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1 Journal of the Korean Electrochemical Society Vol. 11, No. 3, 2008, p w y³ LGyw» l ( : k) The Research and Development Trend of Cathode Materials in Lithium Ion Battery Hong-Kyu Park* Battery Research & Development, LG Chem, Ltd. / Research Park (Received August 12, 2008 : Accepted August 19, 2008) p w. LiCoO 2» w v ù t» w w 4.3 V ƒ¾ ƒ w. wr»»ƒ w p wd y. š w š, LiNi 1 x M x O 2, Li[Ni x Mn y Co z, Li[Ni 1/ 2 w». š ƒ» y w š ƒ v w š, w w LiMn 2, LiFeP w ƒ. w z w š ù š š w w w. Abstract : The cathode materials for lithium ion battery have been developed in accordance with the battery performance. LiCoO 2 initially adapted at lithium ion battery is going to be useful even at the charging voltage of 4.3 V by surface treatment or doping which drastically improved the performance of LiCoO 2. On the other hand, the complicate and multiple functions of recent electronic equipments required higher operational voltage and higher capacity than ever, which is going to be driving force for developing new cathode materials. Some of them are LiNi 1 xm x O 2, Li[Ni x Mn y Co z, Li[Ni 1/2. Other new type of cathode materials having high safety is also developed to apply for HEV (hybrid electrical vehicle) and power tool applications. LiMn 2 and LiFeP are famous for highly stable material, which are expected to give contribution to make safer battery. In near future, the various materials having both capacity and safety will be developed by new technology, such as solid solution composite. Keywords : Cathode, Materials, Performance, Lithium, Battery. 1. p p œw * hkpark1@lgchem.com p, p w, g»k t»». { s w»» y 197

2 198 J. Korean Electrochem. Soc., Vol. 11, No. 3, 2008 w w z w w. m»» w 1-5) p ƒwš. p 1991 (Sony)ƒ y w w t k w 10% w š, x y w t. p œ ¼š w» w w» w š w ù e. p l œ r» t p w» œ š w. y œ w p j w, p, w p w ƒ w. p w w w, 1-20) š» w wš w. 2. p 2-1. w p ü w w w w. (Sony)ƒ» w LiCoO 2 p w y, p» l. 6-9) LiCoO 2 p y ƒ š p ƒ x ¾ š. wr»» w»» y, wy š yƒ š š p ƒ ƒw š y š y w š. 10) LiNiO 2 70% p ƒ Á w t š ƒ w ù w w w. LiMn 2 v û w w k LiCoO 2 ƒ w w ƒÿ. v 11,12) ƒ a-nafeo 2 d w ƒ k w wš w p. ù w w w Mn w ù š w ƒ t y ù. 11,12) HEV x ñš w š w» w w w š ) w wš LiCoO 2 w w ƒ w Ozuku q LiCoO 2, LiNiO 2 LiMn 2 yw w 3 Li[NiMnCo w Ÿ w Fig. 1. y 5.

3 w»ywz, 11 «, 3 y, mw p tw ) Co w ƒ û, Mn w w jš, Ni w ƒ k» w wš. ƒ t w y ey Fe( ) swwš y LiFeP w y w w š. p s³ 16-20)» w 0.2 V û w p ù œ ƒ j» š. Fig. 1 ¾ 3~4 V y wì ùkü. w r š w w ƒ» w w. š w y,»ƒ, m ü w w œw. œ w yww z» NMP(Nmethyl pyrollidone) w w z gq w. w» w œ gqœ w w wƒ k w, (rheology) w w v w. p ƒ šx š w šx 50%» p w. w x k w know-howƒ p, formula,»»» y ƒ ú. œ ü w xw» ww ü w. w p w. p j», j» s, (k, ) w» l w» w. Fig. 2 p œ w. y gqw z w w j» (slitting)w.» w gq kƒ ³ w w ³ w w w³x ù w d y d LiMO 2 (M: ) xk p Fig. 2. p œ.

