TODA europe NCMnca户田工业

TODA KOGYO EUROPE TODA KOGYO EUROPE GMBH Cathode materials for lithium-ion batteries Kazuhiko Kikuya, Osama Sasaki, Hideaki Sadamura, Kenji Ogisu, Dr. Stefan Malcus TODA KOGYO EUROPE Outline •TODAs Position as Material Supplier to the Battery Industry •Current and Future Material Requirements from the Battery Industry •Material Trends and Developments within TODA •Conclusions TODA KOGYO EUROPE TODAs Position as Material Supplier to the Battery Industry TODA can offer a wide range of different powders to the battery industry combined with a long-time experience CoO / CoO*Co NiM1 M2 (OH)2 : reg. /spherical NiM1 M2 (OH)2 : Co- coated NiM1 M2 (OH)2 -precursor LiNi1-x Cox O2 LiNi1-x-z Cox Mez O2 Rechargeable Batteries NiCd-/NiMH-Batteries Cathode Materials Additives Li-Ion- / Polymer- Batteries Cathode Materials LiMn2 O4 LiCoO2 TODA KOGYO EUROPE TODAs Position as Material Supplier to the Battery Industry TODA/Japan Tokyo Office Otake H.Q. R&D Onoda Plant TMC/Kitakyushu China Hong Kong Shanghai Korea TKE/Germany TKE/France TAI/USA TAM/Canada Global Presence of TODA ESC (Energy Solution Company) in the market TODA KOGYO EUROPE TODA sees the major future market in Li-ion batteries LiNi0.80 Co0.15 Al0.05 O2 (NCA) LiNi0.33 Co0.33 Mn0.33 O2 (NCM) M(OH)2 TODA KOGYO EUROPE Requirements for the cathode materials of Li-ion batteries •Low Cost •Secure Supply Situation •High Energy Density •Good Safety •High Power Performance •Long Calendar Life / Cycle life TODA KOGYO EUROPE Price of Cathode Materials LiCoO2 (appr. 60 % Co-content) is still the major cathode material as of today Ni and Co Prices have a tremendous effect on the cathode material prices 0 10 20 30 40 50 60 Ja n.' 06 Ma rch '0 6 Ma i '0 6 Ju ly '06 Se pt. '06 No v.' 06 Ja n.' 07 Ma rch '0 7 Ma i '0 7 Ju ly '07 Se pt. '07 No v.' 07 Ja n.' 08 Ma rch '0 8 Ma i '0 8 m e t a l p r i c e / U S $ / l b s Cobalt Nickel TODA KOGYO EUROPE Price of Cathode Materials LCO is still the major cathode material -> but expensive and volatile in price NCM and NCA emerge as cost saving cathode materials 0 10 20 30 40 50 60 70 80 Ja n.' 06 Ma rch '0 6 Ma i '0 6 Ju ly '06 Se pt. '06 No v.'0 6 Ja n.' 07 Ma rch '0 7 Ma i '0 7 Ju ly '07 Se pt. '07 No v.'0 7 Ja n.' 08 Ma rch '0 8 Ma i '0 8 m e t a l p r i c e / k g a c t i v e m a t e r i a l / ( U S $ ) / k g LCO NCA NCM new NCM TODA KOGYO EUROPE High Energy Density Cathode Materials Big discrepancy in between theoretical and actual capacity Theoretical capacity comes from LiMO2 -> MO2 + Li+ + e- 0 50 100 150 200 250 300 LCO NCM NCA m A h / g 0 50 100 150 200 250 300 actual capacity theoretical capacity NCA can increase the capacity on the cathode side by about 20 % (over LCO) TODA KOGYO EUROPE High Energy Density Cathode Materials Voltage Range determines capacity of battery powders High Ni-containing materials are much higher in capacity than LCO ! 1st. cycle charge/discharge profiles of various Al- and Mn-doped LiNixCo1-xO2 cathode powders 2,7 2,8 2,9 3,0 3,1 3,2 3,3 3,4 3,5 3,6 3,7 3,8 3,9 4,0 4,1 4,2 4,3 4,4 4,5 0 30 60 90 120 150 180 210 240 specific capacity [mAh/g] v o l t a g e [ V v s . L i / L i + ] LiNiCoMn 77/13/10 [charge: CCC: 0,1C / 4,3V] LiNiCoMn 77/13/10 [discharge: CDC: 0,1C / 3,0V] LiNiCoMn 80/10/10 [charge: CCC: 0,1C / 4,3V] LiNiCoMn 80/10/10 [discharge: CDC: 0,1C / 3,0V] LiNiCoAl 80/15/5 [charge: CCC: 0,08C / 4,2V] LiNiCoAl 80/15/5 [discharge: CDC: 0,08C / 3,0V] LiNiCoMn 33/33/33 [charge: CCC: 0,1C / 4,3V] LiNiCoMn 33/33/33 [discharge: CDC: 0,1C / 2,75V] LiCoO2 [charge: CCC: C/6 / 4,3V] LiCoO2 [discharge: CDC: C/6 / 3,0V] TODA KOGYO EUROPE High Energy Density Cathode Materials Voltage Range drastically changes capacity of powder Voltage limits: 3.0 - 4.3/4.5V / CCC & CDC: 0.1C 2,9 3,0 3,1 3,2 3,3 3,4 3,5 3,6 3,7 3,8 3,9 4,0 4,1 4,2 4,3 4,4 4,5 4,6 0 20 40 60 80 100 120 140 160 180 200 220 240 Specific capacity [mAh/g] C e l l v o l t a g e [ V ] v s . L i / L i + LiNi0.77Co0.13Mn0.10O2 [3 - 4.3V] LiNi0.77Co0.13Mn0.10O2 [3 - 4.5V] Charge Discharge TODA KOGYO EUROPE High Energy Density Cathode Materials Cycle Life one critical issue for high voltage applications Electrochemical