Upscaling the Li-ion Battery for Sustainable Energy Storage Applications. Josh Thomas. Ångströmlaboratoriet

Transcription

1 Upscaling the Li-ion Battery for Sustainable Energy Storage Applications Josh Thomas Materialkemi Ångström m Advanced Battery Ångströmlaboratoriet Centre, - UU Ångström m Laboratory, Uppsala University, Sweden. ENERGY 2008+, ATV, DTU, Copenhagen, Denmark,

2 Perhaps the greatest challenge facing us today... Expected energy consumption Oil production expected to peak World population: ca. 9 billion in 2050 (Is there a long-term effect of today s financial crisis???)

3 The green energy challenge... more of what?? nuclear power (Sweden) fossil fuels t

4 The World s energy sources today 6% 1% 0.5% 7% 4% 36% 24% 21% The most common are thedirtiest!!

5 We must clearly promote renewable E-sources! But the wind doesn t blow every day nor does the sun shine when you want it to - or at night! Long-term scenario: Renewable E-sources + efficient E-conversion + E-storage 4% 6% 1% 0.5% + fuel cells + batteries

6 Today s (Li-ion) battery research is focusing on: - cheaper, larger, greener (Li-ion) batteries with higher energy- och power-densities 1. EV/HEV/P-HEV:s 2. Quality electric power supplies 3. Uninterruptible Power Supply (UPS) system transport grid power wind sun wave... with energy from renewable sources

7 The transport problem a stepping stone to sustainable energy storage.

8 The car = environmental enemy #1!? City level Global-scale Global level Exhaust emission C O 2 emission

9 Pollution in the World s cities 2004 The 10 dirtiest cities ( 7 in China) 1. Taiwan 2. Milano!! 3. Beijing 4. Urumchi 5. Mexico City 6. Lanzhou 7. Chongqing 8. Jinan 9. Shijiazhuang 10. Teheran Cars Buses Trucks Projection CO 2 emissions (milj ton) : >300 million cars in Europe

10 The daily pollution in Paris! Length of traffic queues ( ) 231 km 154 km 77 km 0h 4h 8h 12h 16h 20h 24h Time of day

11 The green car challenge...

12 A temporary measure...

13 Energy Management + Battery Energy supply to make up for shortage Energy EV Drive Motor Assist Storage of excess energy Recovery of braking energy Engine turns off Engine output energy with maximum efficiency Time - (picture borrowed from Toyota)

14

15 Evolution of EV/HEV/P-HEVs Current HEVs e.g., PRIUS Fuel Economy Next generation HEVs (with Li-ion ) ICE Vehicles HEV marketability Fun to Drive

16 Later...

17

18 A future vision borrowed from Toyota.... But ALL future vehicle concepts will need (better) batteries!

19 A relatively uncontroversial consensus roadmap ahead towards the ZEVs: ICE HEV PHEV FC-PHEV (P)EV It has been estimated that: Time-scale?... the last totally ICE vehicle will roll of the production line in give or take a year.

20 A longer-term development: sustainable electric power Power gen. Distribution system HT HT HTA (20000V) BT(230V) A sustainable E-system: Centralised och decentralised supply and demand 1 Central battery storage LT KVA LT LT box (Centralised) (Decentralised) Individual battery storage Solar panels 2 Grid-coupled solar panels system 3 Remote (off-grid) 4 1 Unlikely in Sweden (hydro!!)

21 The battery?

22 Where are batteries today after two centuries? Alessandro Volta, 1799 (Cu/Zn) 1839 (Fuel cell) 1859 Pb-acid 1899 Ni-Cd (Swedish!) 1973 Li-metal 1975 Ni-MH 1979 Li-polymer Li-ion: Sony 1990 Li-ion polymer: 2000 The battery industry is very conservative!

23 The rechargable Li-ion (polymer) battery good rechargability = the ability to extract and reinsert an optimal amount of Li many times (1000 s) from the active particles without significant loss in capacity

24 Secondary battery market overview Li-ion now dominates the rechargeable battery World >2 billion batteries sold in 2006 Steadily increasing demand for cell-phones Demand for power tools greater than expected Li-ion will be in HEV s from onward sustainable energy storage!