4 200 J. Korean Electrochem. Soc., Vol. 11, No. 3, 2008 Fig. 3. ƒ e w d». y ƒ d ƒ e w Fig. 3 ABABAB ABCABC. š x w p q p x w.» s(unit cell) ü w ƒ n 2n p n q p ƒ w d x LiMO q ƒ. 3d (Co, Ni, Mn) w ~ p »»ww LiMO 2 2 q p. q ƒà» ƒ p j». ABCABC q p 50% w. s ü MO 2d p q w» O3- š w. 21) q 50% w, w x q MO 6» y w ƒ w MO 6 q 2 œ MO 2d x w. 2 œ d x w M-M y w jš Á v y j z. LiMO 2 yw p,, ƒ (rock salt) [111] ³e O-Li-O-M-O-Li-O-M-O d x w. Fig. 4 x d R-3m y Slab d d p d w š. MO 2 (M = Co)d ü w w x w, MO 2 MO 2 d i w» p Ák ƒ ƒ w 2 s y w ƒ j LiCoO 2 R-3m (rhombohedral) ƒ LiCoO 2 ƒ wš,» wš x y p š. 800 o C w w d LiCoO 2ƒ x Fig. 4. d x LiMO 2 (M = Co).

5 w»ywz, 11 «, 3 y, Fig. 5. LiCoO 2 (A: û t, B: t ). 1,000 C š o w j» 10 um k. wr 400 o C w w v [Li 2 ] 16c [Co 2 ] 16d ƒ x ü w û w»yw p w» wš š w w d LiCoO 2ƒ w. 4,6) Fig. 5 y š LiCoO 2 x. LiCoO 2 ƒ g/cm p ƒ v ƒ w š. w w ƒ š w LiCoO 2 w»» w y ƒ j» w» w. Fig. 6 LiCoO 2 sww š LiCoO 2 p. s³ Li /Li V 4.25 V 150 mah/g š. w p š ƒ š» ƒ š ƒ w w wš. LiCoO 2 p ùƒ MO 2 d w c w ƒ q w, p w ƒ ù. w ƒ Fig. 7 Á ƒ pg p w y ùkü. w p 0.5 wƒ O3 Fig. 6. š LiCoO 2 p. Fig. 7. LiCoO 2 ƒ y.

6 202 J. Korean Electrochem. Soc., Vol. 11, No. 3, 2008 P3 yƒ ù w» š ü (stress)» w. O3 P3 d ƒ k» ƒ ùkù LiCoO 2 50% p ƒ Ák š. ƒ w p k CoO 2 O1 d w ƒ ƒ ù. LiCoO mah/g, 4.25 V¾ w 150 mah/g. ƒ j» w ƒ j š. j j nyƒ ƒ y. 4.5 V Co y ƒ ƒw O-Co-O w¼ ƒ wš xy s a 0.3% w, CoO 2 CoO 2 d» w c 2% ƒw» vƒ q w. p l ù vƒ ƒw k p 0.72 Co y ü k w wƒ» ƒ w. p 4.4 V 50 o C š k Co w k ƒ y ƒ ƒ y ù. w w» w 22) LiCoO 2 t vw ù v w» š. Fig. 8 LiCoO 2 w y gqw 2.75~4.4 V Á p. w LiCoO 2 w t w ƒ w Á p ùkü. Fig. 8. ƒ y t LiCoO 2. y gq gq t š w v wš» w v z» š gq y g Co». w z LiCoO 2 ƒ j» w t» w. 23,24) LiCoO 2 wù wƒ Ni 3ƒ ƒ 2ƒ yw w w yw xw»ƒ. LiCoO 2 Co ƒ 3+ w w Li/Co ƒ œ» w yw LiNiO 2 LiNiO 2 LiCoO 2 ƒ x LiNiO 2 Li 1 xni 1+x O 2ƒ x w Ni ƒ 2ƒ w d p d w»yw p w. p p d w 2+ Ni p ww ƒ j ƒ g ƒ k. w LiNiO 2 w y» j w p. w Ni Co eyw w. Co v 3+ Ni ü y k 2+. ù p d 25,26) Ni x w» ³ w w p ƒw ù» w yw j. Fig. 9 LiNiO 2 LiNiO 2 Co vw LiNi 0.85 Co 0.15 O 2 š ùkü. Coƒ v y š w w w. Ni w ƒw 2+ Ni x v 뻃» d w. ƒ û š y ƒ w d x w w z w ƒ. Ni w š ƒ w swelling ù w ƒ j» w. w Li 1 xnio 2 w û j y w

