Multi-scale Transport , Dynamics, and Morphology in …...Random copolymer membranes μm-scale...
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15 20 25 30 3 6 9 12 15 18 E a (kJ/mol) λ Dispersed Phase-separated 30 25 20 15 3 6 12 15 18 9 15 20 25 30 35 40 0.0 5.0 10.0 15.0 20.0 25.0 E a (kJ/mol) λ LiOTf solution Li-form Nafion Liquid water 0 5 10 15 20 25 35 30 25 20 15 40 1.200 1.400 1.600 1.800 2.000 0 20 40 60 80 0 20 40 60 80 1.2 1.4 1.6 1.8 2.0 E a (kJ/mol) Nanotube diameter (nm) Confined water Liquid water 80 60 40 20 0 1.2 1.6 1.8 2.0 1.4 ~1 nm ~10 nm ~1 mm Drew Korovich, Curt Zanelotti, Rui Zhang, Deyang Yu, Shravan Uppala, Nick Pietra, Syeda Anam Bukhari, Alexis McCarthy We measure and build ion conducting and nanostructured materials, specifically involving multi - scale structure and morphology. Impacts: Clean energy, water, and nanomedicine applications including batteries, fuel cells, and drug delivery . Determining fundamental mechanisms of ion and water transport. Who are we? Physical, analytical, and polymer chemists, materials scientists. Introduction Multi - scale Transport , Dynamics, and Morphology in Materials Multi - Modal NMR Group & Funding Sources Molecular Ionic Composites (MICs) Molecular Transport In Polymer Membranes Combining a Kevlar-like polymer with ionic liquids to enable safer and higher density batteries Problem: Commercial organic electrolytes safety concerns including flammability, leaking, volatility limited battery energy density Solution: Composite electrolyte of PBDT and ionic liquid features : • High ionic conductivity (~1 mS*cm -1 ) • Tunable modulus (0.03 – 3 GPa) • Thermally stable (up to 300°C) • Electrochemical window to 6 V • Long cycling Li-metal batteries Macromolecules (2017 x2, 2018, 3 in prep) Block Copolymer Micelles Nanoconfined Transport Polycaprolactone (PCL): Polyethylene oxide (PEO) Solute (salt, organic molecules, etc.) Water Reverse osmosis membrane Macromolecules (2019) Macromolecules (2018) J Membrane Sci (2013) Nature Materials (2011) Macromolecules (2011) Macromolecules (2010) Macromolecules (2009) + 2 in prep ~ 20 nm ~ 2 nm ~ 100 nm Random copolymer membranes μm-scale heterogeneity observed! Change in diffusion behavior on different length scales Hydration modulated tortuosity! ℑ − = ∞ ℑ − = 0 ∞ + + Kevlar-like polymer forms double helix! MICs held together by collective electrostatic interactions! XRD of PBDT aqueous solution • Diffusion coefficients measured from NMR probes structure/environment on micrometer lengthscale • Activation energy probes local molecular interactions and structure Chem. Comm. (2013), +2 in prep In review Macromolecules (2020) Macromolecules (2015), JPCB (2014) Arrhenius Equation = 0 ൗ − Lithium form Nafion Lithium triflate solutions NMR diffusometry Molecular dynamics simulations Water confined in carbon nanotube • Similar molecular/ionic environment • Physically confined environment vs. bulk NMR spectroscopy: Molecular structure, internal dynamics, associations, alignment Å to nm, ps to days NMR diffusometry : Species - specific and phase - specific transport, confined motion 10s of nm to 10s of m m, ms to s MicroMRI : Spatial resolution of molecular structure, dynamics, transport ≥ 10 m m (devices, tissue…), t - resolved C H H Mechanisms of ion and water transport D water (10 -10 m 2 /s) Able to load MICs with Li + , Na + , Mg 2+ , etc. Thin flexible films Nature Comm (2019) Advanced Materials (2016) Langmuir (2017) ACS Appl. Mater. Interfaces (2019) Macromolecules (2020) Lithium-metal battery Li:MIC:LiFePO 4 J Membrane Sci (2015) Macromolecules (2014) +5 in prep Dispersed Phase-separated Nanoconfinement leads to higher energy barrier Phase separation lead to lower energy barrier 1 10 100 1000 10000 30:70 35:65 40:60 30:70 35:65 40:60 Tortuosity − − HEA:EA HEMA:MMA Polyelectrolyte Molecular Weight Determination Lou Madsen Group Collaboration with Prof. Ralph Colby at Penn State Collaboration with Prof. Diego Troya at VT DMR CHE CBET Collaboration with Prof. Megan Robertson at U. Houston Collaborations with Dingemans (UNC), Colby (PSU), Forsyth (Deakin – Australia), Qiao, Moore, and Lin (VT) Collaborations with Hickner (PSU), Geise (UVA), Moore (VT)…
Transcript of Multi-scale Transport , Dynamics, and Morphology in …...Random copolymer membranes μm-scale...