25 Better batteries Better materials Safer anodes We can upscale with what we have today More stable electrolytes The CATHODE is holding back the upscaling of the technology! Higher capacity ( performance ) Higher power ( performance ) Safer ( performance ) Longer lifetime ( performance ) Lower cost processes ( market ) More abundant materials ( market / environment ) Non-toxic ( environment )

26 A lower-cost EV-cathode material? Today s most common mobile phone/laptop material uses: Li(Co,Ni)O 2, LiNi 1-y-z Co y Al z O 2 Larger batteries demand lower-cost cathode materials the obvious candidate some Fe-based material: - LiFePO 4 (A123, etc.) - Li 2 FeSiO 4 (our focus in my lab in Uppsala) ( Fe- and Si-oxides make up >10% of the Earth s crust! )

27 SEM picture of Li 2 FeSiO 4 200nm particle size: ~100 nm Very porous!

28 Cathode materials: a comparison a) Layered: LiCoO 2 -> Li 0.5 CoO 2 : ~3.9V, ~140 mah/g b) Spinels: LiMn 2 O 4 -> Mn 2 O 4 : ~3V or ~4.0V, 148 mah/g Instability! Solution: doping c) Olivines: LiFePO 4 -> FePO 4, ~3.5V, ~170 mah/g d) Orthosilicates Li 2 FeSiO 4 -> LiFeSiO 4, ~2.85V, ~ 170 mah/g Poor el. conductivity! Solutions: - doping - coating - nano -sizing

29 Our new Fe-based cathode material Li 2 FeSiO 4 an orthosilicate Li 2 Fe 2+ SiO 4 LiFe 3+ SiO 4 + Li + + e - E= 2.85 V vs. Li + /Li (low but safe!!) Q= 169 mah g -1 Advantages: Potentially lower cost, abundant, non-toxic High cycling efficiency High stability Li/Fe ordering!

30 Strategy for further improvement... How can we extract >1 Li to give a higher capacity at a higher voltage? e.g., for x = 0.5 Li Li (Fe2+ (Fe2+ 1-x 1-x Mn2+ Mn2+ x )SiO x )SiO 4 4 Li+ Li+ 1-x 1-x (Fe3+ (Fe3+ 1-x Mn 1-x Mn x )SiO x )SiO (1+x)Li+ (1+x)Li+ + (1+x)e (1+x)e - -

31 A manganese-doped silicate? Li 2 Mn x Fe 1-x SiO 4 Mn Distortion in MnO 4 Mn = 0.1 lithiated delithiated undoped Substitution of Fe by Mn facilitates a >1 Li + transfer (Mn 2+ Mn 3+ Mn 4+ ) Similar X-ray diffraction patterns as for undoped Li 2 FeSiO 4 First redox reaction occurs at > 4V (Mn 2+ Mn 3+ ) during 1st cycling It works!

32 Beyond Li 2 FeSiO 4... e.g., substitution V 169mAh/g 3+ Start material: Li 2 FeSiO 4 Li 2 Fe SiO 4 Li Fe SiO 4 We want to make this box as small as possible! Inert Li! Fe 2+ /Fe 3+ only! Inert polyanion! Transition-metal substitution ~2.85V, ~3.8V 2+/2+ 3+/3+ 169mAh/g Polyanion substitution ~2.2V mAh/g Li 2 Mn x Fe 1-x SiO 4 Kinetics! Reversibility! >4.3V (169x) mah/g 4+/3+ Li Mn x SiO 4 Fe 1-x Li 2 Fe VO 4 ~3.4V 160mAh/g Li Fe VO 4 Li 1-x Mn x Fe 1-x SiO 4 Fe VO 4

33 Strategy to compensate for the low electronic conductivity of Li 2 FeSiO 4 type materials nano-painting with an electronic conductor Conductive enough to distribute e - evenly Thin enough to allow the passage of Li + carbon coated particles

34 Back to this picture... We need renewable E-source! But the wind doesn t blow every day nor does the sun shine when you want it to -or at night! Scenario: Renewable E-sources + efficient E-conversion + E-storage 4% 6% 1% 0.5% + fuel cells + batteries

35 The Hydrogen Economy H 2 Wind Sun Geothermal Biomass Methanol Ethanol Methane Fuel Cell H 2 Hydrogen Storage and Distribution Clean Power

36 A fuel cell electrode Active Layers 10μm 10μm Backing Ref: IRD A/S of Svendborg (

37 The Direct Methanol Fuel Cell (DMFC) e- CH 3 OH H 2 O O 2 H + CO 2 CH 3 OH H 2 O Anode Reaction CH 3 OH + H 2 O CO 2 + 6H + + 6e - Cathode Reaction 6H + + 6e O 2 3H 2 O

38 Fuel-cell R&D must clearly proceed in parallel with battery R&D not as a competitor, but as a complement.

39 Conclusion: We are almost certainly going to see the upscaled (Li-ion) battery playing an ever more important rôle in the development of sustainable transport and subsequently sustainable energy storage solutions in the future.

40 Thank you for listening! Contact: