Development of Solid-State Electrolyte for
Safe and Ultra-High Capacity Batteries for
NASA’s Future Missions
Xiao-Dong Zhou
Yudong Wang
Department of Chemical Engineering
Institute for Materials Research and Innovation
University of Louisiana at Lafayette
Lafayette, LA 70592
Email: [email protected]
LaSPACE Fall 2021 Council MeetingAnnual Meeting of the NASA Space Grant and ASA EPSCoR Programs in Louisiana on October 29, 2021
Greg Guzik (PI), LSU
Outline
2. What are the current research projects at IMRI at UL Lafayette?Energy; manufacturing; space; and environmental biology
1. What are the capabilities at UL Lafayette and who we areInstitute for Materials Research and Innovation
3. NASA EPSCoR project overviewScope of work; team members, partnership, and milestones
4. Current resultsThe origin towards a stable battery
http://lgefund.net/investments/
5. Conclusions and summaries
3 3
Institute for Materials Research and
Innovation (IMRI) at UL Lafayette➢ 10% of US oil reserves in Louisiana
➢ #2 oil-producing state in United States
➢ Natural Gas: larger deposits than oil
➢ 25% of the nation’s supply of natural gas
Microscopy Center
Durability & Manufacturing
Battery and Fuel Cell Testing Lab
Cell Fabrication Lab (SOCs and Batteries)
Two tape casters, plastic extruder, custom-built hydraulic pump (415 MPa); isostatic laminator; two hot press machines; laser cutter (Speedy 360); two glove boxes; three Lindberg/Blue M furnaces (1500oC).
Dr. Gordon XiaResearch ProfessorDr. Gordon Xia
Research Professor
Dr. Yanhua SunPostdoc
Team Members – Solid Oxide Cells (SOCs)
Alex TuckerUnder/graduate Student
Josh WilsonGraduate Student
Christabel TettahGraduate Student
Dr. Yanhua SunResearch Asst. Prof.
Austin SchillingUndergrad Student
Tam TranGraduate Student
April BourletUndergrad Student
Eleanor Stelz-Sullivan Undergrad Student
Noah Richard Undergrad Student
Jacob C Hoffpauir Undergrad Student
Yudong WangGraduate Student
Yudong WangGraduate Student
Barbara MarchettiResearch Assistant Professor
Computational and spectroscopic chemistry
Jonathan RaushAssistant Professor
Alloys and manufacturing
Xingwen YuResearch Associate Professor
Solid state chemistry, batteries, and PEMFC
Sushant SahuInstructor in Chemistry
Carbon chemistry and catalysis
Team Members – IMRI Staff
Rapid Growth in All
Solid-State Batteries
Co
llab
ora
tive
Pro
ject
s, P
ub
lica
tion
s, a
nd
Pro
posa
lsTask 1: Theory •Computation of dendrite growth rates
•Solid-state mechanic model in composite electrolytes
•Atomistic modeling of dendrite-induced failure in
solid-state batteries
Task 2: Component Materials
• Inorganic/polymer composite electrolyte
•Uniform plating in a pouch cell
•NMR analysis of electrodes and electrolytes
Experimental feedbacks to theory
(electrical and mechanical properties)
Theoretical guidelines
for materials design
Task 3: Battery Cells
•All-solid-state batteries with a composite
electrolyte, novel NMC and Li-metal electrodes
•Battery testing under radiation and at low T
•Protected Li-electrode in an all-solid-state battery
Feedbacks from battery test and post
analysis (cyclability, rate-capacity and
electrochemical properties)
Materials and interfaces
with desirable properties for
assembling battery cells
Research Roadmap for the Project
Greg GuzikProfessor of Physics
Principal Investigator
Team Members and Task Leaders
Partners and Their Roles in Each Task
Co
llab
ora
tive
Pro
ject
s, P
ub
lica
tion
s, a
nd
Pro
posa
ls
Support
On the thermodynamic origin for
the formation of Li-dendrites
Institute for Materials Research and InnovationDepartment of Chemical EngineeringUniversity of Louisiana at Lafayette
Yudong Wang Anil VirkarXiao-Dong Zhou
LaSPACE Fall 2021 Council MeetingAnnual Meeting of the NASA Space Grant and ASA EPSCoR Programs in Louisiana on October 29, 2021
13
Laptops HoverboardsE-cigarettes
Cell Phones EVs Battery Factory
Lithium battery can catch fire in many applications; but what’s the real reason?
Photo Source: https://www.rochesterfirst.com/weather/weather-blog/winter-wonders-how-icicles-get-their-unique-shape/https://www.eeweb.com/lithium-battery-performance-degradation/https://blog.rentacomputer.com/2018/07/02/dont-fly-with-your-laptops/https://www.reviewed.com/laptops/features/its-time-to-stop-freaking-out-over-every-battery-that-catches-firehttps://www.thedrive.com/news/28420/parked-teslas-keep-catching-on-fire-randomly-and-theres-no-recall-in-sighthttps://www.cnet.com/news/tesla-battery-fire-renewable-energy-plant-australia/
14
What is the thermodynamic driving force for dendrite formation?
