55
νࣟۻݓڌ -J/J
Y$P
Y0
ǣȤқϊ ܃ܓ ф َߌν
ۤॢń
ۤৠʴ
ۋߏą
Դڌۦ
ţʂԾ
Synthesis and Heat Treatment of LiNi
1 xCo
xO
2Nanopowder for Lithium Batteries
Han Kwon Chang, Hee Dong Jang , Chul Kyung Lee, Yong Jae Suh and Dae Sup Kil
Abstract :The composition-controlled LiNi1-xCoxO2(0 x 1) cathode powders were synthesized by a flame spray pyrolysis from aqueous droplets of nitrate compounds of lithium, cobalt and nickel. The average diameter of the particles was about 20 nm. The as-prepared LiNi0.75Co0.25O2particles were heat-treated to control the morphology and crystal structure at different calcination temperatures and heating times. The primary particle size, the crystallite size and the ratio of crystal parameters increased with an increment of the calcination temperature and heating time.
Spray drying of these nanoparticles led to micron-sized aggregates with enhanced crystallinity.
Key words : LiNi1 xCoxO2, Lithium batteries, Cathode materials, Flame spray pyrolysis
څ أ: LiNO3, Co(NO3)2, Ni(NO3)2ঔ० սڌؚں ьНݗͿ Ԑڌॠي йՃؚۺڷͿ қИ֨ࢇ জّқИَқ ३ ъڿق ۆ३ Ձқۋ ܃رʽLiNi1-xCoxO2(0 x 1)қϊں ०Ձॠٕɰ қϊۆ थŒۓąڹ أ. 20 nmٕɰ.
̚ॢ জّқИَқ३ѪڷͿ ०Ձʽ, LiNi0.75Co0.25O2қϊۆ ۓۙԜ ф Ā܁ ĵܓ ܃رε ڦ३ َߌν ٣ʪ ф
֨Âں Ѻজ֨ࡎɰ َߌν ٣ʪ ф ֨Âق Ҽͻॠي ۓۙࡾş Ā܁ࡾş ф üۙԜս Ҽۆ Éۋ ݒÀॠٕɰ. , .
̚ॢ қИæܓε ࣀॠي Ā܁Ձۋ ॳԜʽ ǣȤۓۙͿ ĵՁʽ υۋࡾ ࡾşۆ ڿݚߕε ०Ձॠٕɰ, .
ܳڅر : LiNi1 xCoxO2, 리튬전지 양극활물질 화염분무열분해법, , 한국지구시스템공학회지
Vol. 43, No. 1 (2006) pp. 55-64
Դ
νࣟࡑь࣡ԓজНLiCoO2 қϊڹ ȭڹ ĵܓۺ ؋܁
ՁڷͿ ۍॠي ۻݓ ߿ѓۻ ֳۋࢁق ەرԴ ܞڹ Ձ ں ҃يܳČ ०Ձॠş ֑ڏ ۤ۾ں ÀݓČ ەر ݓŚū ݓ äۆ Ͽ˜ Ԝڌ νࣟۋ٣ۻݓۆ تŕটНݗͿԴ
࢘ʼر ٵɰ Ŕ͠ǣ ࡑь࣡. Co ۆ ȭڹ Àüę ʫՁڷ Ϳ ۍ३ ۋε ʂߕॣ تŕটНݗ Òьں ڦॢ ψڹ ٍĵ À սॱʼر ١Č ەɰ νࣟɦࡃԓজН. LiNiO2ڹ ǰ ڹ Àüę ȭڹ ߿ѓۻڌ͟ ˺Лق ܞڹ ʂߕНݗ ҃
ۋš ॠǣ ۋۺ تܓՁҼε Íə, LiNiO2ε ०Ձॠ
ş رͷČ ߿ѓۻ ֳۋࢁ Ձۋ ܞݓ ؍ɰə ɳ۾ۋ ە ɰ ۋ͠ॢ. LiNiO2ۆ ɳ۾ں ŕ҄ॠş ڦ३LiNiO2ق ۻۋŚ՚ں ߐÀॠي ĵܓۺ ؋܁জε ƭॢ νࣟɦࡃŚ
՚ԓজНLiNi1 xMxO2 M: ۻۋŚ՚ق ʂॢ ҙɳॢ
ٍĵÀ սॱʼر١Č ەɰMoshtev et al., 2002; Chen ڰտʪ ˣ
et al., 2004; Lee et al., 2004; , 2004 ০. , ɦࡃNi ںCoͿ ࠘ঞॢ νࣟɦࡃࡑь࣡ԓজНLiNi1 xCoxO2ڹLiNiO2ۆ Ҽتۺ ܓՁҼε Ԝɾ০ Çՙ
֨ࡎڷ϶ ࠗÂĵܓε ؋܁জ֨ࡎɰ ۋͿ׆. LiNi1 xCoxO2 қϊڹLiCoO2 қϊں ʂߕॣ Àۤ ۺۼॢ
҃НݗͿ ۍ܁ыČ ەɰ. 1990țʂ ߣъ Ohzuku ˣق ۆ३ ߯ߣͿ νࣟۻݓڌLiNi1 xCoxO2қϊۋ ܃ܓʼؽ Č ԜՃॢ ۻşজॡۺ ՁथÀÀ ۋΘرܐɰOhzuku et al., 1993 .
