Workshop on a “Drug Discovery”

Approach to Breakthroughs in Batteries

Introduction
Nick Delgass
School of Chemical Engineering
Purdue University
(Core expertise – heterogeneous catalysis)

1
 The Problem with Discovery
• NOT business as usual
• Descriptor (search) space is huge – 106 – 1018
e.g. elements of the periodic table 4 at a time

You are here

• NOT only traditional scientific method

• Breakthrough means NOT an extrapolation
from where you are. Need new approach.
2
 Navigating Descriptor Space

• Designed broad search – statistical analysis

Fast, helps identify descriptors
• Model-based search – incorporate knowledge,
including fundamental
• “Only” need better, not best, performance
• Intelligent search is an absolute necessity
• Need a lot of data (information)

3
 Navigating Descriptor Space
• Experimental Data (parallel) - synthesis,
performance, and materials characterization
Primary (high throughput, 1or 2 parameters)
Secondary(lower data rate, more parameters)
Tertiary (lowest data rate, real conditions)
• Theory –
Guide or drive models, calculate descriptors,
cover space not accessible to experiments
• Informatics – Handling and using data
Searching, sharing, and archiving
Tools for knowledge extraction, model building
• TEAMS – Success requires all of the above 4
 Example
Search for a new catalyst

W. Pryz, R. Vijay, J. Binz, Jochen

Lauterbach, and D.J. Buttrey,
“Characterization of K-Promoted Ru
Catalysts for Ammonia Decomposition
Discovered Using High-Throughput
Experimentation”, Topics in Catalysis, 2008,
online

5
High-Throughput - Reactor

Reactant
Side view of Reactor
16-way Flow split
16 sample capacity

Individual temperature
monitoring
Capillaries

16 stainless steel reactor

tubes
Effluent

RJ Hendershot, et al, Applied Catalysis A (2003) 6

 Truly Parallel Screening
1 .2

1 .0
0 .6
Effluent In Effluent Out

Absorbance
0 .4
128
pixels 0 .2

0 .0
4000 3500 3000 2500 2000 1500
30 cm
W a v e n u m b e rs (c m )
-1

MCT FTIR
FPA Spectrometer

C.M. Snively, G. Oskarsdottir, and J. Lauterbach, Angewandte Chemie, 40(2001)

Snively, C.M. and J. Lauterbach Applied Spectroscopy 59 (2005)
R. Hendershot, P. Fanson, C.M. Snively, and J. Lauterbach, Angewandte Chemie, 42(10); (2003). 7
 The Next Step: Promotion of Ru/γ-Al2O3
Catalysts
100 ■ Model Development Points

90

Model Predicted % NH3 Conversion

80

70

60

50

40

30

20

10
Term Coefficients
Constant 35.7 0
Ba -1.8 0 10 20 30 40 50 60 70 80 90 100

K 22.3 Experimental % NH3 Conversion

Cs -2.6
Ba*Ba -0.5
K*K 5.6
Cs*Cs -3.0 R = C +α1(Ba) +α2 (K) +α3 (Cs)......+ β1(Ba)2 + β2 (K)2......+ λ1(Ba* K) + λ2 (Ba*Cs).....
Ba*K -0.9
Ba*Cs -1.0
K*Cs -4.7
8
 Promotion of Ru Catalyst

4 Ru/12 K
100
4 Ru/12 Rb
4 Ru/12 Na
4 Ru/12 Cs
80
4 Ru/12 Ba
4 Ru
% NH3 Conversion

60

40

20

200 250 300 350 400 450 500

T[°C]

9
K-Promotion: Effect on Morphology
4Ru / γ-Al2O3 4Ru-12K / γ-Al2O3

1 μm 1 μm

80

KRu4O8
% NH3 Conversion

60

40
T=
350oC 20

0
4Ru
4Ru/12K

W. Pyrz, R. Vijay, J. Binz, J. Lauterbach, and D. Buttrey, Topics in Catalysis 10

 Our Research Philosophy - HT Catalytic
Science
R. J. Hendershot, Modeling + UHV + Spectroscopy + Synthesis
C.M. Snively,
and J. Lauterbach,
Chemistry –
A European Journal,
11; 806-814, 2005

Catalyst Characterization Design of Experiment

♠ − ΒaCO3
• − Co3O4
♦ − Al2O3
♠ ♦
• •
♠ ♦
•
♠ ♦
5Co/15Ba
♠

♠
♠♦ ♦
Intensity [a.u.]

