Badger Electrochemists
Giddings Award Symposium
Leslie J. Lyons
Department of Chemistry
Grinnell College
Grinnell, Iowa 50112
Congratulations
Alanah!
Outline
• Badger Electrochemists (1952 - present)
• Analytical Chemistry at Grinnell
– Teaching: Introductory and Advanced
– Research: Silicon Electrolytes for Lithium Battery
Applications
• Acknowledgements
Badger Electrochemistry Home
This photograph, from 1978, shows the Daniels building from the northeast,
on the corner of University Avenue and Mills Street.
Photo courtesy of UW-Madison University Communications.
Shain Chemistry Research Tower
Irving Shain
Photos courtesy of UW-Madison University Communications.
The Shain Tower Dedication
Primitive cyclic voltammetry in 1963.
Students in the laboratory in
1962 (L to R): R.
Nicholson, B. Schwarz, B.
K. Hovsepiar, and D. Polcyn
Photos courtesy of Irving Shain and UW Dept. of Chemistry
NanoBucky
http://hamers.chem.wisc.edu/research/nanofibers/index2.htm
Sarah Baker
Grinnell ‘01
UW ‘06
Teaching Analytical Chemistry
at Grinnell
• CHM 130: Inorganic and Analytical
Chemistry
– Texts: Daniel Harris, Exploring Chemical
Analysis, 3rd Ed. and Luther Erickson,
Water Module Guidebook
• CHM 358: Instrumental Analysis
– Text: Skoog, Holler, Nieman, Principles of
Instrumental Analysis, 5th Ed.
Instrumental Analysis:
Electrochemistry Labs
•
•
•
•
•
•
•
Iodide Ion Selective Electrode
Polarography of Pb
Anodic Stripping Voltammetry
Cyclic Voltammetry
Rotating Ring Disk Voltammetry
Impedance Spectroscopy
Spectroelectrochemistry
CHM 130 Text Topics
•
•
•
•
•
•
•
•
Review of Monoprotic Acid/Base Equilibria
Titrations and Buffers
Polyprotic Acids
Activity
Spectrophotometry and Atomic Spectroscopy
Transition Metal and Coordination Chemistry
Chromatography and Mass Spectrometry
Nuclear Chemistry
Water Module Overview
• 5 weeks of lab; 4 weeks of class
• Question driven discussion of solubility
equilibria, carbonate equilibria, atomic
spectroscopy, and electrochemistry
• Lab analyses of drinking water from around
the country with Grinnell, Chicago, Des
Moines, and bottled water providing
benchmarks
• Lab concludes with student poster
presentations
Water Module: Class Sessions
(Week 1)
• Session 1. Formulating the Questions and
Limiting the Exploration: Focus on Ionic
Composition
• Session 2. Dissolved Ionic Solids: Which ionic
salts are present in typical water samples and how
did they get there?
• Session 3. Major species vs. minor species: Why
are so many different concentration units
employed to describe concentration levels of the
several species present in water samples?
Water Module: Class Sessions
(Week 2)
• Session 4. Carbon dioxide and dissolved
carbonates: Why do virtually all fresh water
samples contain bicarbonate as a principal
species?
• Session 5. Hard water: What is meant by hard
water and why does degree of hardness matter?
• Session 6. Sodium and yellow flames: How can
we determine how much sodium is in the water?
Water Module: Class Sessions
(Week 3)
• Session 7. Galvanic Cells and Ion Concentrations:
How can galvanic cells be used to determine ion
concentrations?
• Session 8. Potentiometric Titrations: How do ion
concentrations change in the course of a titration?
• Session 9. Ion-Selective Electrodes and ppm
Concentrations: How can we determine ion
concentrations at the 1 ppm level?
Water Module: Class Sessions
(Week 4)
• Session 10. Conservation of Mass and
Charge: Does it all add up? (including
poster preparation)
• Session 11. What does it all mean? What
does the complete chemical analysis reveal
about the source and treatment of our water
samples?