Gibbs free energy ∆𝐺 =𝐺𝑓 − 𝐺𝑖𝑝, 𝑇 = 𝐶𝑜𝑛𝑠𝑡.
• ∆𝐺 < 0 : process is spontaneous
• ∆𝐺 > 0 : reverse process is spontaneous
• ∆𝐺 = 0 : equilibrium
∆𝐺 = 𝑁(𝜇𝐻2𝑂 𝑠 − 𝜇𝐻2𝑂 𝑙 )
𝐻2𝑂 𝑙 ↔ 𝐻2𝑂 𝑠
T > 0oC
T < 0oC
𝜇𝐻2𝑂 𝑠 − 𝜇𝐻2𝑂 𝑙 > 0
𝜇𝑗 is the chemical potential of j
• Function of T• Function of partial pressure in
the gas/gas mixture. Ideal gas:
𝜇𝑗 = 𝜇𝑗0 + 𝑅𝑇𝑙𝑛(
𝑝𝑗
𝑝0)
• Function of its concentration, 𝑐𝑗, in the ideal solution
𝜇𝑗 = 𝜇𝑗0 + 𝑅𝑇𝑙𝑛(
𝑐𝑗
𝑐0)
𝜇𝐻2𝑂 𝑠 − 𝜇𝐻2𝑂 𝑙 < 0
Ice or snow melts into water
Water freezes into icicle.
𝐿𝑖 ? ↔ 𝐿𝑖 𝑠
∆𝐺 = 𝑁(𝜇𝐿𝑖 𝑠 − 𝜇𝐿𝑖 ? )
𝜇𝐿𝑖 𝑠 − 𝜇𝐿𝑖 ? < 0
Dendrite forms
Q: What is the form of Li in the solution?How to calculate 𝜇𝐿𝑖 ?
Wang, Virkar, and Zhou, J. Electrochem. Soc., 168, 100503, 2021
How does a Li-Battery work?
Anode CathodeElectrolyte
Loading
Li+ e-
Discharging: 𝜇𝐿𝑖𝑎𝑛𝑜𝑑𝑒 > 𝜇𝐿𝑖
𝑐𝑎𝑡ℎ𝑜𝑑𝑒
Lithium ion (through the electrolyte) and electrons (mainly via external circuit) moves from anode to cathode
How does a Li-Battery work?
Anode CathodeElectrolyte
Power supply
Li+ e-
Charging: External power supply driven
Lithium ions (through the electrolyte) and electrons (mainly via external circuit) moves from cathode to anode
Discharging: 𝜇𝐿𝑖𝑎𝑛𝑜𝑑𝑒 > 𝜇𝐿𝑖
𝑐𝑎𝑡ℎ𝑜𝑑𝑒
Lithium ions (through the electrolyte) and electrons (mainly via external circuit) moves from anode to cathode
Solid electrolyte interphase (SEI):A layer between anode and electrolyte formed by reaction between lithium and electrolyte. Lower ionic conductivity than electrolyte.
Part of lithium ions don’t go further inside and form metal deposit near the SEI. Dendrite initiates.
Wang, Virkar, and Zhou, J. Electrochem. Soc., 168, 100503, 2021
How to use thermodynamics to understand the dendrite formation?
• Two independent charge carriers: 𝐿𝑖+ and 𝑒−
• Corresponding current density:
𝑰𝒊 = −𝜎𝑖
𝐹𝛁𝜇𝐿𝑖+ and 𝑰𝒆 = −
𝜎𝑒
𝐹𝛁𝜇𝑒−
• Governing equations at steady state:Charge balance: 𝛁 ∙ (𝑰𝒊 + 𝑰𝒆) = 0
Lithium balance: 𝛁 ∙𝑰𝒊
𝑭= 0
Electrochemical potential:𝜇𝑀𝑚+ = 𝜇𝑀𝑚+ +mFAbstract, cannot be measured directly, etc..
• Local chemical equilibrium assumption 𝜇𝐿𝑖 Ԧ𝑟 = 𝜇𝐿𝑖+ Ԧ𝑟 + 𝑚𝜇𝑒− Ԧ𝑟
Li Ԧ𝑟 ⇌ Li+ Ԧ𝑟 + 𝑒− Ԧ𝑟
𝜇𝐿𝑖+, 𝜇𝑒− are converted into 𝜇𝐿𝑖, 𝜑.
• Electrical potential is defined:
𝜑 = −𝜇𝑒−
𝐹• Cell voltage = 𝜑𝑐 − 𝜑𝑎 keeps constant in
the simulation
Electrolyte
Anode (a)
𝜇𝐿𝑖𝑎
𝜑𝑎
𝜑
Iee-
Ii𝐿𝑖+
za
𝜇𝐿𝑖
z0
na
SEI Wang, Virkar, and Zhou, J. Electrochem. Soc., 168, 100503, 2021
Dendrite is not always formed!What are the conditions for the dendrite formation?