15
20
25
30
3 6 9 12 15 18
Ea
(kJ/m
ol)
λ
Dispersed
Phase-separated
30
25
20
153 6 12 15 189
15
20
25
30
35
40
0.0 5.0 10.0 15.0 20.0 25.0
Ea
(kJ/m
ol)
λ
LiOTf solution
Li-form Nafion
Liquid water
0 5 10 15 20 25
35
30
25
20
15
40
1.200 1.400 1.600 1.800 2.000
0
20
40
60
80
0
20
40
60
80
1.2 1.4 1.6 1.8 2.0
Ea
(kJ
/mo
l)
Nanotube diameter (nm)
Confined water
Liquid water
80
60
40
20
01.2 1.6 1.8 2.01.4
~1 nm
~10 nm
~1 mm
Drew Korovich, Curt Zanelotti, Rui Zhang, Deyang Yu, Shravan Uppala, Nick Pietra, Syeda Anam Bukhari, Alexis McCarthy
We measure and build ion conducting and nanostructured
materials, specifically involving multi-scale structure and
morphology.
Impacts: Clean energy, water, and nanomedicine applications
including batteries, fuel cells, and drug delivery. Determining
fundamental mechanisms of ion and water transport.
Who are we? Physical, analytical, and polymer chemists,
materials scientists.
Introduction
Multi-scale Transport , Dynamics, and Morphology in Materials
Multi-Modal NMR
Group & Funding Sources
Molecular Ionic Composites (MICs)Molecular Transport
In Polymer MembranesCombining a Kevlar-like polymer
with ionic liquids to enable safer
and higher density batteries
Problem:
Commercial organic electrolytes
safety concerns including
flammability, leaking, volatility
limited battery energy density
Solution:Composite electrolyte of PBDT and
ionic liquid features:
• High ionic conductivity (~1 mS*cm-1)
• Tunable modulus (0.03 – 3 GPa)
• Thermally stable (up to 300°C)
• Electrochemical window to 6 V
• Long cycling Li-metal batteries
Macromolecules (2017 x2, 2018, 3 in prep)
Block Copolymer
Micelles
Nanoconfined Transport
Polycaprolactone
(PCL):
Polyethylene oxide
(PEO)
Solute (salt, organic
molecules, etc.)Water
Reverse
osmosis
membrane
Macromolecules (2019)
Macromolecules (2018)
J Membrane Sci (2013)
Nature Materials (2011)
Macromolecules (2011)
Macromolecules (2010)
Macromolecules (2009)
+ 2 in prep
~ 20 nm ~ 2 nm~ 100 nm
Random copolymer membranes μm-scale heterogeneity observed! Change in diffusion behavior on different length scales
Hydration modulated tortuosity!
ℑ𝐿−𝐵 =𝐷𝑙𝑜𝑐𝐷∞
ℑ𝜇−𝐵 =𝐷0𝐷∞
+
+
Kevlar-like polymer forms double helix!
MICs held together by
collective electrostatic
interactions!XRD of PBDT
aqueous solution
• Diffusion coefficients measured from
NMR probes structure/environment
on micrometer lengthscale
• Activation energy probes local
molecular interactions and structure
Chem. Comm. (2013), +2 in prep
In review Macromolecules (2020)
Macromolecules (2015), JPCB (2014)
Arrhenius Equation
𝐷 = 𝐷0𝑒ൗ−𝐸𝑎𝑅𝑇
Lithium form Nafion
Lithium triflate
solutions
NMR diffusometry
Molecular dynamics simulations
Water confined in carbon nanotube
• Similar molecular/ionic environment
• Physically confined environment vs.
bulk
NMR spectroscopy: Molecular structure,
internal dynamics, associations, alignment
Å to nm, ps to days
NMR diffusometry: Species-specific and
phase-specific transport, confined motion
10s of nm to 10s of mm, ms to s
MicroMRI: Spatial resolution of molecular
structure, dynamics, transport
≥ 10 mm (devices, tissue…), t-resolved
C
H
H
Mechanisms of ion and water transport
Dw
ater
(10
-10
m2/s
)
Able to load MICs with Li+, Na+, Mg2+, etc.
Thin flexible films
Nature Comm (2019)
Advanced Materials
(2016)
Langmuir (2017)
ACS Appl. Mater.
Interfaces (2019)
Macromolecules (2020)Lithium-metal battery Li:MIC:LiFePO4
J Membrane Sci (2015)
Macromolecules (2014)
+5 in prep
Dispersed Phase-separated
Nanoconfinement leads to
higher energy barrier
Phase separation lead to
lower energy barrier
1
10
100
1000
10000
30:70 35:65 40:60 30:70 35:65 40:60
Tort
uosity
𝕴𝒍𝒐𝒄𝒂𝒍−𝒃𝒖𝒍𝒌 𝕴𝒎𝒊𝒄𝒓𝒐𝒏−𝒃𝒖𝒍𝒌
HEA:EA HEMA:MMA
Polyelectrolyte Molecular
Weight Determination
Lou Madsen Group
Collaboration with Prof.
Ralph Colby at Penn State
Collaboration with Prof. Diego Troya at VT
DMR
CHE
CBET
Collaboration
with Prof. Megan
Robertson at
U. Houston
Collaborations with Dingemans
(UNC), Colby (PSU), Forsyth (Deakin –
Australia), Qiao, Moore, and Lin (VT)
Collaborations with
Hickner (PSU), Geise
(UVA), Moore (VT)…
