Advanced Lithium-ion battery materials for plug-in hybrid electric vehicles

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Advanced Lithium-ion battery materials for plug-in hybrid electric

vehicles

Duncan, Hugues; Courtel, Fabrice; Abu-Lebdeh, Yaser; Yim, C.-H.;

Whitfield, Pamela; Niketic, Svetlana; Davidson, Isobel

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H. Duncan, F. Courtel, Y. Abu-Lebdeh, C.-H. Yim, P. Whitfield, S. Niketic and I. Davidson

National Research Council Canada, 1200 Montreal Road, Ottawa, Ontario, CANADA K1A 0R6, e-mail: Isobel.Davidson@nrc-cnrc.gc.ca

Institute for Chemical Process and

Environmental Technology

Institut de technologie des procédés

chimiques et de l'environnement

Advanced Lithium-ion Battery Materials for Plug-in Hybrid

Electric Vehicles (PHEV)

Background

Cathode

Electrolyte

Anode

Requirements for new cathode materials

• High voltage • High capacity • High thermal stablility (no release of O2) • Low capacity fade (longer cycle life), especially at high temperature • Low cost

Spinels: LiMn

1.5

Ni

0.5

O

4 Advantages • High voltage cathode material; operates at ~ 5V • More stable in charged state vs. layered oxides (eg. LiCoO2, LiNiO2) • Low cost (Mn: US$ 1/lb, Ni: US$ 6.5/lb) • Environmentally friendly Achievements1,2_: • Materials with high energy density at high cycling rates • Long cycle life at room temperature and 55°C (vs. LiMn2O4)

Cathode liquid electrolyteNon-aqueous Anode

Cathode Electrolyte Anode

Lithium metal oxide Lithium salt in an organic solvent Graphite LiCoO2Æ Li1-xCoO2+ xLi++ xe- Li+PF6-in EC:DMC xLi++ xe-+ 6C Æ LixC6

Requirements for new electrolytes

•Non volatility and low flammability.

•Wide electrochemical window.

•High ionic conductivity (especially at low temperatures) and low viscosity.

•Compatibility with electrode materials.

Aliphatic Dinitriles

1,2

• High electrochemical stability • High thermal stability

• High conductivity (3.6 mS/cm) and moderate viscosity (14.5 cP) • Resistance to Aluminium corrosion (4.4V) • Commercially available and relatively cheap

Spiro‐ammonium imide salts

3 • Ionic liquids with plastic crystalline phases • Non‐flammable and non‐volatile • High ionic conductivity even in the solid state • X‐ray diffraction was used to identify crystalline and plastic crystalline phases

Sulfones

•High electrochemical (anodic) stability •Stable with metal oxide anodes •Commercially available and relatively cheap

Li‐ion batteries: ubiquitous in portable electronics

9 High operating voltage: ~3.7 V 9 High energy and power densities: 160 Wh/Kg; 1800 W/Kg 9 Low self discharge: < 5% per month. 9 Good cycle life 2 Safety 2 Cost

Requirements for PHEVs

• Concurrent high energy and power densities • Enhanced safety • Significant cost reductions without loss of performance • Enhanced high and low temperature operation

Current research

• Non‐flammable, non‐volatile electrolytes • Higher potential cathodes and anodes ‐ less reactive on rupture • Higher volumetric and gravimetric energy densities • Greater electronic and thermal conductivity

Olivines: LiMPO

₄

M = Fe, Mn, Co, Ni

Advantages • High voltage cathode material (by varying metallic cation): LiFePO4(3.4V) LiMnPO4(4.0V) LiCoPO4(4.8 V) LiNiPO4(5.2 V) • More stable in charged state vs. layered oxides • Environmentally friendly, low cost, safe Current work: • 3D Solid Object Modeler (3DOM) synthesis using monodispersed polystyrene sphere (shown above) . • Porous nanomaterial ‐ enhance power density • Microwave synthesis: reduce sintering time, nanosized material 0 20 40 60 80 100 120 0 20 40 60 80 100 S pe c if ic C a pa c it y ( m A h/g) Cycle number ADN GLN PMN SEN SUN Current work2_: • Development of new synthetic methods to reduce synthesis time and control morphology: ‐ Microwave assisted‐synthesis ‐ Co‐precipitation methods • Doping with Ti (LiMn1.5Ni0.45Ti0.05O4) to increase stability

