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NanomaterialsNanomaterials--Based Electrodes for Energy Based Electrodes for Energy Storage Devices with Fast Rate CapabilitiesStorage Devices with Fast Rate Capabilities

Amit Singhal and Ganesh Skandan Nanopowder Enterprises Inc.

Dr. Glenn AmatucciTelcordia Technologies

Acknowledgments Acknowledgments

US Department of Energy, Energy Storage Research ProgramUS DOE Small Business Innovative Research (SBIR)

DOE 2002 Project

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NEI Nanopowder Enterprises Inc. www.nanopowderenterprises.com

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NEI MarketsNEI Markets-Nano enables the application of-

• Polymer Nanocomposites: coatings and bulk• Nanoparticles for Drug Delivery

• Nanoparticle laden fluids• Specialty Nanopowders• Rechargeable Batteries

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High Rate Energy Storage DevicesHigh Rate Energy Storage Devices

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Goals of the ProgramGoals of the Program• Develop nanostructured anodes for a new type of

high rate energy storage device called Asymmetric Hybrid Cell

• Fabricate prototype Asymmetric Hybrid Cell with following features-– Capable of working efficiently over a wide temperature

range (-30oC to 70oC)– Long cycle life (> 100,000 cycles)– Power density as good as that of a supercapacitor– Energy density comparable to, or higher than, that of

Pb-acid batteries– Fast rate of charge (complete charge in 1 min.)

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Concept of High RateConcept of High RateAsymmetric Hybrid CellAsymmetric Hybrid Cell

Courtesy Telcordia Technologies

A thin, flexible, highly manufacturable and non-aqueous plastic laminar device

Reference: Amatucci et al., Journal of The Electrochemical Society, 148 (8), A930 (2001)

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UltrafineUltrafine Electrodes ExhibitElectrodes ExhibitFaster Rate CapabilitiesFaster Rate Capabilities

- Li4Ti5O12 Electrodes -

0

50

100

150

200

0 10 20 30 40 50 60 70

5C1CC/2

10C

Li / LiPF6 EC:DMC / LTOC/2 discharge

120

100

80

60

40

20

0

% D

isch

arge

cap

acity

108642Discharge rate ( x C)

Coarse Li4Ti5O12

Fine Li4Ti5O12

Cap

acity

(mA

h/g)

Cycle#

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Long Cycle Life of Prototype Hybrid CellsLong Cycle Life of Prototype Hybrid Cells

0

0.02

0.04

0.06

0.08

0.1

1 10 100 1000 104 105

Dis

char

ge c

apac

ity, A

h

Cycle number

charge : 2A to 3.0 Vdischarge : 2A to 1.5 V Telcordia Technologies

6”X4” AH

Cathode: High surface area activated carbon (700 – 2000 m2/g)Anode: Ultrafine Li4Ti5O12; Electrolyte: 1M LiPF6 in 2:1 volume ratio of ethylene carbonate: dimethyl carbonateDimensions: 6” X 4” (Courtesy Telcordia Technologies)

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Rationale for Lithium Rationale for Lithium Intercalating Anode MaterialsIntercalating Anode Materials

Intercalation voltage

Carbon: ~ -3V SHE

Li4Ti5O12: -1.5V SHE

WO2: - 2.3V SHE

Courtesy Telcordia Technologies

Carbonaceous materials are unsafe to operate in high rateapplications, because of the risk of Li plating

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WOWO22 has the Highest Output Voltagehas the Highest Output Voltage

Courtesy Telcordia Technologies

Use of WO2 anodes will enhance the energy densityof asymmetric hybrid cell

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Low Temperature Synthesis Low Temperature Synthesis

Inte

nsity

80604020 2θ

WO

2

WO

2

WO

2W

O2

WO

2

WO

2

WO

2W

O2

W

600 oC 550 oC 500 oC

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Spherical Particles with Spherical Particles with UltrafineUltrafine CrystallitesCrystallites

750 nm2.8 µm

Spherical particles will result in high packing density of electrodesSurface area = 15 m2/g

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UltrafineUltrafine WOWO22 PowdersPowdersAre Electrochemically ActiveAre Electrochemically Active

3.0

2.5

2.0

1.5

1.0

0.5

Volta

ge

35302520151050Time (hr)

Discharge rate: 22.72 mA/g WO2 - 550oC

WO2 - 600oC

250

200

150

100

50

Capa

city

(mAh

/g)

3.02.52.01.51.0Cycle

WO2 - 600oC

WO2 - 550oC

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Electrochemical DataElectrochemical Datain An Asymmetric Hybrid Cellin An Asymmetric Hybrid Cell

V(a) vs (b)

V(b) vs (c)

Spring

Current Collector

Counter Electrode (a)

Separators

Ref. Electrode (b)

Working Electrode (c)

Plungers

-3

-2

-1

0

1

2

3

4

-5Po

tent

ial v

s. A

g qu

asi r

efer

ence

or

full

Out

putV

WO2

vs. ref.

activated C vs. ref

full cell output V

60 mAh/g

0 5 10 15 20Time (hr)

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Program OverviewProgram Overview

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• Develop nanostructured anode powders

• Scale up the synthesisprocess

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• Develop nanostructured anode powders

• Scale up the synthesisprocess

Battery Manufacturers

Partner with batterymanufacturer to produce

Asymmetric Hybrid Batteries

Battery Manufacturers

Partner with batterymanufacturer to produce

Asymmetric Hybrid Batteries

TelecordiaTelecordia

Fabricate and characterize

prototype asymmetric hybrid cell

Supply anode materials

Sandia National Laboratories

Research supportand

scientific input

Sandia National Laboratories

Research supportand

scientific input

Manufacturers ofEnergy Storage

Systems

Manufacturers ofEnergy Storage

Systems

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