Aging Mechanisms in Li-ion Batteries

Shrikant C. Nagpure (ME) Prof. Bharat Bhushan (ME)

(Bhushan.2@osu.edu)

Prof. Sudarsanam Suresh Babu (IWSE) Prof. Giorgio Rizzoni (ME/ECE) Prof. Yann Guezennec (ME/ECE)
Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Center for Automotive Research

Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Center for Automotive Research

Outline
Li-ion Batteries Introduction and Objective Multi-scale Characterization Plan Results
Cell Cycling Thermography and SEM
Heat Diffusion Proposed Mechanism

AFM electrical resistance on nanoscale l ti l i t l

Surface Resistance Proposed Mechanism

Summary

Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Center for Automotive Research

Li-ion Batteries - Introduction

Comparison with Different Battery Chemistries

Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Center for Automotive Research

Li-ion Cell i i C ll

Anode and cathode with a separator and electrolyte in between, are rolled and packed in a can to form a cylindrical cell. Positive Electrode (Cathode): Lithiated Metal Phosphate p nanoparticles coating with carbon bonded on an Al substrate with Polyvinylidene Difluoride (PVDf) binder Negative Electrode (Anode): Graphitic Carbon bonded on copper substrate Organic Electrolyte: Lithium Hexafluorophosphate Alkylene Carbonates (LiPF6 salt in ethylene carbonate (EC) diethyl carbonate (DEC))
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Length = 5 feet ; Width = 2.5 Thickness = 0.2 mm Nominal Operating Voltage: 3.3 V Nominal Capacity: 2.3 Ah

Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Center for Automotive Research

Li-ion Li ion Cell Operation

Charging: Li in cathode ionizes and intercalates within anode layers LiFePO4 +

(Cathode)

6C
(Anode)

Li1-xFePO4
(Delithiated Cathode)

LixC6
(Lithiated Anode)

Discharging: Li de intercalates from anode and migrates back to de-intercalates cathode to form original compound
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Harris S., Lithium-ion batteries, OSU, Seminar, 2009

Typical A i M h i T i l Aging Mechanisms for Cathode f C th d

Structural disordering Disordering f Di d i of crystal structure t l t t during synthesis Phase transition Phase changes during repeated intercalation/de-intercalation of Li in the host lattice Metal dissolution Dissolved metal forms deposits on the cathode and also on anode Electrolyte decomposition Surface films due to electrolyte oxidation

Vetter,J.,Novak,P.,Wagner,M.R.,Veit,C.,Moller,K.C.,Besenhard,J.O.,Winter,M.,WohlfahrtMehrens,M.,Volger,C., Hammouche,A.,Ageing mechanismsinlithiumionbatteries,J.PowerSources,147 (2005)269281 Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Center for Automotive Research 6

Problem Statement
A good understanding of relevant mechanisms does not exist. Aging is known to be a result of several simultaneous g g physiochemical processes. Multi-scale characterization is needed to understand the aging effects at various length scales, as well as a function of aging g , g g process. Understand the aging mechanisms in the Li-ion batteries
Understand the kinetics of material degradation in the cathode

Objectives

Identify precursors in material degradation for improved material selection. Based on understanding of aging mechanisms, predict the battery life as a function of design, geometry, materials and service conditions
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Multi-scale Characterization Plan

Task 1: Generation of Cathode Surfaces from Batteries with Different Aging Characteristics - Batteries aged to 0, 25, 50, 75 100 % of their life Task 2: Thermography Mapping to study material degradation on millimeter scale. Also identify the p y potential regions ( 2) of material g (m degradation within a large cathode area (m2). Task 3: Micro- and Nano-scale Surface Characterization -Investigate Micro Nano scale Investigate the identified areas further for surface roughness, grain coarsening, chemical compositional changes or formation of nanocrystalline deposits, structural changes and surface electrical p p p , g properties

Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Center for Automotive Research

Proposed Experimental Plan

Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Center for Automotive Research

Cell C li C ll Cycling

Nominal capacity (Ah) decreases as a function of aging cycles. The direct measure of cell aging is the increase in cell impedance. impedance This increase can be attributed to the increase in surface resistance of the anode and cathode. The surface resistance affects the battery operation because battery reactions occur at the surfaces of anodes and cathodes. cathodes

Cell is aged under very harsh electrical duty cycles at high temperature (55 C) and high C-rate (16C ) (1C = 2 3Ah) C rate 2.3Ah)

Nagpure S. C., Marano V., Rizzoni G., Babu. S. S., Guezennec and Bhushan B., Aging and Material Characterization Studies of Lithium-ion Batteries at The Ohio State University, 1st ANL conference on Advanced Lithium Battery for Automotive Applications Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Center for Automotive Research

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Thermography
It is believed that thermal properties are a measure of electrical impedance, thus is of importance in aging studies on a mm scale. It helps to understand whether aging process is uniform over the entire cathode surface. High intensity short duration thermal p g y pulse incident on front face of the sample IR camera captures the thermal data from the rear face

ASTM Note: E 1461 - 92 Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Center for Automotive Research 11

The cathode is divided in 5 sections, 2 X 2 inch each Darker spots are colder.