7 w»ywz, 11 «, 3 y, Fig. 9. LiNiO 2 LiNi 0.85 Co 0.15 O 2 š. Fig. 10. ZrO 2 t w LiNiO 2»yw p. w. ù w wš Ni ƒ š» š y w š š. t» w wš Li[Ni 1 xm x (M = Co) ƒ š. 26) LiCoO 2 w y t w»yw p w k. Fig. 10 Fig. 11. CeO 2 gq LiNi 0.8 Co 0.2 O V z DSC. ZrO 2 y gqw LiNiO 2»yw p ùkü. gqw» Á š š j p j w. w t t y j»». t m w t y k t l w w y y ƒ g j z ƒ. Fig. 11 CeO 2 gq LiNi 0.8 Co 0.2 O 2 DSC (differential scanning calorimetry) ùk ü. gqw w vj ƒ j w w ƒw. 27) Li[NiMnCo 3 Ni, Mn Co k w 3 LiNiO 2, LiMnO 2 LiCoO 2 ƒƒ

8 204 J. Korean Electrochem. Soc., Vol. 11, No. 3, 2008 Fig p. ƒ d» y w š ) 3 ƒ w p š. Fig. 12 p y. p ƒ w ƒ Li[Ni 1/3 Mn 1/3 Co 1/3 3 œ y š. a A, c A LiCoO 2 w d š superlattice w w. 152 mah/g(4.25 V vs Li + /Li) š ƒ 4.75 g/cc LiCoO 2 w» w k š w ƒ ƒw» š. Fig. 13 š p. 4.5 V w w p 4.6 V w w z 3 w yƒ w w» ƒ. w z Fig. 13. Li[Ni 1/3 Mn 1/3 Co 1/3 p. Fig. 14. Li 1 x[ni 1/2 y X- z.

9 w»ywz, 11 «, 3 y, w ƒ ƒƒ w w. 13) x ƒ Li[Ni 1/2, Li[Ni 1/3 Co 1/3 Mn 1/3 ƒ f ƒ 1:1 w p p d 2+ƒ Ni w NiO Li 2 ƒ x p w k. Li[Ni 1/2 w d» LiCoO mah/g Li 1 x[ni 1/2 0 x 1 w O3 w» 4.5 V ¾ 260 mah/g. 28) Fig. 14 Li 1 x[ni 1/2 y w t X- z. w z š w LiMn 2 v yw v LiM 2 (M = Mn, Ti, V,) yw ABCABC x w w 32e w. t v y (Li) 8a [Mn 2 ] 16d [ ] 32e a =8.245Å. Mn t w ƒ wš y ey, w w» (HEV: hybrid electrical vehicle) š w w. ù Mn y Li/Mn,, w» +2~+4ƒ ƒ w, v Mn y q w» w y w»yw p j. Fig. 15 w y y ùkü. Fig. 15. w y y. Fig. 16. d v MO 6 q d v ƒ q w, d wù MO 6 6 MO 6 2 v wù MO 6 6 MO 6 Fig š. w y» w. Mn 3+ O 6 Mn 4+ O 6 w s Mn-O w ƒ» r w s w w ƒ ³ w s w q y w. w (Mn 2 ) 3 w 1 w p l Mn Mn ƒ» ƒ 8a ew. p 4+ Mn 3+, Mn ƒƒ 8a 16d q w (Li) 8a [Mn 2 ] 16d [ ] 32e w s. v yw œ wš q l x w, Á p m ƒ» w. 12) Mn v»yw p p w 4.0 V 3.0 V ù. Li 1 xmn 2 0 x 1 p w 4V Á k, Li 1+x Mn x 2 16c q p 3V LiMn 2 Li 2 Mn 2 ƒ ù Á k. Fig. 17 x LiMn 2 v y š. 3+/4+ Mn yáy LiMn 2 8a p Li 2 Mn 2 16c q p e w 1V ƒ w. 4.0 V Li 1 xmn 2 (0 x 0.73) p 8a p 50%ƒ k ¾ Mn s³ y w w, x > 0.5 Mn s³ y