LiNi1 xCoxO2ə ܳͿ ČԜজॡъڿѪ ܖ, õѪPasq- uali et al., 2004; Liu et al., 2004 ėࠞѪ, Chen et al., 2004 ˣڷͿ ܳͿ ०ՁʼČ ەɰ ČԜজॡъڿقԴə. ČԜъڿНݗۆ ٰѹॢ ъڿں ڦ३Դ ێъۺڷͿ12֨ Â ۋԜۆ ۤ֨Âق èࠚ қթق ۆॢ ঔ०ė܁ۋ ज़ս
ț ښ ێ ۿս ț ښ ێ ࢘
2005 11 15 , 2006 1 25
1 ॢĶݓݗۙڙٍĵڙ ǣȤНݗٍĵࣳ
2 Ś١ėęʂॡİ ֪ՙۦ֨֟ࢰėॡҙ
*Corresponding Author ۤৠʴ E mail; [email protected]
Address; Nano-Materials Group, Korea Institute of Geoscience and Mineral Resources, Dajeon 305-350, Korea
ٍĵȦЛ
ۺۋ϶ ۋìڹ ۤ֨Âۆ ܃ܓė܁ڷͿ ۍॠي Ԧԓমڱ ۹ॠ ф ԦԓҼڌۆ ݒʂε ߣ͒ॠó ʽɰLee et al., 2004 ܖ. õѪڹ ۤ֨Âق èࠚ Àَں ࣀॢ ܖۆ Ԧ Ձ ۺۼॢ ٣ʪقԴۆ Àَں ࣀॢ õ ԦՁ ŔνČ Ā, ,
܁Ձ ॳԜں ڦॢ َߌν ˣۆ ɰɳćۆ ҄ۡॢ ė܁ں ä࠘дͿ ۋ ̚ॢ ०Ձ֨Âۋ ١͒ èνə ɳ۾ں ؋Č ەɰ ėࠞѪ ̚ॢ սԓজН ࠞۻė܁ę ࠞۻН қν ė. ,
܁ ф ۤ֨Âق èࠚ ॠՙę܁ں ä࠘дͿ ė܁ۋ ҄ۡ, ॠČ қϊ०Ձ ė܁ۋ মڱۺۋݓ Їॠɰ ˰͆Դ ݥڹ.
֨Âق মڱۺڷͿ تݗۆLiNi1 xCoxO2 تŕটНݗε
܃ܓॣ ս ەə ė܁ę ०Ձʽ қϊۆ Ձ ф Ձқ܃ر À ڌۋॢ ė܁ۆ Òьۋ څĵʽɰ ߯Ŗ. Jang et al.
2004 ڹ ъڿڌؚں ߣڼࣷқИşε ۋڌॠي йՃؚ
ۺڷͿ қИॢ ۋε ۋբÀ֟ε ۋڌॠي জّڷͿ ʪۓ֨ࡈ йՃؚۺں ԓজ َқ३֨ࢅə জّқИ,
َқ३Ѫں ۋڌॢ LiCoO2 ǣȤқϊ ०Ձė܁ں Òь ॠٕČ জّ ǴقԴLiCoO2қϊۆ ԦՁ ϭ࠶ɦݏں ३ Եॠٕɰ.
҆ ٍĵقԴə νࣟ ࡑь࣡ ɦࡃ ݗԓজНں ьН, , ݗͿ Ը࢘ॠČ ۋε ߣڼࣷқИşε ۋڌॠي йՃؚۺ ڷͿ қИॢ জّق ʪۓ֨ࡈ ԓজ َқ३ę܁ں ä ߝ জّқИَқ३Ѫں ۋڌॠي Ձқۋ ܃رʽ Č, տʪۆLiNi1 xCoxO20 x 1 қϊں ܃ܓॠٕڷ϶ Ԧ, Ձʽ ǣȤқϊۆ ۓۙࡾş ф Ā܁ ܃رε ڦ३ َߌ ν ֬ॹں սॱॠٕɰ ьНݗۆ ঔ०Ҽۆ ܓۼق ˰. δ ԦՁқϊۆ ՁқѺজ َߌν ٣ʪ ф ֨Âق ˰δ ۓ,
ۙԜ ࡾş Ҽशϸۺ Ā܁ࡾş ф üۙԜսۆ Ѻজق, , , ěॠي ܓԐॠٕɰ.
֬ॹѓѪ
֨أ
জّқИَқ३Ѫں ۋڌॢ νࣟ ࡑь࣡ ɦࡃ ݗԓ, , জ०Н ьڌؚۆ υۋࡾ ࡾş قرͿܖ ؚۺڷͿҙ ࢢLiNi1 xCoxO20 x 1 ۓۙۆ ०Ձڹ ɰڼę Ïڹ ߪĜজॡъڿ֩ڷͿ ǣࢍǷ ս ەɰ.
LiNO3aq. + xCo NO3 2aq. + 1 x Ni NO3 2aq.
LiNi1 xCoxO2s
LiNi1 xCoxO2०Ձں ڦॢ ьНݗͿ ڌ३ʪÀ ȭČ
َқ३ ٣ʪÀ ǰڹ ݗԓνࣟLiNO3, 98.0%, Junsei Ch- emical Co., ݗԓࡑь࣡II گսজН Co NO3 2 6H2O, 98.0%, Junsei Chemical Co. ݗԓɦࡃ, II گսজН Ni NO3 2 6H2O, 97.0%, Junsei Chemical Co. ˣۆ ݗԓ
ّں ڙΒНݗͿ Ը࢘ॠٕɰ ݗԓνࣟں ݒΪսق ȥي.
ۆ ݗԓνࣟսڌؚ ε ܵҼॠČ ъڿڌؚ ܼ
3 M 100 ml ,
νࣟ ࡑь࣡ ф ɦࡃ ڙՙۆ ЃȬʪҼε, 1:x: 1 x Ϳ ڮ ݓॠş ڦ३ ݗԓࡑь࣡ ф ݗԓɦࡃں ݒΪսق ȥي
ۆ ݗԓࡑь࣡սڌؚ ф
3x M 100 ml 3 1 x Mۆ ݗԓ ɦࡃսڌؚ100 mlε ÁÁ χ˜ Á ڌؚں ঔ०ॠي
ьڌؚڷͿ Ԑڌॠٕɰ ̚ॢ. LiNi1 xCoxO2߯ܛ ԦՁ қϊ ܼ ࡑь࣡ ф ɦࡃ ڙՙ ՁқҼε ܓۼॠş ڦ३ xÉں0 1ѩڦقԴ0.25ÂüڷͿ Ѻজ֨ࡈ ьН ݗ ڌؚں ܵҼॠٕɰ.
