1. Breakthrough in Battery Technologies
Nitash Balsara
John Newman
Venkat Srinivasan
BATT Program
LBNL

2. Summary of battery energy
John Newman, my mentor

3. BATT snapshot Lithium batteries for transportation Electrolyte:
Liquid organic solvents
Polymers
Gels
Ionic liquids
Cathode:
Transition-metal oxides
Spinel-based
Olivine-based
Anode:
Carbon-based
Alloys and intermetallics
Oxides
Lithium-metal
Lithium batteries for transportation

4. Lithium-ion battery story
Beginning of electronics…
Bell Labs announced the discovery of the transistor in 1947.
Start-ups like Fairchild and Intel beat giants like GE and RCA in electronics manufacturing.
License for personal electronic devices sold to Ibuka and Morita for $25,000.
gas tubes - to - solid state
Sony introduces a game-changing wireless device (pocket transistor) in 1957.
Sony recognizes the importance of powering electronic circuits (rather than the importance of Moore’s law) and introduced the lithium-ion cell in 1990.
Every handheld device in the world today has a lithium-ion battery.
None of the batteries are made outside Asia.
…affects batteries
transistor radio – to – lithium battery 4

5. History of battery specific energy?
Li-Ion
Specific Energy (Wh/kg)
Lead Acid
Ni-Cd
Ni-MH 5 5

6. Coupling of safety and energy
Safety problems begin with flammability and electrochemical instability of electrolyte
Worse with more energy
Cost to industry >$1B in recent years
Small 1 Wh computer batteries are not perfectly safe.
Of 22 US airline Li battery fires, 11 happened in last 3 years. 6
Takeshita 2008 6

7. Safety of 5 kWh batteries
Enough alkyl carbonate to annihilate a car.
Li-ion batteries die quickly if operated at 60 oC and explode at 80 oC.
Modified Prius
plug-in-toyota-prius-catches-fire-explodes.html

8. Replace liquid electrolyte by a solid
Conventional Li Ion
Li Polymer
Cu Current Collector
Porous Graphite Anode Composite
Liquid Electrolyte
Porous Cathode Composite
Al Current Collector
Solid Separator
Polymer Cathode Composite
Solid anode
Flammable liquid electrolyte
Solid state, no flammables
Li Ion: <200 Wh/kg
Li Polymer: ~250 Wh/kg
Poor lifetime and capacity fade
Stable polymer for best lifetime
Activity began with California’s Zero Emission mandate in the 1990s 8 8

9. Dendrite growth during charging
Conventional Li Ion
Li Polymer
Dendrite growth was a problem
Cu Current Collector
Porous Graphite Anode Composite
Solid anode
Liquid Electrolyte
Solid Separator
Porous Cathode Composite
Polymer Cathode Composite
Al Current Collector
Al Current Collector
Make polymer hard to prevent deformation
Modulus=109 Pa, Monroe and Newman, 2005 9 9

10. Previous polymer electrolytes
Ionic mobility is mediated by polymer chain motion.
Fast polymer motion implies high conductivity and low modulus.
Increasing modulus must decrease conductivity.
Anion -
polymer chain
Li+
Polyethylene oxide showed promise.
Unfortunately batteries failed due to lithium dendrite growth.
Stiffness
Limitation of prior polymer electrolytes 10
Conductivity 10

11. Solid polymer electrolyte- +
Dendrites ~ mm + -
LiTFSI salt
r = [Li+]/[EO]
Nanostructured conductor ~ 10 nm 11 11

12. Consequences of plug-in EV
Basis: 100M EVs with 16 kWh batteries, 40 mi driving range
CO2 emission reduced by 0.75 GT per year.
1.6 TWh of distributed energy storage.
Potential solution to the renewable energy storage dilemma.

13. A Recent Success Story
John Goodenough (U. Texas) proposes FePO4 as a cathode for Li batteries in 1997 but poor transport properties prevented implementation.
Yet-Ming Chiang (MIT) shows that nanostructuring FePO4 solves the transport problem and establishes A123 in 2002.
A123 goes public in September FePO4 is the likely cathode for first generation plug-in EVs.

14. Need for fundamental understanding
The most misleading conclusion in (1)…” 180 kW is needed to charge a 15 kWh battery in 5 minutes” …. one must remember that the internal resistance of the battery will be of the order of R=1/4 ohm so that the power dissipated … is typically what you need to heat a four-story building!
FePO4
15 kW battery can be charged in 5 min
Kang and Cedar, Nature, 2009
Goodenough, et al. J. Power Sources, 2009
Cedar claims that slow ion transport in FePO4 is due to slow surface diffusion, based on simulations, but in the absence of direct experimental proof. This claim is strongly disputed by Goodenough et al. based on indirect arguments. Experimental measurements of bulk and interfacial transport would be useful.

15. Missing LBNL Battery Initiative
Fundamental Studies on Battery Materials ($5M/year)
Designing new electrodes (NERSC).
Making model batteries with well-defined oxide nanoparticles (Foundry).
Tracking atoms and orbitals through charge-discharge cycles (NCEM, ALS).
Couple LBNL scientists who are not battery experts with battery experts.
Fundamental study of the other charge carrier.
This work is not consistent with the goals of the existing BATT program (supported by EERE). A new BES-supported program is needed for this work.

16. Future landscape Product
We emit more than 1 molecule of CO2 for every J of electricity we produce in a coal plant.
Product
Emission at 1 place.
CO2 is concentrated.
Easier to control, use, and legislate.
Other alternative is to use clean energy (e.g. solar and wind).

17. A possible option

18. Not an option Car with cement factory
Interactions between Battery Center and Carbon Dioxide and Renewable Energy Centers is essential.

19. Summary Impact: 0.75 GT of CO2 emission, 1.6 TWh of storage.
Major Obstacles: We may have arrived at the fundamental limit of today’s workhorse (Li-ion). Making next generation chemistries work is difficult to place on a Gandt chart. Lack of fundamental understanding of thermodynamics and transport impedes progress. Policies that reward lack an environmental footprint are essential as carbon-based energy will continue to be far more effective in terms of cost and energy density.
Current battery work at LBNL is conducted within the BATT program.
Connection between batteries, carbon capture, and renewable energy programs are natural.
LBNL current expertise is more at the basic end of spectrum. LBL/ANL appear to have synergistic capabilities to basic-to-manufacturing spectrum.
Industrial partners: Johnson Control, Dow Chemicals, A123 (BYD, Sanyo, LG Chem), IBM, Applied Materials.
Viable funding plan: A new $25 M ANL/LBL Collaboration. A new $5 M program housed at MSD on fundamental studies on battery materials.