10 206 J. Korean Electrochem. Soc., Vol. 11, No. 3, 2008 Fig. 17. LiMn 2 Á y š. p k v w y y ƒ wì 8a û ù p w w. Li 0.5 Mn 2 k w w yƒ 4.0~4.1 V sk ùkù. 29) v LiMn 2 t w ƒ ƒ. ƒ j 3+ Mn w Jahn-Teller distortion w y Mn. x w, 1ƒ 2ƒ vw Mn s³ ƒ 3.5 ƒ k. ù yáy w Mn 3+ w» w. 4 V Li 1.05 Mn mah/g. 30,31) Fig. 18 1ƒ 2ƒ vw p. vw p j w. ù ù x w» w p w ƒwš w. LiMn 2 ƒ j š Mn. Mn t ³x y (disproportionation, 2Mn 3+ =Mn +Mn ) 4+ w 2+ƒ Mn. 2+ƒ Mn w LiMn 2 y w 2+ Mn p ww ù, w y w w w k. p š ƒ j ù w». Li 1.06 Mn 1.95 Al 0.05 Mn Al eyw Mn y ƒ š w g š p v w HEV wš. w» w t gqw š y wš, t v w v ƒ ü y w w v z w p. 32) Mn v p wùƒ» d y w w p. w w z ƒ y ƒ ww wù» w wš. v w Li 4 Mn 5 O 12 Fig. 18. v Li 1+x Mn 2 xm x p.

11 Li 1+x Mn 2 x x = 0.33 LiMn 2 w»ywz, 11 «, 3 y, d q 1/6 p ey Li[Li 1/3 Mn 5/3 ]. Li 4 Mn 5 O 12 Mn y ƒ +4»yw p. Li 4 Mn 5 O 12 3V y y ƒ w 163 mah/g š 130~140 mah/g. ù Mn s³ y ƒ +4 Li 4 Mn 5 O 12 w» w w. w LiMn 2 w j» w š w. 3. Fe t LiFeP ƒ t w wù Co { ƒ y ey. 2+ Fe 3+ /Fe 3.2 V ƒ P 2 w w P-O œ w w z w 3.4 V ) LiFeP œ Pmnb ƒ ü Fe M 2 q š p M 1 q w. Fig. 19 LiFeP ùkü. p c w œ q x, Fe Õ œ w x wš. ƒ p P œ w. œ ƒ - i. œ q p /k d yw LiMO 2 (M = Co, Ni) /k w LiMO 2 Li-O w MO 2 d p v ww LiFeP w Fe w P v ww Fig. 19. LiFeP. Fig. 20. LiFeP š w. LiFeP g/cm w û r 170 mah/g (2.0~4.2 V). Fig. 20 LiFeP Á š x š skw ùkù. Á p w w, ³e w LiFeP FeP k Á 2 (two-phase) yáy» Gibbs š p yw ƒ w» ) w xk LiFeP k FeP ƒ Á (phase boundary)ƒ w w. t l p k p w α x y w β œ w w ƒ w.» ƒ α ë ƒ (one-phase) y w w. w ü p y ww p j. p ü w w p ù. LiFeP w w w ) LiFeP ƒ j wù,» ƒ û. P 2 sww p, ƒw x ú ü ³ y