evaluation of Lithium-Ion cathode powders: LiNixxCoyyMnzzO2 Voltage limits: 3.0 - 4.3/4.5 V / Half cell test vs. Li/Li+ at 20°C 130 140 150 160 170 180 190 200 210 220 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 Cycle number D i s c h a r g e c a p a c i t y [ m A h / g ] sample 1 #1 [0.1C, 4.5V] sample 1 #2 [0.1C, 4.5V] sample 2 #1 [0.1C, 4.5V] sample 2 #2 [0.1C, 4.5V] TODA KOGYO EUROPE High Energy Density Cathode Materials Effect of charging voltage on thermal behaviour (DSC measurements on NCA) 0 1 2 3 4 5 150 200 250 300 350 Temperature [℃] D S C [ m W / m g ] 4.1V 4.3V 4.5V 4.8V 5.0V 4.1V 4.3V4.5V 4.8V 5.0V TODA KOGYO EUROPE High Energy Density by High Tap Density Materials Critical Factors : •Particle Size •Spherical Shape •Porosity •Surface Smoothness TODA KOGYO EUROPE High Energy Density by High Tap Density Materials 5 µm grade 10 µm grade 15 µm grade TODA can offer a wide variety of material compositions and particle size materials with nearly ideal spherical shape ! Different Grades of doped Ni(OH)2 precursors for lithiated cathode materials TODA KOGYO EUROPE High Energy Density by High Tap Density Materials Doped Ni(OH)2 precursor mainly determines particle size, morphology, tap density of the calcined, finished materials (NCA, NCM) 1,20 1,40 1,60 1,80 2,00 2,20 2,40 2,60 2,80 3,00 1,20 1,40 1,60 1,80 2,00 2,20 2,40 2,60 2,80 3,00 Tap Density Ni(OH)2 / g/cc T a p D e n s i t y L N C O / g / c c 0,00 5,00 10,00 15,00 20,00 25,00 0 , 1 0 1 , 0 0 1 0 , 0 0 1 0 0 , 0 0 D50 / µm 15 µm Ni(OH)2 15 µm LNCO 10 µm Ni(OH)2 10 µm LNCO 5 µm Ni(OH)2 5 µm LNCO TODA KOGYO EUROPE High Energy Density by High Tap Density Materials Effect of physical parameters on electrochemical performance -> Coarser Material has reduced gravimetric discharge capacity in half cell testing Electrochemical evaluation of cathode powders: LiNi80Co15Al5O2 Voltage range: 3 - 4.2 V / CCC & CDC: @ C/13 Half cell test vs. Li/Li+ at 20°C 160 165 170 175 180 185 190 0 1 2 3 4 Cycle number D i s c h a r g e c a p a c i t y [ m A h / g ] 5 µm 10 µm 15 µm TODA KOGYO EUROPE High Energy Density by High Tap Density Materials Electrochemical evaluation of cathode powders: LiNi0.80Co0.15Al0.05O2 Voltage range: 3 - 4.2 V / CCC & CDC: @ C/13 Half cell test vs. Li/Li+ at 20°C 360 380 400 420 440 460 480 500 0 1 2 3 4 Cycle number D i s c h a r g e c a p a c i t y [ m A h / c c ] 5 µm grade 10 µm grade 15 µm grade Effect of physical parameters on electrochemical performance -> Coarser Material can show improved volumetric discharge capacity TODA KOGYO EUROPE Safety Behaviour of Cathode Materials DSC Measurement Heating rate 5 K/min. 150 ml/min Ar -2,0 0,0 2,0 4,0 6,0 8,0 10,0 170 190 210 230 250 270 290 310 330 Temperature [°C] D S C / m W / m g LCO LiNi0.77Co0.13Mn0.10O2 LiNi0.70Co0.10Mn0.20O2 LiNi0.60Mn0.40O2 LiNi0.33Co0.33Mn0.33O2 148 mAh/g 210 mAh/g 170 mAh/g 208 mAh/g 178 mAh/g Chemical composition of cathode material is one key factor affecting the thermal safety behaviour -> depending on composition NCM can be much safer than LCO ! TODA KOGYO EUROPE Conclusions TODA can offer a wide range of cathode materials for the Li-ion industry tailor-made for a variety of different application profiles NCA and NCM are emerging cathode materials offering significant price savings over LCO NCA is a high capacity cathode material that allows the achievement of larger energy densities than can be achieved with LCO as cathode material Higher operating voltages will potentially allow for larger capacity levels in the future TODA provides cathode materials with excellent spherical shape and morphology that contribute to futherly expanding battery capacities TODA offers different NCM cathode materials with higher safety than LCO TODA can vary the physical and chemical properties of its cathode materials according to the demand of the market Foliennummer 1 Foliennummer 2 Foliennummer 3 Foliennummer 4 Foliennummer 5 Foliennummer 6 Foliennummer 7 Foliennummer 8 Foliennummer 9 Foliennummer 10 Foliennummer 11 Foliennummer 12 Foliennummer 13 Foliennummer 14 Foliennummer 15 Foliennummer 16 Foliennummer 17 Foliennummer 18 Foliennummer 19 Foliennummer 20