An Application of Lithium Insertion Materials to 12 V lead-free Batteries (Subject has been changed) Tsutomu Ohzuku Electrochemistry and Inorganic Chemistry Laboratory, Graduate School of Engineering, Osaka City University (OCU), Osaka 558-8585, Japan Presented at the Almaden Research Center on August 27, 2009 Reasons why I have changed the subject today Backgrounds for the clean energy technologies What is lithium-ion batteries? LiCoO2 / graphite ? power sources for mobile phones & laptop computers What is the meaning of pure electric vehicles? long-range driving for more than 500 km per charge What can we do for solar home systems in off-grid area? solar/wind hybrid systems in rural area What are the possible solution to cope with the problems? High-energy density secondary batteries worldwide Energy density of current lithium-ion batteries (18650) 550 Wh/dm3 with 200 Wh/kg or more T. Ohzuku and R. Brodd, J. Power Sources, 174, 843-846(2007) What is lithium-ion ( shuttlecock ) battery ? e- Positive Electrode Negative Electrode e- Li+ ion on Charge on Discharge LiMeO2 + □C6 Charge Discharge □MeO2 + LiC6 ( Me : Transition Metal ) Lithium ions move back and forth between two insertion electrodes storing and delivering electricity Electrochemistry of Layered Materials for Batteries 6 0 Q / mAh g-1 based on LiCoO2 or NMC 50 150 200 Current lithium-ion batteries 5 4.3 V line LiCoO2 4 E / V 100 LiCo1/3Ni1/3Mn1/3O2 3 Constant current & constant voltage (CCCV) charging mode is essential for layered materials 2 1 Graphite 0 0 100 Q / mAh g -1 200 300 based on Graphite 400 Change in Energy Density of 18650 Gravimetric Energy Density (Wh/kg) High-energy densities more than 550 Wh/dm3 or 200 Wh/kg 225 Saturated ? 2005 200 175 2600mAh 2004 2001 2002 Charging voltage 2000mAh 4.10 to 4.20V Positive electrode 1420mAh LiCoO2, LiCo1/3Ni1/3Mn1/3O2, 1900mAh 1700mAh 1251994 LiAl0.05Co0.15Ni0.8O2 1995 1260mAh 2400mAh 2200mAh 1998 1996 150 2000 2900 mAh < Negative electrode 1370mAh Graphite 100 250 300 350 400 450 500 550 Volumetric Energy Density (Wh/dm3) 600 650 700 Note that Current lithium-ion batteries 550 Wh/dm3 with 200 Wh/kg or more Keys: layered materials with CCCV charging mode Poor Examples on Lithium Insertion Materials in 1998 Positive-electrode materials 5 Li[Ni1/2Mn3/2]O4 Li[Li0.1Mn1.9]O4 4 V LiCo1/2Ni1/2O2 Li[Li1/3Mn5/3]O4 E / 3 2 LiV2O4 Negative-electrode materials Li[Li1/3Ti5/3]O4 1 Graphite (1/2 reduction in capacity) 0 0 50 100 Q -1 / mAh･g 150 200 Secondary Batteries Available Worldwide The 12 V lead-acid batteries More than 135 years old, only available worldwide in capacities ranging from 5 to 1000Ah or more Specification on the12 V lead-acid batteries Charge-end voltage : 14.4 V typical (14.8 V maximum) Discharge-end voltage : 10.2 V (5h rate) 7.2 V at burst of energy supply for short period of time Note that one cannot make 12 V batteries by connecting current lithium-ion batteries in series Single Cell Required for the 12 V Batteries Characteristic Value in V for 12V Batteries Number of cells connected in series 6 5 4 3 14.4 V 2.4 2.9 3.6 4.8 Nominal Voltage 12 V 2.1 2.5 3.1 4.15 Discharge-end 10.2 V 1.7 2.0 2.55 3.4 Cut-off voltage 7.2 V 1.2 1.4 1.8 2.4 0 I II Charge-end Generation III The 12V lead-acid batteries consist of 6 cells connected in series (Energy densities ranging from 20 to 40 Wh kg-1) To fruitfully discuss in our mutual interest Home-made Pure Electric Vehicle with 12 V Lead-acid Batteries Series Connection of Twenty-four 12 V Batteries 12V – 55 Ah lead-acid battery (21 kg) 24 batteries connecting in series (288V) total weight 504 kg 120 – 150 km drive per one charge / total mileage ca. 20000 km Total weight of PEV : 1318 kg (Note that Honda Civic 1500cc is originally 1000kg) What we have learned from Dr. Asida’s PEV trials 1. Batteries : 288V-55Ah (15 kWh on the Vehicle) 2. 