Biologically Inspired High-Power Batteries

Daniel E. Morse

Center for Energy Efficient Materials

Institute for Energy Efficiency
University of California, Santa Barbara
 ENABLING THE VISION:
• Alternative, renewable sources of energy
• Electric cars, trains, ships; air & space launches
• Faster, denser digital information processing
• Smart grid distribution systems…

…ALL need better, higher

capacity, more powerful,
safe BATTERIES
for storage of electrical energy.
Synthesis of
Nanostructured
Semiconductor-
and Metal-Based
Nanocomposite
Electrodes for
High-Power
Batteries…

Biological
inspiration:

Living organisms
make remarkable
nanostructures of
silica Institute for Collaborative Biotechnologies
Army-Industry Collaboration Conference
February 8-9, 2011
Sponges make skeletons
of nanostructured silica
Silicateins enzymatically catalyze and
template the synthesis of silica fibers
- at low temperature

Institute for Collaborative Biotechnologies

Army-Industry Collaboration Conference
February 8-9, 2011
Translating the
biomolecular
mechanism to
practical chemistry
and materials
synthesis…..

Lessons Learned from Biology:

•  Slow catalysis of synthesis
from molecular precursor
⇒ kinetic control
•  Vectorial control of crystal
growth to regulate polymorph,
orientation & connectivity
Bio-Inspired, Low-T Nanofabrication of Semiconductors
and Metals Offers Advantages for Wide Range of Applications

Lightweight,
Higher Power
Safe
Lithium-Ion
Batteries 2007
Hybrid
electric
Low-cost Tesla
Solar Energy
Discovered Molecular
Mechanism of Biological
Nanofabrication of Silica
Infrared
detectors
for Medical
Translated to New Bio-inspired,
Low-temperature, Low-Cost Diagnosis
Synthesis of Nanostructured
Semiconductor Thin-films and
Nanoparticles High-resolution 3-
-  Generic; >50 Semiconductors D Medical
-  Novel Structures;
Ultrasound,
Uniquely Useful Properties
High-power,
High Energy-Density,
Safe
Li-ion Batteries
Catalytic Growth of Nanocrystalline Tin in Graphite
Yields Exceptionally High Power Anode

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

Gentle,
low-temperature
catalysis retains
crystallinity and porosity
of graphite !

The resilient graphite “breathes” to accommodate large volume changes accompanying

each cycle of Li alloying and de-alloying on charging and discharging, yielding exceptionally
high power, stability and cyclability:
(b) 600
Sn(15 wt.%)@NG
Retains nearly 500 Nanocomposite NG
Nanocomposite
50% capacity after 400

t
discharge at 50 C 300
Graphite alone
200
Fully reversible! High Power 100 High Energy
0
0 5 10 15 20
Cycle number
The Value of High Power:

Full recovery after

Cell Phones, very high rate
Computers, discharge !
I-pods, etc.
Power Tools
Electric Cars
Trucks & Military

Present
commercial

Graphite
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.

Our CATALYTIC Solution:

Carbon Nanotubes

Form nanocomposite
precursor

Catalysis

Desired CNT-based
High-Power
Nanocomposite
Disperse uniformly in
Anodes & Cathodes
solution with metal or
metal oxide precursor
Catalytic growth of metal nanocrystals inside the conductive
and resilient matrix of dispersed carbon nanotubes

800

Capacity (mAh/g)
600 High-Energy Nanocomposite

400

200
CNTs alone
0
0 1 2 3 4 5 6 7 8 9
Cycle number

! Sn !
Intensity (a.u.)

!
! !!
!! !
!

10 20 30 40 50 60 70 80 90
2!
Calculated performance of CEEM s High-Power
and High-Energy Anodes in combination with
commercial LiFePO4 cathode:

40% more
energy
10x more
power !
Catalytic Synthesis of CNT-based Nanocomposite Cathode:
High Crystallinity and Unparalleled Mixing
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
Voltage( V vs. Li/Li+)

1st
4.5 2nd
4.2
3.9
3.6
3.3
3.0
0 50 100 150 200
Capacity (mAh/g)
 Safe High Energy Storage:
Protection Against Overheating and Fire
BaSrTiO3 nanocrystalline ceramic Electrophoretic
coatings for electrodes or current deposition and double-
collectors for explosion-proof annealing of BaSrTiO3
rechargeable Li-ion batteries nanocrystals yields
Very fine grain BaSrTiO3 smooth, uncracked films
nanocrystalline ceramic Protection results from unique 

Positive Thermal Coefficient of
with low initial
resistivity, lower Tc, and
Resistance:
strong PTCR protection:
4.0x108
Experimental
Fit

3.0x108
Resistance (Ohm)

PTCR = 104 PTCR = 105 !

2.0x108

1.0x108 Tc = 130 oC
Tc = 52 oC

0.0
0.0 50.0 100.0 150.0 200.0 250.0 300.0

T (oC)

2.5 µm

Manufacturers Recall Millions

La-doped and sintered ceramic:

high crystallinity & conductivity of Batteries Because of Fire Threat
Syntheses of Anode, Cathode and Safety Protectant
are “Chemical,” and Readily Scalable
Three Essential Elements:
• Vapor Diffusion Catalysis
Glove
Box
or
Bag
 • Low Temperature
• Unprecedented Kinetic
Control
catalyst
 precursor


Lab Scale: 100 mg

2 kg/batch
1-2 Kg Batch

N2 carrier gas Gas out

in

BaTiO3

catalyst precursor

250 gm (99% yield) ultrasonicator

Highly crystalline 6.9 nm
Pure
Combines advantages of kinetic
control with high-throughput 17
 Enabling the Vision
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