ǣȤқϊ ܃ܓ
ۋۻݓ تŕটНݗڌ LiNi1 xCoxO2 ǣȤқϊ ܃ܓ ε ڦॢ ֬ॹۤ࠘əFig. 1ۆ ۻߕ ֬ॹۤ࠘ Ò͜ʪقԴ ǣࢍǶ ìę Ïۋ ьڌؚ ܳۓҙۍ ߣڼࣷқИۤ࠘, ۓۙ ԦՁ ф Ձۤۋ ۋΘرݓə জّъڿş ܃ܓʽ ۓ,
ۙε पݚॠş ڦॢ қϊपݚҙͿ ࡾó Ճ ҙқڷͿ ǣ Ɍر܋ ەɰJang, 1999 ߣڼࣷқИۤ࠘. 1.7 MHz ε ۋڌॠي ݗԓّঔ०սڌؚۆ ьНݗں ࡾş 10
܁ʪۆ йՃؚۺڷͿ қИ֨ࢇ ڏъÀ֟ۍ ؉βĎ À
֟99.95% ٮ ॥ƍ জّъڿş ܼ֮ěں äߝ জّڷͿ
ܳۓॠٕɰ ۋ ˺ қИ͟ں ێ܁ॠó ڮݓ֨ࢅş ڦ३.
ܳԐऒ॒ε ۋڌॠي ьڌؚں ێ܁ॢ ڮ͟ڷͿ ߣڼ
ࣷқИۤ࠘Ϳ ܳۓ֨ࡈ қИۤ࠘Ǵ қИڌؚۆ ҙक़ε ێ܁ॠó ڮݓॠٕɰ ؚۺۋ ъڿॠə জّѣȃə ݔą. ۋ ɰδ Òۆ ֟ࢬۍν֟ ࣲ֟ěں ʴ֮ڙڷͿ ѕَॠ5 ي ܃ۚॠٕڷ϶ ѣȃȤݎۆ ߯ǴĚ ܼ֮ěۆ Ǵąڹ, 8
߯ٽĚ ěۆ ٽąڹ ۋ϶ ѣȃۆ ߪţۋə
mm, 36 mm ,
ۋɰ ঝԓজّѣȃۆ ٍΒÀ֟Ϳə սՙ
300 mm . 99.
995% ԓজÀ֟Ϳə ԓՙ, 99.95% ф ėşÀ Ԑڌʼ ؽɰ জّѣȃۆ ؋ޅ ܼ֮ěڷͿҙࢢ տۺڷͿ ؉β. Ď ۋբÀ֟ ьڌؚۆ йՃؚۺ ܼ֮ě ؉βĎ, 2 ѥݫ ě սՙ, 3ѥݫ ě, ԓՙ4ѥݫ ě ф ėş ߯ٽ Ě ě ۆ տڷͿ À֟ε ܳۓ֨ࡎڷ϶ Á À֟ۆ ڮ͟ڹ ق ǣࢍǴؽɰ ̚ॢ ٽҙėş ζڷͿҙࢢ জ Table 1 . ,
ّں ҃ॠş ڦ३ ȤݎԜҙق ݔą37 mm, ţۋ100 ۆ ֟ࢬۍν֟ ࣲ֟ěں Ժ࠘ॠٕɰ জّқИَқ
mm .
३Ѫق ۆ३ ०ՁʽLiNi1 xCoxO2ۓۙε पݚॠş ڦॠ ي ݔą100 mm, ţۋ300 mmۆ ڮνěں ܃ۚॠي ѣȃĵͿҙࢢ200 mmԜҙق Ժ࠘ॠٕɰ ڮνě Ǵ. ҙق ǼÁսε ėś॥ڷͿ׆ Č٣À֟ ܼۆ ۓۙ˞ۋ َ
ٖʴইԜthermophoresis ق ۆॠي Àڏ ڮνě शϸ ق ҙʼʪ ॠٕɰ.
қϊ َߌν
জّқИَқ३ѪڷͿ ०Ձʽ LiNi1 xCoxO2 қϊۆ
ۤॢń ۤৠʴ ۋߏą Դڌۦ ţʂԾ
ॢĶݓĵ֨֟ࢰėॡধݓ 58
Ā܁Ձ ॳԜں ڦॠيMuffleۻşͿقԴۆ қϊ َߌ νٮ қИæܓѪں ۋڌॢ َߌνε սॱॠٕɰ. Muffle ۻşͿε ۋڌॢ қϊ َߌνə ێ܁͟ۆ ǣȤқϊں ؎ Θйǣ ҃࣡ق ȏر ۻşͿق ۤۓॢ 700 900 ѩ ڦقԴ0.5 2֨Âʴ؋ ėşқڦş ܼقԴ ۋΘرܐɰ.
ॢठ қИæܓѪں ۋڌॢ ąڍə ०Ձʽ ǣȤқϊں, ݒΪսق3 wt.% ȬʪͿ қԓ֨ࢅČ ߣڼࣷқИۤ࠘ε ۋڌॠي қԓڌؚں ࡔͿۋ˚ ؚۺڷͿ қИ֨ࢇ 2 ڮ͟ۆ ėşε ܳۓ֨ࡈ ؚۺں ۆ Եٖě
l/min 27 mm
ۋ ۤʽ ţۋ550 mmۆ ۻşͿق ʪۓ֨ࡈ900 ق Դ َߌνॠٕɰ.
қϊ ՁथÀ
०Ձ ݔ ф َߌνۆ қϊۆ Ԝ ф ࡾşə ܳԐ
ۻۙইйąSEM, JEOL, Model JSM 6380LA ф ࣊ę
ۻۙইйąTEM, Philips, Model CM12 ں ۋڌॠي қԵॠٕڷ϶ ۓۙۆ Ҽशϸۺڹ, Brunauer Emmett
eller BET, Micrometrics, Model ASAP 2400 Ѫں ۋڌॠي 196 قԴ ݗՙড়ں ࣀॠي ࠑ܁ʼؽɰ.
ۓۙۆ ڙՙқԵڹSEMق ۤʽEDX Energy Disper- sive X ray Spectroscope)ε ۋڌॠي қԵॠٕڷ϶ ̚,
ॢ ۓۙۆ Ā܁ԜڹXԸ ধۼқԵşXRD, Rigaku Co., Model RTP 300 RC ε Ԑڌॠي ࠑ܁ॠٕڷ϶ Ā܁ĵ, ܓ ࣷ͆йࢢ ф Ā܁ࡾş ࠑ܁ں ڦ३ XRD Rigaku Co., DMAX 2200 PC ۆ ֟ࢱ֟ࠬ Ͽ˚قԴ0.002°ۆ
֟ࢱÂüڷͿ Á ֟ࢱɾ0.2ߣۆ ՚ʪͿ ܁нࠑ܁ॠٕ
ɰ ۋͩó صرݕ ধۼःࢤ ܼ. Cu Kα2ق ۆॢ ধۼʚۋ ࢢ ф ѕąʚۋࢢε ܃äॠČ pseudo Voigt profileق fittingॠٕɰ.
Āę ф Č
জّқИَқ३Ѫں ۋڌॢ LiNi1 xCoxO2 ǣȤқϊ
܃ܓ
জّқИَқ३Ѫق ۆ३ ०Ձʽ ǣȤқϊۆEDX ֟ घ࣡ͤںFig. 2ق ǣࢍǴؽڷ϶, Ni фCoۆ ڙՙ॥͟
ڹ ÁÁ74.5ф25.5 at.%ε ǣࢍǴؽɰ ۋ͠ॢ. EDX
֟घ࣡ͤ ĀęقԴ ؎ ս ەˢۋ জّқИَқ३Ѫق ۆ ३ ०ՁʽLiNi0.75Co0.25O2 қϊ ܼNi фCoۋٽۆ ҝ տН Ձқۋ êʼݓ ؍ؕڷ϶ Á ڙՙۆ ॥͟ۋ ь, ڌؚ ܼNi фCoڙՙ॥͟ę ێ࠘ॠə Āęε صؽɰ.
ČͿ ڮʪĀ० ॔͆υICP, Inductively Coupled Plasma қġ қԵşε ۋڌॠي ०Ձʽ қϊۆ জॡܓ Ձں ܁нқԵॢ ĀęLi, NiфCoۆ ॥͟ڹ ÁÁ0.91,
ф Ϳ ǣࢍǮɰ
0.76 0.21 mol .
জّқИَқ३Ѫں ۋڌॢ LiNi1 xCoxO2 0 x 1 қϊۆ Ձқ܃رε ڦ३ ьڌؚ ܼNi NO3 2 фCo
NO3 2 ڌؚۆ ঔ०Ҽڱں ܓۼॠي қϊ०Ձ ֬ॹں Ar
centera
Ar 2ndb
H2 3rdb
O2
4thb
Air 5thb
Flow rates l/min 2 1 7 6 13
aCenter corresponds to the injection tube for the droplets of precursor solution located at the innermost of the burner in Fig. 1.
bNumber in parenthesis successively corresponds to the injection tubes next to the central tube in Fig. 1.
Table 1. Flow rates for the synthesis of LiNi1 xCoxO2 cathode particles
Cooling water
O2 Air Thermophoretic Sampler
Diffusion Flame Burner
Ultrasonic Atomizer H2
Ar Ar
Syringe pump
Precursor solution
Fig. 1. A schematic of experimental apparatus for the synthesis of LiNi1 xCoxO2 nanoparticles by flame spray pyrolysis.
սॱॠٕɰ. ०Ձʽ LiNi1 xCoxO2қϊںEDXқԵں ࣀ ३x Éں ࠑ܁ॠٕڷ϶ۋε تۺx Éę Ҽİॠي ʂڿԸę ॥ƍ ق ʪ֨ॠٕɰ ۻ ًٖقԴ
1:1 Fig. 3 . x
تۺxÉęEDX қԵڷͿ صرݕxÉڹ ۞ ێ࠘ॠ Č ەڼں ؎ ս ەɰ ۋə ҆ ٍĵقԴ ࢘ॠČ ەə. জّқИَқ३Ѫۋ ߯ܛԦՁқۆ Ձқں ֖ó ܃رॣ
ս ەə ڍսॢ ѓѪےں ۓݒॠə ìۋɰ.
ə জّқИَқ३Ѫق ۆ३ Ձқں ܃رॠي Fig. 4
०ՁॢLiNi1 xCoxO2 қϊۆxÉق ʂॢ ҼशϸۺқԵ Āęε ǣࢍǶ ìڷͿԴxÉۋ ࠶ݗս ࡑь࣡ ॥,
͟ۋ ȭ؉ݗս Ҽशϸۺʪ ݒÀ॥ں ؎ ս ەɰ ۋə. ࡑь࣡ ॥͟ۋ ȭ؉ݗս ۓۙࡾşÀ ۚ؉ݙں ۆйॠ əʚ ϼঝॢ ڙۍں ؎ ս ػڷǣ ࡑь࣡ ф ɦࡃۆ ۋ, ٣ࡾşε ԕट҃ϸ ࡑь࣡ ۋ٣ۆ ࡾşÀ ɦࡃ ۋ٣ۆ
ࡾş҃ɰ ۚ؉Դ ࡑь࣡ ॥͟ۋ ȭ؉ݗս ۻߕ Ā܁ü
ۙۆ ࡾşÀ ÇՙॠČ ۋͿ ۍ३ ۓۙࡾşÀ ۚ؉ݕ ì ڷͿ يûݕɰ ڰտʪ ˣ, 2004 .
