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    ํ•™์œ„๋…ผ๋ฌธ (์„์‚ฌ)-- ์„œ์šธ๋Œ€ํ•™๊ต ๋Œ€ํ•™์› : ํ™˜๊ฒฝ๋Œ€ํ•™์› ํ™˜๊ฒฝ์กฐ๊ฒฝํ•™๊ณผ, 2018. 8. ์†์šฉํ›ˆ.๊ฒ€์€์ƒ‰ ํ˜„๋ฌด์•” ๋Œ๋“ค์ด ๋ฐญ์„ ์ค‘์‹ฌ์œผ๋กœ ๋Š์ž„์—†์ด ์ด์–ด์ ธ ํ˜๋Ÿฌ๊ฐ€๋Š” ๋ชจ์Šต์ด ๋งˆ์น˜ ํ‘๋ฃก์„ ์—ฐ์ƒํ•œ๋‹ค ํ•˜์—ฌ ๋ถ™์—ฌ์ง„ ํ‘๋ฃก๋งŒ๋ฆฌ ์ œ์ฃผ ๋ฐญ๋‹ด์€ ๊ตญ๊ฐ€์ค‘์š”๋†์—…์œ ์‚ฐ์„ ๊ธฐ์ ์œผ๋กœ ์„ธ๊ณ„๋†์—…๊ธฐ๊ตฌ์ธ FAO๋กœ๋ถ€ํ„ฐ ๋…ํŠนํ•œ ๋†์—…์œ ์‚ฐ์‹œ์Šคํ…œ์˜ ๊ฐ€์น˜๋ฅผ ์ธ์ •๋ฐ›์•„ ์„ธ๊ณ„์ค‘์š”๋†์—…์œ ์‚ฐ์œผ๋กœ ์ง€์ •๋˜์—ˆ๋‹ค. ํ•˜์ง€๋งŒ ์ตœ๊ทผ ์ œ์ฃผ์— ๋Œ€ํ•œ ๊ฐœ๋ฐœ ์••๋ ฅ๊ณผ ๋†์—…์˜ ๋ชฐ๋ฝ, ๋†์—…ํ˜•ํƒœ ๋“ฑ์˜ ๋ณ€ํ™”๋กœ ์ธํ•ด ๋ฐญ๋‹ด์€ ํ•„์š”์— ๋”ฐ๋ผ ์ œ๊ฑฐ๋˜๊ฑฐ๋‚˜ ํ›ผ์†๋˜๊ณ  ์žˆ๋‹ค. ์ด๋Š” ์•„์ง๊นŒ์ง€ ๋‹จ์ˆœํ•œ ๋†์—… ๋งค๊ฐœ์ฒด๋กœ ์ธ์‹๋˜๊ณ  ์žˆ๋Š” ๊ฒฐ๊ณผ์ด๋ฉฐ, ์ œ์ฃผ์˜ ๊ด€๊ด‘๊ฐœ๋ฐœํ˜„ํ™ฉ์œผ๋กœ ๋ฏธ๋ฃจ์–ด๋ณผ ๋•Œ ๋”์šฑ ๊ธ‰์†ํ™” ๋  ๊ฒƒ์œผ๋กœ ์ „๋ง๋œ๋‹ค. ๋”ฐ๋ผ์„œ ๋ณธ ์—ฐ๊ตฌ์—์„œ๋Š” ๊ตฌ์ฒด์ ์ธ ๋Œ€์ƒ์ง€์ธ ๊ตฌ์ขŒ์ ์›”์ •๋ฆฌ ์ผ๋Œ€๋ฅผ ์ค‘์‹ฌ์œผ๋กœ ๋ฐญ๋‹ด์˜ ๋†์—…์œ ์‚ฐ์  ๊ด€์ ์—์„œ์˜ ๊ฒฝ๊ด€ ํŠน์ง•์ด ๋ฌด์—‡์ธ์ง€ ๋„์ถœํ•˜์—ฌ ์ถ”ํ›„ ๋ณด์ „๊ณผ ํ™œ์šฉ์— ์žˆ์–ด์„œ ์‹ค๋งˆ๋ฆฌ๋ฅผ ์ œ๊ณตํ•˜๊ณ ์ž ํ•˜์˜€๋‹ค. ๋จผ์ € ๋Œ€์ƒ์ง€์ธ ๊ตฌ์ขŒ์ ์›”์ •๋ฆฌ ์ผ๋Œ€ ๋ฐญ๋‹ด์— ๋Œ€ํ•ด ๋ณด์ „ํ˜„ํ™ฉ์ด ์–ด๋– ํ•œ์ง€ ์ง„๋‹จํ•ด๋ณด๊ณ  ๊ณ ๋ คํ•ด์•ผ ํ•  ์š”์†Œ๋“ค์€ ๋ฌด์—‡์ธ์ง€ ํŒŒ์•…ํ•˜๊ณ ์ž ํ•˜์˜€๋‹ค. ํŠนํžˆ, ๋ฐญ๋‹ด์€ ๋†์—…ํ™œ๋™์ด ํ˜„์žฌ๊นŒ์ง€๋„ ์ง„ํ–‰๋˜๊ณ  ์žˆ๋Š” ๋†์—…์œ ์‚ฐ ์ž์›์ด๋ผ๋Š” ์ ์—์„œ ๋‹จ์ˆœํžˆ ๋ฌผ๋ฆฌ์ ์ธ ๋ฐญ๋‹ด ๊ฒฝ๊ด€๋ฟ๋งŒ ์•„๋‹ˆ๋ผ ๊ด€๊ณ„๋˜๋Š” ์—ฌ๋Ÿฌ ํ† ์ง€์ด์šฉ์‹œ์Šคํ…œ์ ์ธ ์ธก๋ฉด ๋˜ํ•œ ์‚ดํŽด๋ณด๊ธฐ ์œ„ํ•ด ๋†๋ฏผ๋“ค๊ณผ์˜ ์‹ฌ์ธต ์ธํ„ฐ๋ทฐ๋ฅผ ํ†ตํ•ด ํŒŒ์•…ํ•˜๊ณ ์ž ํ•˜์˜€๋‹ค. ๋ณธ ์—ฐ๊ตฌ์—์„œ ๋„์ถœํ•ด๋‚ธ ๊ฒฐ๊ณผ๋Š” ๋‹ค์Œ๊ณผ ๊ฐ™๋‹ค. ์ฒซ์งธ, ์›”์ •๋ฆฌ ๋ฐญ๋‹ด์˜ ๋†์—…๊ฒฝ๊ด€์€ ๋ฌด์—‡๋ณด๋‹ค๋„ ์ง€์—ญ ํŠน์œ ์˜ ์ž์—ฐํ™˜๊ฒฝ๊ณผ ๋ฐ€์ ‘ํ•œ ๊ด€๊ณ„๋ฅผ ๋งบ๊ณ  ์žˆ์—ˆ์œผ๋ฉฐ, ์ฒ™๋ฐ•ํ•œ ํ™˜๊ฒฝ ์†์—์„œ๋„ ๋Œ€์ƒ์ง€์˜ ์กฐ๊ฑด์— ๋งž๋Š” ์ตœ์ ํ™”๋œ ๊ทœ๋ชจ๋กœ ๋ฐญ๋‹ด์ด ํ˜•์„ฑ๋˜๊ณ  ์žˆ์—ˆ๋‹ค. ๊ฒฝ์ง€๋ฅผ ๋‘˜๋Ÿฌ์‹ธ๊ณ  ์žˆ๋Š” ๋ฐญ๋‹ด์€ ํ‘๋ฃก๋งŒ๋ฆฌ๋ผ๋Š” ์ˆ˜์‹์–ด์ฒ˜๋Ÿผ ๊ฒน๊ฒน์ด ์Œ“์—ฌ ์—ฐ์†์„ฑ์„ ๋ณด์ด๊ณ  ์žˆ์—ˆ์œผ๋ฉฐ ์ œ์ฃผ์˜ ๋†์—…๊ฒฝ๊ด€ ํŒจํ„ด์„ ํ™•์ธํ•  ์ˆ˜ ์žˆ์—ˆ๋‹ค. ๋‘˜์งธ, ์›”์ •๋ฆฌ์—์„œ๋Š” ๋ฐญ ํ‘œ๋ฉด๋ณด๋‹ค ๋‚ฎ๊ฒŒ ๋ฌผ๊ธธ์„ ๋‚ด์–ด ๋ฐฐ์ˆ˜ ๊ธฐ๋Šฅ์„ ํ•˜๋Š” ์ˆ˜๋กœ ์ž์›์ด ์กด์žฌํ•˜๋ฉฐ, ํ† ์–‘์˜ ์œ ์‹ค์„ ๋ฐฉ์ง€ํ•˜๊ณ ์ž ๋ณ„๋„ ํ˜•ํƒœ์˜ ๋ฐญ๋‹ด ์ˆ˜์ž์› ๊ด€๋ฆฌ ๊ฒฝ๊ด€์„ ํ™•์ธํ•  ์ˆ˜ ์žˆ์—ˆ๋‹ค. ์…‹์งธ, ์›”์ •๋ฆฌ์—์„œ๋Š” ๋‚ด๋ฅ™์ง€๋ฐฉ๊ณผ ๊ตฌ๋ถ„๋˜๋Š” ๋งค์žฅ๋ฌธํ™”๊ฐ€ ๊ณณ๊ณณ์— ์กด์žฌํ•˜๋ฉฐ, ์‚ฐ๋‹ด ๊ฒฝ๊ด€์€ ๋†์—…ํ™œ๋™์„ ์‹œํ–‰ํ•˜๊ณ  ์žˆ๋Š” ํ•„์ง€์™€ ์ƒ๋ฐ˜๋˜์–ด์ง€๋Š” ๊ณต๊ฐ„ ๋Œ€๋น„๋กœ์„œ ์ œ์ฃผ๋งŒ์˜ ๋…ํŠนํ•œ ๋ฌธํ™”์  ๊ฒฝ๊ด€์„ ํ™•์ธํ•ด๋ณผ ์ˆ˜ ์žˆ๋‹ค. ๋„ท์งธ, ์›”์ •๋ฆฌ์—์„œ๋Š” ์˜ค๋žœ ๊ธฐ๊ฐ„ ๋™์•ˆ ๋†์—…ํ™œ๋™์„ ์‹œํ–‰ํ•˜๊ณ  ์žˆ๋Š” ๋†๋ฏผ๋“ค์ด ์ €๋งˆ๋‹ค ๋‹ค๋ฅธ ํ† ์ง€์—ฌ๊ฑด์„ ๊ณ ๋ คํ•œ ์ด์šฉ ์‹œ์Šคํ…œ ์ฒด๊ณ„๋ฅผ ์‹œํ–‰ํ•˜๊ณ  ์žˆ์—ˆ์œผ๋ฉฐ, ์ด๋Š” ๊ณง ์›”์ •๋ฆฌ๋งŒ์˜ ๋…ํŠนํ•œ ๊ฒฝ๊ด€ ํ˜•์„ฑ์œผ๋กœ ๊ด€๊ณ„๋˜์–ด์ง์„ ์•Œ ์ˆ˜ ์žˆ์—ˆ๋‹ค. ๋”ฐ๋ผ์„œ ๊ธฐ์กด์— ๊ฑฐ์‹œ์ ์ธ ์ธก๋ฉด์—์„œ๋งŒ ๋…ผ์˜๋˜์—ˆ๋˜ ๋†์—…์œ ์‚ฐ์— ๋Œ€ํ•œ ๋ฐญ๋‹ด์˜ ๊ฒฝ๊ด€์  ๊ฐ€์น˜๋ฅผ ๋ณธ ์—ฐ๊ตฌ์—์„œ๋Š” ๊ตฌ์ฒด์ ์ธ ๋Œ€์ƒ์ง€๋ฅผ ํ†ตํ•ด ์‚ดํŽด๋ด„์œผ๋กœ์จ ์˜์˜๋ฅผ ํ™•์ธ ํ•  ์ˆ˜ ์žˆ์—ˆ๋‹ค. ๋˜ํ•œ ๋ฐญ๋‹ด ๊ฒฝ๊ด€์„ ๊ด€๋ฆฌํ•จ์— ์žˆ์–ด์„œ ๋‹จ์ˆœํžˆ ๋ฌผ๋ฆฌ์ ์ธ ๊ฒฝ๊ด€์˜ ๋ณด์ „๋ฟ๋งŒ ์•„๋‹ˆ๋ผ, ๊ด€๋ จ๋˜์–ด์ง„ ์—ฌ๋Ÿฌ ์‹œ์Šคํ…œ์  ์š”์†Œ๊นŒ์ง€ ๊ตฌ์ฒดํ™”ํ•˜์—ฌ ์ถ”ํ›„ ๊ด€๋ฆฌ ๋ฐ ํ™œ์šฉํ•  ์ˆ˜ ์žˆ์„ ๊ฒƒ์œผ๋กœ ๊ธฐ๋Œ€๋œ๋‹ค.์ œ1์žฅ ์„œ๋ก  1 1์ ˆ ์—ฐ๊ตฌ์˜ ๋ฐฐ๊ฒฝ ๋ฐ ๋ชฉ์  1 2์ ˆ ์—ฐ๊ตฌ์˜ ๋ฒ”์œ„ 5 1. ๊ณต๊ฐ„์  ๋ฒ”์œ„ 5 2. ๋‚ด์šฉ์  ๋ฒ”์œ„ 5 3์ ˆ ์—ฐ๊ตฌ์˜ ๋ฐฉ๋ฒ• ๋ฐ ํ๋ฆ„ 6 ์ œ2์žฅ ์ด๋ก ์  ๊ณ ์ฐฐ 9 1์ ˆ ๋†์—…์œ ์‚ฐ ์ œ๋„์˜ ๊ฐœ๋… ๋ฐ ์˜์˜ 9 1. ์„ธ๊ณ„์ค‘์š”๋†์—…์œ ์‚ฐ(GIAHS) 9 2. ๊ตญ๊ฐ€์ค‘์š”๋†์—…์œ ์‚ฐ(NIAHS) 9 3. ์†Œ๊ฒฐ 10 2์ ˆ ๋†์—…์œ ์‚ฐ์œผ๋กœ์„œ ์ œ์ฃผ ๋ฐญ๋‹ด์˜ ๊ฐ€์น˜ 12 1. ์‹๋Ÿ‰๊ณผ ์ƒ๊ณ„์ˆ˜๋‹จ์˜ ํ™•๋ณด 12 2. ์ƒ๋ฌผ๋‹ค์–‘์„ฑ๊ณผ ์ƒํƒœ๊ณ„์˜ ๊ธฐ๋Šฅ 13 3. ์ง€์‹์‹œ์Šคํ…œ ๋ฐ ์ ์‘๊ธฐ์ˆ  15 4. ๋ฌธํ™” ๊ฐ€์น˜์ฒด๊ณ„ ๋ฐ ์‚ฌํšŒ์กฐ์ง 16 5. ํ˜„์ €ํ•œ ๊ฒฝ๊ด€ ํ† ์ง€์™€ ์ˆ˜์ž์› ๊ด€๋ฆฌ ๊ธฐ๋Šฅ 17 3์ ˆ ์„ ํ–‰์—ฐ๊ตฌ ๊ณ ์ฐฐ 18 1. ๋†์—…์œ ์‚ฐ๊ณผ ๊ด€๋ จํ•œ ์—ฐ๊ตฌ 18 2. ์ œ์ฃผ ๋ฐญ๋‹ด ๋ฐ ๋Œ๋‹ด์— ๊ด€ํ•œ ์—ฐ๊ตฌ 22 3. ๊ฒฝ๊ด€์— ๊ด€ํ•œ ์—ฐ๊ตฌ 24 4. ์—ฐ๊ตฌ์˜ ์ฐจ๋ณ„์„ฑ 26 ์ œ3์žฅ ๊ตฌ์ขŒ์ ์›”์ •๋ฆฌ ์ผ๋Œ€ ๋ฐญ๋‹ด์˜ ํ˜„ํ™ฉ 27 1์ ˆ ๋Œ€์ƒ์ง€ ์„ ์ • ๋ฐ ๊ฐœ์š” 27 1. ๋Œ€์ƒ์ง€ ์„ ์ •์˜ ํƒ€๋‹น์„ฑ 27 2. ๋Œ€์ƒ์ง€ ๊ฐœ์š” 28 2์ ˆ ์›”์ •๋ฆฌ ์ผ๋Œ€ ๋ฐญ๋‹ด ํ˜„ํ™ฉ ๋ฐ ๋ถ„์„ 30 1. ์ž์—ฐํ™˜๊ฒฝํ˜„ํ™ฉ 30 2. ์ธ๋ฌธํ™˜๊ฒฝํ˜„ํ™ฉ 32 3์ ˆ ์†Œ๊ฒฐ 38 ์ œ4์žฅ ๋†์—…์œ ์‚ฐ์  ๊ด€์ ์œผ๋กœ์„œ ์›”์ •๋ฆฌ ๋ฐญ๋‹ด ๊ฒฝ๊ด€ ํŠน์ง• 39 1์ ˆ ์›”์ •๋ฆฌ ๋ฐญ๋‹ด ๊ฒฝ๊ด€์˜ ๊ตฌ์„ฑ์š”์†Œ 39 1. ๋†์—…์œ ์‚ฐ์  ๊ด€์ ์œผ๋กœ์„œ ๋ฐญ๋‹ด ๊ฒฝ๊ด€์ž์› ๊ตฌ์„ฑ์˜ ํŠน์„ฑ 39 2. ์›”์ •๋ฆฌ ๋ฐญ๋‹ด ๊ฒฝ๊ด€์œ ํ˜• ๋ฐ ์ž์›์š”์†Œ 40 2์ ˆ ๋†์—…์œ ์‚ฐ์  ๊ด€์ ์œผ๋กœ์„œ ์›”์ •๋ฆฌ ๋ฐญ๋‹ด ๊ฒฝ๊ด€ ํŠน์ง• 43 1. ํ‘๋ฃก๋งŒ๋ฆฌ ์›”์ •๋ฆฌ ๋ฐญ๋‹ด์˜ ๋†์—…๊ฒฝ๊ด€ ํŒจํ„ด 43 2. ์›”์ •๋ฆฌ์˜ ๋…ํŠนํ•œ ์ˆ˜์ž์› ๊ด€๋ฆฌ ๋ฐญ๋‹ด ๊ฒฝ๊ด€ 49 3. ์›”์ •๋ฆฌ ๋ฐญ๋‹ด์˜ ๋ฌธํ™”์  ์š”์†Œ๋ฅผ ์—ฟ๋ณผ ์ˆ˜ ์žˆ๋Š” ์‚ฐ๋‹ด ๊ฒฝ๊ด€ 55 4. ์›”์ •๋ฆฌ์—์„œ ํ˜„์กดํ•˜๊ณ  ์žˆ๋Š” ๋†์—…ํ™œ๋™ ๊ฒฝ๊ด€ 59 3์ ˆ ํŠน์ง•๋ณ„ ๋ถ„์„์˜ ์ข…ํ•ฉ 68 1. ํ‘๋ฃก๋งŒ๋ฆฌ ์›”์ •๋ฆฌ ๋ฐญ๋‹ด์˜ ๋†์—…๊ฒฝ๊ด€ ํŒจํ„ด 68 2. ์›”์ •๋ฆฌ์˜ ๋…ํŠนํ•œ ์ˆ˜์ž์› ๊ด€๋ฆฌ ๋ฐญ๋‹ด ๊ฒฝ๊ด€ 71 3. ์›”์ •๋ฆฌ ๋ฐญ๋‹ด์˜ ๋ฌธํ™”์  ์š”์†Œ๋ฅผ ์—ฟ๋ณผ ์ˆ˜ ์žˆ๋Š” ์‚ฐ๋‹ด ๊ฒฝ๊ด€ 73 4. ์›”์ •๋ฆฌ์—์„œ ํ˜„์กดํ•˜๊ณ  ์žˆ๋Š” ๋†์—…ํ™œ๋™ ๊ฒฝ๊ด€ 75 ์ œ5์žฅ ๊ฒฐ๋ก  78 ์ฐธ ๊ณ  ๋ฌธ ํ—Œ 80Maste

    Oxygen redox reactions of iron-based Li-rich rocksalt cathode materials for lithium ion batteries

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    ํ•™์œ„๋…ผ๋ฌธ(๋ฐ•์‚ฌ)--์„œ์šธ๋Œ€ํ•™๊ต ๋Œ€ํ•™์› :๊ณต๊ณผ๋Œ€ํ•™ ํ™”ํ•™์ƒ๋ฌผ๊ณตํ•™๋ถ€,2020. 2. ์ด๊ทœํƒœ.๋ณธ ์—ฐ๊ตฌ์—์„œ๋Š” ์ฒ  ๊ธฐ๋ฐ˜์˜ ๋ฆฌํŠฌ ๊ณผ์ž‰ ์•”์—ผ ๊ตฌ์กฐ ๋ฌผ์งˆ๋“ค์„ ๋ฆฌํŠฌ ์ด์˜จ ์ „์ง€ ์–‘๊ทน ์†Œ์žฌ๋กœ์จ ํ…Œ์ŠคํŠธํ•˜์˜€๋‹ค. ๊ธฐ์กด์˜ LiFeO2 ์•”์—ผ ๊ตฌ์กฐ ์–‘๊ทน ์†Œ์žฌ๋Š” Ni, Co, Mn์„ ๊ธฐ๋ฐ˜์œผ๋กœ ํ•˜๋Š” ์ธต์ƒ ๊ตฌ์กฐ ๋ฌผ์งˆ๋“ค์— ๋น„ํ•ด ์ƒ๋Œ€์ ์œผ๋กœ ๋œ ์ฃผ๋ชฉ๋ฐ›์€ ์†Œ์žฌ์ด๋‹ค. ๊ทธ๋Ÿฐ ์ด์œ ์—๋Š” ์ข‹์ง€ ์•Š์€ ์„ฑ๋Šฅ๊ณผ ์ถฉ/๋ฐฉ์ „ ๊ณผ์ •์—์„œ ๋ฐœ์ƒํ•˜๋Š” ํฐ ์ด๋ ฅ ํ˜„์ƒ์ด ์ฃผ๋ฅผ ์ด๋ฃจ๊ณ  ์žˆ๋‹ค. ํ•˜์ง€๋งŒ ์›๋ž˜ ๋น„์‹ผ ์ฝ”๋ฐœํŠธ์˜ ๊ฐ€๊ฒฉ๊ณผ ์ ์  ๋น„์‹ธ์ง€๋Š” ๋‹ˆ์ผˆ์˜ ๊ฐ€๊ฒฉ์œผ๋กœ ์ธํ•˜์—ฌ ๋” ์ €๋ ดํ•œ ์†Œ์žฌ๋ฅผ ๋ฐ”ํƒ•์œผ๋กœ ํ•˜๋Š” ์–‘๊ทน ์†Œ์žฌ์— ๋Œ€ํ•œ ์—ฐ๊ตฌ๊ฐ€ ์ฃผ๋ชฉ์„ ๋ฐ›๊ณ  ์žˆ๋‹ค. ์ด์™€ ๋งž๋ฌผ๋ ค์„œ ๊ธฐ์กด์˜ ๋ฆฌํŠฌ๊ณผ ์ „์ด ๊ธˆ์†์˜ ๋น„์œจ์ด 1 : 1์ธ ์•”์—ผ ๊ตฌ์กฐ ๋ฌผ์งˆ์„ ๋„˜์–ด์„œ ๋ฆฌํŠฌ ๊ณผ์ž‰์˜ ์•”์—ผ ๊ตฌ์กฐ ๋ฌผ์งˆ์ด ์ƒˆ๋กœ์šด ๊ณ ์„ฑ๋Šฅ ์–‘๊ทน ์†Œ์žฌ๋กœ์„œ ์ฃผ๋ชฉ์„ ๋ฐ›๊ณ  ์žˆ๋Š” ์ถ”์„ธ์ด๋‹ค. ๋ณธ ์—ฐ๊ตฌ์—์„œ๋Š” ์ด๋Ÿฐ ์ฒ ์„ ๊ธฐ๋ฐ˜์œผ๋กœ ํ•œ ๋ฆฌํŠฌ ๊ณผ์ž‰ ์•”์—ผ ๊ตฌ์กฐ ๋ฌผ์งˆ์— ๋Œ€ํ•ด ์—ฐ๊ตฌ๋ฅผ ํ•˜์˜€๊ณ , ๋ฆฌํŠฌ์ด ๊ณผ์ž‰์œผ๋กœ ๋“ค์–ด๊ฐ€๋Š” ์ƒํ™ฉ์—์„œ ์กฐ์„ฑ์‹ ๋ฐ ์‚ฐํ™”์ˆ˜ ๊ท ํ˜•์„ ์œ ์ง€ํ•˜๊ธฐ ์œ„ํ•ด ์ „์ด ๊ธˆ์†์— ์‚ฐํ™”์ˆ˜๊ฐ€ ๋†’์€ ์›์†Œ๋ฅผ ์‚ฌ์šฉํ•˜๋Š” ๋ฒ•๊ณผ ๊ฒฉ์ž ์‚ฐ์†Œ๋ฅผ ์‚ฐํ™”์ˆ˜๊ฐ€ -1์ธ ๋ถˆ์†Œ๋กœ ์น˜ํ™˜ํ•˜๋Š” 2๊ฐ€์ง€ ๋ฐฉ๋ฒ•์„ ํ†ตํ•ด Li1+xFe1-2xTaxO2์™€ Li2FeO2F 2๊ฐ€์ง€ ์กฐ์„ฑ์˜ ๋ฆฌํŠฌ ๊ณผ์ž‰ ์–‘๊ทน ์†Œ์žฌ๋ฅผ ํ•ฉ์„ฑํ•˜์˜€๊ณ , ์ด๋“ค์˜ ์ „๊ธฐํ™”ํ•™์  ํ™œ์„ฑ ๋ฐ ๋ฐ˜์‘ ๋งค์ปค๋‹ˆ์ฆ˜์— ๋Œ€ํ•ด์„œ ๋ถ„์„์„ ์ง„ํ–‰ํ•˜์˜€๋‹ค. ํƒ„ํƒˆ๋ฅจ์„ ํฌํ•จํ•˜๋Š” ๋ฆฌํŠฌ ๊ณผ์ž‰ ์‚ฐํ™”๋ฌผ์˜ ๊ฒฝ์šฐ 60โ„ƒ์—์„œ ์•ฝ 248.5mAh g-1์ด, ๋ฆฌํŠฌ ์ฒ  ์‚ฐํ™”๋ถˆ์†Œํ™”๋ฌผ์˜ ๊ฒฝ์šฐ 30โ„ƒ์—์„œ ์•ฝ 350mAh g-1์˜ ์šฉ๋Ÿ‰์„ ๋ฐœํ˜„ํ•˜์˜€๊ณ , ์ด๋Š” ๊ฐ๊ฐ์˜ ์ด๋ก  ์šฉ๋Ÿ‰์„ ์ƒํšŒํ•˜๋Š” ์šฉ๋Ÿ‰์ด๋‹ค. ๋”ฐ๋ผ์„œ ์ด๋Ÿฐ ๋ฐ˜์‘ ๋งค์ปค๋‹ˆ์ฆ˜์„ ๋ถ„์„ํ•˜๊ธฐ ์œ„ํ•ด ์ฒ ์˜ K-edge์™€ ์‚ฐ์†Œ์˜ K-edge์— ๋Œ€ํ•œ X์„  ํก์ˆ˜ ์ŠคํŽ™ํŠธ๋Ÿผ (X-ray absorption spectroscopy) ๋ถ„์„์„ ์ง„ํ–‰ํ•˜์˜€๋‹ค. ๋‘ ์‹คํ—˜์„ ๋ฐ”ํƒ•์œผ๋กœ ๋ฐ˜์‘ ๋งค์ปค๋‹ˆ์ฆ˜์„ ๋ถ„์„ํ•ด๋ณธ ๊ฒฐ๊ณผ ๋‘ ๋ฌผ์งˆ ๋ชจ๋‘ ์ถฉ์ „ ๊ณผ์ •์—์„œ ์ฒ ์˜ ์‚ฐํ™” ๋ฟ๋งŒ ์•„๋‹ˆ๋ผ ์‚ฐ์†Œ์˜ ์‚ฐํ™”๊ฐ€ ๋ฐœ์ƒํ•˜์˜€๋‹ค. ํ•˜์ง€๋งŒ ํƒ„ํƒˆ๋ฅจ์˜ ๊ฒฝ์šฐ ์‚ฐ์†Œ์˜ ์‚ฐํ™” ๋ฐ˜์‘์ด ๋น„๊ฐ€์—ญ์ ์œผ๋กœ ์‚ฐ์†Œ ๊ฐ€์Šค ํ˜•ํƒœ๋กœ ๋ฐฉ์ถœ๋˜๊ณ  ๊ทธ ์ดํ›„๋Š” ์ฒ ์˜ ์ถ”๊ฐ€์ ์ธ ํ™˜์›์„ ์ด์šฉํ•ด์„œ ์šฉ๋Ÿ‰์ด ๋ฐœํ˜„๋˜๋Š” ๊ฒƒ์„ ํ™•์ธํ•˜์˜€๋‹ค. ๋ฆฌํŠฌ ์ฒ  ์‚ฐํ™”๋ถˆ์†Œํ™”๋ฌผ์˜ ๊ฒฝ์šฐ ์—ญ์‹œ ์ฒซ ์ถฉ์ „์—์„œ ์‚ฐ์†Œ ๊ธฐ์ฒด์˜ ๋ฐฉ์ถœ์ด ์žˆ๋Š” ๊ฒƒ์ด ๋ณด์˜€์ง€๋งŒ, ๋ฐฉ์ „ ๊ณผ์ •์—์„œ ์ผ๋ถ€ ์‚ฐํ™”๋œ ์‚ฐ์†Œ์˜ ํ™˜์›๊ณผ ์ฒ ์˜ ํ™˜์›์„ ํ†ตํ•ด์„œ ์ด๋ก  ์šฉ๋Ÿ‰์„ ๋›ฐ์–ด๋„˜๋Š” ๊ณ ์šฉ๋Ÿ‰์„ ๋ฐœํ˜„ ํ•˜๋Š” ๊ฒƒ์œผ๋กœ ํ™•์ธ๋˜์—ˆ๋‹ค. ๋˜ํ•œ ๊ฒฉ์ž ๋ถˆ์†Œ์˜ ์—ญํ• ์„ ์•Œ์•„๋ณด๊ธฐ ์œ„ํ•ด LiFeO2, Li1.15Fe0.7Ta0.15O2, Li2FeO2F ์„ธ ๋ฌผ์งˆ์„ ๊ฐ™์€ ๋ณผ ๋ฐ€ ์กฐ๊ฑด์„ ๊ฑฐ์นœ ํ›„์— ์ „๊ธฐํ™”ํ•™์  ํ…Œ์ŠคํŠธ๋ฅผ ์ง„ํ–‰ํ•˜์˜€๋‹ค. ๊ฒฉ์ž ๋‚ด์— ๋ถˆ์†Œ๊ฐ€ ์žˆ๋Š” Li2FeO2F์˜ ๊ฒฝ์šฐ ๋‹ค๋ฅธ ๋‘ ๋ฌผ์งˆ๊ณผ ๋‹ฌ๋ฆฌ ์ถฉ์ „ ๊ณผ์ •์—์„œ ๊ณผ์ „์••์ด ๋งค์šฐ ์ ๊ฒŒ ๊ฑธ๋ ค์„œ ๊ฒฉ์ž ๋‚ด์˜ ๋ฆฌํŠฌ์„ ๋งŽ์ด ๋นผ ์“ธ ์ˆ˜ ์žˆ๋‹ค๋Š” ๊ฒƒ์„ ํ™•์ธํ•˜์˜€๋‹ค.In this research, novel iron(Fe3+)-based lithium-rich cation-disordered rocksalt materials are reported. Firstly, Li1+xFe1-2xTaxO2 (x= 0.15, 0.2 and 0.25) were synthesized. Li1.15Fe0.7Ta0.15O2 was tested as cathode materials and it shows 248.5 mAh g-1 of specific capacity at first cycle, 60โ„ƒ. The second iron-based material is Li2FeO2F. The 1st discharging capacity of lithium iron oxyfluoride is 350 mAh g-1 at 30โ„ƒ and 423.5 mAh g-1 at 60โ„ƒ For both materials, they exceeds their theoretical capacity (calculated based on Fe 3+/4+ redox). To elucidate their redox mechanism, hard XAS (X-ray absorption spectroscopy) of Fe K-edge and soft XAS of O K-edge were analyzed. For Li1.15Fe0.7Ta0.15O2, we found the evidence of oxidized oxygen On- in FY spectra of O K-edge. However full charge to 4.8 V makes severe oxygen loss. No reversible oxygen reduction was occur and iron is more reduced after 1st discharging, compared to bare state(Fe3+). In case of Li2FeO2F, although oxygen loss also exist in this material, at discharging, there is an oxygen reduction peak at differential capacity plot. STXM O K-edge spectra reveals that partially reversible anionic redox exist in Li2FeO2F. There are two signs of oxygen redox in the spectra of Li2-xFeO2F, electrochemically induced