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 Microstructural transport and chemistry within
Li-ion battery cathodes

Colorado Fuel Cell Center Earth • Energy • Environment

Robert J. Kee, Huayang Zhu

John Berger, Andreas Wiedemann, Veruska Malavé

Mechanical Engineering

Colorado School of Mines, Golden, CO 80401

Scott Barnett, Zhao Liu

Northwestern University, Evanston, IL 03766

Graham Goldin

ANSYS, Inc., Lebanon, NH 60208



rjkee@mines.edu

(303) 273-3379





Presented:

Office of Naval Research

Washington, DC

October 7, 2013

ONR_October2013
1

Our primary focus is on fundamental chemistry and

transport in electrochemical power sources

Colorado Fuel Cell Center Earth • Energy • Environment

Delphi, 30 cell

Li-ion batteries
SOFC stack

ONR_October2013

Over 50 archival papers published with ONR support
2
 Our early research introduced detailed reforming
kinetics and electrochemistry into SOFC modeling

Colorado Fuel Cell Center Earth • Energy • Environment

ONR_October2013
3

Patterned electrodes enable the investigation of

fundamental charge-transfer kinetics

Colorado Fuel Cell Center Earth • Energy • Environment

SEM of UMCP pattern

•Ni sputtered on YSZ

Goodwin, Zhu, Colclasure, and Kee,

J. Electrochem. Soc., 156:B1004-B1021, 2009
ONR_October2013
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The H-spillover mechanism represents the
Mizusaki experiments over wide operating ranges

Colorado Fuel Cell Center Earth • Energy • Environment

There is important elementary information in these experiments

• Cathodic polarization is important to establish microscopic reversibility

• Independent control of partial pressures establishes reaction orders

Goodwin, Zhu, Colclasure, and Kee, J. Electrochem. Soc., 156:B1004-B1021, 2009
ONR_October2013
5

With rate-limiting assumptions, modified Butler-

Volmer rate expressions can be developed

Colorado Fuel Cell Center Earth • Energy • Environment

Goodwin, Zhu, Colclasure, and Kee, J. Electrochem. Soc., 156:B1004-B1021, 2009

ONR_October2013
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The first fully coupled three-dimensional SOFC model
with detailed reforming and electrochemistry

Colorado Fuel Cell Center Earth • Energy • Environment

ONR_October2013
7

High-fidelity modeling provides direct assistance

to SOFC system design and development

Colorado Fuel Cell Center Earth • Energy • Environment

ONR_October2013
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System design and control rests on the foundation
of predictive fundamental understanding

Colorado Fuel Cell Center Earth • Energy • Environment

ONR_October2013
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MPC depends upon low-order linear models that are

derived from the high-fidelity physical model

Colorado Fuel Cell Center Earth • Energy • Environment

The model-predictive controller (MPC) enables real-time optimization

• Controller satisfies constraints on actuation and observables

• Multiple-input--multiple output (MIMO) enables sensor fusion

ONR_October2013
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The controller makes a complex set of decisions
to meet load demand and satisfy constraints

Colorado Fuel Cell Center Earth • Energy • Environment

•Colclasure, Sanandaji, Vincent, Kee, J. Power Sources, 196:196-207 (2011)

•Sanandaji, Colclasure, Vincent, Kee, J. Power Sources, 196:208-217 (2011)

ONR_October2013
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Micro-channel reactors can effectively integrate

heat-exchanger and fuel reformer functions

Colorado Fuel Cell Center Earth • Energy • Environment

ONR_October2013
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New algorithms were developed to model detailed
reforming chemistry in shell-and-tube reactors

Colorado Fuel Cell Center Earth • Energy • Environment

ONR_October2013
13

Our objective is to develop microstructural models to

improve understanding of the electrode performance

Colorado Fuel Cell Center Earth • Energy • Environment

Reconstruct Li-ion battery cathodes

• FIB-SEM experiments

•Computational reconstruction

Develop 3D microscale models

•Electrochemical performance

•Thermal response

•Structural behavior

Model electrode performance

•Ordinary operation

•Abnormal environments

Upscale from the microscale

•Derive effective properties

• Apply at the cell scale

Focus on early times for shorts

• Prior to complex chemistry

• Electrolyte and SEI decomposition

ONR_October2013
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 Actual electrode microstructure can be
quite different from packed spheres

Colorado Fuel Cell Center Earth • Energy • Environment

Cell models benefit from predictive knowledge at the electrode microscale

ONR_October2013
15

One-dimensional models are usually based upon

assuming detached spherical electrodes

Colorado Fuel Cell Center Earth • Energy • Environment

Colclasure and Kee, Electrochem.

ONR_October2013
Acta, 55:8960-8973 (2010).
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 Actual electrode microstructures can be
reconstructed from tomographic interrogation

Colorado Fuel Cell Center Earth • Energy • Environment

ONR_October2013
•Wiedemann, Goldin, Barnett, Zhu, Kee, Electrochimica Acta, 88:580-588 (2013)
17

FIB-SEM capabilities enable high-resolution imaging

and analysis at the microscale and nanoscale


Colorado Fuel Cell Center Earth • Energy • Environment

ONR_October2013
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 Reconstructed electrode structures are discretized
as the basis for detailed computational analysis

Colorado Fuel Cell Center Earth • Energy • Environment

Actual 3D geometry is discretized

•Solid phase and pore phase

•We have developed robust algorithms



Model transport and chemistry

•Multicomponent transport in pores

•Heterogeneous catalysis on surfaces

• Electrochemical charge transfer

•Thermal behavior at the microscale



Important questions can be answered

• How does microstructure performance?

•What are the effective properties?

•How does pore space affect ion transport?

• How does microstructure influence heating?

1M polyhedra cells, 4.3M faces, 2.9M nodes

Li-ion battery cathode

•Wiedemann, et al., Electrochimica Acta, 88:580-588 (2013)

ONR_October2013
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Models represent electrochemical and thermal

behavior in the complex 3D electrode microstructures

Colorado Fuel Cell Center Earth • Energy • Environment

ONR_October2013
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 Butler-Volmer is used to represent charge-transfer
kinetics at the electrode-electrolyte interfaces

Colorado Fuel Cell Center Earth • Energy • Environment

ONR_October2013
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The model is typically exercised using

Galvanostatic discharge at a specified C rate

Colorado Fuel Cell Center Earth • Energy • Environment

One face is current collector

•Galvanostatic discharge

•Specify C rate



Other faces symmetry boundaries

• Zero gradients



Thermal model

•All faces insulated

ONR_October2013
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 Under ordinary operating conditions the Li gradients
are much greater in the electrode than the electrolyte

Colorado Fuel Cell Center Earth • Energy • Environment

ONR_October2013
23

Local composition and electric potential can vary

significantly within the electrode structures

Colorado Fuel Cell Center Earth • Energy • Environment

ONR_October2013
•Wiedemann, et al., Electrochimica Acta, 88:580-588 (2013)
24

 Three-dimensional models show good
predictions of measured performance

Colorado Fuel Cell Center Earth • Energy • Environment

ONR_October2013
25

The local voltages can be very different

from the terminal voltage


Colorado Fuel Cell Center Earth • Energy • Environment

Controllers only know about

terminal voltage

ONR_October2013
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 Li-ion batteries are in your laptop and
also in the news

Colorado Fuel Cell Center Earth • Energy • Environment

Photo: Japanese Transportation Safety Board

ONR_October2013
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Initially, internal heat generation is caused by

Faradaic and Ohmic contributions

Colorado Fuel Cell Center Earth • Energy • Environment
Faradaic

• Caused by irreversible polarization at electrode-electrolyte interfaces

• Heat generation rates increase at higher charge-transfer rates

• Typically a smaller heat source than Ohmic heat generation



Ohmic (Joule heating)

•Caused by electrical current within resistive materials (i2R heating)

• Heat generation rates increase greatly at higher charge-transfer rates

• Major contributor to internal battery heating



Objective is to understand heating at the electrode microscale

•Normal operation, leading to long-term performance degradation

• External shorts in abnormal accident environments

• Internals shorts, caused by dendrite growth or internal damage



At sufficiently high temperatures

• Exothermic SEI decomposition and oxidation chemistry

• Electrolyte solvent chemistry

•Combustion

ONR_October2013
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 Faradaic heating is caused by charge-transfer
polarization at electrode-electrolyte interfaces

Colorado Fuel Cell Center Earth • Energy • Environment

ONR_October2013
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Ohmic heat generation rates increase in necking

regions where electrode particles join

Colorado Fuel Cell Center Earth • Energy • Environment

Significant variations in heat generation

• Small physical dimensions

•Relatively large thermal conductivity

• Relative small temperature variations

ONR_October2013
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 The model is used to characterize internal and
external short circuits at the microscale

Colorado Fuel Cell Center Earth • Energy • Environment

External short

• Current through full face

Internal short

Specify a very high C rate
• Current through a small spot

(e.g., 120 C)

ONR_October2013
31

Temperature variations at the microscale are small,

even with very high heat generation rates

Colorado Fuel Cell Center Earth • Energy • Environment

120 C external short

(after 1 s)

Relatively high conductivity effectively spreads heat over small distances

ONR_October2013
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 A small contact internal short can produce
significant local variations, even on the microscale

Colorado Fuel Cell Center Earth • Energy • Environment

120 C internal short

(after 1 s)

Microscale temperature variations remain small,

even with strong local heat generation

ONR_October2013
33

Li-ion 18650 cell are usually fabricated

using a jelly-roll architecture

Colorado Fuel Cell Center Earth • Energy • Environment

Typical 18650 cells
Jelly roll construction

ONR_October2013
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The jelly-roll architecture produces a
heterogeneous thermal medium