LiNi0.75Co0.25O2 қϊۆ َߌν ф Ā܁ĵܓ қԵ জّқИَқ३Ѫق ۆ३ ०Ձʽ LiNi0.75Co0.25O2 ۓ
ۙۆ a َߌν ۋۻTEM Ԑݕ ф b 700 , c 80 0 , d 900 قԴ30қ ʴ؋ َߌνॢ ۆSEMԐݕ ںFig. 5ق ÁÁ ǣࢍǴؽɰ. TEM фSEM ԐݕقԴ
؎ ս ەˢۋ Ͽ˜ ܓæقԴ ۓۙ˞ڹ Œێॢ ࡾşқप ε ݓɦ϶ ҝő࠙ॢ ɰϸߕۆ Ҽ֦ॢ Ԝں ݓɫں
؎ ս ەڷ϶ َߌν ٣ʪÀ, 900 Ϳ ݒÀ॥ق ˰͆ ɰ ϸߕԜۋ ʌڎ ̤३ݙں ؎ ս ەɰ ̚. ॢ َߌν٣ ʪε ݒÀ֨ࢉق ˰͆ ۓۙࡾşə ϼі০ ݒÀॠٕɰ.
জّқИَқ३Ѫق ۆ३ ०Ձʽ ݔ ێۓۙۆ थŒ
ࡾşə أ20 nmۋ϶ َߌν ٣ʪε, 700 قԴ 900 Ϳ ݒÀ֨ࢉق ˰͆ ێۓۙۆ थŒࡾşÀ ߯ʂ1 ࡾ
şūݓ ݒÀ॥ں ؎ ս ەؽɰ َߌν ۻ ф Á َߌν. ٣ʪقԴ ֨Â ʴ؋ۆ َߌνε äࠚ ۓۙۆ Ҽशϸۺ1 ڹTable 2ق ܃֨ॢ цٮ Ïۋ َߌνε ࣀ३ śü০ Ç ՙॠٕڷ϶ ۋə َߌνε ࣀॠي ۍۿॢ ۓ, ۙ˞ęۆ ՙĀͿ ۍॢ Ā܁Ձۤۋ ۋΘرܐڼں ۆйॢɰ.
LiNi1 xCoxO2ۆ Ā܁ڹO3ࢍۓۆ ࠗÂĵܓε ۋΘČ ەڷ϶ Ni фCo ঔ०ࠗę Li ࠗۋ ԓՙslab Ԑۋق İॠي Ǜڗ܋ ەə ĵܓε ॠČ ەɰ. Fig. 5ə জّ
қИَқ३Ѫق ۆ३ ०Ձʽ ݔۆLiNi0.75Co0.25O2 қ ϊę ي͠ َߌν٣ʪ ф ֨Âق ˰δXRDধۼःࢤں
Stoichiometric x in LiNi1-xCoxO2
0.0 0.2 0.4 0.6 0.8 1.0
x determined by EDX
0.0 0.2 0.4 0.6 0.8 1.0
Fig. 3. Comparison of the stoichiometric x in LiNi1 xCoxO2
and the x determined by EDX analysis.
Stoichimetric x in LiNi1-xCoxO2
0.0 0.2 0.4 0.6 0.8 1.0 1.2
Specific surface area [m2/g]
0 20 40 60 80 100
Fig. 4. Specific surface area with respect to the stoichiometric x in LiNi1 xCoxO2 particles prepared by flame spray pyrolysis.
Fig. 2. Energy disperse X ray spectrum of as prepared LiNi0.75Co0.25O2 nanoparticles.
ۤॢń ۤৠʴ ۋߏą Դڌۦ ţʂԾ
ॢĶݓĵ֨֟ࢰėॡধݓ 60
ǣࢍǶ ìۋɰ َߌν ۻ. a ę 700 b, c, d قԴ َߌ νॢ қϊۆ XRD ধۼःࢤقԴə 18° ҙŖۆ 003
À ҃ۋš ॠݓχ ҙŖۆ
peak , 64° 018 ф 110 peak ۆ ٰۻॢ қνÀ ۋΘرݓݓ ؍؉ ؉ݔ ĵܓۺ ܁͵ۋ
ٰۻ০ ۋΘرݓݓ ؍ؕڼں ǣࢍǶɰGao et al., 1998. َߌν٣ʪÀ 800 ۋԜقԴə 18° ҙŖۆ 003 peakÀ ̤ॠČ, 38° ҙŖۆ 006 ф 012
ۆ қνٮ ҙŖۆ
peak 64° 018 ф 110 peakۆ ٰѹ
ॢ қνə Ā܁ۆ ĵܓۺ ܁͵ۋ ˃˚͠ݓó ۋΘرܐڼ ں ǣࢍǶɰČ ॣ ս ەɰOh et al., 2005 ॠݓχ. , 90 0 قԴ ֨Â َߌν॥قʪ ҝĵॠČ2 104 peakق Ҽ ३ 003 peakÀ ǰɰə ìڹ νࣟ ࠗۆ ࣻϸߕ ۙνق
ওڹ ۋ٣ۋ ڦ࠘ॠČ ەɰə ìں ۆйॠ϶
Co Ni ڰ
տʪ ˣ, 2004 ۋìڹ νࣟۋʴąͿقԴ νࣟۆ ԙ, , ۓ ν ъڿں ѓ३ॠə ڙۍڷͿ ۚڌॠó ʽɰ/ .
قԴ ʪ֨ʽ Òۆ
Fig. 6 10 X Ը ধۼ peakͿҙࢢ ߯ ՙ֧ۙѪڷͿ ćԓʽ Á َߌν٣ʪ ф ֨Âق ˰δ Ā
܁Ԝս ф ɳڦՆ ҙक़εTable 3ق ǣࢍǴؽɰ َߌν. ٣ʪ ф ֨Âۋ ݒÀ॥ق ˰͆ üۙԜսa ə äۆ2.87 ق ϢИδ ъϸ üۙԜս, c Éڹ 14.140 قԴ 14.221 ūݓ ݒÀॠə تԜں ٕ҃ɰ ۋ͠ॢ üۙԜս. Éۆ ݒÀə ࠗԜĵܓǴقԴ νࣟۋ٣ ۋʴąͿۆ ঝ c
ۤں ۆйॠ϶ νࣟۋ٣ۆ ঝԓ۹२ۋ Çՙॠó ʽɰ Kalyani et al., 2004 . 800 ۋԜقԴ َߌνʽ ۓۙ˞
ۆ ۋ͠ॢ 018 ф 110 peakۆ қνٮ üۙԜսcÉ ۆ ݒÀͿҙࢢ ۻşজॡۺ ՁॳԜں şʂॣ ս ەɰ.
