2. Battery Research Group www.keri.re.kr Secondary Li Battery Technology for Next Generation Nov. 30, 2006 Hyun-Soo Kim Battery Research Group Korea Electrotechonology Research Institute - 4th CEPRI-CRIEPI-KERI Technical Meeting-

3. Battery Research Group www.keri.re.kr Merits of Lithium-Ion Battery  High energy density  No memory effect  High operation voltage  Environment-friendly

4. Battery Research Group www.keri.re.kr Application of Lithium-Ion Battery motor scooter Electric wheel chair HEV Electric bicycle Golf cart Mobile IT appliance

5. Battery Research Group www.keri.re.kr Market of Secondary Battery 20032004200520062007200820092010 Growth rate (%) Ni/MH730704685670635605580550 ▽ 0.4 LIB8861,0841,2241,4571,7302,0512,4352,89018.4 LIPB8810913416620525531539023.7 * Yano Report 2004 Lithium-Ion battery Lithium-ion polymer battery Ni/MH battery 200 400 600 3,000 2,000 1,000 800 Million Cell

6. Battery Research Group www.keri.re.kr R&D Trends of Secondary Battery 100 200 400 800 1,400 Spec. Power Density (W/kg) Spec. Energy Density (Wh/kg) 50 100 150 200 Lead Acid Ni/Cd Ni/MH Lithium-Ion Battery High Power LIB High Energy LIB Mobile IT HEV Next Generation Battery ?

7. Battery Research Group www.keri.re.kr Cathode Materials for Lithium-Ion Battery LiCoO2LiNiO2LiMn2O4 Li[Co⅓Ni⅓ Mn⅓]O 2 LiNi½Mn½ O 2 LiFePO4LiMnO2 StructureLayered SpinelLayered OlivineLayered Theoretical Capacity 274mAh/g275mAh/g148mAh/g285mAh/g 170mAh/g344mAh/g Practical Capacity 140mAh/g180mAh/g120mAh/g170mAh/g 150mAh/g 180mAh/g 4.4-3V:90 3-2.0V:90 Operation Voltage 3.6V3.5V3.8V3.6V 3.45V3.4V Merits High electric conductivity, easy preparation High capacity Low cost, nontoxic High capacity & thermal stability, low cost High capacity Low cost, thermal stability Low cost, nontoxic Demerits High cost, toxicity Hard preparation, Low thermal stability Mn dissolution (@E.T.) Low tap density Low electric conductivity Hard preparation, Mn dissolution

8. Battery Research Group www.keri.re.kr Synthesis of Li[Ni 1/3 Mn 1/3 Co 1/3 ] (1-x) Zr x O 2 Li, Ni, Mn, Co Nitrates in Ethanol (stoichiometric) ZrOCl 2 hydrate (Zirconyl Chloride) Drying (80 ℃ ) ‘Mud’ of Chemical Compounds ㆍ 450 ℃, 3hr : Calcination ㆍ Grinding ㆍ 650 ℃, 5hr : Melt Li salts ㆍ 950 ℃, 5hr : Oxide Structure Stirring for 0.5 hr Heat Treatment

9. Battery Research Group www.keri.re.kr XRD Patterns of Li[Ni 1/3 Mn 1/3 Co 1/3 ] (1-x) Zr x O 2  No impurity phase up to about 4.0 at% Zr doping  Zirconia-like impurity was formed over than about 5.0 at% Zr doping

10. Battery Research Group www.keri.re.kr Morphologies of Li[Ni 1/3 Mn 1/3 Co 1/3 ] (1-x) Zr x O 2  Primary particle : ~ 300 nm  After heat-treatment, the particles agglomerated to form a secondary particle with ~5 ㎛.

11. Battery Research Group www.keri.re.kr Rate Capability of Li[Ni 1/3 Mn 1/3 Co 1/3 ] (1-x) Zr x O 2 Current Rate Un-dopedZr-doped Capacity (mAh/g) Ratio (%) Capacity (mAh/g) Ratio (%) 0.2C174100.0179100.0 0.5C15890.817195.9 1.0C15086.216793.3 2.0C14080.516190.0

12. Battery Research Group www.keri.re.kr Cycle Performance of Li[Ni 1/3 Mn 1/3 Co 1/3 ] (1-x) Zr x O 2  Un-dopied material; 153 mAh/g@1th, 130 mAh/g@50th (84.2%)  Zr-doped material; 170 mAh/g@1th, 166 mAh/g@50th (97.6%)  Cycle performance of the Zr-doped material : 13% up (after 50 th cycle).

13. Battery Research Group www.keri.re.kr Lattice Parameter of Li[Ni 1/3 Mn 1/3 Co 1/3 ] (1-x) Zr x O 2  A-axis decreased slightly with Zr-doping.  C-axis increased remarkably with Zr-doping and it caused to enhanced rate-capability.