♠
♠
♠
♦ ♦
1Pt/15Ba
♦
•
♦
•
•
• ♦
♦
5Co
γ-Al2O3
20 25 30 35 40 45 50 55 60 65 70 75 80 85 90
2θ [°]

Reactor
0.6

N 2O
0.4
↑

A NO 2
0.2
NO CO

0.0
75 2200
50 2000
←
t/s 25 1800
ν~/cm
-1 →
0 1600
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 1- Hexene Polymerization by Titanium
Catalysts
with Phenoxy based ligands
A large number of available substituted phenols allow
tunability of steric and electronic variation of the catalyst.
Steric
O

O Ph Ph
L1 P
O
O
Ph Ph
Ph Ph

+ Me Me
M C.I.
Ph

O O

L2
H2C n-Bu O O O

Electronic
O
O Ph Ph
Ph Ph
O O O O O Ph Ph
Br

M = Ti, Zr, Hf O
Br

C.I. = [MeB(C6F5)3]- I
O O O O O
O

Ph Ph

[B(C6F5)4]- Br Br Br Br Br
O
CH3

Ph Ph

H3C CH3 - Cl

{ }
L1 = O

- -
O
F F

H3C CH3
F

F
L2 ligand

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 Structure-Activity Correlation in Single-Site,
Aryl-Oxide, Olefin Polymerization Catalysts

Universal
correlation

Family-dependent correlation of
propagation rate versus EIPS

DFT-Based Structure Model: The solid-angle available for

monomer approach (4πγ) to Ti-center is related to the OAr- and
Cp’-ligand exclusion cone-angles (θ) and a steric factor (f) “f”
related to the counter-anion exclusion.

θOAr
The propagation rate constant correlates with ion-pair
separation energy (EIPS ) in a univeral manner: θCp’
Cp’

T.A. Manz, K. Phomphrai, G. Medvedev, B.B. Krishnamurthy, S. Sharma,

Sharma, J. Haq, K.A.
Novstrup, K.T. Thomson, W.N. Delgass, J.M. Caruthers, M.M Abu-
Abu-Omar, J. Am. Chem. Soc.
2007, 129, 3776. 13
 Computer-aided Product
Formulation/Design
(Discovery Informatics)
Forward Problem
Prediction

P1, P2, P3, ...Pn

Product Descriptors Product Performance

Design
Inverse Problem

• Forward Problem: Prediction

– Estimate Product Performance from Descriptors
– Quantitative forward model
• Inverse Problem: Design
– Determine a set of products that satisfy desired
performance criteria
– Guided stochastic search (e.g. genetic algorithm)
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 Search for New Surfactant Molecules
Forward model: First-Principles Model of Additive
Degradation + neural net model of engine performance
Breakage of this bond
removes “dirt” carrying Breaking of these bonds control “length”
capacity totally

Component “length” directly

indicative of stability of additive

Chemical nature of this component

(polar/non-polar) controls “dirt” removing
capacity

The first-principle model tracks the structural distribution of fuel-additive with time due to reactive
degradation

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 Results of GA Inverse Search
Predicted IVD
Run Rank/Identifier Fitness Structural Description
(PLS-NN Model)

1, I-1 0.997 11.4 mg Novel Structure. Infrequently used linker.

Objective: Novel Structure. Same tails as best

2, I-2 0.996 11.5 mg
structure, different heads and linkers
Determine a I

structure with IVD < Variant of structure found in the BMW

6, I-6 0.993 12.0 mg database. Same head and linkers, different
10 mg
tails

Novel Structure. Different from I-1 .

1, II-1 0.999 10.1 mg
Infrequently used linker component.
Population Size: 25;
Generations: 25 Slight variant of additive structure found
II 12.6 mg in BMW and HONDA databases.
2, II-2 0.989
Different tails but same head and linker

Minor variation of structure II-2 above.

4, II-4 0.983 13.2 mg
Slight modification of the head

1, III-1 1.00 8.9 mg Novel Structure. Different from

I-1 and II-1 . Commonly used components
Variant of III-1 . One linker and tail
III 2, III-2 0.994 11.9 mg
modified.

Variant of structure II-2 above. Slight

3, III-3 0.993 12.1 mg modification of head. A linker and tail
inserted.
19thNAM May 26, 2005
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Norskov d-band Center Descriptor (DFT)

E. Christoffersen, P. Liu, A. Ruban, H.L. Skiver, and J. K. Norskov, “Amode Materials for Low-Temperature Fuel
Cells: A Density Functional Theory Study”. J. Catal., 199, 123-131 (2001).
17
Correlation of ΔHads with d-Band Center

E. Christoffersen, P. Liu, A. Ruban, H.L. Skiver, and J. K. Norskov, “Amode Materials for Low-Temperature Fuel Cells: A Density
Functional Theory Study”. J. Catal., 199, 123-131 (2001).
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Drug Discovery Approach to Breakthroughs in
Batteries
Informatics in Drug Discovery Ernst R. Dow, Eli Lilly

Electrochemical energy storage and extended-range electric

vehicles Mark Verbrugge, GM

Data handling and informatics tools for model-based discovery

James Caruthers, Purdue

New High Energy/Power Devices Ralph J. Brodd, Broddarp

High-throughput ab-initio computing and data mining

methods for the prediction of crystal structure Gerbrand Ceder,
MIT

Materials Informatics: An “omics” approach to materials

based design for battery technology Krishna Rajan, Iowa State
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 Discussion at dinner tonight
Breakout Groups (Tuesday)
• Two discussion sessions
• One writing session

Objective
• Report:
Define and justify opportunities for significant
advancement in battery technology.
Suggest guidelines for program structure
• Website: Maintain as a resource for the
community. Start by uploading slides of talks
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Computed surface segregation energies

E. Christoffersen, P. Liu, A. Ruban, H.L. Skiver, and J. K. Norskov, “Amode Materials for Low-Temperature Fuel Cells: A
Density Functional Theory Study”. J. Catal., 199, 123-131 (2001).
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