)). ๋‹ค๊ณต์„ฑํƒ„์†Œ์˜ ์œจ์† ํŠน์„ฑ์ด ์ฆ๊ฐ€ํ•˜๋Š” ์ด์œ ๋Š” ์ˆ˜์šฉ์•ก ์ „ํ•ด์งˆ๋‚ด ์ด์˜จ์ด ๋‹ค๊ณต์„ฑ ํ‘œ๋ฉด์œผ๋กœ ๋น ๋ฅด๊ฒŒ ์ด๋™ํ•˜์˜€๊ธฐ ๋•Œ๋ฌธ์ด๋‹ค. ๋”ฐ๋ผ์„œ ๋†’์€ ์œจ์† ํŠน์„ฑ์€ ๋‹ค๊ณต์„ฑ ํƒ„์†Œ๋‚ด ํ‰๊ท  ๊ธฐ๊ณต ํฌ๊ธฐ ์ฆ๊ฐ€๋ฅผ ๊ฐ„์ ‘์ ์œผ๋กœ ๋ณด์—ฌ์ฃผ๋Š” ๊ฒฐ๊ณผ์ด๋‹ค. ์ผ์ • ์ด์ƒ์˜ DBU๋ฅผ ์‚ฌ์šฉํ•˜์—ฌ ํ•ฉ์„ฑ๋œ ๋‹ค๊ณต์„ฑ ํƒ„์†Œ๊ฐ€ ๋น„์Šทํ•œ ์œจ์† ํŠน์„ฑ์„ ๋ณด์ด๋Š” ์ด์œ ๋Š” ์•ž์˜ ๊ธฐ๊ณต ๋ถ„ํฌ๋„ ๊ฒฐ๊ณผ์—์„œ ํ™•์ธํ•œ ๊ฒƒ์ฒ˜๋Ÿผ ์ƒ์„ฑ๋œ ๊ธฐ๊ณต์€ ๋ชจ๋‘ ๋ฉ”์กฐ ๊ธฐ๊ณต์œผ๋กœ๋งŒ ๊ตฌ์„ฑ๋˜์–ด ์žˆ๊ธฐ ๋•Œ๋ฌธ์œผ๋กœ ์ƒ๊ฐ๋œ๋‹ค. ์•ž์„œ PVDF์ „๊ตฌ์ฒด๋ฅผ DBU๋กœ ํƒˆ๋ถˆํ™”์‹œ์ผœ ํ•ฉ์„ฑํ•œ PVDF-10DBU ์ƒ˜ํ”Œ์€ PVDF์˜ ์ง์ ‘์ ์ธ ํƒ„ํ™”๋กœ ํ•ฉ์„ฑ๋œ PVDF-only ์ƒ˜ํ”Œ์— ๋น„ํ•ด์„œ ์œจ์† ํŠน์„ฑ์ด ๊ฐ์†Œํ•˜์˜€๋‹ค. ์ด๋Ÿฌํ•œ ์œจ์†ํŠน์„ฑ์˜ ๊ฐ์†Œ๋Š” ํƒˆ๋ถˆํ™”์— ์˜ํ•œ ๋งˆ์ดํฌ๋กœ ๊ธฐ๊ณต์˜ ํ˜•์„ฑ์ด ์–ต์ œ๋˜์—ˆ๊ธฐ ๋•Œ๋ฌธ์œผ๋กœ ์ƒ๊ฐ๋˜์—ˆ๋‹ค. ๊ทธ์— ๋ฐ˜ํ•ด PVDF์™€ PTFE์˜ ํ˜ผํ•ฉ ์ „๊ตฌ์ฒด๋ฅผ ํƒˆ๋ถˆํ™”ํ•œ ํ›„ ํ•ฉ์„ฑ๋œ ํƒ„์†Œ์˜ ๊ฒฝ์šฐ์—๋Š” ๋งˆ์ดํฌ๋กœ ๊ธฐ๊ณต๋Ÿ‰์˜ ๊ฐ์†Œ์™€ ํ•จ๊ป˜ ๋ฉ”์กฐ ๊ธฐ๊ณต๋Ÿ‰์ด ์ฆ๊ฐ€ํ•˜์˜€๊ณ  ๊ทธ์— ๋”ฐ๋ผ ์œจ์† ํŠน์„ฑ์ด ํ–ฅ์ƒ๋˜์—ˆ๋‹ค.