Á َߌν ܓæقԴFig. 6ۆXRD peakͿҙࢢ ߯ՙۙ
֧ѪڷͿ ĵ३ݕ Ā܁ࡾş ÉںTable 4ق ǣࢍǴؽɰ.
َߌν ۻ қϊۆ Ā܁ࡾşə 9.5 nmۋؽڷǣ َߌν ٣ʪ ф ֨Âں ݒÀ֨ࢉق ˰͆ ߯ʂ70.1 nmūݓ ݒÀ ॠٕɰ ۋìڹ َߌν ٣ʪ ф ֨Âق ˰͆ ۓۙࡾşÀ. ݒÀॠٕʏFig. 5ۆ ۻۙইйą Ԑݕę Ҽİ॰ں ˺ ۺ
܁ॢ Āę͆ ॣ ս ەڷ϶ Ͽ˜ َߌν ٣ʪܓæقԴ, қۋۻۆ ߣş Ā܁Ձۤ՚ʪÀ ӇβČ ۋ َߌν֨
30
Âں ݓ՚ॠʌ͆ʪ ߣş Ā܁Ձۤق Ҽ३ ԜʂۺڷͿ
َߌν֨Âۋ Ā܁Ձۤق й࠘ə ٖॳۋ ǰڼں ؎ ս ەɰ.
100 nm
(a)
(d) (b)
(c)
Fig. 5. TEM and SEM micrographs of LiNi0.75Co0.25O2particles prepared by flame spray pyrolysis a without calcination and with calcination at b 700 , c 800 , d 900 for 30 min.
Calcination temperature [ ]
Specific surface area [m2/g]
without calcination 44.7
700 8.8
800 6.1
900 5.4
Table 2. Specific surface areas of LiNi0.75Co0.25O2particles prepared by flame spray pyrolysis a before calcination and after calcination at various temperatures for 1 hr
2θ [degree]
15 20 25 30 35 40 45 50 55 60 65 70
Intensity
(a) (b) (c) (d) (e) (f) (g)
(003) (101) (006) (104) (015) (107) (018) (110) (113)(012)
(h) (i) (j)
Fig. 6. X ray diffraction patterns of the LiNi0.75Co0.25O2particles of a as prepared and calcined at various temperature and times (b) 700 , 30 min; (c) 700 , 60 min; (d) 700 , 120 min; (e) 800 , 30 min; (f) 800 , 60 min; (g) 800 120 min; (h) 900 , 30 min; (i) 900 , 60 min; (j) 900 , 120 min
Calcination temperature [ ]
Calcination time [min]
a [ ]
c
[ ] c/a cell volume
[ 3]
700 30 2.878 14.140 4.914 101.42
700 60 2.878 14.151 4.918 101.48
700 120 2.874 14.150 4.924 101.21
800 30 2.872 14.200 4.945 101.41
800 60 2.872 14.204 4.946 101.45
800 120 2.873 14.209 4.946 101.54
900 30 2.874 14.207 4.943 101.65
900 60 2.877 14.221 4.942 101.97
900 120 2.873 14.206 4.945 101.55
Table 3. Crystal parameters of the particles prepared at various calcination temperatures and times
ۤॢń ۤৠʴ ۋߏą Դڌۦ ţʂԾ
ॢĶݓĵ֨֟ࢰėॡধݓ 62
қИæܓѪق ۆॢ ܓʂ ĵڿݚߕۆ ܃ܓ
تŕটНݗڌ қϊۆ ۓąۋ ۚڹ ąڍ ۻݓ܃ܓ ė܁
ԜقԴ қϊࠄśۋ ϔڍ رͲڗ ێъۺڷͿ ۻݓԓغق Դə5 ۋԜۆ تŕটНݗڌ қϊۋ ԐڌʼČ ەɰ.
˰͆Դ ҆ ٍĵقԴə জّқИَқ३ѪڷͿ ०Ձʽ ǣ Ȥқϊں қИæܓѪں ۋڌॠي қϊۆ Ā܁ॳԜ ф ܓ ʂۓۙজε ڦॢ şߣٍĵε սॱॠٕɰ জّқИَқ. ३ѪڷͿ ०ՁॢLiNi0.75Co0.25O2 ǣȤқϊں3 wt %ۆ ȬʪͿ ݒΪսق қԓ֨ࡈ ࡔͿۋ˚ڌؚں χ˞Č ߣڼ
ࣷқИşε ۋڌ३ қИ֨ࢇ (a) 700 , (b) 800 , (c)-(e) 900 Ϳ َٚʽ ڙ ۻşͿق (a)-(c) 2.0 l/min, ф ۆ ۋբėş ڮ͟ڷͿ ʪۓ (d) 0.5 l/min (e) 4.0 l/min
֨ࡈ қИæܓѪڷͿ َߌνॢ LiNi0.75Co0.25O2 қϊۆ
Ԑݕں ق
SEM Fig. 7 ǣࢍǴؽɰ Ͽ˜ ܓæقԴ ǣȤࡾ. şۆ ş҆ۓۙ˞Ϳ ĵՁʽ ĵۆ ڿݚߕÀ ܃ܓʼؽ ɰ қИæܓε ڦॢ ۻşͿ ٣ʪε ݒÀ֨ࢉق ˰͆ ڿ. ݚߕ ࡾşə ۚ؉ܐČ ۋբėşۆ ڮ͟ں Çՙ֨ࢉق
˰͆ ş҆ۓۙۆ ࡾşÀ ݒÀॠٕڼں ؎ ս ەɰ ۋə. ۻşͿ ٣ʪÀ ȭ؉ݓČ қϊۆ ۻşͿ Ǵ ߕΪ֨Âۋ ţرݙق ˰͆ ڿݚߕ Ǵۆ ş҆ۓۙ˞ۋ ԴͿ ՙĀॠ ي Ձۤॠó ʼČ ۋͿ ۍ३ ڿݚߕə ҃ɰ ࠘нॢ ĵܓ ε Àݓó ʿق ˰͆ ڿݚߕ ࡾşə ۚ؉ݕ ìڷͿ يû ݕɰ.