1. S. Niketic, P.W. Whitfield, and I.J. Davidson, Meet. Abstr. – Electrochem. Soc. 801 (2008) 155 2. I. Davidson, A. Abouimrane, Y. Abu-Lebdeh, S. Niketic and P. whitfield, Meet. Abstr. – Electrochem. Soc. 802 (2008) 564 3. H. Duncan, Y. Abu-Lebdeh, and I.J. Davidson, Meet. Abstr. – Electrochem. Soc. 901(2009) 440

1.Y. Abu-Lebdeh, I. Davidson, J. Electrochem. Soc. 156 (2009) A60

2.Y. Abu-Lebdeh, I. Davidson, J. Power Sources 189 (2009) 576

3.Y. Abu-Lebdeh, E. Austin, I. Davidson, Meet. Abstr. – Electrochem. Soc. 901 (2009) 123

Problems with current Li‐ion technology

LiCoO2cathode •Thermally unstable in charged state: • O2released reacts with organic electrolyte and high surface area Carbon ‐ serious safety issue • High cost and abundance of Cobalt (US$ 14/lb) • Toxicity of cobalt Liquid or Gelled electrolyte •Organic solvent: volatile and flammable ‐ safety issue • Corrosive and reactive salt LiPF6 ‐ safety and environmental issues • Relatively high freezing point Graphite anode • Poor volumetric energy density (battery size) • Potential near Lithium metal • Safety issue Simplified PHEV3 2

Requirements for new anode materials

• High specific capacity • Low potential range • Non‐flammable compounds Current material

• Graphitic carbon: LiC6, 372 mAh/g (830 Ah/L) Pros : stable and reversible specific capacity

Cons : low theoretical capacity; low volumetric energy density Alternatives:

metal‐lithium alloys

• Silicon: Li4.4Si, 4210 mAh/g (9805 Ah/L) Pros : very high capacity – both gravimetrically and volumetrically

• Tin: Li4.4Sn, 993 mAh/g (7313 Ah/L) potential shifted from Li deposition

• Antimony: Li3Sb, 660 mAh/g (4420 Ah/L) Cons: high volume expansion upon cycling ~300%

capacity fade Metal oxides

• SnO2: 783 mAh/g (5442 Ah/L) Pros : high capacity, potential shifted from Li deposition, Li2O matrix

• Sb2O3: 552 mAh/g (2870 Ah/L) Cons: non‐decomposable Li2O (irreversible capacity)

Nano‐SnO

2

Coated Silicon

• Development of a microwave‐assisted polyol method1 • SiC‐SiO2coating

Nano‐SnO

2

coating on Carbon

1

• Microwave‐assisted polyol method

Alternative Binders

1 • Accommodation of the volume expansion

1.F. Courtel, E. Baranova, Y. Abu-Lebdeh, I. Davidson, Meet. Abstr. – Electrochem. Soc. 901 (2009) 444

• Polyvinylidene Fluoride • Sodium CarboxyMethyl Cellulose • water soluble • non expensive • PEDOT/PSS aka Baytron P • water soluble • electrical conductor (10 mS/cm) Nano-SnO2 Carbon SnO2

1. J.-M. Tarascon and M. Armand, Nature 414 (2001) 359 2. Department of Energy: www.energy.gov

3. R. Gilbert, PHEV Workshop at the National research Council Canada, Ottawa, July 2006

1 1 n 3Glutaronitrile, GLN 4Adiponitrile, ADN 5Pimelonitrile, PMN 6Suberonitrile, SUN 8Sebaconitrile, SEN