๋ณธ ์—ฐ๊ตฌ์—์„œ๋Š” PVDF์™€ PTFE์˜ ํ˜ผํ•ฉ ํด๋ฆฌ๋จธ๋ฅผ DBU ์šฉ๋งค๋ฅผ ์ด์šฉํ•˜์—ฌ ํƒˆ๋ถˆํ™”ํ•œ ์ „๊ตฌ์ฒด๋ฅผ ํƒ„ํ™”ํ•˜์—ฌ ์ ์€ ๋งˆ์ดํฌ๋กœ ๊ธฐ๊ณต๊ณผ ๋†’์€ ๋ฉ”์กฐ ๊ธฐ๊ณต ๋น„์œจ์„ ๊ฐ–๋Š” ๋‹ค๊ณต์„ฑ ํƒ„์†Œ๋ฅผ ํ•ฉ์„ฑํ•˜๊ณ ์ž ํ•˜์˜€๋‹ค. DBU์‚ฌ์šฉ๋Ÿ‰ ์ฆ๊ฐ€์— ๋”ฐ๋ผ ๋‹ค๊ณต์„ฑ ํƒ„์†Œ๋‚ด ๋งˆ์ดํฌ๋กœ ๊ธฐ๊ณต์˜ ๊ฐ์†Œ๋Š” ์ค„์–ด๋“  ๋น„ ์ „๊ธฐ ์šฉ๋Ÿ‰์œผ๋กœ ํ™•์ธ๋˜์—ˆ๋‹ค. ๋˜ํ•œ ๋ฉ”์กฐ ๊ธฐ๊ณต ๋น„์œจ์˜ ์ฆ๊ฐ€๋Š” ์ฆ๊ฐ€๋œ ์œจ์† ํŠน์„ฑ์œผ๋กœ ํ™•์ธ๋˜์—ˆ๋‹ค. ์ฆ‰, ํƒˆ๋ถˆํ™”์‹œ ์‚ฌ์šฉํ•˜๋Š” DBU์˜ ์–‘์— ๋”ฐ๋ผ ํ•ฉ์„ฑ๋œ ๋‹ค๊ณต์„ฑ ํƒ„์†Œ์˜ ๋งˆ์ดํฌ๋กœ ๊ธฐ๊ณต ์–‘๊ณผ ๋ฉ”์กฐ ๊ธฐ๊ณต ๋น„์œจ์„ ์กฐ์ ˆํ•  ์ˆ˜ ์žˆ๋‹ค๋Š” ๊ฒƒ์„ ๋ณด์—ฌ์ค€๋‹ค. ๊ธฐ๊ณต์˜ ๋ณ€ํ™” ์ด์™ธ์—๋„ ์‚ฌ์šฉํ•˜๋Š” DBU์–‘์— ๋”ฐ๋ผ ์ƒ์„ฑ๋œ ํƒ„์†Œ์˜ ์นœ์ˆ˜์„ฑ์ด ๋ณ€ํ™”ํ•˜์˜€๋‹ค. ๋ณธ ์—ฐ๊ตฌ์—์„œ ํ•ฉ์„ฑ๋œ ์ฆ๊ฐ€๋œ ๋ฉ”์กฐ ๊ธฐ๊ณต ๋น„์œจ๊ณผ ์นœ์ˆ˜์„ฑ์„ ๊ฐ–๋Š” ๋‹ค๊ณต์„ฑ ํƒ„์†Œ๋Š” ์ˆ˜์šฉ์•ก๋‚ด์—์„œ ํฐ ์ž…์ž๋ฅผ ๋ถ„๋ฆฌํ•˜๊ธฐ ์œ„ํ•œ ํ•„ํ„ฐ ์†Œ์žฌ๋กœ ์‚ฌ์šฉ๋  ์ˆ˜ ์žˆ๋‹ค๋Š” ๊ฒƒ์„ ๋ณด์—ฌ์ค€๋‹ค.

4. ๊ฒฐ ๋ก 

๋ณธ ์—ฐ๊ตฌ์—์„œ๋Š” PVDF์ „๊ตฌ์ฒด๋ฅผ DBU๋กœ ํƒˆ๋ถˆํ™”ํ•˜์—ฌ ๋งˆ์ดํฌ๋กœ ๊ธฐ๊ณต ์ƒ์„ฑ ๋ฉ”์ปค๋‹ˆ์ฆ˜์„ ์–ต์ œํ•˜๋Š” ๋™์‹œ์— ๋ฉ”์กฐ ๊ธฐ๊ณต์„ ๊ฐ–๋Š” ๋‹ค๊ณต์„ฑ ํƒ„์†Œ๋ฅผ ํ•ฉ์„ฑํ•˜๊ณ ์ž ํ•˜์˜€๋‹ค. ๋ฉ”์กฐ ๊ธฐ๊ณต ํ˜•์„ฑ์„ ์œ„ํ•˜์—ฌ PTFE๋ฅผ PVDF์™€ ํ•จ๊ป˜ ํ˜ผํ•ฉํ•œ ์ „๊ตฌ์ฒด๋ฅผ ํƒ„ํ™”ํ•˜์—ฌ ๋ฉ”์กฐ ๊ธฐ๊ณต์„ ์œ ๋„ํ•˜์˜€๋‹ค. ํƒˆ๋ถˆํ™” ๊ณต์ •์—์„œ ์‚ฌ์šฉํ•˜๋Š” DBU ์šฉ๋งค์˜ ์–‘์ด ํ•ฉ์„ฑ๋œ ๋‹ค๊ณต์„ฑ ํƒ„์†Œ์˜ ๊ธฐ๊ณต ๊ตฌ์กฐ์— ๋ฏธ์น˜๋Š” ์˜ํ–ฅ์„ ๋ถ„์„ํ•˜์˜€๋‹ค. PVDF์™€ PTFE์˜ ํ˜ผํ•ฉ ์ „๊ตฌ์ฒด๋ฅผ DBU/vinylidene fluoride = 1์˜ ๋น„์œจ๋กœ DBU๋ฅผ ์‚ฌ์šฉํ•˜์—ฌ ํ•ฉ์„ฑํ•œ ํƒ„์†Œ๋Š” ๋†’์€ ๋น„ํ‘œ๋ฉด์ (1357.1 m2 g-1)์„ ๊ฐ–๋Š” ํƒ„์†Œ๊ฐ€ ํ•ฉ์„ฑ๋˜์—ˆ๋‹ค(1DBU ์ƒ˜ํ”Œ). ์ฒจ๊ฐ€ํ•˜๋Š” DBU ์–‘์ด ์ฆ๊ฐ€ํ•จ์— ๋”ฐ๋ผ ๋งˆ์ดํฌ๋กœ ๊ธฐ๊ณต๋Ÿ‰์ด ๊ฐ์†Œํ•˜๋Š” ๋™์‹œ์— ์ƒ๋Œ€์ ์ธ ๋ฉ”์กฐ๊ธฐ๊ณต๋Ÿ‰์ด ์ฆ๊ฐ€ํ•˜์˜€๋‹ค. ์ด๋Š” ๋งŽ์€ DBU ์‚ฌ์šฉ์— ๋”ฐ๋ผ ์šฉ์ดํ•ด์ง„ ํƒˆ๋ถˆํ™” ๊ณต์ •์œผ๋กœ ๋งˆ์ดํฌ๋กœ ๊ธฐ๊ณต ํ˜•์„ฑ์ด ์–ต์ œ๋˜์—ˆ๊ธฐ ๋•Œ๋ฌธ์œผ๋กœ ์ƒ๊ฐ๋œ๋‹ค. ๋งˆ์ดํฌ๋กœ ๊ธฐ๊ณต์€ ๋น„ํ‘œ๋ฉด์  ํ–ฅ์ƒ์— ๊ธฐ์—ฌํ•˜๋ฏ€๋กœ DBU์–‘์„ ์ฆ๊ฐ€ํ•˜์—ฌ ํ•ฉ์„ฑํ•œ 10DBU์™€ 20DBU ์ƒ˜ํ”Œ์˜ ๊ฒฝ์šฐ ๊ฐ๊ฐ 450.4 m2 g-1์™€ 481.8 m2 g-1์˜ ๋‚ฎ์€ ๋น„ํ‘œ๋ฉด์ ์ด ์–ป์–ด์กŒ์œผ๋ฉฐ ํƒ„์†Œ์ „๊ทน์˜ ๋น„ ์ „๊ธฐ์šฉ๋Ÿ‰ ๊ฐ’ ๊ฐ์†Œ๋กœ๋„ ํ™•์ธ๋˜์—ˆ๋‹ค. ์ฆ๊ฐ€ํ•œ ๋ฉ”์กฐ ๊ธฐ๊ณต ๋น„์œจ์€ ํ–ฅ์ƒ๋œ ์œจ์† ํŠน์„ฑ์œผ๋กœ๋„ ํ™•์ธ๋˜์—ˆ๋‹ค.

