Nanowire Lithium-Ion Batteries as Advanced Electrochemical Energy Storage Yi Cui Department of Materials Science and Engineering & Geballe

Laboratory for Advance Materials Stanford University

Importance of Energy Storage Portable Electronics Vehicle Electrification Tesla Roadster Storage for Renewable Energy and Grid Implantable Devices Solar Wind

Energy Storage Technologies Capacitor Supercapacitor (Electrochemical capacitor) + +

solution + +

Metal Metal ++++ + ----

Electrical double layer dielectrics 1 E = CV 2 2

Batteries (Ag-Zn)

Ag + + e...Ag Battery voltage 2+ Zn 2e ...Zn + 2+ 2Ag + Zn ...Ag + Zn , .G =-2FV Reaction free energy Faraday constant

Fuel Cells http://en.wikipedia.org/wiki/Fuel_cell

Comparison of Energy Storage Technologies Specific power (w/kg) 106 105 104 103 102 10 1 Capacitors Sacitors upercapBatteries Fuel cells 10-2 10-1 1 10 102 103 Specific energy (wh/kg) Important parameters: -Energy density (Energy per weight or volume) -Power density (Power per weight or volume) -Cycle life and safety -Cost

Why Li Ion Batteries? Li-related batteries have larger energy density than other batteries. J.-M. Tarascon & M. Armand. Nature 414, 359 (2001) .

Existing Li Ion Battery Technology Graphite: 370 mAh/g LiCoO2: 140 mAh/g The energy density can not meet the application needs. 1. Energy density: -Anode and cathode Li storage capacity -Voltage 2. Power density: -Li ion moving rate -Electron transport 3. Cycle, calendar life and safety: strain relaxation and chemical stability. 4. Cost: Abundant and cheap materials

Electrode Materials Anode: low potential Cathode: high potential J.-M. Tarascon & M. Armand. Nature. 414, 359 (2001)

Two Types of Electrode Materials

Li Li Existing Tech. Future Tech. New Materials Mechanism Intercalation Displacement/alloy Volume change Small Large Li diffusion rate Fast Slow Specific capacity Low High

We work on the future generation of battery materials. C. K. Chan, Y. Cui and co-workers, Nano Letters 7, 490 (2007). C. K. Chan, Y. Cui and co-workers, Nano Letters 8, 307 (2007) C. K. Chan, R. Huggins, Y. Cui and co-workers Nature Nanotechnology 3, 31 (2008)

Nanowires as Li Battery Electrodes

What nanowires can offer: -Good strain relaxation: new materials possible -Large surface area and shorter distance for Li diffusion -Interface control: (better cycle life) . -Continuous electron transport pathway.

Example: Si as Anode Materials C anode: the existing anode technology. LiC6 C6 Theoretical capacity: 372 mA h/g Si anode Si Li4.4Si Theoretical capacity: 4200 mA h/g Problem for Si: 400% volume expansion.

Vapor-Liquid-Solid (VLS) Growth of Si Nanowires Au nanoparticles SiH4 400-500 C chemical vapor deposition Metal substrate Au Nanoparticles: Si Nanowires Scanning Electron Micrograph Scanning Electron Micrograph 5 m

Structure of Si Nanowires High Resolution Transmission Electromicrograph 10 nm10 nm -Single crystal -1-3 nm amorphous SiO2

Nanowire Battery Testing Beaker Cell Flat Cell Measured parameters: current, voltage, time.

Ultrahigh Capacity Si Nanowire Anodes At C/20 rate Si nanowires show 10 times higher capacity than the existing carbon anodes. Si nanowires show much better cycle life than the bulk, particle and thin film. C. K. Chan, R. Huggins, Y. Cui and co-workers Nature Nanotechnology 3, 31 (2008)

Power Rate-Dependence

Diameter Change of Si Nanowire Anodes Before After The diameter changes to 150% but nanowires don t break.

Length Change of Si Nanowire Anodes EDX mapping Before Li-cycling After Li-cycling

Structure Change of Si Nanowire Anodes X-ray diffraction Li insertion

Structure Change of Si Nanowire Anodes Li insertion progression HRTEM Pristine 100 mV 50 mV 10 mV

Acknowledgement Candace K. Chan Prof Robert Huggins