2018 Science Undergraduate Laboratory Internship(SULI) project. Involved the design, synthesis and evaluation of less flammable electrolytes.

1. Argonne National Laboratory is a U.S. Department of Energy
laboratory managed by UChicago Argonne, LLC.
1. Dziniel, T.; Pupek, K.; Krumdick, G. Continuous Flow Processes: an Advanced Manufacturing Platform for Electrolyte Materials, 2017.
2. Finegan, D. P. et al. In-operando high-speed tomography of lithium-ion batteries during thermal runaway. Nat. Commun. 6:6924 doi: 10.1038/ncomms7924 (2015).
3. J. Feng, L. LuA novel bifunctional additive for safer lithium ion batteries. J. Power Sources, 243 (2013), p. 29
OPTIMIZATION OF ELECTROLYTE SYNTHESIS
FOR SAFER LITHIUM ION BATTERIES
Davis L. Martinec, Trevor L. Dzwiniel and Krzysztof Z. Pupek, Energy Systems Division of Argonne National Laboratory
Abstract: A novel synthetic procedure have been developed for safer, less hazardous lithium ion battery electrolytes. The synthetic procedure has been optimized for future scale out in continuous flow chemistry and eventual industry applications. Commercially available and non
hazardous reagents were utilized when possible so to make production environmentally friendly and cost effective for large scale production.
Complete optimization of reaction time
Minimize formation of side products and impurities
Test optimized parameters in continuous flow process
IMPACT
METHODS
MOTIVATION
 Lithium ion batteries (LIBs) have been used with great success in small electronic
devices, and now, because of that success, the focus has been to find new
applications of LIB beyond small electronic devices. LIBs have, in recent years,
have been investigated for their application in electric vehicles and large-scale
renewable energy storage.3
 Extensive use and scale-up of LIBs has brought some hazards to light; LIBs are
prone to fires and explosions.
 New battery electrolytes need to be synthesized that are 1) are safe i.e.
nonflammable or explosive and 2) do not compromise the performance of the
battery.
Figure 1. From left to right: Structure of dimethyl carbonate, ethyl methyl carbonate and diethyl carbonate.
All of which are commonly used as electrolytes in LIBs.
Flash point: 17°C
Figure 2. A thermal image
from Finegan et al. of a
LIB showing thermal
runaway1, which is caused
by an overheated battery
and eventually leads to
fires and explosions. The
bright red/orange areas
indicate high
temperatures; the two
areas of high temperature
at the top of the battery
are open flames.
RESULTS
MOVING FORWARD
This work is supported by the U.S. Department
of Energy and Argonne National Laboratory.
Thank you to Trevor L. Dzwiniel, Krzysztof Z.
Pupek and Erik Dahl for their support during
this project, thanks to Michael Murphy for his
help with coin cell photos, a sincere thank you
to Abbey Lewis, for her help on this project by
providing insight and guidance and thank you
to the Science Undergraduate Laboratory
Internship for providing the opportunity to work
and learn at Argonne National Laboratory.
ACKNOWLEDGEMENTS
 Critical material: ethyl((trimethylsilyl)methyl)carbonate
 (ETMSMC)
 Factors impacting synthetic efficiency were optimized
individually
 Catalyst, temperature, time, solvent and reagent
quantities
 Reaction monitoring and product evaluation accomplished via
gas chromatography-mass spectrometry(GC-MS)
Image reproduced from Finegan et al under a creative commons license.
Figure 3. The general reaction scheme of ETMSMC, a promising new
electrolyte material for LIBs. ETMSMC has shown flame retardant properties
without negative effects on performance.
Flash point: 25°CFlash point: 24°C
 Optimized factors include:
 Catalyst- Tetrabuylammonium bromide (TBAB)
 Solvent- Heptane
 Additional findings indicate possible optimums:
 Ethylchloroformate (ClCO2Et) 2.25 eq.
 Sodium Hydroxide(NaOH) at 50% concentration
Flash point: 57.5°C
ETMSMC
0
10
20
30
40
50
60
70
0.0 5.0 10.0 15.0 20.0 25.0
RelativePercentProduct
Time(hrs)
Acetonitrile
MTBE
THF
Heptane
Figure 4. A plot of relative percent product formation over
time for the top five performing catalysts. The inset graph
shows all screened catalysts.
Figure 5. A plot of relative percent product formation
over time for all screened solvents. TBAB was the
catalyst used in each trial.
0
10
20
30
40
50
60
0.45 0.65 0.85 1.05 1.25 1.45 1.65 1.85 2.05
RelativePercentProduct
Time(hrs)
TetraButyl Cl
Bu4N OH
TetraOctyl
Aliquat 336
TetraButyl Br
ClCO2EtTMS
TBAB
Figure 8. Recent results indicate the reaction is nearly
complete after 15 minutes. The graphs shows the
relative percent product vs. starting material and
impurities over the first 15 minutes of the reaction.
4
5
6
7
8
0 2 4 6 8 10 12 14 16
RelativePercentArea
Time(min) Reactant Product Total Impurities
80
83
86
89
92
Figure 9. A cartoon
diagram showing a
continuous flow reactor.
Product is continuously
produced in this
technique.
Figure 8. Right: A coin
cell being tested at
Argonne’s Cell Analysis,
Modeling and Prototyping
(CAMP).
Left: The individual
components of a
prototype coin cell, which
in the future could utilize
an ETMSMC electrolyte.
10
20
30
40
50
60
70
80
90
0.45 1.45 2.45 3.45 4.45
RelativePercentProduct
Time (hrs)
3.00 Eq. NaOH
4.00 Eq. NaOH
5.00 Eq. NaOH
6.00 Eq. NaOH
Control40
45
50
55
60
65
70
75
0.95 1.45 1.95 2.45 2.95 3.45 3.95 4.45
RelativePercentProduct
Time (hrs)
2.00 vs. 2.50
2.00 vs. 2.25
2.25 vs. 2.50
2.25 vs. 2.25
Control 1
Figure 7. A plot of relative percent product formation over
time for the screening of equivalents of 50% NaOH, in
heptane with TBAB and 2.25 eq. of ClCO2Et.
Figure 6. A plot of relative percent product formation over
time while screening equivalents of ClCO2Et and 25%
NaOH, in heptane with TBAB. The plot shows equivalents
of ClCO2Et vs equivalents of 25% NaOH.
REFERENCES