Buddie Mullins Chemical Engineering

& Chemistry

UT-Austin

mullins@che.utexas.edu

http://research.engr.utexas.edu/mullins//

Adam Heller Chemical Engineering

UT-Austin

heller@che.utexas.edu http://www.che.utexas.edu/faculty-staff/faculty-

directory/heller/

Participating PhD & PostDoctoral Students

Paul

Abel

Li- and Na-Ion Battery Research (as of July 16, 2014)

Emily

Powell

Kyle

Klavetter

Sean

Wood

Hoang

Dang

Konda

Shiva

Our research activities are generously supported by the Welch Foundation.

Undergraduate Battery Researchers

Sindhu

Nathan

Codey

Pham

Han

Tu

Meredith

Fields

Pedro

De Souza

Li- and Na-Ion Battery Research Goals

The training of graduate students for productive

research careers in industry, national laboratories,

or academia.

Studies of the safe operation and design of

batteries and their components.

The discovery, synthesis and

characterization of novel materials as well

as the engineering of materials

morphologies and electrode architectures

for use in high performance batteries.

SEM Image of Li dendrite growing out of anode.

Dendrite formation in batteries is a safety issue.

Image from: J. Cryst. Growth, 34, 239-244 (1976).

Image of Sn-Cu nanoparticle with relative

abundance of each element. Image from:

ACS Appl. Mater. Interfaces 5, 8273-8277 (2013).

http://dx.doi.org/10.1021/am4023994

How does a Li-ion Battery Operate? Below are schematics to accompany this brief explanation regarding the operating principles of a

common commercial lithium ion battery: In the left schematic below the battery is discharging and

lithium ions move from their higher energy (charged) state in the graphite anode to a lower energy

state in the LiCoO2 cathode through the ion conducting (but not electron conducting) electrolyte.

Electrons must travel through a percolating network of conductive additive (carbon) particles to the

metal foil in order to exit the battery and perform work … the electrons meet back up with the lithium

ion in the cathode. The reverse occurs in charging the battery, but energy must be supplied to move

the lithium (and electrons) uphill in energy from the cathode to the anode.

Anode Active

Material (graphite)

Cathode Active

Material (LiCoO2)

Cu Al

Li+

Li+

Li+

Electrolyte

e-

e- e- e- e-

e-

e- e-

Conductive

Additive

Polymer

Binder

Cu Al

Li+

Li+

Li+

Electrolyte

e-

e- e- e- e-

e-

e- e-

Anode Active

Material (graphite)

Cathode Active

Material (LiCoO2)

Conductive

Additive

Polymer

Binder

Discharging Recharging

Battery Electrodes Are Complex! This makes their improvement challenging! What are the issues?

• Increasing the material capacity is desirable but the active material

frequently expands, crumbles and there is a loss of electrical

connectivity

• There are reactions between the electrolyte and solids causing a loss

of lithium

• Would like to maximize the voltage of the battery and this strains the

electrolyte

• We desire high discharge and recharge rates and this can damage the

battery materials

• Safety is critical and high energy density batteries are intrinsically

hazardous

• We want high cycling stability (recharge/discharge cycles) and

coulombic efficiency (i.e., little loss of lithium to side reactions)

Battery Research Activities

Synthesis of candidate battery electrodes and

electrochemical testing including different

architectures and electrolytes

◦ Synthesis of slurry-cast electrodes (like the

industrial method of fabrication)

◦ Electrode construction by evaporative deposition

(for more scientifically related studies)

Electrodes by Wet Synthesis and Slurry-Casting

Silicon Nanoparticles in Carboxymethyl-

Cellulose Binder w/Carbon Nanoparticles Yong-Mao Lin, etal., “High performance silicon nanoparticle

anode in fluoroethylene carbonate-based electrolyte

for Li-ion batteries,” Chem. Commun. 48, 7268-7270 (2012). http://dx.doi.org/10.1039/C2CC31712E

Cu Al Li+

Li+

Li+

Cathode Active Material

Electrolyte

e-

e- e- e- e-

e-

e- e-

Anode Active Material

Slurry-Cast Cathode and Anode

Electrodes are slurry-cast using active material (e.g., iron

oxide nanorods), mixed with polymer binder, and carbon

nanoparticles to provide a percolating, electron conducting

network. The electrodes are then electrochemically tested

for performance and durability.