12 208 J. Korean Electrochem. Soc., Vol. 11, No. 3, 2008 w ù. LiFeP» w j», k t gq, Nb vw š. w š ƒ,» ù ³ w w Fe w 3+ Fe 2 O 3, Li 3 Fe 2 (P ) 3 x yw w. ù š š w w» j»ƒ ƒw t wš p y w w š. y w» w w w v ƒ. 4. š yw š yw ƒ yw š x wš, t Li 2 Li[Ni 1/2 š Li[Ni x Li 1/3 2x/3Mn 2/3 x/3ƒ. (1 x)li 2 xlimo 2 (M = Ni, Co, Cr), LiMO 2 -LiMnO 2 LiMO 2 -LiMnO 2 -Li 2, 3b w ƒ 1, y w +3. p» y 3+/4+ Mn yáy ù š 4+ Mn y k w» 3+ Mn Jahn- Teller z w wƒ ùkù. 36,37,41) š, y š w p. Fig. 21 ¾ š w p Fig Li 2 0.7LiMn 0.5 Ni 0.5 O 2» Á š (5.0~2.0 V). ùkù. Fig. 22 t š 0.3Li 2 0.7LiMn 0.5 Ni 0.5 O 2» Á š. 4.8 V¾ w, ƒƒ mah/g, 4.5 V sk ùk ù. sk» ƒ ƒ Li 2 ƒ Li 2 O x w» w š š.» xli 2 (1 x)limo V¾ LiMO 2 l p k w xli 2 (1 x)mo 2 x wš 4.4 V Li 2 O wì (x δ)li 2 δmno 2 (1 x)mno 2 x. (1) Li 2 p k w Li 2 Oƒ x š MnO 2. Li 2 xli 2 O + ymno 2 +(1 x y)li 2 (1) Li 2 ƒ š (x δ) Li 2 δlimno 2 (1 x)limno 2ƒ Fig. 21. x z Spot ql, (a) Li[Cr Li Mn 0.520, (b) Li[Cr Li Mn and (c) Li[Cr Li Mn

13 w»ywz, 11 «, 3 y, Fig. 23. xk Li 2 -Li[Ni 1/2 -LiNiO 2 -LiCoO 2 Phase Diagram ) (cut off) w Li 2» w w v w. ù š û š w» w w ƒ w š. Y.S. Hong w j» w LiCoO 2 sw g Li 2 -Li[Ni 1/2 -LiCoO 2š w w w g.» 42-44) M y k 3+ LiCoO 2 - LiNiO 2 -LiMnO 2 Li 2 ƒ g Ni 2+, Mn y k 4+ 4 š y (Li 2 -LiCoO 2 -LiNiO 2 -LiMnO 2 ) y k. Li[Ni 1/2 -LiNiO 2 - LiCoO 2» Li 2 sw j, Fig. 23 ü y ƒ w ) w w LiCoO 2 w ù y w 4.5 V w w» w 4.6 V w w v. y š w p y LiNi 0.20 Li 0.20 Mn 0.60 O mah/g š, k ƒ j» w v LiCoO 2 w û» w». ù wì š w p š w y ƒ j š w. w j» w š. 5. ƒ z w» w e w š. p» { s ù p», y w xk ƒ» w. w ³» x»» p p w» yƒ. x LiCoO 2 š š 3, p w Fe w z w. p š š w z w p. š x 1. K. Mizushima, P. C. Jones, P. J. Wiseman, and J. B. Goodenough, Mater. Res. Bull., 15, 1159 (1993). 2. J.-M. Tarascon and M. Armand, Nature, 414, 359 (2001). 3. M. Wakihara, Materials Science and Engineering R33, (2001). 4. R. J. Gummow, D. C. Liles, and M. M. Thackeray, Mater. Res. Bull. 28, 235 (1993). 5. Y. Nishi, Journal of Power Sources, 100, (2001). 6. M. mladenov, R. Stoyanova, E. Zhecheva, and S. Vassilev, Electrochemistry Comm., 3, (2001). 7. D. D. MacNail and J. R. Dahn, Journal of The Electrochemical Society, 149, A912-A919 (2002). 8. D. D. MacNail, L. Christensen, J. Landucci, J. M. Paulsen, and J. R. Dahn, Journal of The Electrochemical Society, 147, (2000). 9. R. J. Gummow, M. M. Thackeray, W. I. F. David, and S. Hull, Mater. Res. Bull. 27, 327 (1992). 10. A. M. Adnersson, D. P. Abraham, R. Haasch, S. Maclaren, J. Liu, and K. Amine, Journal of The Electrochemical