14. Battery Research Group www.keri.re.kr Inter-slab Space Model  In the LiNiO2 system the dramatic deterioration of electrochemical performances is strongly related to the change in oxidation state of the extra nickel ions, which induces local collapses of the structure and hinders not only lithium diffusion in the inter-slab space but also lithium reintercalation in the six sites around each extra nickel ion.  In the LiNiMgO2 system, the magnesium ions, with a size very close to that of lithium, remain in the divalent state during cell charge. Therefore, their presence in the inter-slab space does not strongly affect lithium reintercalation because no shrinkage of the structure appears upon cycling.  The size of Mg2+ and Zr4+ is similar to Li+ ion and this result explains why the Zr-substituted phases have good cycling properties. Li x Ni 1+z O 2 systemLi x Ni 1-y Mg y O 2 system (Source; C. Delmas et al., J. Electrochem. Soc., 147 (2000) p. 2061)

15. Battery Research Group www.keri.re.kr LiNi 1/3 Mn 1/3 Co 1/3 O 2 C 9 H 21 AlO 3 Heat treatments Preheating at 130 ℃ for 10h O 2 Sintering at 700 ℃ for 5h in O 2 Measurement of Electrochemical Properties Cell : Al 2 O 3 -coated LiNi 1/3 Mn 1/3 Co 1/3 O 2 /Li cell. Separator : Polypropylene (15 ㎛ ). Electrolyte : 1.15M LiPF 6 EC/EMC/DEC=3/5/2. Cycle-life : 1C rate, 4.5~2.8V, 50cycle. Rate capability : 0.2C, 0.5C, 1C, 2C. Temperature : room temperature. Cell : Al 2 O 3 -coated LiNi 1/3 Mn 1/3 Co 1/3 O 2 /Li cell. Separator : Polypropylene (15 ㎛ ). Electrolyte : 1.15M LiPF 6 EC/EMC/DEC=3/5/2. Cycle-life : 1C rate, 4.5~2.8V, 50cycle. Rate capability : 0.2C, 0.5C, 1C, 2C. Temperature : room temperature. Al 2 O 3 coating by a Sol-gel method Surface Treatments of LiNi 1/3 Mn1/3Co1/3O 2 High purity ethanol-stirred for 1h at 50 ℃

16. Battery Research Group www.keri.re.kr XRD Patterns of Al 2 O 3 -coated LiNi 1/3 Co 1/3 Mn 1/3 O 2 203040506070 Intensity (A.U.) Al 2 O 3 coated (003) (113) (110) (018) (107) (015) (104) (012) (006) (101)  LiNi 1/3 Co 1/3 Mn 1/3 O 2

17. Battery Research Group www.keri.re.kr (b) Al 2 O 3 coated(a) LiNi 1/3 Co 1/3 Mn 1/3 O 2 Morphologies of Al 2 O 3 -coated LiNi 1/3 Co 1/3 Mn 1/3 O 2

18. Battery Research Group www.keri.re.kr Rate Capability of Al 2 O 3 -coated LiNi 1/3 Co 1/3 Mn 1/3 O 2

19. Battery Research Group www.keri.re.kr Cycle Performances of Al 2 O 3 -coated LiNi 1/3 Co 1/3 Mn 1/3 O 2 Al 3+ diffuse and formed for a thin layer of Li-Al-O solid solution phase during the heat treatment and the charging/discharging process. This reaction layer has not only high Li-ion conductivity but also stabilize the layered structure. The lattice parameters might be slightly changed during the charging/discharging process. [1] A. Bibby and L. Mercier, Chem. Mater., 14, 1594 (2002).[2] J. Cho, Y.J. Kim, and B. Park, Chem. Mater., 12, 3788 (2000).

20. Battery Research Group www.keri.re.kr Nyquist plot of Al 2 O 3 -coated LiNi 1/3 Co 1/3 Mn 1/3 O 2

21. Battery Research Group www.keri.re.kr DSC Profiles of Al 2 O 3 -coated LiNi 1/3 Co 1/3 Mn 1/3 O 2

22. Battery Research Group www.keri.re.kr Crosslink-Type Gel Polymer Electrolyte Separator Electrode Heat Cure Filling of Precursor Whole Gelation Precursor Heat Cure(Gelation) Electrolyte Filling Core Cell

23. Battery Research Group www.keri.re.kr Manufacturing Process of Polymer Battery CathodePE/PP SeparatorAnode (+)/(-) tab Al Pouch Electrolyte + Monomer + Initiator Winding/Stacking Vacuum Sealing Formation Aging Precursor Filling Vacuum Drying Core cell Insertion Ultrasonic Welding Curing ALB 25 ℃, 3days 80 ℃, 1hr

24. Battery Research Group www.keri.re.kr Electrode Coating Process Mixer Press Slitter Coater Mixer Press Slitter Coater Mixing Coating Pressing Slitting Mixing Coating Pressing Slitting

25. Battery Research Group www.keri.re.kr Winding & Precursor Filling Process Winding J/R Pressing Pouch Forming Precursor Filling

