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Biologically Inspired High-Power Batteries

Daniel E. Morse

Center for Energy Efficient Materials

Institute for Energy Efficiency

University of California, Santa Barbara

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Alternative, renewable sources of energy

Electric cars, trains, ships; air & space launches

Faster, denser digital information processing

Smart grid distribution systems

ENABLING THE VISION:

ALL need better, higher

capacity, more powerful,

safe BATTERIES

for storage of electrical energy.

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Institute for Collaborative BiotechnologiesArmy-Industry Collaboration Conference

February 8-9, 2011

Synthesis ofNanostructuredSemiconductor-

and Metal-BasedNanocompositeElectrodes forHigh-PowerBatteries

Biologicalinspiration:

Living organismsmake remarkablenanostructures ofsilica

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Sponges make skeletonsof nanostructured silica

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Translating thebiomolecular

mechanism topractical chemistry

and materialssynthesis..

Lessons Learned from Biology: Slow catalysis of synthesis

from molecular precursor

kinetic control

Vectorial controlof crystalgrowth to regulate polymorph,orientation & connectivity

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Bio-Inspired, Low-T Nanofabrication of Semiconductors

and Metals Offers Advantages for Wide Range of Applications

Translated to New Bio-inspired,Low-temperature, Low-Cost

Synthesis of Nanostructured

Semiconductor Thin-films and

Nanoparticles

-Generic; >50 Semiconductors-Novel Structures;Uniquely Useful Properties

Discovered MolecularMechanism of Biological

Nanofabrication of Silica

Lightweight,

Higher PowerSafeLithium-Ion

Batteries

Low-cost

Solar Energy

Infrareddetectors

for MedicalDiagnosis

High-resolution 3-D Medical

Ultrasound,

2007Hybrid

electric

Tesla

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High-power,High Energy-Density,

Safe

Li-ion Batteries

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Catalytic Growth of Nanocrystalline Tin in Graphite

Yields Exceptionally High Power Anode

Gentle,low-temperaturecatalysis retainscrystallinity and porosityof graphite !

Kinetically controlled catalytic synthesis grows Sn nanocrystals in situ, inside the pores ofthe compliant, conductive carbon matrix of graphite

0 5 1 1 2123456 Sn1w%@NGNGt

Cy e um

(b)

The resilient graphite breathes to accommodate large volume changes accompanyingeach cycle of Li alloying and de-alloying on charging and discharging, yielding exceptionallyhigh power, stability and cyclability:

Retains nearly50% capacity afterdischarge at 50 C

Fully reversible!

Nanocomposite

Graphite alone

Nanocomposite

High Power High Energy

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The Value of High Power:

Presentcommercial

Graphite

Cell Phones,Computers,I-pods, etc.

Power Tools

Electric Cars

Trucks & Military

Full recovery aftervery high ratedischarge !

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Our CATALYTIC Solution:

Disperse uniformly in

solution with metal ormetal oxide precursor

Form nanocomposite

precursor

Catalysis

Desired CNT-based

High-Power

Nanocomposite

Anodes & Cathodes

Carbon Nanotubes

Carbon Nanotube-based Nanocomposites

Recently discovered new form of matter. Highly conductive; cost-competitive; freedom from

monopoly on strategic natural resource, but: very difficult to mix with metals or metal

oxides to form good anodes or cathodes.

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Catalytic growth of metal nanocrystals inside the conductiveand resilient matrix of dispersed carbon nanotubes

0 1 2 3 4 5 6 7 8 90

200

400

600

800

Capacity(mAh/g)

Cyclenumber

CNTs alone

High-Energy Nanocomposite

10 20 30 40 50 60 70 80 90

!!!

!!!

!

!

!

!

!

Intensity(

a.u.)

2 !

Sn!!

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Calculated performance of CEEMs High-Power

and High-Energy Anodes in combination with

commercial LiFePO4 cathode:

10x more

power !

40% moreenergy

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Catalytic Synthesis of CNT-based Nanocomposite Cathode:High Crystallinity and Unparalleled Mixing

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0 50 100 150 2003.0

3.33.6

3.9

4.2

4.51st2nd

Capacity (mAh/g)

Voltage(Vv

s.

Li/Li+)

High Power, High Voltage CNT-based Nanocomposite Cathode

96% retention of original capacity after discharge at 10 C

>80% capacity retention at the exceptionally high rate of 20 C

Full recovery after complete discharge at 50C

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BaSrTiO3 nanocrystalline ceramiccoatings for electrodes or current

collectors for explosion-proofrechargeable Li-ion batteries Protection results from unique

Positive Thermal Coefficient ofResistance:

Safe High Energy Storage:Protection Against Overheating and Fire

0.0 50.0 100.0 150.0 200.0 250.0 300.0

0.0

1.0x108

2.0x108

3.0x108

4.0x108

Experimental

Fit

Re

sistance(Ohm)

T (oC)

Tc = 130oC

PTCR = 104

Very fine grain BaSrTiO3nanocrystalline ceramic

Manufacturers Recall Millions

of Batteries Because of Fire ThreatLa-doped and sintered ceramic: high crystallinity & conductivity

Electrophoreticdeposition and double-

annealing of BaSrTiO3nanocrystals yieldssmooth, uncracked films

with low initialresistivity, lower Tc, andstrong PTCR protection:

PTCR = 105 !Tc = 52

oC

2.5 m

S th f A d C th d d S f t P t t t

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Syntheses of Anode, Cathode and Safety Protectantare Chemical, and Readily Scalable

17

catalyst precursor

GloveBoxorBag

Lab Scale: 100 mg

250 gm (99% yield)

N2 carrier gasin

catalyst precursorultrasonicator

Gas out

Combines advantages of kineticcontrol with high-throughput

1-2 Kg Batch2 kg/batch

Highly crystalline 6.9 nmPure

BaTiO3

Three Essential Elements:

Vapor Diffusion Catalysis

Low Temperature

Unprecedented Kinetic

Control

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Bio-inspired, kinetically controlled, low-temperature

catalytic nanofabrication offers batteries with:

Exceptionally high power - even at 50C! Higher cyclability and stability

Increased safety

Readily scalable manufacturing

Generic platform technology

Broad range of applications Opportunities for strategic industry partnerships

We gratefully acknowledge support from:

CEEM and IEE DOE

Enabling the Vision

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