Schematic of Li-Ion Battery Discharging

Iron Oxide Nanorods Grown Hydrothermally Yong-Mao Lin, et al., “α-Fe2O3 nanorods as

anode material for lithium ion batteries,”

J. Phys. Chem. Lett. 2, 2885-2891 (2011). http://dx.doi.org/10.1021/jz201363j

Thin Film Electrodes by Glancing Angle

Deposition

Different compositions of alloys can

be synthesized by co-evaporation

and controlling the relative

deposition rates of the two

evaporation sources (e.g., SiGe - Paul R. Abel, et

al., "Nanostructured Si(1-x)Gex for tunable thin film lithium-ion

battery anodes," ACS Nano 7, 2249-2257 (2013).

http://dx.doi.org/10.1021/nn3053632.)

Controlled composition and morphology of candidate anode

materials for Li-ion batteries under ultra high vacuum.

Morphology and surface area of a

deposited film can also be fine-tuned

by controlling the deposition angle,

substrate temperature, and reactive

gas atmosphere.

Yong-Mao Lin, et al., “Morphology

Dependence of the Lithium Storage

Capability and Rate Performance of

Amorphous TiO2 Electrodes,” J. Phys.

Chem. C 115, 2585-2591 (2011). http://dx.doi.org/10.1021/jp110474y

200 nm

SEM of 1:3 Si:Ge Film

Glancing Angle Deposition

SEM of TiO2 Film

We frequently test candidate electrode materials in coin cells like those depicted on the left. The

internal structure of a coin cell is shown in schematic form on the right.

Top case

Electrode to be

tested

Lithium metal

Bottom case

Polypropylene

separator/electrolyte

Wave spring

Spacer

Assembly of a Coin Cell

Prof. Gyeong S. Hwang http://www.che.utexas.edu/gshwang/

Chia-Yun Chou

Prof. John B. Goodenough http://www.me.utexas.edu/directory/faculty/goodenough/john/32/

Dr. Asha Gupta

Collaborators

MULLINS & HELLER GROUP BATTERY-RELATED

PUBLICATIONS (2011 – June 2014)

Kyle C. Klavetter, Jonathan L. Snider, J. Pedro de Souza, Han Tu, Trevor H. Cell, Joon Hee Cho, Christopher J. Ellison, Adam

Heller, and C. Buddie Mullins, "A free-standing thin, flexible lithium-ion anode formed from an air-dried slurry cast of high tap

density SnO2, CMC polymer binder and Super-P Li," J. Mater. Chem. A. submitted.

Paul R. Abel, Meredith G. Fields, Adam Heller, and C. Buddie Mullins, "Tin-Germanium alloys as anode materials for sodium-

ion batteries," ACS Appl. Mater. Interfaces submitted.

Kyle C. Klavetter, Stephany Garcia, Naween Dahal, Jonathan L. Snider, J. Pedro de Souza, Trevor H. Cell, Mark A. Cassara, Adam

Heller, Simon M. Humphrey, and C. Buddie Mullins, "Li- and Na-reduction products of meso-Co3O4 form high-rate, stably

cycling battery anode materials," J. Mater. Chem. A. submitted.

Paul R. Abel, Kyle C. Klavetter, Adam Heller, and C. Buddie Mullins, "Thin nanocolumnar Ge0.9Se0.1 films are rapidly

lithiated/de-lithiated," J. Phys. Chem. C submitted.

Sean M. Wood, Kyle C. Klavetter, Adam Heller, and C. Buddie Mullins, "Fast lithium transport in PbTe for lithium-ion battery

anodes," J. Mater. Chem. A. 2, 7238-7243 (2014). http://dx.doi.org/10.1039/C4TA01167H

Hoang X. Dang, Yong-Mao Lin, Kyle C. Klavetter, Trevor Cell, Adam Heller, and C. Buddie Mullins, "Lithium insertion/de-

insertion characteristics of nanostructured amorphous tantalum oxide thin films," ChemElectroChem. 1, 158-164

(2014). http://dx.doi.org/10.1002/celc.201300139

Paul R. Abel, Yong-Mao Lin, Tania de Souza, Asha Gupta, John B. Goodenough, Adam Heller, and C. Buddie Mullins,

“Nanocolumnar Germanium Thin Films as a Sodium-Ion Battery Anode Material,” J. Phys. Chem. C 117, 18885-18890 (2013). http://dx.doi.org/10.1021/jp407322k

Asha Gupta, C. Buddie Mullins, and John B. Goodenough, “Na2Ni2TeO6: Evaluation as a cathode for sodium battery,” J. Power

Sources 243, 817-821 (2013). http://dx.doi.org/10.1016/j.jpowsour.2013.06.073

Yong-Mao Lin, Paul R. Abel, Asha Gupta, John B. Goodenough, Adam Heller, and C. Buddie Mullins, “Sn-Cu alloy anodes for

rechargeable sodium ion batteries,” ACS Appl. Mater. Interfaces. 5, 8273-8277 (2013). http://dx.doi.org/10.1021/am4023994

Kyle C. Klavetter, Sean M. Wood, Yong-Mao Lin, Jon L. Snider, Nicholas C. Davy, Aaron M. Chockla, Dwight K. Romanovicz,

Brian A. Korgel, Joo-Woon Lee, Adam Heller, and C. Buddie Mullins, "A high-rate gemanium-particle slurry cast Li-ion anode

with high Coulombic efficiency and long cycle life," J. Power Sources 238, 123-136 (2013). http://dx.doi.org/10.1016/j.jpowsour.2013.02.091

BATTERY-RELATED PUB’s (2011 – June 2014 cont.)

Paul R. Abel, Aaron M. Chockla, Yong-Mao Lin, Vincent C. Holmberg, Justin T. Harris, Brian A. Korgel, Adam Heller, and C.

Buddie Mullins, "Nanostructured Si(1-x)Gex for tunable thin film lithium-ion battery anodes," ACS Nano 7, 2249-2257 (2013). http://dx.doi.org/10.1021/nn3053632

Yong-Mao Lin, Kyle C. Klavetter, Adam Heller, and C. Buddie Mullins, “Storage of lithium in hydrothermally synthesized GeO2

nanoparticles,” J. Phys. Chem. Lett. 4, 999-1004 (2013). http://dx.doi.org/10.1021/jz4003058

Yong-Mao Lin, Kyle C. Klavetter, Paul R. Abel, Nicholas C. Davy, Jonathan L. Snider, Adam Heller, and C. Buddie Mullins,

“High performance silicon nanoparticle anode in fluoroethylene carbonate-based electrolyte for Li-ion batteries,” Chem.

Commun. 48, 7268-7270 (2012). http://dx.doi.org/10.1039/C2CC31712E

Yong-Mao Lin, Rajaram K. Nagarale, Kyle C. Klavetter, Adam Heller, and C. Buddie Mullins, “SnO2 and TiO2-supported-SnO2

lithium battery anodes with improved electrochemical performance,” J. Mater. Chem. 22, 11134-11139 (2012). http://dx.doi.org/10.1039/c2jm16328d

Paul R. Abel, Yong-Mao Lin, Hugo Celio, Adam Heller, and C. Buddie Mullins, “Improving the stability of nanostructured silicon

thin film lithium ion battery anodes through their controlled oxidation,” ACS Nano 6, 2506-2516 (2012). http://dx.doi.org/10.1021/nn204896n

David W. Flaherty, Nathan T. Hahn, R. Alan May, Sean P. Berglund, Yong-Mao Lin, Keith J. Stevenson, Zdenek Dohnalek, Bruce D.

Kay, and C. Buddie Mullins, “Reactive Ballistic Deposition of Nanostructured Model Materials for Electrochemical Energy

Conversion and Storage,” Acc. Chem. Res. 45, 434-443 (2012). http://dx.doi.org/10.1021/ar200164u

Jing Wu, Nellymar Membreno, Wen-Yueh Yu, Jaclyn D. Wiggins-Camacho, David W. Flaherty, C. Buddie Mullins, and Keith J.