DBU์— ์˜ํ•œ ํƒˆ๋ถˆํ™” ๊ณต์ •์„ ๊ฑฐ์น˜๊ณ  ๋‚˜๋ฉด ํŠน์ • ์ž‘์šฉ๊ธฐ๊ฐ€ ํ˜•์„ฑ๋˜์—ˆ๋Š”๋ฐ, DBU์‚ฌ์šฉ๋Ÿ‰ ์ฆ๊ฐ€์— ๋”ฐ๋ผ ์นœ์ˆ˜์„ฑ ์ž‘์šฉ๊ธฐ์ธ ํŽ˜๋†€๊ณผ ์นด๋ฅด๋ณต์‹ค์‚ฐ ์ž‘์šฉ๊ธฐ์˜ ์–‘์ด ๊ฐ์†Œํ•˜์˜€๋‹ค. ๋”ฐ๋ผ์„œ, ๋งŽ์€ ์–‘์˜ DBU๋ฅผ ์‚ฌ์šฉํ•˜์—ฌ ํ•ฉ์„ฑ๋œ ํƒ„์†Œ๋Š” ๋ฌผ๊ณผ์˜ ๋‚ฎ์€ ์ –์Œ์„ฑ์„ ๋ณด์—ฌ์ฃผ์—ˆ๋‹ค. ์นœ์ˆ˜์„ฑ์€ ์ˆ˜์ฒ˜๋ฆฌ ํ•„ํ„ฐ๊ฐ€ ๊ฐ€์ ธ์•ผํ•  ํŠน์„ฑ์œผ๋กœ ํ•ฉ์„ฑ๋œ ํƒ„์†Œ๋ฅผ ์ˆ˜์ฒ˜๋ฆฌ์šฉ ํ•„ํ„ฐ๋กœ ํ™œ์šฉํ•˜๊ธฐ ์œ„ํ•ด์„œ๋Š” DBU์˜ ์‚ฌ์šฉ์–‘์„ ์ค„์—ฌ์•ผ ํ•  ๊ฒƒ์œผ๋กœ ์ƒ๊ฐ๋œ๋‹ค. ๋”ฐ๋ผ์„œ ๋ณธ ์—ฐ๊ตฌ ๊ฒฐ๊ณผ๋Š” PVDF์™€ PTFE์˜ ํ˜ผํ•ฉ ์ „๊ตฌ์ฒด๋ฅผ DBU๋กœ ํƒˆ๋ถˆํ™” ํ•œ ํ›„ ํƒ„ํ™”ํ•˜์—ฌ ๋‹ค๊ณต์„ฑ ํƒ„์†Œ๋ฅผ ํ•ฉ์„ฑํ•  ๋•Œ, ์‚ฌ์šฉํ•˜๋Š” DBU์–‘์€ ๊ธฐ๊ณต์˜ ํฌ๊ธฐ์™€ ์นœ์ˆ˜์„ฑ์„ ์กฐ์ ˆํ•  ์ˆ˜ ์žˆ๋‹ค๋Š” ๊ฒƒ์„ ๋ณด์—ฌ์ค€๋‹ค.