oxygen hole signals and peroxide-like (O2)2- signals. Comparing with Li1.15Fe0.7Ta0.15O2, we can say that oxygen holes are created at the surface and peroxide-like dimer was formed in bulk signals. Furthermore, by comparison between LiFeO2, Li1.15Fe0.7Ta0.15O2 and Li2FeO2F, the benign effect for lattice fluorine substitution was elucidated. The lattice fluorine reduces resistance at charging process which makes more facile delithiation compare to LiFeO2 and Li1.15Fe0.7Ta0.15O2.์ œ 1 ์žฅ ์„œ ๋ก  1 ์ œ 2 ์žฅ ๋ฌธํ—Œ ์—ฐ๊ตฌ 5 2.1 ๋ฆฌํŠฌ ์ด์˜จ ์ „์ง€ ์–‘๊ทน ์†Œ์žฌ 5 2.1.1 ์ธต์ƒ ๊ตฌ์กฐ 5 2.1.2 ์˜ฌ๋ฆฌ๋นˆ ๊ตฌ์กฐ 7 2.1.3 ์Šคํ”ผ๋„ฌ ๊ตฌ์กฐ 8 2.1.4 ์•”์—ผ ๊ตฌ์กฐ 9 2.2 ๋ฆฌํŠฌ ์–‘๊ทน ์†Œ์žฌ์˜ ๋ฐ˜์‘์›๋ฆฌ 12 2.2.1 ์ „์ด ๊ธˆ์†์˜ ์‚ฐํ™”/ํ™˜์› 12 2.2.2 ๊ฒฉ์ž ์‚ฐ์†Œ์˜ ์‚ฐํ™”/ํ™˜์› 13 ์ œ 3 ์žฅ ์‹คํ—˜ ๋ฐฉ๋ฒ• 16 3.1 ๋ฌผ์งˆ ํ•ฉ์„ฑ 16 3.2 ๋ฌผ์งˆ ํŠน์„ฑ ๋ถ„์„ 17 3.3 ์ „๊ธฐํ™”ํ•™ ์‹คํ—˜ ์กฐ๊ฑด 19 ์ œ 4 ์žฅ ๊ฒฐ๊ณผ์™€ ๊ณ ์ฐฐ 20 4.1 Li1+xFe1-2xTaxO2 20 4.1.1 ํ•ฉ์„ฑ ๋ฐ ํ™•์ธ 20 4.1.2 ์ „๊ธฐํ™”ํ•™ ์„ฑ๋Šฅ ํ™•์ธ 26 4.1.3 ํ•ฉ์„ฑ ๋ฐ ํ™•์ธ 31 4.1.4 ๊ฒฐ๋ก  38 4.2 Li2FeO2F 41 4.2.1 ํ•ฉ์„ฑ ๋ฐ ํ™•์ธ 41 4.2.2 ์ „๊ธฐํ™”ํ•™ ์„ฑ๋Šฅ ํ™•์ธ 46 4.2.3 ๋ฐ˜์‘ ๋งค์ปค๋‹ˆ์ฆ˜ ๋ถ„์„ 50 4.2.4 LiFeO2, Li1.15Fe0.7Ta0.15O2, Li2FeO2F ๋น„๊ต 65 4.2.5 ๊ฒฐ๋ก  69 4.3 ๊ณ ์ฐฐ 70 Abstract 72 ์ฐธ๊ณ ๋ฌธํ—Œ 74Docto

    Improved electrochemical performance of LiCoO2 through in situ electrochemical coating

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    ํ•™์œ„๋…ผ๋ฌธ (์„์‚ฌ)-- ์„œ์šธ๋Œ€ํ•™๊ต ๋Œ€ํ•™์› : ํ™”ํ•™์ƒ๋ฌผ๊ณตํ•™๋ถ€, 2017. 2. ์ด๊ทœํƒœ.๊ฐ€์žฅ ๋„๋ฆฌ ์‚ฌ์šฉ๋˜๊ณ  ์žˆ๋Š” ๋ฆฌํŠฌ ์–‘๊ทน ํ™œ๋ฌผ์งˆ์ธ LiCoO2๋Š” ๋ฆฌํŠฌ์„ 0.5๊ฐœ๊นŒ์ง€ ์‚ฌ์šฉํ•˜์˜€์„ ์‹œ ๋ฆฌํŠฌ๋Œ€๋น„ ์•ฝ 4.2V๊นŒ์ง€ ์ „์••์ด ์˜ฌ๋ผ๊ฐ€๋ฉฐ, 140mAh/g์˜ ์šฉ๋Ÿ‰์„ ๊ฐ€์—ญ์ ์œผ๋กœ ์‚ฌ์šฉํ•  ์ˆ˜ ์žˆ๋Š” ๋ฌผ์งˆ์ด๋‹ค. ํ•˜์ง€๋งŒ ๋ฆฌํŠฌ์„ ๋” ๋งŽ์ด ์‚ฌ์šฉํ•˜์—ฌ ๊ณ ์ „์••๊นŒ์ง€ ์ถฉ์ „์„ ํ•˜์˜€์„ ๊ฒฝ์šฐ ๊ฒฉ์ž๊ตฌ์กฐ์˜ ๋น„๊ฐ€์—ญ์ ์ธ ๋ถ•๊ดด, ์ „์ด๊ธˆ์†์ธ ์ฝ”๋ฐœํŠธ์˜ ์šฉ์ถœ, ์ „ํ•ด์งˆ ๋ถ€์‚ฐ๋ฌผ๊ณผ์˜ ๋ถ€๋ฐ˜์‘ ๋“ฑ์˜ ๋ฌธ์ œ๋“ค์ด ๋ฐœ์ƒํ•œ๋‹ค. ์ด ์ค‘ ์ „์ด๊ธˆ์†์˜ ์šฉ์ถœ๊ณผ ์ „ํ•ด์งˆ ๋ถ€์‚ฐ๋ฌผ๊ณผ์˜ ๋ถ€๋ฐ˜์‘์€ ํ™œ๋ฌผ์งˆ์— ์ฝ”ํŒ…์„ ํ•ด์„œ ์–ต์ œ์‹œํ‚ฌ ์ˆ˜ ์žˆ๋Š”๋ฐ, ์ฝ”ํŒ…์œผ๋กœ ์ธํ•ด ์ถ”๊ฐ€๋˜๋Š” ๊ณต์ •์ด ํ™œ๋ฌผ์งˆ์˜ ๋Œ€๋Ÿ‰์ƒ์‚ฐ์— ๋ฐฉํ•ด๊ฐ€ ๋˜๊ฑฐ๋‚˜, ๋น„์‹ผ ๋น„์šฉ์ ์ธ ๋ฉด์—์„œ ๋‹จ์ ๋“ค์„ ๊ฐ€์ง€๊ณ  ์žˆ๊ธฐ์—, ์ข€ ๋” ๊ฐ„ํŽธํ•˜๊ณ  ์ €๋ ดํ•œ ๋ฐฉ๋ฒ•์˜ ์ฝ”ํŒ…๋ฐฉ๋ฒ•์ด ํ•„์š”ํ•˜๋‹ค. ๊ทธ๋ ‡๊ธฐ์— ์ „ํ•ด์งˆ์— ๋ฌด๊ธฐํ™”ํ•ฉ๋ฌผ ์—ผ์„ ์ถ”๊ฐ€๋กœ ๋„ฃ์–ด ์ „์ง€๊ฐ€ ์ถฉ๋ฐฉ์ „ ๋˜๋Š”๋™์•ˆ ์ฝ”ํŒ…์ด ๋˜๋Š” ๋ฐฉ๋ฒ•์„ ๊ณ ์•ˆํ–ˆ๊ณ , Mg(ClO4)2๋ฅผ ์‚ฌ์šฉํ•˜์—ฌ ์ด๋ฅผ ์„ฑ๊ณต์‹œ์ผฐ๋‹ค. ๊ทธ๋ฆฌ๊ณ  ์ด๋ฅผ ํ™•์ธํ•˜๊ธฐ ์œ„ํ•ด ์ถ”๊ฐ€์ ์ธ XANES ๋ฐ TEM, XPS ๋ถ„์„์„ ํ†ตํ•ด LiCoO2์— Mg๊ฐ€ ์‚ฝ์ž…๋˜์ง€ ์•Š๊ณ , ํ‘œ๋ฉด์— ์ฝ”ํŒ…๋ง‰์ฒ˜๋Ÿผ ์ถ•์ ๋˜๋Š” ๊ฒƒ์„ ํ™•์ธํ•˜์˜€๋‹ค. Mg์˜ ๊ฒฝ์šฐ LiCoO2์˜ ํ‘œ๋ฉด์—์„œ MgF2์˜ ํ˜•ํƒœ๋กœ ์กด์žฌํ•˜๋Š” ๊ฒƒ์„ ํ™•์ธํ•˜์˜€๋‹ค. ๋˜ํ•œ Mg(ClO4)2์˜ ์–‘์— ๋”ฐ๋ผ์„œ ์ˆ˜๋ช…ํŠน์„ฑ์˜ ๊ฐœ์„ ๋˜๋Š” ์ •๋„๊ฐ€ ์•ฝ๊ฐ„์”ฉ ์ฐจ์ด๊ฐ€ ์žˆ๊ธฐ๋Š” ํ–ˆ์ง€๋งŒ, 45โ„ƒ, 60โ„ƒ์—์„œ ๋ชจ๋‘ ๊ธฐ์กด ๋ฆฌํŠฌ ์—ผ๋งŒ ์‚ฌ์šฉํ•œ ์ „์ง€๋ณด๋‹ค ์„ฑ๋Šฅ์ด ๊ฐœ์„ ๋˜๋Š” ๋ชจ์Šต์„ ๋ณผ ์ˆ˜ ์žˆ์—ˆ๋‹ค. ๊ทธ๋ฆฌ๊ณ  ์ด๊ฒƒ์ด ํ‘œ๋ฉด์— ์ƒ์„ฑ๋œ MgF2 ์ฝ”ํŒ…๋ง‰์— ์˜ํ•œ ๊ฒƒ์ž„์„ ํ™•์ธํ•˜์˜€๊ณ , 45โ„ƒ, 60โ„ƒ, 85โ„ƒ์—์„œ์˜ ์ €์žฅ์‹คํ—˜์„ ํ†ตํ•ด MgF2 ์ฝ”ํŒ…๋ง‰์ด ์ƒ๊ฒผ์„ ๊ฒฝ์šฐ ์ฝ”๋ฐœํŠธ ์šฉ์ถœ์ด ์–ต์ œ๋˜์–ด์„œ LiCoO2์˜ ์•ˆ์ •ํ™”์— ๊ธฐ์—ฌํ•œ๋‹ค๋Š” ๊ฒƒ์„ ํ™•์ธํ•˜์˜€๋‹ค.์ œ 1 ์žฅ ์„œ ๋ก  1 ์ œ 2 ์žฅ ๋ฌธํ—Œ ์—ฐ๊ตฌ 5 2. 1. ๋ฆฌํŠฌ ์ด์˜จ ์ „์ง€ 5 2. 1. 1. ๋ฆฌํŠฌ ์ด์˜จ ์ „์ง€ ์‹œ์Šคํ…œ 5 2. 1. 2. ์–‘๊ทน์žฌ๋กœ์จ LiCoO2 6 2. 1. 3. ๊ณ ์ „์•• ๋ฐ ๊ณ ์˜จ์—์„œ์˜ LiCoO2์˜ ๋ฌธ์ œ์  6 2. 2 ํ™œ๋ฌผ์งˆ์˜ ์ฝ”ํŒ… 12 2. 2. 1. ํ™œ๋ฌผ์งˆ ์ฝ”ํŒ…์˜ ์žฅ์  12 2. 2. 2. ํ™œ๋ฌผ์งˆ ์ฝ”ํŒ… ๋ฐฉ๋ฒ• 12 2. 2. 2. 1. ์Šต์‹ํ™”ํ•™ ํ•ฉ์„ฑ 12 2. 2. 2. 2. ํ™”ํ•™์  ๊ณ ๋ถ„์ž ์ค‘ํ•ฉ 13 2. 2. 2. 3. ์ฆ์ฐฉ ๋ฐฉ์‹ 14 ์ œ 3 ์žฅ ์‹คํ—˜ ๋ฐฉ๋ฒ• 17 3. 1. ๋ฌผ์งˆ ํ•ฉ์„ฑ ๋ฐ ์„ ์ • 17 3. 1. 1. ๋ฌผ์งˆ ํ•ฉ์„ฑ 17 3. 1. 2. ๋ฌผ์งˆ ๋ถ„์„ 17 3. 1. 