Stevenson, "Influence of hydrofluoric acid formation on lithium ion insertion in nanostructured V2O5," J. Phys. Chem. C 116,

21208-21215 (2012). http://dx.doi.org/10.1021/jp305937b

Aaron M. Chockla, Kyle C. Klavetter, C. Buddie Mullins, and Brian A. Korgel, "Tin-seeded silicon nanowires for high-capacity

lithium-ion batteries," Chem. Mater. 24, 3738-3745 (2012). http://dx.doi.org/10.1021/cm301968b

Aaron M. Chockla, Timothy D. Bogart, Colin M. Hessel, Kyle C. Klavetter, C. Buddie Mullins, and Brian A. Korgel, "Influences of

gold, binder and electrolyte on silicon nanowire performance in Li-ion batteries," J. Phys. Chem. C 116, 18079-18086 (2012). http://dx.doi.org/10.1021/jp305371v

Aaron M. Chockla, Kyle C. Klavetter, C. Buddie Mullins, and Brian A. Korgel, "Solution grown germanium nanowire anodes for

lithium-ion batteries," ACS Appl. Mater. Interfaces 4, 4658-4664 (2012). http://dx.doi.org/10.1021/am3010253

Asha Gupta, C. Buddie Mullins, and John B. Goodenough, "Electrochemical probings of Li1+xVS2," Electrochim. Acta 78, 430-433

(2012). http://dx.doi.org/10.1016/j.electacta.2012.06.020

BATTERY-RELATED PUB’s (2011 – June 2014 cont.)

Aaron M. Chockla, Matthew G. Panthani, Vincent C. Holmberg, Colin M. Hessel, Dariya K. Reid, Timothy D. Bogart, Justin T.

Harris, C. Buddie Mullins, and Brian A. Korgel, “Electrochemical lithiation of graphene-supported silicon and germanium for

rechargeable batteries,” J. Phys. Chem. C 116, 11917-11923 (2012). http://dx.doi.org/10.1021/jp302344b

Asha Gupta, Ramaswamy Murugan, M. Parans Paranthaman, Zhonghe Bi, Craig A. Bridges, Masahiro Nakanishi, Alexei P.

Sokolov, Kee Sung Han, Ed Hagaman, Hui Xie, C. Buddie Mullins, and John B. Goodenough, “Optimum lithium-ion conductivity

in cubic Li7-xLa3Hf2-xTaxO12,” J. Power Sources 209, 184-188 (2012). http://dx.doi.org/10.1016/j.jpowsour.2012.02.099

Aaron M. Chockla, Justin T. Harris, Vahid A. Akhavan, Timothy D. Bogart, Vincent C. Holmberg, Chet Steinhagen, C. Buddie

Mullins, Keith J. Stevenson, Brian A. Korgel, "Silicon Nanowire Fabric as a Lithium Ion Battery Electrode Material," J. Am. Chem.

Soc. 133, 20914-20921(2011). http://dx.doi.org/10.1021/ja208232h

Yong-Mao Lin, Paul R. Abel, Adam Heller, and C. Buddie Mullins, “α-Fe2O3 nanorods as anode material for lithium ion

batteries,” J. Phys. Chem. Lett. 2, 2885-2891 (2011). http://dx.doi.org/10.1021/jz201363j

Yong-Mao Lin, Paul R. Abel, David W. Flaherty, J. Wu, Keith J. Stevenson, Adam Heller, and C. Buddie Mullins, “Morphology

Dependence of the Lithium Storage Capability and Rate Performance of Amorphous TiO2 Electrodes,” J. Phys. Chem. C 115,

2585-2591 (2011). http://dx.doi.org/10.1021/jp110474y

Battery Lab Alumni

Yong-Mao Lin

Ph.D. Aug. 2013

Intel Corp.

Former Graduate Students and Post-Docs

Undergraduate Researchers

Trevor Cell

now at Univ. of Washington

Mark Cassara Katy Coggins

now at UT Southwestern

Medical School

Battery Lab Alumni (Cont.)

Undergraduate Researchers

Nick Davy

now at Princeton Univ.

Jon Snider

now at Stanford Univ. Tania de Souza

Sean Wood reading a paper.

Paul working on an

electron beam evaporator.

Yong-Mao with a secondary

glancing angle deposition tool.

Mullins & Heller Battery Lab Photo-Gallery

Nick Davy (now in grad. school at

Princeton) at glove box using

coin cell fabrication tools.

Paul using our primary glancing

angle deposition tool.

Jon Snider (now in grad. school

at Stanford) with ball miller

and vacuum oven.

Yong-Mao with automatic

thin film coater.

Archive Battery Lab Photo-Gallery

Katy Coggins making XPS measurements.

Archive Battery Lab Photo-Gallery

Kyle Klavetter working in the glove box.

Paul Abel and Yong-Mao Lin working

on glancing angle deposition.

Mullins Research Group Photo – April 2014