14 210 J. Korean Electrochem. Soc., Vol. 11, No. 3, 2008 Society, 149, A1358-A1369 (2002). 11. A. M. Kannan et al., Electrochem. Solid State Lett., 5, A167 (2002). 12. ( v»yw)j. M. Tarascon, E. Wang, F. K. Shokoohi, W. R. McKinnon, and S. Colson, J. Electrochem. Soc. 138, 2859 (1991). 13. T. Ohzuku, K. Ariyoshi, Y. Makimura, N. Yabuuchi, and K. Sawai, Electrochemistry, 73, (2005). 14. Y. Koyama, I. Tanaka, H. Adachi, Y. Makimura, and T. Ohzuku, Journal of Power Sources, , (2003). 15. Y. Koyama, N. Yabuuchi, I. Tanaka, H. Adachi, and T. Ohzuku, Journal of Electrochemical Soc. 151, A1545- A1551 (2004). 16. A. K. Padhi, K. S. Nanjundaswamy, and J. B. Goodenough, J. Electrochem. Soc., 144, 1188 (1997). 17. D. Morgan, A. Van der Ven, andg. Ceder, Electroche. Solid-State Lett. 7, A30 (2004). 18. M. S. Whittingham, Y. Song, S. Lutta, P. Y. Zavalij, and N. A. Cheronva, J. Mater. Chem., 15, 3362 (2005). 19. A. Yamada and S.-C. Chung, J. Electrochem. Soc., 148, A960 (2001). 20. A. Yamada, et al., J. Power Sources, 119, 232 (2003). 21. L. Sebastaian and J. Gopalakrishman, J. Mater. Chem., 13, (2003). 22. S. Venkatraman, Y. Shin, and A. Manthiram, Electrochem. Solid State Lett. 6, A9 (2003). 23. J. Cho, Y. J. Kim, and B. Park, Chem. Mater., 12, (2000). 24. J. Cho et al., Angew. Chem. Int. Ed. 40, 3367 (2001). 25. T. Ohzuku, A. Ueda, and M. Nagayama, J. Electrochem. Soc., 140, 1862 (1993). 26. S. Sivaprakash, S. B. Majumder, S. Nieto, and R. S. Katiyar, Journal of Power Sources 170, (2007). 27. K. Kim et al., Electrochem. Acta, 50, 3764 (2005). 28. C. P. Grey, W.-S. Yoon, J. Reed, and G. Ceder, Electrochemical and Solid-State Letters, 7, A290-A293 (2004). 29. J. M. Tarascon, E. Wang, F. K. Shokoohi, W. R. McKinnon, and S. Colson, J. Electrochem. Soc., 138, 2859 (1991). 30. H. Abiko, M. Hibino, and Tetsuichi Kudo, Journal of Power Sources, 124, (2003). 31. K. Araki and N. Sato, Journal of Power Sources, 24, Issue 1, 1 October (2003). 32. S.-W. Lee, K.-S. Kim, H.-S. Moon, H.-J. Kim, B.-W. Cho, W.-I. Cho, J.-B. Ju, and J.-W. Park, Journal of Power Sources, Volume 126, Issues 1-2, 16 February 2004, Pages J. B. Goodenough, A. K. Padhi, K. S. Nanjundaswamy, and C. Masquelier, US pat, (1999). 34. A. Yamada, S. C. Chung, K. Hinouma, J. Electrochem. Soc. 148, A224 (2001). 35. A. Yamada, Y. Kudo, and K.-Y Liu J. Electrochem. Soc. 148, A747 (2001) Z. Lu, D. D. MacNeil, and J. R. Dahn, Electrochem Solid-State Lett. 4 A191 2 (2001). 37. T. Ohzuku and Y. Makimura, Chem. Lett. 7, 642 (2001). 38. Z. Lu, D. D. MacNeil, J. R. Dahn, Electrochem. Solid- State Lett. 4, A200 (2001). 39. Z. Lu and J. R. Dahn, J. Electrochem. Soc. 149, A815 (2002). 40. A. D. Robertson and P. G. Bruce, Chem. Mater. 15, 1984 (2003). 41. C. W. Park et al., Materials Research Bull., 42, 1374 (2007). 42. J. Jiang, K. W. Eberman, L. J. Krause, and J. R. Dahn, J. Electrochem. Soc., 152, A1879 (2005). 43. y, p, yw, 46, 45 (2006). 44. Y.-S. Hong, Y. J. Park, K. S. Ryu, and S. H. Chang, Solid State Ionics, 176, (2005).

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