能源材料-4

能源æ...

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Unformatted text preview: (Energy Materials) -4 Map of proved oil reserves at end 2006 Crude oil prices since 1861 LiFePO4 Li+ + e- +FePO4 Fe(III) Fe(II) PO43- P-O Fe2+/Fe3+ Li/Li+ LiFeO2 Li+ + e- +FeO2 Fe(VI) Fe(III) Fe-O 1. Nontoxic 3. Cheap 5. Steady cycle life LiFePO4 Fe-O Fermi level Fe3+/Fe4+ Fermi level Li/Li+ 2. Environmentally friendly 4. Theoretical specific capacity 170 mAh/g 6. High- Power Energy XRD Capacity Charge/discharge voltage Lift cycle olivine 170 mAh/g 3.4 V (Li/Li+) 1000 : LiFePO4 • • C-rate e- • S/cm), C-rate? , :10-3 S/cm 2C rate 20C rate Mass transfer Current (A) (Fe2+/Fe3+) • (Mn+) • Li+ • V=IR electron transfer :(e’s transfer ) • • : Voltage (V) (10-9 Li+ e- :(Mass transfer) / LIB Cleaners Sanitary E-Bicycle E-Scooter Power tools 2113 • 2112 (AAGR:64%) , ,cleaner, shaver ,2013 , 4.3 , 15% • 2008 2111 2110 Years 2009 2008 2007 2006 2005 2004 2003 0 50 100 150 200 250 300 350 High-Power Li BatteryDemand A mounts(Mcells) 400 450 (AAGR:1%) HEV $ 7200 million HEV $ 3600 million LEV $ 500 million Power Tool $ 100 million Energy Storage System $ 1250 million Energy Storage System $ 500 million 2008 Sources: LEV $ 1000 million 2010 , Chimera ,IIT 2015 Tesla Motors---Roadster From:IIT HEV Plug-in 2010 2015 2030 1 1 1.5 7 1 1/2 1/7 1/40 NEDO Car type DOE Prius II Prius III MSL Aggressive Target Cell type - 168 cell 56 cell Li-ion 40 cell Li-ion 40 cell LMO 45 cell LFPO 201.6V*6.5Ah NiMH(1.2V,6.5Ah) 201.6V*3.8Ah 148V*8Ah 148V*8Ah 148V*8Ah 0.766kWh 1.184kWh 1.184kWh 1.184kWh Modular spec. Modular Energy >2kWh (to have 0.5kWh available energy of 30%DOD) 1.31kWh Discharge power 40kW for 10s 20kW, 1129W/kg 40kW for 10s 50kW for 10s 1250W/cell 357A/cell 3000W/kg @40%SOC 50kW for 10s 1111W/cell 370A/cell 3330W/kg @40%SOC Regen. power -35kW for 10s -14.5kW -25kw for 10s -40kW for 10s -40kW for 10s Cycle life 300K cycles 300K cycles 300K cycles Calander life 15 years 15 years 15 years Cell weight 60kg pack weight 15kg cells 0.375kg cell 80Wh/kg 15kg cells 0.118kg cell 80Wh/kg 45 liters volume <50Wh/day S-D Operation Temp. range -30~52 Pack Price $800 @100K/y -40~66 • • Capacity vs Discharge Power 80-10-10 Configuration 160 • 140 Specific Capacity (mAh/g) 120 100 80 60 6,2 mg/cm2 6,1 mg/cm2 4,2 mg/cm2 2,5 mg/cm2 2,4 mg/cm2 1,2 mg/cm2 40 20 0 0,1 1 10 Rate (xC) 100 Cathode Composition (weight) – 80% C-LiFePO4, grade Phos-Dev-12 – 10% Carbon EBN-10-10 (Superior Graphite) – 10% PVDF Cell Configuration – Carbon-Coated Aluminium current collector – 1.54 cm2 cathode – Electrolyte: EC-DMC 1-1 LiClO4 1M – Anode: Metallic Lithium Experimental conditions: – Room temperature – Voltage limits: 2.2 – 4V – Charge: C/4 up to 4V, then potentiostatic at 4V until I < C/24 High Power Lithium Batteries for Power Tools Company Material System (cathode) Samsung Sanyo Sony Cell Type 18650 ( LiCoO2/LiMn2O4 LiFePO4 18650 LiNiCoMnO2 LiCoO2/LiMn2O4 A123 26650 18650 ) ( ) ( ) ( ) Capacity(Ah) 1.3 1.5 1.3 2.3 Voltage(V) 3.65 3.75 3.75 3.3 Energy (Wh) 4.8 5.56 4.85 7.59 Peak Current(A) 13 15 15.6 70 Power (W/Kg) 1135 1200 1310 3120 Weight(g) 40.0 44.8 41.2 70.0 0.2 C ---Energy Density (Wh/Kg) 118 126 117 108 Rate Capability (C rate) 10 10 12 20~30 20 C---Energy Density (Wh/Kg) ---- ---- ---- 83 • • Capacity vs Discharge Power 80-10-10 Configuration 160 • 140 Specific Capacity (mAh/g) 120 100 80 60 6,2 mg/cm2 6,1 mg/cm2 4,2 mg/cm2 2,5 mg/cm2 2,4 mg/cm2 1,2 mg/cm2 40 20 0 0,1 1 10 Rate (xC) 100 Cathode Composition (weight) – 80% C-LiFePO4, grade Phos-Dev-12 – 10% Carbon EBN-10-10 (Superior Graphite) – 10% PVDF Cell Configuration – Carbon-Coated Aluminium current collector – 1.54 cm2 cathode – Electrolyte: EC-DMC 1-1 LiClO4 1M – Anode: Metallic Lithium Experimental conditions: – Room temperature – Voltage limits: 2.2 – 4V – Charge: C/4 up to 4V, then potentiostatic at 4V until I < C/24 High Power Lithium Batteries for Power Tools Company Material System (cathode) Samsung Sanyo Sony Cell Type 18650 ( LiCoO2/LiMn2O4 LiFePO4 18650 LiNiCoMnO2 LiCoO2/LiMn2O4 A123 26650 18650 ) ( ) ( ) ( ) Capacity(Ah) 1.3 1.5 1.3 2.3 Voltage(V) 3.65 3.75 3.75 3.3 Energy (Wh) 4.8 5.56 4.85 7.59 Peak Current(A) 13 15 15.6 70 Power (W/Kg) 1135 1200 1310 3120 Weight(g) 40.0 44.8 41.2 70.0 0.2 C ---Energy Density (Wh/Kg) 118 126 117 108 Rate Capability (C rate) 10 10 12 20~30 20 C---Energy Density (Wh/Kg) ---- ---- ---- 83 Valence power cell A123 power tool cell LFP-C LFP-Pure LFP/CaF2 LFP-Pure 4904/1000 XS=275 (Å) LFP-C 3476/1000 749(Å) ( LFP-Pure LFP-C 15~20 m 1.57 m LFP-C 0.67 m ) 0.67 k Pure LiFePO4 TEM 800 800 092905-A A 700 600 500 500 Counts 600 C ounts 092905-C B 700 400 300 O 200 100 C P Fe 100 Fe C u 0 0 2 4 300 200 Fe Si 400 6 Energy(keV ) 8 10 0 0 1 2 3 4 5 6 7 Energy(keV) 8 9 10 LiFePO4/C TEM (a) (b) B A 800 800 (C) A 700 600 C ounts 600 Counts (D ) B 700 500 400 Fe P 300 O 200 Fe Cu 0 0 400 300 200 C Fe Si 100 500 2 4 6 Energy(keV) 8 C O 100 Cu Si Cu 0 10 0 2 4 6 E nergy(keV ) 8 10 HRTEM and SAD analysis of Pure-LiFePO4 HRTEM Zone axis=[3,-1,2] Pure LiFePO4(MCL) Pure SAD Selected Area Diffraction EELS mapping analysis of LiFePO 4/C(MCL) composite The Inside Carbon Network of LiFePO4 Particles Carbon network Second Particle ( 5 m) m) resin C LiFePO4 The width of carbon channels is about 10~30 nm. C-Rate Test: 5 Cycle Test: 160 Capacity(mAh/g) 4 Voltage( V ) R Discharge:3C Charge:1C, E SD 5-L -775 84(12 C)/145(0.2 7 5 R E S D 5 -L -7 C)=58% 3 0 .1 C 0 .1 C 0 .2 C 2 1C 140 120 1C /3C 100 80 2C 3C LFP-C 5C 8C 12C 1 0 40 80 120 C a p a city ( m A h /g ) 5 0 160 160 L F P -Pure 2 1 2 0 5 -C Y -2 LFP -S D -1 40 80 120 C ycle N um ber 160 CL FP+R E SD 5-L -2-1(55) harge:1C, Discharge:1C 0.1C 1C /1C Capacity(mAh/g) 4 Voltage( V ) LFP-C at room temperature 60 3 2 1C 0.2C 0.1C 1 0 40 80 120 C a p a c ity ( m A h /g ) 160 120 80 40 LFP-C at 55 0 0 40 80 C ycle N um ber 120 LiFePO4(MCL) & LiFePO4(Phostech) 4.5 4.5 LFP-MCL LFP-PHOSTECH 4.0 3.5 3.5 0.1C 0.2C 1C 2C 3C 5C 8C 12C 3.0 2.5 2.0 0 20 40 60 Voltage( V ) Voltage( V ) 4.0 3.0 0.1C 0.2C 1C 2C 3C 5C 8C 12C 2.5 2.0 80 100 120 140 160 180 0 20 40 Capacity( mAh/g ) 100 120 140 160 180 LFP-PHOSTECH 160 140 140 0.2C/0.2C 120 0.5C/1C 1C/3C 100 80 60 40 Capacity(mAh/g) Capacity(mAh/g) 80 Capacity( mAh/g ) LFP-MCL 160 60 0.2C/0.2C 120 0.5C/1C 1C/3C 100 80 60 40 20 LFP:KS-4:SP:PVDF=84:4:4:8 0 