26. Battery Research Group www.keri.re.kr Sealing & Formation Process Sealing Pouch Folding Formation & Grading

27. Battery Research Group www.keri.re.kr Manufacture of Gel Polymer Electrolyte Battery (GPB)  Electrode Formulation ;  Cathode : LiCoO 2 + ECP-04 + PVDF (95.65 : 1.5 : 2.85 wt%)  Anode : Graphite + ECP-04 + PVDF (90 : 2 : 8 wt%)  Separator ;  Polypropylene (Asahi)  Thick. 20 ㎛, Porosity 40%, permeability 85~92 sec/100cc  Electrolyte, Monomer & Initiator ;  Electrolyte : 1.1M LiPF 6 /EC+PC+DMC+EMC+DEC (30/10/10/30/20 wt%)  Monomer : Polyurethane acrylate (PUA), Polyoxyalkylene glycol acrylate (POGA, Elexcel TA-140, Daiichi Kogyo Seiyaku 사 )  Initiator : Bis-(4-tert-butylcyclohexyl)peroxy-dicarbonate (BBP)

28. Battery Research Group www.keri.re.kr Cell Design of GPEB  Design of GPEB  Design Capacity ; 800 mAh  Electrode Size ; 4.6x5.05 mm (Cathode), 4.6x5.2 mm (Anode)  Electrolyte ; 3ml/Cell (3.4g per 1000mAh)  Aging ; 40 ℃, 2days  Specification of Electrode CathodeAnode Thick Thickness 134 ㎛ 163 ㎛ Loading density 3.22 g/cm 3 1.40 g/cm 3 38.98 mg/cm 2 21.0 mg/cm 2 Thin Thickness 127 ㎛ 143 ㎛ Loading density 3.07 g/cm 3 1.39 g/cm 3 35 mg/cm 2 18 mg/cm 2

29. Battery Research Group www.keri.re.kr Rate Capability of PUA-based GPEB  Polymerization condition  60 ℃, 90min  Charge/discharge  0.2C, 0.5C, 1.0C and 2.0C  Discharge capacity  0.2C ; 1969 mAh  0.5C ; 1952 mAh (99.1%)  1.0C ; 1928 mAh (98.0%)  2.0C ; 1896 mAh (96.3%)  Polymerization condition  60 ℃, 90min  Charge/discharge  0.2C, 0.5C, 1.0C and 2.0C  Discharge capacity  0.2C ; 1969 mAh  0.5C ; 1952 mAh (99.1%)  1.0C ; 1928 mAh (98.0%)  2.0C ; 1896 mAh (96.3%)

30. Battery Research Group www.keri.re.kr Temper. Dependences of PUA-based GPEB  Polymerization ; 60 ℃, 90min  Charge/discharge  20, 0, -10, -20 ℃  0.5C/0.5C  유지시간 ; 20 h  Discharge capacity  20 ℃ ; 1969 mAh (100%)  0 ℃ ; 1952 mAh (98.9%)  -10 ℃ ; 1928 mAh (95.6%)  -20 ℃ ; 1775 mAh (91.2%)  Polymerization ; 60 ℃, 90min  Charge/discharge  20, 0, -10, -20 ℃  0.5C/0.5C  유지시간 ; 20 h  Discharge capacity  20 ℃ ; 1969 mAh (100%)  0 ℃ ; 1952 mAh (98.9%)  -10 ℃ ; 1928 mAh (95.6%)  -20 ℃ ; 1775 mAh (91.2%)

31. Battery Research Group www.keri.re.kr Cycle Performances of PUA-based GPEB  Polymerization Conditon  60 ℃, 90min  Charge/discharge  0.5C/0.5C, 4.2/3.0V, 20 ℃  Discharge capacity  1st; 1960 mAh  200th; 1753 mAh (90.5%)  Polymerization Conditon  60 ℃, 90min  Charge/discharge  0.5C/0.5C, 4.2/3.0V, 20 ℃  Discharge capacity  1st; 1960 mAh  200th; 1753 mAh (90.5%)

32. Battery Research Group www.keri.re.kr Overcharge Test for PUA-based GPEB  Volt. & Tem. Profile  After test  Test procedure  Charge 2.5 times of the capacity at a constant current of 1C rate for the full-charged cell  Charge at a CV over 12V.  Requirements  No fire and no explosion  Test Result  PASS

33. Battery Research Group www.keri.re.kr Crush Test for PUA-based GPEB  Test procedure (IEC 61960-1)  Apply force approximately 13 kN for 1 min on the cell.  Both the wide and narrow sides are tested. (20±5 ℃ )  Requirements  No fire and no explosion  Test Result  PASS  Before test  After side crush test  After crush test

34. Battery Research Group www.keri.re.kr Nail Penetration Test for PUA-based GPEB  Test procedure  Penetrate on the center of the full-charged cell using nail with a diameter of 5 mm.  Requirements  No fire and no explosion  Max Temp. <100 ℃  Test Result  PASS  After test

35. Battery Research Group www.keri.re.kr Thermal Exposure Test for PUA-based GPEB  Test procedure  The full-charged cell was kept at a oven maintained at 130±2 ℃ for 30 min.  Requirements  No fire and no explosion  Test Result  PASS  After test

36. Battery Research Group www.keri.re.kr Thank you for your attention !