Badger ElectrochemistsGiddings Award Symposium

Leslie J. Lyons

Department of Chemistry

Grinnell College

Grinnell, Iowa 50112

CongratulationsAlanah!

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.

Irving ShainPhotos courtesy of UW-Madison University Communications.

Shain Chemistry Research Tower

The Shain Tower Dedication

Primitive cyclic voltammetry in 1963.

Photos courtesy of Irving Shain and UW Dept. of Chemistry

Students in the laboratory in 1962 (L to R): R. Nicholson, B. Schwarz, B. K. Hovsepiar, and D. Polcyn

NanoBucky

http://hamers.chem.wisc.edu/research/nanofibers/index2.htmSarah BakerGrinnell ‘01UW ‘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 [F-] (ppm) [NO3-] (ppm) [Cl-] (ppm) [Na+] (ppm) [Ca2+] (ppm) [Hardness] (ppm) HCO3- (ppm) TDS (ppm) Calc. TDS

London 0.950 3.88 36.1 15.4 227 228 179 635 463 Chicago 6.08 0.238 14.6 2.92 83.1 123 104 318 251 Memphis 9.31 0.140 5.50 7.27 18.2 33.3 38.5 109 94 St. Paul 1.03 0.450 31.1 6.12 49 70.8 46.3 266 156 Chicago 6.65 0.448 15.6 2.35 81.2 186 99.1 315 310 Grinnell 10.8 0.448 28.4 255 42.2 96.7 240 1420 631 Des Moines 7.03 6.29 53.3 49.4 78.6 182 61.9 517 360

Dasani 0.190 0.196 4.27 0.0971 2.58 21.1 7.44 55.3 33.3

Gillis, Goodwin-Kucinsky, Patnaik, Peters, and Yohannes

Silicon Electrolytes for Lithium Battery Applications

Si Si

SiSi

OSiRC

Grinnell College

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

Doping Level (Li / EO )

0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14

log

σ

-5.25

-5.00

-4.75

-4.50

-4.25

-4.00

-3.75

-3.50

-3.25

-3.00

2 oxygens 3 oxygens 4 oxygens5 oxygens 6 oxygens 7 oxygens 8 oxygens

Si O

OO

OO

m

m

n

Macromolecules, 2001, 34, 931-934.

LiTFSI

Cross-linked Polysiloxane Gel Electrolytes

Si

CH3

H

O[ ] n

O OCH3

()3

Si

CH3

O[ ]m ( )OO 13+ CF S

O

O

N S

O

O

C F

F

F F

FLi +_

+

THF solution

LiTFSI

vacuum

12h

high Vacuum line

10-5 torr,48h

heating80oC,12h

SPETHF

10

30

50

70

90

1000150020002500300035004000

Wavenumber, cm -1-4.40

-4.20

-4.00

-3.80

-3.60

-3.40

-3.20

-3.00

4 14 24 34 44 54 64 EO / Li+

25 oC37 oC50 oC70 oC

Macromolecules, 2003, 36, 9176.

σ

Liquid Siloxane Electrolytes

- 1 1 5 . 0 0

- 1 0 5 . 0 0

- 9 5 . 0 0

- 8 5 . 0 0

- 7 5 . 0 0

0 . 0 0 0 . 0 2 0 . 0 4 0 . 0 6 0 . 0 8 0 . 1 0

L i : E O

T

g

(ºC)

4 . 3 a

3 . 3 a

3 . 4 a

4 . 2 a

O : L i = 3 2 : 1

O : L i = 1 0 : 1

u n d o p e d

O : L i = 3 2 : 1

O : L i = 1 0 : 1

O : L i = 3 2 : 1

O : L i = 1 0 : 1

u n d o p e d

Chem. Mater., 2006, 18, 1289.

Atlanta ACS Meeting

1000/T (1/K)

2.9 3.0 3.1 3.2 3.3 3.4 3.5 3.6 3.7

log (

σ)

-3.8

-3.6

-3.4

-3.2

-3.0

-2.8

-2.6

-2.4

1NM3 15:11NM4 10:11NM6 15:11NM7.2 10:1

VT Conductivities of 1NMx/LiTFSI

NMR Studies of Electrolytes

OO

OO

Si

h

h

g

ch

ef

ef d

ba

Li+/Eo

0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14 0.16 0.18 0.20 0.22

Δ δ ( ) ppm

-0.02

0.00

0.02

0.04

0.06

0.08

0.10

0.12

0.14

0.16

0.18

abcd & mef

abcd & mef

abcd & mef

abc

d & mef

1NM3

Acknowledgements: Grinnell College

Marie Mapes Douglas SchumacherFelipe Bautista Jay JinDavid Clipson Kate MorcomYanika Schneider Jacob BarreraLori Cooke Scott HarringMegan Straughan James TaggartT. Andrew MobleyNSF-REU, NSF-MRI (2), HHMI, Grinnell College3M

Luther E. Erickson, “The Water Module Guidebook”

Acknowledgements: Organosilicon Research Center

Robert West David Moline Richard HooperQinzheng WangDavid SherlockRyan West Zhengcheng ZhangNicholas A. A. RossiLingzhi Zhang

UW University-Industry Relations GrantNIST-ATP

Si Si

SiSi

OSiRC