Colorado Fuel Cell Center Earth • Energy • Environment

Effective properties can be derived from the reconstructed microstructures

ONR_October2013
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Effective properties can be homogenized from

microscale electrode simulations

Colorado Fuel Cell Center Earth • Energy • Environment

Physical properties

• Density and heat capacity

•Volume-weighted average



Conductivity

• Solve heat-conduction problem

• Evaluate heat fluxes

• Derive effective conductivity



Volumetric heat release rate

• Specify temperature

•Specify discharge rate

•Solve electrochemistry problem

Simulated transport through a
• Evaluate local heat release

reconstructed composite cathode
• Average over microscale sample





The reconstructed electrode samples are small, but representative

•Millions of finite-volume cells

ONR_October2013
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 Average heat-generation rates can be extracted
from the three-dimensional model predictions

Colorado Fuel Cell Center Earth • Energy • Environment

ONR_October2013
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A thermal model can be used to predict temperature

distributions at the cell scale

Colorado Fuel Cell Center Earth • Energy • Environment

Effective properties are derived from the reconstructed microstructures

ONR_October2013
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 Single particles can be extracted from the
reconstructed electrode cube

Colorado Fuel Cell Center Earth • Energy • Environment

ONR_October2013
39

Closely coupled electrochemical, thermal, and

mechanical behaviors can be predicted

Colorado Fuel Cell Center Earth • Energy • Environment

Model electrochemical response (Fluent)

• Electrostatic potential fields

•Li-concentration fields

•Temperature field



Communicate 3D fields to mechanical model

• Different meshing structures



Model mechanical response (ANSYS Mech.)

•Stress and strain fields

•Evaluate Li diffusion coefficients



Communicate fields to electrochemical model



Models quantify important phenomena

•Effects of electrochemistry on structure

Single LiCoO2 cathode • Effects of strain on Li diffusion

particle extracted from a 3D • Mechanical damage, such as crack growth

reconstruction

ONR_October2013
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 Li intercalation and thermal variations affect the
mechanical behavior of the electrode particles

Colorado Fuel Cell Center Earth • Energy • Environment

ONR_October2013
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LixCoO2 experiences volume and phase changes

as functions of temperature and intercalation

Colorado Fuel Cell Center Earth • Energy • Environment

• Influence on mechanical strain is significant

•Crystal anisotropy is significant

ONR_October2013
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 Intercalated Li diffusion rates within the electrode
are affected by the stress field

Colorado Fuel Cell Center Earth • Energy • Environment

ONR_October2013
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The solution algorithm is designed to couple

physical processes in complex 3D microstructures

Colorado Fuel Cell Center Earth • Energy • Environment

ONR_October2013
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The local hydrostatic stress depend significantly
on the discharge rates

Colorado Fuel Cell Center Earth • Energy • Environment

ONR_October2013
45

Intercalation and thermal strain can cause crack

growth and mechanical damage in electrode particles

Colorado Fuel Cell Center Earth • Energy • Environment

ONR_October2013
46
 In-operando observations using X-ray tomography
reveal electrode fracture with repeated cycling

Colorado Fuel Cell Center Earth • Energy • Environment

ONR_October2013
47

The models can consider anisotropies associated

with crystal orientation and current directions

Colorado Fuel Cell Center Earth • Energy • Environment

ONR_October2013
48
Despite significant success, numerous challenges
remain in high-fidelity electrochemical modeling

Colorado Fuel Cell Center Earth • Energy • Environment

Length-scale disparity

• Electrode microstructure is characterized on micron scale



• Devices are characterized on much longer length scales

Evaluate effective transport properties to be used at longer length scales

• Porosity, permeability, tortuosity,… (especially for fluid phases)

• Effective conductivities (especially for solid phases)

• Possibly non-ideal equations of state and thermodynamics

• Mechanical properties (e.g., structural parameters, phase-changes,…)



• Use microstructural models to predict macroscopic properties

Incorporate chemistry and electrochemistry (application dependent)

• Heterogeneous catalysis between fluid and solid phases

• Electrochemical charge transfer between phases

• Elementary reactions and rates are largely unknown

General approaches have broad applicability, beyond fuel cells and batteries

• Catalysis and catalyst supports for chemical processing

• Permselective membranes and membrane reactors

•Electrolysis for fuel synthesis

ONR_October2013
49

Acknowledgements

Colorado Fuel Cell Center Earth • Energy • Environment

Office of Naval Research

• Dr. Michele Anderson

Prof. Scott Barnett

Northwestern University

Dr. Graham Goldin

Ansys, Inc.

Profs. Huayang Zhu, John Berger, …

Veruska Malavé, Andreas Wiedemann, …

ONR_October2013
50