জّқИَқ३Ѫق ۆ३ ०Ձʽ LiNi0.75Co0.25O2 қ ϊ ф қИæܓ900 , 2.0 l/min ʽ қϊۆXRD ःࢤ ںFig. 8ق ʪ֨ॠٕɰ қИæܓ ߌνʽ қϊڹ জّқ. Иَқ३Ѫق ۆ३ ०Ձʽ қϊ҃ɰ Ā܁Ձۋ ॳԜʼؽ ڼں ঝۍॣ ս ەɰ. 18° ҙŖۆ 003 peakÀ ॳԜʼ ؽڷǣ, 38° ҙŖۆ 006 ф 012 peakۆ қνٮ64°
ҙŖۆ 018 ф 110 peakۆ қνÀ ۋΘرݓݓ ؍؉
؉ݔ ĵܓۺ ܁͵ۋ ٰۻ০ ۋΘرݓݓ ؍ؕڼں ঝۍॣ
ս ەɰ.
Ā
νࣟ ࡑь࣡ ɦࡃۆ ݗԓজНۋ ڌ३ʽ սڌؚڷͿ, , ҙࢢ জّқИَқ३Ѫں ۋڌॠي Ձқۋ ܃رʽ νࣟ
ۻݓڌ تŕটНݗۍ LiNi1 xCoxO20 x 1 ǣȤқϊ ں ܃ܓॠٕɰ ܃ܓʽ ǣȤқϊں ʂԜڷͿ. Muffle ۻ şͿε ۋڌॢ َߌν ф қИæܓ َߌνε ࣀॠي қ ϊۆ Ԝ Ҽशϸۺ Ā܁ĵܓ Ѻজق ʂॢ ٍĵε սॱ, , ॠي صڹ ܳڅ Āڹ ɰڼę Ïɰ.
1. LiNO3, Ni(NO3)2 фCo(NO3)2 ঔ०սڌؚں ь НݗͿ Ԑڌॠي জّқИَқ३ѪڷͿ LiNi1 xCoxO2
0 x 1 қϊ०Ձ֨ ьНݗۆ ȬʪҼ ܓۼں ࣀ३
߯ܛ қϊۆ Ձқں ֖ó ܃رॣ ս ەؽČ ̚ॢEDX қԵĀęε ࣀ३ ҝտНۆ ܕۦيҙε ঝۍॠٕɰ ۋε. ࣀ३ জّқИَқ३Ѫۋ Čտʪ ҄०қϊۆ Ձқ܃ر ق ەرԴ ڍսॢ ०ՁѓѪےۋ ۓݒʼؽɰ.
জّқИَқ३Ѫق ۆ३ ०Ձʽ
2. LiNi0.75Co0.25O2
қϊں ėşқڦşقԴMuffle ۻşͿε ۋڌॠي َ ߌν֨ َߌν ٣ʪ ф ֨Âق Ҽͻॠي ۓۙࡾş ф Ā܁ࡾşÀ Ձۤॠٕɰ ŔνČ. XRDধۼःࢤڷͿҙࢢ 003 peakۆ Ìʪ ॳԜ, 006 peakٮ 012 peakۆ қ ν ф 018 peakٮ 110 peakۆ қν ˣę Ïڹ Ā܁
ۆ ĵܓۺ ܁͵ۋ ۋΘرܐڼں ঝۍॠٕڷ϶ ̚ॢ қ, ϊۆ üۙԜս қԵں ࣀ३ üۙԜսc/aÉۋ ݒÀॠٕ
Č ۋͿ׆ ॳԜʽ ۻşজॡۺ Ձں şʂॣ ս ەؽɰ. қИæܓ َߌνε ࣀ३ ǣȤқϊں ş҆ۓۙͿ ॠ 3.
Calcination Temperature [ ] Calcination Time [min] Crystallite Size [nm]
as prepared particles 9.5
700 30 16.1
700 60 17.7
700 120 19.6
800 30 35.5
800 60 43.3
800 120 47.5
900 30 68.2
900 60 68.9
900 120 70.1
Table 4. Crystallite size of the particles prepared at various calcination temperatures and times
ə йࡾ ࡾşۆ ڿݚߕқϊں ०Ձॠٕڷ϶ қИæܓ ق Ԑڌʽ ۻşͿۆ ٣ʪε ݒÀ֨ࢉق ˰͆ ڿݚߕ ࡾ şə ۚ؉ܐČ ۋբėşۆ ڮ͟ں Çՙ֨ࢉق ˰͆ ş҆
ۓۙۆ ࡾşÀ ݒÀॠٕڼں ؎ ս ەؽɰ.
ČЛॶ
윤순도 이재천 박혜령, , , 2004, “리튬 차전지용 양극재료2 LiNi1 yCoyO2의 합성 및 전기화학적 특성 연구,” J.
Korean Ind. Eng. Chem., Vol. 15, No. 2, pp. 170 175.
Chen, Y., Wang, G. X., Tian, J. P., Konstantinov, K. and Liu, H. K., 2004, “Preparation and properties of spherical LiNi0.75Co0.25O2as a cathode for lithium ion batteries,”
Electrochim. Acta, Vol. 50, No. 2 3, pp. 435 441.
Gao, Y., Yakovleva, M. V. and Ebner, W. B., 1998, “Novel LiNi1 xTix/2Mgx/2O2compounds as cathode materials for safer lithium ion batteries,” Electrochem. Solid State Lett., Vol. 1, No. 3, pp. 117 119.
(a) (b)
(c) (d)
(e)
Fig. 7. SEM micrographs of LiNi0.75Co0.25O2 particles spray dried at various furnace temperatures and flow rates of air: a 700 , 2.0 l/min; b 800 , 2.0 l/min; c 900 , 2.0 l/min; d 900 , 0.5 l/min; e 900 , 4.0 l/min.