3. ์‹œ์•ฝ ์„ ์ • 17 3. 2. ํ‘œ๋ฉด์˜ ๋งˆ๊ทธ๋„ค์Š˜ ์ถ•์  ์—ฌ๋ถ€ ํ™•์ธ 18 3. 2. 1. ์…€ ๊ตฌ์„ฑ ๋ฐ ์ „๊ธฐํ™”ํ•™ ํ…Œ์ŠคํŠธ 18 3. 2. 2. ๋งˆ๊ทธ๋„ค์Š˜์˜ ์ถ•์  ์—ฌ๋ถ€ ํ™•์ธ 18 3. 3. ๋งˆ๊ทธ๋„ค์Š˜ ์—ผ์„ ์ด์šฉํ•œ ์‹ค์‹œ๊ฐ„ ์ฝ”ํŒ… 20 3. 3. 1. ์ „ํ•ด์งˆ ์ œ์กฐ 20 3. 3. 2. ์ „๊ธฐํ™”ํ•™์  ์…€ ๊ตฌ์„ฑ ๋ฐ ์‹คํ—˜์กฐ๊ฑด 20 3. 3. 3. ๋งˆ๊ทธ๋„ค์Š˜ ์ฝ”ํŒ… ๋ถ„์„ 21 3. 3. 4. ์ €์žฅ ์‹คํ—˜ 21 ์ œ 4 ์žฅ ๊ฒฐ๊ณผ ๋ฐ ๊ณ ์ฐฐ 22 4. 1. Mg์˜ ์ฝ”ํŒ…์—ฌ๋ถ€ ํ™•์ธ 22 4. 1. 1. LiCoO2์˜ ํ•ฉ์„ฑํ™•์ธ 22 4. 1. 2. Mg์˜ ์‚ฝ์ž… ๋ฐ ์ถ•์  ์—ฌ๋ถ€ ํ™•์ธ 25 4. 1. 3. ํ‘œ๋ฉด์˜ Mg ๋ถ„์„ 30 4. 2. ์‹ค์‹œ๊ฐ„ Mg ์ฝ”ํŒ… 33 4. 2. 1. ์ „๊ธฐํ™”ํ•™์  ์„ฑ๋Šฅ ์ธก์ • ์‹คํ—˜ 33 4. 2. 2. ํ‘œ๋ฉด์˜ Mg ๋ถ„์„ 35 4. 2. 3. MgF2์˜ ํ˜•์„ฑ ๋งค์ปค๋‹ˆ์ฆ˜ 39 4. 2. 4. ์ €์žฅ์‹คํ—˜ 40 ์ œ 5 ์žฅ ๊ฒฐ๋ก  43 ์ฐธ๊ณ ๋ฌธํ—Œ 45 Abstract 50Maste

    A Study on the Landscape Characteristics of Jeju Woljeong-ri Batdam as an Agricultural Heritage Systems

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    The purpose of this study was to examine the area of Woljeong-ri, Jeju, as a target site in order to derive the landscape features of Jeju Batdam, designated as an agricultural heritage. The summary of the research results is as follows. First, the Batdam of Woljeong-ri is closely related to the local natural envrionment, forming a unique landscape pattern in terms of shape and scale. Second, the site where drainage management is important due to its geological characteristics has a water resource management Batdam landscape for effective drainage management. Third, the farmers in Woljeong-ri, who have been engaged in agricultural activities for a long time, have implemented a utilization system that considers different land conditions. As a result, the landscape of Batdam in Woljeong-ri, Jeju, shows the characteristics of the landscape that is constantly evolving.N
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