120-150 km per one charge : 8 – 10 km per 1 kWh (We can drive 1 km if we consume 100 Wh) Problems: 12V lead-acid batteries are too heavy and bulky in the EV Total weight of 12V lead-acid batteries : 504 kg out of 1318 kg (about 40%) : Energy density of batteries 30 Wh kg-1 Dr. Asida’s desire was “light-weight compact 12V batteries” to replace Motivation on 12 V lead-free batteries Each lithium insertion material has the characteristic value which has not been evaluated because of the energy density Li[Li1/3Ti5/3]O4 (LTO); zero-strain insertion material, extremely flat operating voltage of 1.55 V vs. Li, no limitation on cycle life, high-rate capability Li[Al0.1Li0.1Mn1.8]O4 (LAMO); manganese-based material, operating voltage of ca. 4 V vs. Li with ca. 100 mAh g-1 of rechargeable capacity, good cycleability & rate capability Li[Ni1/2Mn3/2]O4 (LiNiMO); manganese-based material, extremely flat operating voltage of 4.7 V vs. Li with 135 mAh g-1 of rechargeable capacity Our Final Goals of 12 V “lead-free” Batteries Long Life for more than 10 years Five (one) second burst of energy for starter Stability on constant voltage charge, so-called float charge, typically at 14.4 (13.8) V for 14 V line. 3600 cycles for deep 8 h charge and 8 h discharge for stationary or PEV applications, e.g., solar power generation systems especially for off-grid remote areas or long-range driving more than 500 km per charge High-energy density >> 30 Wh kg-1 (lead-acid batteries) Materials economy Environmental friendliness, not listed in RoHS & ＷEEE 12 V lead-free batteries consisting of insertion materials for clean energy technologies including for HEV, PEV, or advanced solar home systems based on the 12 V batteries T. Ohzuku and K. Ariyoshi, Chem. Lett., 35, 848-849(2006) K. Ariyoshi and T. Ohzuku, J. Power Sources, 174, 1258-1262(2007) Single Cell Required for 12 V Batteries Characteristic Number of cells connected in series Value in V for 12V Batt. 6 5 4 3 Charge-end 14.4 V 2.4 2.9 3.6 4.8 Nominal Voltage 12 V 2.1 2.5 3.1 4.15 Discharge-end 10.2 V 1.7 2.0 2.55 3.4 Cut-off voltage 7.2 V 1.2 1.4 1.8 2.4 0 I II Generation III The 12V lead-free batteries consist of insertion materials Materials Selected for 12 V lead-free Batteries 6 5 Li[Ni1/2Mn3/2]O4 4.3 V line LiCoO2 LAMO 4 3 The 3D framework structure is selected for 12 V application, not layered structure E / V LiCo1/3Ni1/3Mn1/3O2 2 Li[Li1/3Ti5/3]O4 1 Graphite (1/2 reduction in capacity) 0 0 50 100 Q / 150 mAh g -1 200 Possibility of 12 V lead-free batteries The first generation Combination of LTO and LAMO T. Ohzuku and K. Ariyoshi, Chem. Lett., 35, 848-849(2006) K. Ariyoshi et al., Electrochem. Solid State Lett., 8, A557-A560(2006) K. Ariyohsi and T. Ohzuku, J. Power Sources, 174, 711-715(2007) M. Imazaki et al., J. Electrochem. Soc., 156, A780-A786(2009). The first generation of 12 V lead-free batteries Characteristic Number of cells connected in series Value in V for 12V Batt. 6 5 4 3 Charge-end 14.4 V 2.4 2.9 3.6 4.8 Nominal Voltage 12 V 2.1 2.5 3.1 4.15 Discharge-end 10.2 V 1.7 2.0 2.55 3.4 Cut-off voltage 7.2 V 1.2 1.4 1.8 2.4 0 I II Generation III The first generation of 12V lead-free batteries consists of lithium titanium oxide (LTO) and lithium aluminum manganese oxide (LAMO) having the 3D structure Single Cell for The First Generation of 12 V Batteries Q (LAMO) / mAh g 6 0 20 40 60 -1 80 100 120 5 Lithium aluminum manganese oxide (LAMO) E / V 4 Terminal voltage of the single cell 3 2.9 V 2.5 V 2.0 V 2 Lithium titanium oxide (LTO) 1 0 0 50 100 Q (LTO) / mAh g -1 150 200 Possibility of 12 V lead-free batteries The second generation Combination of LTO and LiNiMO T. Ohzuku et al., Chemistry Letters, 30, 1270-1271(2001). K. Ariyoshi et al., J. Power Sources, 119-121, 959-963(2003). K. Ariyoshi et al., Electrochemistry (Tokyo, Japan), 76, 46-54(2008). M. Imazaki et al., J. Ceramic. Soc. Jpn., in press(2009). The second generation of 12 V lead-free batteries Characteristic Number of cells connected in series Value in V for 12V Batt. 6 5 4 3 Charge-end 14.4 V 2.4 2.9 3.6 4.8 Nominal Voltage 12 V 2.1 2.5 3.1 4.15 Discharge-end 10.2 V 1.7 2.0 2.55 3.4 Cut-off voltage 7.2 V 1.2 1.4 1.8 2.4 0 I II Generation III The second generation of 12V lead-free batteries consists of lithium titanium oxide (LTO) and lithium nickel manganese oxide (LiNiMO) Single Cell for The Second Generation of 12 V Batteries Q (LiNiMO) / mAh g 6 0 50 -1 100 150 5.4 V Lithium nickel manganese oxide (LiNiMO) 5 E / V 4 Terminal voltage of the single cell 3.6 V 3.1 V 3 2.55 V 2 Lithium titanium oxide (LTO) 1 0 0 50 100 Q (LTO) / mAh g -1 150 200 Possibility of 12 V lead-free batteries The third generation Combination of OCU-X and LiNiMO (still in basic research stage at OCU) The second generation of 12 V lead-free batteries Characteristic Number of cells connected in series Value in V for 12V Batt. 6 5 4 3 Charge-end 14.4 V 2.4 2.9 3.6 4.8 Nominal Voltage 12 V 2.1 2.5 3.1 4.15 Discharge-end 10.2 V 1.7 2.0 2.55 3.4 Cut-off voltage 7.2 V 1.2 1.4 1.8 2.4 0 I II III Generation The third generation of 12V lead-free batteries is basically possible, but problems to be solved still remain at present. Hurdle is very high to cope. Single Cell for The Third Generation of 12 V Batteries Q (LiNiMO) / mAh g 6 0 50 -1 100 150 5.4 V Lithium nickel manganese oxide (LiNiMO) 5 4.8 V 4.15 V E / V 4 Terminal voltage of the single cell 3.4 V 3 2 1 0 OCU-X under way to improve 0 50 100 150 Q (X) / mAh g -1 200 Single Cells Proposed for 12 V Lead-free Batteries 6 5 Gen. III OCU-X(200) / LiNiMO(130) E / V 4 Gen. II LTO(160) / LiNiMO(130) 4.1 V cell 3.15 V cell 3 2.5 V cell 2 Gen. I LTO(160) / LAMO(100) 1 0 0 20 40 60 80 Q / Ah kg-1 based on electrode couple 100 Three Types of 12 V Lead-free Batteries 20 Gen. I 14.4 V line Gen. III E / V 15 Gen. II 12 V line 10 10.2 V line We have four options in selecting 12 V batteries for clean energy technologies 5 0 5 10 15 20 25 Q / Ah kg-1 based on the electrode couple 30 Energy Densities Estimated for 12 V Lead-free Batteries Energy Density / Wh kg -1 250 Specific gravities of the batteries are estimated to be 2 – 2.5 g/cm3 200 X / LiNiMO 180 – 220 150 LTO / LiNiMO 120 – 150 100 50 Initial stage of our basic study Lead-Acid LTO / LAMO 25 – 40 60 – 100 Final stage of our basic study Prototype stage Available worldwide 0 Gen. 0 Gen. I Gen. II Gen. III Practical Reality of the 12 V Lead-free Batteries The First Generation Charge and discharge curves of the LTO/LAMO cell at 25oC -1 20 40 60 80 100 120 25 LAMO against Li auxiliary electrode 4 20 E / V 1253th 1000th 800th 600th 400th 200th 1st 3 15 Terminal voltage Negligibly small capacity fading 2 LTO against Li auxiliary electrode 1 4.43 mA cm-2 (200 mA g-1) 0 50 5 Positive-electrode mix 50.4 mg, 146 μm Negative-electrode mix 33.0 mg, 130 μm QLAMO100/QLTO170 = 0.898 OH-Cell No.621 Li[Li1/3Ti5/3]O4 / Li[Li0.1Al0.1Mn1.8]O4 Auxiliary electrode : Lithium electrode Electrolyte : LiPF6(EC : DMC = 3 : 7) Sample : A.B. : PVdF = 88 : 6 : 6 Positive Mix 50.4 mg (146 μ m) Negative Mix 33.0 mg (130 μ m) 8.86 mA/ 2 cm2 , polyvinylalcohol × 2 , 1.0~3.0 V QLAMO100/QLTO170= 0.898 0 10 -1 100 Q / mAh g based on LTO 150 0 E / V for 5 cells connected