2θ [degree]
15 20 25 30 35 40 45 50 55 60 65 70
Intensity
(a) (b)
Fig. 8. XRD spectra of LiNi0.75Co0.25O2 particles a prepared by flame spray pryolysis and then
b spray dried at 700 of the furnace temperature and with 2.0 l/min of the flow rate of the carrier air.
ۤॢń ۤৠʴ ۋߏą Դڌۦ ţʂԾ
ॢĶݓĵ֨֟ࢰėॡধݓ 64
Jang, H. D., 1999, “Generation of silica nanoparticles from tetraethylorthosilicate TEOS vapor in a diffusion flame,”
Aerosol Sci. Technol., Vol. 30, No. 5, pp. 477 488.
Jang, H. D., Seong, C. M., Suh, Y. J., Kim, H. C. and Lee, C. K., 2004, “Synthesis of lithium cobalt oxide nanoparticles by flame spray pyrolysis,” Aerosol Sci.
Technol., Vol. 38, No. 10, pp. 1027 1032.
Kalyani, P., Kalaiselvi, N., Renganathan, N. G. and Raghavan, M., 2004, “Studies on LiNi0.7Al0.3 xCoxO2so- lid solutions as alternative cathode materials for lithium batteries,” Mater. Res. Bull., Vol. 39, No. 1, pp. 41 54.
Lee, S. W., Jung, B. Y., Han, K. S., Lee, Y., Kim, D., Kim, M. G., Ryu, K. S., Kang, E. Y. and Jeong, J. H., 2004,
“Acetate self mixing and direct thermal reaction for preparation of LiNi0.7Co0.3O2,” Electrochim. Acta, Vol.
50, No. 2 3, pp. 479 483.
Liu, H., Wu, Y. P., Rahm, E., Holze, R. and Wu, H. Q., 2004, “Cathode materials for lithium ion batteries pre- pared by sol gel methods,” J. Solid State Electrochem.,
Vol. 8, No. 7, pp. 450 466.
Moshtev, R., Zlatilova, P., Bakalova, I. and Vassilev, S., 2002, “Synthesis, XRD characterization, and cycling performance of cobalt doped lithium nickelates,” J. Po- wer Sources, Vol. 112, No. 1, pp. 30 35.
Oh, S. H., Jeong, W. T., Cho, W. I., Cho, B. W. and Woo, K., 2005, “Electrochemical characterization of high performance LiNi0.8Co0.2O2cathode materials for rechar- geable lithium batteries,” J. Power Sources, Vol. 140, No. 1, pp. 145 150.
Ohzuku, T., Ueda, A., Nagayama, M., Iwakoshi, Y. and Komori, H., 1993, “Comparative study of LiCoO2, LiNi1/2Co1/2O2 and LiNiO2 for 4 volt secondary lithium cells,” Electrochim. Acta, Vol. 38, No. 9, pp. 1159 1167.
Pasquali, M., Passerini, S. and Pistoia, G., 2004, Trends in cathode materials for rechargeable batteries. In: Nazri, G. A. and Pistoia, G. ed Lithium batteries science and technology, Massachusetts, Kluwer, pp. 315 360.
ۤ ॢ ń ۤ ৠ ʴ
ț ښ ٖǫʂॡİ ঞąėॡę ė 1998 2
ॡԐ
ț ښ ٖǫʂॡİ ঞąėॡę ėॡ 2000 2
ԵԐ
ț ښ ێ҆ ʂॡ জॡė 2003 3 Hiroshima
ॡę ėॡчԐ
ț ښ ԴÌʂॡİ জॡėॡę ė 1982 2
ॡԐ
ț ښ ԴÌʂॡİ ʂॡڙ জॡė 1984 2
ॡę ėॡԵԐ
ț ښ ԴÌʂॡİ ʂॡڙ জॡė 1993 2
ॡę ėॡчԐ
ț ښ ێ҆ ʂॡ Нݗ
2005 9 Hiroshima জॡ֨֟ࢰėॡ ėॡчԐ ইۦ ॢĶݓݗۙڙٍĵڙ ۙڙটڌՙۦٍĵҙ ǣȤНݗٍĵࣳ
Ըےٍĵڙ
E-mail; [email protected]
ইۦ ॢĶݓݗۙڙٍĵڙ ۙڙটڌՙۦٍĵҙ ǣȤНݗٍĵࣳ
ےٍĵڙ ࣳۤ/
E-mail; [email protected]
ۋ ߏ ą Դ ڌ ۦ
ț ښ Դڐʂॡİ ۙڙėॡę ė 1984 2
ॡԐ
ț ښ Դڐʂॡİ ʂॡڙ ۙڙėॡ 1990 8
ę ėॡчԐ
ț ț ॢĶݓݗۙڙٍĵڙ ۙڙ 1991 -2002
টڌՙۦٍĵҙ ےٍĵڙ
ț ښ ॢتʂॡİ şćėॡę ė 1989 2
ॡԐ
ț ښ ॢĶęॡşցڙ şćėॡ 1991 2
ę ėॡԵԐ
ț ښ ॢĶęॡşցڙ şćėॡ 1996 2
ę ėॡчԐ
ইۦ ĶςŚ١ėęʂॡİ ֪ՙۦ֨֟ࢰėॡҙ İս E-mail; [email protected]
ইۦ ॢĶݓݗۙڙٍĵڙ ۙڙটڌՙۦٍĵҙ ǣȤНݗٍĵࣳ
Ըےٍĵڙ
E-mail; [email protected]
ţ ʂ Ծ
ț ښ ॢєʂॡİ ۦΒėॡę ė 1994 2
ॡԐ
ț ښ ߿ǫʂॡİ ۦΒėॡę ėॡ 1996 2
ԵԐ
ț ښ ėܳʂॡİ ۦΒėॡę ėॡ 2006 2
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ইۦ ॢĶݓݗۙڙٍĵڙ ۙڙটڌՙۦٍĵҙ ǣȤНݗٍĵࣳ
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