Acknowledgements

This work was supported by the National Research Foundation of Korea (NRF) grant funded by the Korean government (Ministry of Science, ICT & Future Planning) (NRF-2020R1F1A1075601) (NRF-2021R1A4A2001658).

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Figures and Tables

Fig. 1.

(a) Pore size distribution of the carbon samples derived from the PVDF precursor and the DBU-processed PVDF (DBU/vinylidene fluoride unit = 10) and (b) cyclic voltammogram of the corresponding samples measured at a scan rate of 5 mV s-1 (inset: rate capability).

../../Resources/kim/KJMM.2021.59/kjmm-2021-59-5-336f1.jpg
Fig. 2.

SEM micrographs of the carbon samples derived from the DBU-processed PVDF precursors (DBU/vinylidene fluoride unit = 1, 5, 10, 20) (upper row: ร—300, upper row: ร—3000).

../../Resources/kim/KJMM.2021.59/kjmm-2021-59-5-336f2.jpg
Fig. 3.

(a) N2 adsorption-desorption (isotherm) curve and (b) pore size distribution of the carbon samples derived from the DBU-processed PVDF precursors (DBU/vinylidene fluoride unit = 1, 5, 10, 20).

../../Resources/kim/KJMM.2021.59/kjmm-2021-59-5-336f3.jpg
Fig. 4.

High resolution XPS spectra of C 1s for the synthesized carbon samples (gray line: experimental value, black line: fitting value).

../../Resources/kim/KJMM.2021.59/kjmm-2021-59-5-336f4.jpg
Fig. 5.

Contact angle measurements of the pellet-type carbon electrodes using the deionized water droplet for 60 s.

../../Resources/kim/KJMM.2021.59/kjmm-2021-59-5-336f5.jpg
Fig. 6.

Raman spectra of the carbon samples synthesized from the DBU-processed PVDF precursors.

../../Resources/kim/KJMM.2021.59/kjmm-2021-59-5-336f6.jpg
Fig. 7.

(a) specific capacitance and (b) rate performance measured on the carbon samples fabricated from the PVDF and DBU-processed PVDF precursors.

../../Resources/kim/KJMM.2021.59/kjmm-2021-59-5-336f7.jpg
Table 1.

Specific surface area, mesopores ratio, and specific capacitance obtained from the synthesized carbon samples.

Specific surface area Mesopores ratio Specific capacitance
PVDF-only 971 m2 g-1 17% 78.4 F g-1
PVDF-10DBU 93 m2 g-1 100% 2.8 F g-1
Table 2.

Elemental composition of carbon and oxygen measured on the DBU-processed carbons (EDS analysis result).

Sample C (At.%) O (At.%)
1DBU 82.34 17.66
5DBU 92.61 7.39
10DBU 88.53 11.47
20DBU 91.82 8.18
Table 3.

Specific surface area and mesopores ratio of the fabricated carbon samples

Sample Specific surface area Mesopores ratio
1DBU 1357.1 m2 g-1 25%
5DBU 641.1 m2 g-1 100%
10DBU 450.4 m2 g-1 100%
20DBU 481.8 m2 g-1 100%
Table 4.

Compositional ratio of the functional groups in the synthesized carbons based on XPS analysis.

C-C (carbon) C-OH (phenol) C=O (quinone) -COOH (carboxylic acid)
1DBU 54.1 24.1 17.1 4.6
5DBU 46.5 38.4 10.7 4.4
10DBU 55.3 29.0 11.3 4.3
20DBU 54.0 35.1 9.4 1.5
Table 5.

D and G band measured from the Raman spectra.

ฮฝD (cm-1) ฮฝG (cm-1) ID IG ID/IG
1DBU 1340.49 1589.27 14.11690 15.95100 0.8850
5DBU 1350.14 1583.48 20.30373 22.75510 0.8923
10DBU 1350.14 1583.48 20.38520 22.28600 0.9147
20DBU 1353.99 1589.27 19.51626 21.51157 0.9072