Nagpure S. C., Dinwiddie R., Babu S. S., Rizzoni G., Bhushan B., and Frech T., Thermal Diffusivity Study of Aged Li-ion Batteries Using Flash Method, J. Power Sources, (in press) Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Center for Automotive Research

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Thermal diffusivity calculated from:

0.13879 L2 = t1 / 2

where L = thickness, t1/2 = time for , rear face to reach half-maximum

Thermal diffusivity of aged samples is higher compared to unaged samples

Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Center for Automotive Research

Nagpure S. C., Dinwiddie R., Babu S. S., Rizzoni G., Bhushan B., and Frech T., Thermal Diffusivity Study of Aged Li-ion Batteries Using Flash Method, J. Power Sources, (in press)

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SEM
SEM micrographs were taken to investigate g mechanisms for the increase in thermal diffusivity.

Washed in 1-methyl-2-pyrolidinone to dissolve PVdF binder SEM micrographs reveal the coarsening of the nanoparticles for aged sample , believed to be due to sintering. Coarsening leads to a decrease in the effective surface area of the particles and porosity porosity. It can also lead to the de-bonding of these particles from the aluminum substrate

Nagpure S. C., Dinwiddie R., Babu S. S., Rizzoni G., Bhushan B., and Frech T., Thermal Diffusivity Study of Aged Li-ion Batteries Using Flash Method, J. Power Sources, (in press) Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Center for Automotive Research

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Heat Diffusion - Proposed Mechanism p

Due to coarsening of the nanoparticles, porosity decreases - the effective surface area per unit volume decreases. A decrease in porosity of the medium leads to an increase in the thermal diffusivity. th l diff i it
Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Center for Automotive Research

Nagpure S. C., Dinwiddie R., Babu S. S., Rizzoni G., Bhushan B., and Frech T., Thermal Diffusivity Study of Aged Li-ion Batteries Using Flash Method, J. Power Sources, (in press) 15

AFM Surface Resistance Measurements

Spreading Surface Resistance Measurement (SSRM) Setup

As indicated earlier, an increase in impedance of a cell after aging can be attributed to the increase in the surface resistance . SSRM is used to measure the surface resistance of a circular contact formed between the LiFePO4 nanoparticles and the conductive AFM tip on a nanoscale. nanoscale

Nagpure. S. C., Bhushan B., Babu S. S., Rizzoni G., Scanning Spreading Resistance Characterization of Aged Li-ion Batteries Using Atomic Force Microscopy, Scripta Mater. 60, 933936 (2009) Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Center for Automotive Research 16

Surface height and change in the surface resistance of LiFePO4 cathode as a result of aging. g g

Surface height: The LiFePO4 nanoparticles tend to coarsen in the aged samples. Surface resistance: The lower voltage output in the case of lt t t i th f aged samples indicates higher surface resistance as compared to unaged sample sample.

Bias: +1 V Scale: V 1/R

Note the difference in scale

Nagpure. S. C., Bhushan B., Babu S. S., Rizzoni G., Scanning Spreading Resistance Characterization of Aged Li-ion Batteries Using Atomic Force Microscopy, Scripta Mater. 60, 933936, (2009) Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Center for Automotive Research 17

Surface Resistance - Proposed Mechanism

Total Resistance Unaged Aged (R1)u (R1)a + (R2)a

The resistance of the LiFePO4 nanoparticles increases as the cells are cycled. because of the coarsening of the particles, as is seen in the height image. The coarsening also causes loss of the carbon coating which leads to the further increase in the resistance of these particles. In addition to this, the total surface resistance of the aged sample increases due to the additional resistance from the nanocrystalline deposits (NCD) formed on the cathode surface. NCD is formed due to the chemical reactions taking place at the surface of the cathode

Nagpure. S. C., Bhushan B., Babu S. S., Rizzoni G., Scanning Spreading Resistance Characterization of Aged Li-ion Batteries Using Atomic Force Microscopy, Scripta Mater. 60, 933936, (2009) Nanoprobe Laboratory for Bio- & Nanotechnology and Biomimetics Center for Automotive Research 18

Summary
The direct measure of cell aging is the increase in cell impedance. This increase can be attributed to the increase in surface resistance of the anode and cathode. The surface resistance affects the battery operation because battery reactions occur at the surfaces of anodes and cathodes. d d th d Based on thermography, damage is non-uniform over the cathode surface Grain coarsening of cathode surface occurs during aging of cells
Coarsening is observed at nano-scale using SEM micrographs Porosity decreases due to coarsening leading to change in the thermal diffusivity as measured by Flash method, a measure of surface resistance. Coarsening also l d t i C i l leads to increase i th surface resistance as in the f i t observed in SSRM studies.

Future plans: Chemical analysis: EELS, EDX, Raman; Structural analysis: TEM; Surface analysis: KPM
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References
Nagpure S. C. and Bhushan B. , In Applied Scanning Probe Microscope Methods Biomimetics and Industrial Applications Vol. 13, (B. Bhushan and H. Fuchs, eds.) pp. 203-233, (Springer-Verlag, Heidelberg, Germany, 2009). G 2009) Nagpure S. C., Bhushan B., Babu S. S., and Rizzoni G., Scanning Spreading Resistance Characterization of Aged Li-ion Batteries Using Atomic Force Microscopy, Scripta Mater. 60, 933936, (2009) Nagpure S. C., Dinwiddie R., Babu S. S., Rizzoni G., Bhushan B., and Frech T., Thermal Diffusivity Study of Aged Li-ion Batteries Using Flash , y y g g Method, J. Power Sources (in press)

http://www.mecheng.osu.edu/nlbb/ http://car.osu.edu/ http://car osu edu/

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Acknowledgements

Institute of Materials Research (IMR) Center for Automotive Research Battery Consortium Oak Ridge National Laboratory (ORNL) Edison Welding Institute (EWI) Edi W ldi I tit t