li- and na-ion battery research...li- and na-ion battery research goals the training of graduate...
TRANSCRIPT
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Buddie Mullins Chemical Engineering
& Chemistry
UT-Austin
http://research.engr.utexas.edu/mullins//
Adam Heller Chemical Engineering
UT-Austin
[email protected] 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.
mailto:[email protected]://research.engr.utexas.edu/mullins//mailto:[email protected]://www.che.utexas.edu/faculty-staff/faculty-directory/heller/http://www.che.utexas.edu/faculty-staff/faculty-directory/heller/http://www.che.utexas.edu/faculty-staff/faculty-directory/heller/http://www.che.utexas.edu/faculty-staff/faculty-directory/heller/http://www.che.utexas.edu/faculty-staff/faculty-directory/heller/http://www.welch1.org/
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Undergraduate Battery Researchers
Sindhu
Nathan
Codey
Pham
Han
Tu
Meredith
Fields
Pedro
De Souza
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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
http://www.google.com/url?sa=i&rct=j&q=&esrc=s&frm=1&source=images&cd=&cad=rja&uact=8&docid=8BUU4yFvpQ9hlM&tbnid=VEpAUj0NCG0geM:&ved=0CAUQjRw&url=http%3A%2F%2Fareweanycloser.wordpress.com%2F2013%2F06%2F21%2Fdendritic-lithium-and-battery-fires%2F&ei=G32fU5jCEYaLqAb1uoHoBg&bvm=bv.68911936,d.b2k&psig=AFQjCNF7HM1PNBS0x53dXa7NyecUW5qyGw&ust=1403047418620300http://dx.doi.org/10.1021/am4023994
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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
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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)
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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)
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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
http://dx.doi.org/10.1039/C2CC31712Ehttp://dx.doi.org/10.1021/jz201363j
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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
http://dx.doi.org/10.1021/nn3053632http://dx.doi.org/10.1021/nn3053632http://dx.doi.org/10.1021/nn3053632http://dx.doi.org/10.1021/nn3053632http://dx.doi.org/10.1021/nn3053632http://dx.doi.org/10.1021/nn3053632http://dx.doi.org/10.1021/nn3053632http://dx.doi.org/10.1021/nn3053632http://dx.doi.org/10.1021/nn3053632http://dx.doi.org/10.1021/nn3053632http://dx.doi.org/10.1021/nn3053632http://dx.doi.org/10.1021/nn3053632http://dx.doi.org/10.1021/jp110474yhttp://dx.doi.org/10.1021/jp110474yhttp://dx.doi.org/10.1021/jp110474yhttp://dx.doi.org/10.1021/jp110474yhttp://dx.doi.org/10.1021/jp110474yhttp://dx.doi.org/10.1021/jp110474yhttp://dx.doi.org/10.1021/jp110474yhttp://dx.doi.org/10.1021/jp110474yhttp://dx.doi.org/10.1021/jp110474yhttp://dx.doi.org/10.1021/jp110474yhttp://dx.doi.org/10.1021/jp110474yhttp://dx.doi.org/10.1021/jp110474yhttp://dx.doi.org/10.1021/jp110474y
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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
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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
http://www.che.utexas.edu/gshwang/http://www.che.utexas.edu/gshwang/http://www.me.utexas.edu/directory/faculty/goodenough/john/32/http://www.me.utexas.edu/directory/faculty/goodenough/john/32/
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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
http://dx.doi.org/10.1039/C4TA01167Hhttp://dx.doi.org/10.1002/celc.201300139http://dx.doi.org/10.1021/jp407322khttp://dx.doi.org/10.1016/j.jpowsour.2013.06.073http://dx.doi.org/10.1021/am4023994http://dx.doi.org/10.1016/j.jpowsour.2013.02.091
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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
http://dx.doi.org/10.1021/nn3053632http://dx.doi.org/10.1021/jz4003058http://dx.doi.org/10.1039/C2CC31712Ehttp://dx.doi.org/10.1039/c2jm16328dhttp://dx.doi.org/10.1021/nn204896nhttp://dx.doi.org/10.1021/ar200164uhttp://dx.doi.org/10.1021/jp305937bhttp://dx.doi.org/10.1021/cm301968bhttp://dx.doi.org/10.1021/jp305371vhttp://dx.doi.org/10.1021/am3010253http://dx.doi.org/10.1016/j.electacta.2012.06.020
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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
http://dx.doi.org/10.1021/jp302344bhttp://dx.doi.org/10.1016/j.jpowsour.2012.02.099http://dx.doi.org/10.1021/ja208232hhttp://dx.doi.org/10.1021/jz201363jhttp://dx.doi.org/10.1021/jp110474y
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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
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Battery Lab Alumni (Cont.)
Undergraduate Researchers
Nick Davy
now at Princeton Univ.
Jon Snider
now at Stanford Univ. Tania de Souza
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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
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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
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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.
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Mullins Research Group Photo – April 2014