in series 0 5 Q / mAh g based on LAMO Charge and discharge curves of a LTO/LAMO cell -1 20 40 60 80 100 120 25 25oC, 6 cycles E / V LAMO against Li auxiliary electrode 4 20 3 15 Terminal voltage 10 2 LTO against Li auxiliary electrode 1 0 Positive-electrode mix 47.6 mg, 138 μm Negative-electrode mix 37.9 mg, 144 μm QLAMO100/QLTO170 = 0.739 OH-Cell No.369 Li[Li1/3Ti5/3]O4 / Li[Li0.1Al0.1Mn1.8]O4 Auxiliary electrode : lithium Electrolyte : LiPF6(EC : DMC = 3 : 7) Sample : A.B. : PVdF = 88 : 6 : 6 Positive Mix 47.6 mg (138 μm) Negative Mix 37.9 mg (144 μm) 2 8.38 mA/ 2 cm , cellulose × 2 , 1.0~3.0 V QLAMO100/QLTO170= 0.7388 0 50 -1 100 Q / mAh g based on LTO 5 0 150 E / V for 5 cells connected in series 0 5 Q / mAh g based on LAMO The 3600-cycle Test at 55oC for LTO/LAMO Cell -1 20 40 60 80 100 120 25 OH-Cell No.369 Li[Li1/3Ti5/3]O4 / Li[Li0.1Al0.1Mn1.8]O4 Auxiliary electrode : lithium Electrolyte : LiPF6(EC : DMC = 3 : 7) Sample : A.B. : PVdF = 88 : 6 : 6 Positive Mix 47.6 mg (138 μm) Negative Mix 37.9 mg (144 μm) 2 8.38 mA/ 2 cm , cellulose × 2 , 1.0~3.0 V QLAMO100/QLTO170= 0.7388 55oC, 4.19 mA cm-2, 3627 cycles 20 4 E / V 3600th 3000th 2000th 1000th 1st 3 15 Terminal voltage 10 2 1 0 Positive-electrode mix 47.6 mg, 138 μm Negative-electrode mix 37.9 mg, 144 μm QLAMO100/QLTO170 = 0.739 0 50 5 80% rechargeable capacity even after the 3600 cycle-test -1 100 Q / mAh g based on LTO 150 0 E / V for 5 cells connected in series 0 5 Q / mAh g based on LAMO Capacity Fading at 55oC for LTO/LAMO Cell 120 4.19 mA cm-2 at 55oC for 3627 cycles or 3283 h (136 days & 19 h) Q / mAh g -1 100 Targeted line charge capacity discharge capacity 80 3627 cycles Total charge capacity : 13.742 Ah Total discharge capacity : 13.738 Ah 60 40 More than 4 month with deep charge & discharge 20 Positive-electrode mix 47.6 mg, 138 μm Negative-electrode mix 37.9 mg, 144 μm QLAMO100/QLTO170 = 0.739 OH-Cell No.369 Li[Li1/3Ti5/3]O4 / Li[Li0.1Al0.1Mn1.8]O4 Auxiliary electrode : lithium Electrolyte : LiPF6(EC : DMC = 3 : 7) Sample : A.B. : PVdF = 88 : 6 : 6 μ 0 Positive Mix 47.6 mg (138 m) Negative Mix 37.9 mg (144 μ m) 8.38 mA/ 2 cm2 , cellulose × 2 , 1.0~3.0 V QLAMO100/QLTO170= 0.7388 0 1000 2000 cycle number 3000 4000 Prototype : The First Generation of 12 V Lead-free Batteries 16 No need to charge in CCCV 14.8 V CCCV 0.1 A cutoff LTO/LAMO System Nominal capacity; 5.8 Ah 14 E / V (0.49 dm3 1.05 kg) 12 0.2 C-rate or 5 h rate (1.16 A) Good for solar home systems 10 10 V cutoff Energy density 70 Wh/kg 150 Wh/dm3 (Trial batteries are not optimized yet) 8 0 1 2 3 4 Q / Ah 5 6 7 Original data obtained from home-made PEV 1. Batteries : 288V-55Ah 504 kg (15 kWh on the Vehicle) 2. Energy density of lead-acid batteries 30 Wh kg-1 3. 120-150 km per one charge : 8 – 10 km per 1 kWh The first generation of 12 V batteries (70 Wh kg-1) is applied to the PEV; 504 kg – 35 kWh – ca. 350 km drive per charge or 150 km drive – 15 kWh – 215 kg of battery weight The second generation of 12 V batteries (ca. 140 Wh kg-1) is applied to the PEV; 504 kg – 70 kWh – ca. 700 km drive per charge or 150 km drive – 15 kWh – 107 kg of battery weight Concluding remarks The 12 V lead-free batteries may be applicable to HEV (Gen. I), PEV (Gen. I & II depending on desired mileage per charge), and the advanced solar home systems (SHS). Long-range driving more than 500 km is possible (50 kWh <) for the PEV with the second generation of 12 V lead-free batteries High-rate capabilities of 12 V lead-free batteries for PEV and SHS, such as 2C, 10C, or 100C-rate, are no meaning because it takes about 5 hours to drive PEV for 500 km, meaning that the 1/5C rate is enough for 5 hour electric supply for PEV and SHS.