0 20 40 60 80 100 120 140 160 180 200 Cycle Number 20 LFP:KS-4:SP:PVDF=84:4:4:8 0 0 20 40 60 80 100 120 140 160 180 200 Cycle Number Rate Capacity of LiFePO4 Battery 4 .0 0 C -R a te T e s t 3 .8 0 0 .2 C 10C 3 .6 0 15C 20C 25C 3 .4 0 0 .2 C Voltage(V) 3 .2 0 3 .0 0 2 .8 0 10C 2 .6 0 15C 2 .4 0 20C 2 .2 0 25C 2 .0 0 1 .8 0 1 .6 0 0 25 50 75 100 125 150 175 200 C a p a c ity (m A h ) 225 250 275 300 325 Long-Term Cyclability and High Thermal Stability of LiFePO4 The specific capacity reduction after 6000 cycles was only 14%. J. of Electrochem. Soc., 152 (2005) A899. Photographs of the anode and the cathode electrode sheets and the separator after 8000 cycles The surface of the cathode electrode sheet was very smooth, and no obvious damage. The anode electrode sheet partly adhered to the separator, and seemed to be slightly rough. Li0FePO4 EC/DEC • Heated with EC/DEC solvent LiPF6 or LiBOB ARC • Heated with LiPF6 or LiBOB EC/DEC solvent Onset temp. Onset temp. Onset temp. LiFePO4 onset temp. (300 ) are higher than Li0.5CoO2 (150 ). Electrochem. Comm., 6 (2004) 724. 190 240 Journal of Physics and Chemistry of Solids 67 (2006) 1338 Electrochemical behaviour of C/LiFePO4 (synthesized by mechanochemical activation) in function of the operating temperature of the cell. LiFePO4/C-MCL Journal of Power Sources 159 (2006) 702 Discharge curves of Li/LiFePO4 cell with a 1.0m(0.9LiBF4–0.1LiBOB)1:1:3 PC/EC/EMC electrolyte, which were recorded at 1C by charging the cell at 20 ◦C and then discharging at a specific temperature. coin cell C-rate Cyclic life LiFePO4 crystallization Carbon LiFePO4 e- + Li+ Li ion + FePO4 Li hoping J. AM. CHEM. SOC. 2006 , 128, 11416-11422 a Schematic representation of the Li0.26FePO4, Li0.45FePO4, and Li0.75FePO4 particles obtained by chemical delithiation of LiFePO4. CHEM. Mater. 2006 hoping LiFePO4 1. Simulation 2. XRD LiFePO4 lattice XRD 3. EELS-Spectra O K-edge Fe L-edge LiFePO4 Bulid LiFePO4 & LiFePO4:C(C beside Fe, Oct.) & LiFePO4:C(C beside P, Tet.) Structure Structure & Energy Calc. E>0 delta Energy Calc. E<0 C can’t insert into LiFePO4 C can insert into LiFePO4 Stop Calc. And compare band gap & DOS between three structure Calc. Method correction (spin & LDA+U) Energy gap increase Confirm XRD between calc. And expt. Compare calc. Results with expt. data Energy gap decrease Calc. XRD for this three structure LiFePO4 simple monoclinic LiFePO4:C (C beside Fe) triclinic 255.79 1.045 LiFePO4:C (C beside P) simple monoclinic 267.28 1.075 275.03 9.73 10.26 9.87 5.70 5.60 5.92 4.61 4.65 4.72 44.8553 1.064 90.00 47.7090 1.037 89.66 46.5864 90.00 90.01 88.02 92.90 90.00 90.00 90.00 -191.47 -.195.79 -196.25 The Li ions diffused direction of Olivine structure is one -dimension along to b axis. Fermi level Valence band ~0.8 eV Conduction band ~0.3 eV Gap decrease ~0.5 eV From: 20000 MCLpure MCL4K5000 MCL5Q10000 18000 16000 Intensity 8855 14000 a=5.974; b= 10.616; c=4.821 C:4.2 wt% 12000 10000 9643 a=5.978; b= 10.618; c=4.823 8000 C:2.2 wt % 6000 9841 a=5.978; b= 10.608; c=4.820 4000 0% 2000 0 0 10 20 2 ( =0.774903 Angstrom) 30 EELS-Spectra comparison (ITRI vs EELS ) ...
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