• Session 12. Exam
Water Module: Laboratory
• L1. pH and Alkalinity by Potentiometric Titration with
HCl
• L2. Water Hardness (Total and Ca) by EDTA Titration
• L3. Chloride by Potentiometric Titration with Silver
Nitrate
• L4. Sodium Determination by Atomic Emission
Measurements
• L5. Nitrate by Potentiometry with Ion Selective Electrode
• L6. Fluoride by Potentiometry with Ion Selective
Electrode
• L7. Total Dissolved Solids by Electrical Conductivity
Water Module Student Data
Location
London
Chicago
Memphis
St. Paul
Chicago
Grinnell
Des Moines
Dasa ni
-
[F ] (ppm)
0.950
6.08
9.31
1.03
6.65
10.8
7.03
0.190
3-
-
+
2+
[NO ] (ppm) [Cl ] (ppm) [Na ] (ppm) [Ca ] (ppm) [Hardness] (ppm)
3.88
36.1
15.4
227
228
0.238
14.6
2.92
83.1
123
0.140
5.50
7.27
18.2
33.3
0.450
31.1
6.12
49
70.8
0.448
0.448
6.29
0.196
15.6
28.4
53.3
4.27
2.35
255
49.4
0.0971
81.2
42.2
78.6
2.58
186
96.7
182
21.1
-
HCO 3 (ppm) TDS (ppm) Calc. TDS
179
635
463
104
318
251
38.5
109
94
46.3
266
156
99.1
240
61.9
7.44
315
1420
517
55.3
Gillis, Goodwin-Kucinsky, Patnaik, Peters, and Yohannes
310
631
360
33.3
Silicon Electrolytes for Lithium
Battery Applications
Grinnell College
Si
Si
OSiRC
Si
Si
Lithium Battery Group
Argonne National Laboratory
Quallion, LLC
Sylmar, CA
In the News
• R&D 100 Award, September, 2005
• Scientists craft lithium batteries
• by John Potratz
• Badger Herald Wednesday, October 5, 2005
• New battery stimulates damaged nerves
• By ASTARA MARCH
• Science Daily, Oct. 3, 2005
Linear Polysiloxane Ionic Conductivities
-3.00
2 oxygens
3 oxygens
4 oxygens
5 oxygens
6 oxygens
7 oxygens
8 oxygens
-3.25
-3.50
O
O
m
-3.75
Si O
n
O
log 
-4.00
O
-4.25
-4.50
-4.75
LiTFSI
-5.00
-5.25
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
Doping Level (Li / EO )
Macromolecules, 2001, 34, 931-934.
m
Cross-linked Polysiloxane Gel Electrolytes
CH3
[
Si
CH3
O
]n [
Si
O ]m
H
O
THF
O
+
(
THF solution
(
+
O ) 13
F O Li +O F
_
F C S N S C F
F O
O)
3 CH3
vacuum
12h
O F
LiTFSI
high Vacuum line
-5
10 torr,48h
heating
o
80 C,12h
SPE
Macromolecules, 2003, 36, 9176.
Liquid Siloxane Electrolytes
undoped
4.3a
-75.00
4.2a
T g (јC)
-85.00
3.3a
-95.00
O:Li = 32:1
3.4a
-105.00
-115.00
O:Li = 10:1
0.00
0.02
0.04
0.06
Li:EO
0.08
0.10
Chem. Mater., 2006, 18, 1289.
Atlanta ACS Meeting
VT Conductivities of
1NMx/LiTFSI
-2.4
1NM3
1NM4
1NM6
1NM7.2
-2.6
15:1
10:1
15:1
10:1
log ()
-2.8
-3.0
-3.2
-3.4
-3.6
-3.8
2.9
3.0
3.1
3.2
3.3
1000/T (1/K)
3.4
3.5
3.6
3.7
a
b
a
c
b
d&m
a
c
e
b
d & mf
c
e
d & mf
e
f
NMR Studies of Electrolytes
h
h
h O
g
O
c
d
ef
O
ef
1NM3
O
a
b
0.18
a
b
c
d&m
e
f
0.16
0.14
0.12
0.10
 (ppm)
Si
0.08
0.06
0.04
0.02
0.00
-0.02
0.00
0.02
0.04
0.06
0.08
0.10
+
Li /Eo
0.12
0.14
0.16
0.18
0.20
0.22
Acknowledgements: Grinnell College
Marie Mapes
Douglas Schumacher
Felipe Bautista
Jay Jin
David Clipson
Kate Morcom
Yanika Schneider
Jacob Barrera
Lori Cooke
Scott Harring
Megan Straughan
James Taggart
T. Andrew Mobley
NSF-REU, NSF-MRI (2), HHMI, Grinnell College
3M
Luther E. Erickson, “The Water Module Guidebook”
Acknowledgements:
Organosilicon Research Center
Robert West
David Moline
Richard Hooper
Qinzheng Wang
David Sherlock
Ryan West
Zhengcheng Zhang
Nicholas A. A. Rossi
Lingzhi Zhang
Si
Si
OSiRC
Si
UW University-Industry Relations Grant
NIST-ATP
Si