𝐿𝑖(𝑒𝑙) ⇌ 𝐿𝑖(𝑠)
∆𝐺 = 𝜇𝐿𝑖𝑆 − 𝜇𝐿𝑖
𝑒𝑙 +𝑊
𝑊 is the additional work need to form a lithium metal phase in the electrolyte (or SEI layer), e.g. surficial tension, normal stress..
𝑊 ≈ 0 in the liquid electrolyte
𝜇𝐿𝑖𝑆 = 0 by definition
∆𝐺 < 0 only if 𝜇𝐿𝑖𝑒𝑙 > 0
The formation of lithium metal is thermodynamically preferred
• High SEI ionic conductivity
To suppress the lithium deposition in near the SEI
• Low SEI electronic conductivity
Conditions when dendrite is formed
(1) Increase 𝜎𝑖𝑆𝐸𝐼 by 10 times Almost no impact
(2) Increase 𝜎𝑒𝑆𝐸𝐼 from 10-6 to 0.01 and 0.1 S/m
0.000 0.005 0.0100
10
20
30
40
50
Vo
lum
e o
f lit
hiu
m p
recip
ita
te (
10
-24 m
3)
Time (s)
sSEIe
10-6 S m-1
10-2 S m-1
10-1 S m-1
Growth of Dendrite, with nonuniform SEI
• The thickness of SEI may not be uniform – the kinetics of SEI formation is slower than lithium deposition.
• The tip of the lithium deposit has a thinner SEI layer thickness than other regions
• The difference in 𝜎i bents the flux curve • Growing rate is proportional to the lithium flux
perpendicular to electrode surface
𝑞 = −𝑉𝐿𝑖
𝐹𝑰𝒊 ∙ 𝒏𝒑 Wang, Virkar, and Zhou, J. Electrochem.
Soc., 168, 100503, 2021
Growth of Dendrite, conductivity effect
-0.4 -0.2 0.0 0.2 0.40.0
0.2
0.4
0.6
0.8
sSEI
e=10
4s
el
e
z/−m
x/−
m
0.019 m, 0 s
0.1 m, 0.344 s
0.15 m, 0.592 s
0.2 m, 0.821 s
0.25 m, 1.035 s
0.3 m, 1.239 s
0.4 m, 1.629 s
0.5 m, 1.995 s
0.6 m, 2.342 s
sSEI
i=0.1s
el
i
-0.4 -0.2 0.0 0.2 0.40.0
0.2
0.4
0.6
0.8
sSEI
e=s
el
e
z/−m
x/−
m
0.019 m, 0 s
0.1 m, 0.344 s
0.15 m, 0.592 s
0.2 m, 0.821 s
0.25 m, 1.035 s
0.3 m, 1.239 s
0.4 m, 1.629 s
0.5 m, 1.995 s
0.6 m, 2.342 s
sSEI
i=0.1s
el
i
• 𝜎𝑒𝑆𝐸𝐼 does not
affect the deposition on the lithium electrode
-0.4 -0.2 0.0 0.2 0.40.0
0.2
0.4
0.6
0.8
sSEIe =sel
e
z/1
0-6
m
x/10-6m
0.019 m, 0 s
0.1 m, 0.344 s
0.15 m, 0.592 s
0.2 m, 0.821 s
0.25 m, 1.035 s
0.3 m, 1.239 s
0.4 m, 1.629 s
0.5 m, 1.995 s
0.6 m, 2.342 s
sSEIi =0.1sel
i
-0.4 -0.2 0.0 0.2 0.40.0
0.2
0.4
0.6
0.8
sSEIe =sel
e
z/1
0-6
m
x/10-6m
0.019 m, 0 s
0.1 m, 0.512 s
0.15 m, 0.829 s
0.2 m, 1.142 s
0.25 m, 1.451 s
0.3 m, 1.757 s
0.4 m, 2.362 s
0.5 m, 2.953 s
0.6 m, 3.530 s
sSEIi =0.01sel
i
-0.4 -0.2 0.0 0.2 0.40.0
0.2
0.4
0.6
0.8
sSEIe =sel
e
z/1
0-6
m
x/10-6m
0.019 m, 0 s
0.1 m, 0.832 s
0.15 m, 1.353 s
0.2 m, 1.874 s
0.25 m, 2.395 s
0.3 m, 2.916 s
0.4 m, 3.958 s
0.5 m, 4.998 s
0.6 m, 6.037 s
sSEIi =0.001sel
i
• Keeps spherical shape
• Growing rate is faster with larger 𝜎𝑖𝑆𝐸𝐼
0 1 2 3 4 5 6
0
10
20
30
40
50
Volu
me o
f lit
hiu
m d
endri
te (
10
-20 m
3)
Time (s)
sSEI
i/s
el
i
0.1
0.01
0.001
Uniform SEI layer
-0.6 -0.4 -0.2 0.0 0.2 0.4 0.60.0
0.2
0.4
0.6
0.8
1.0
z/(
10
-6 m
)
x/(10-6 m)
0.0198 m, 0 s
0.1 m, 0.2263 s
0.3 m, 0.6883 s
0.6 m, 1.3929 s
1 m, 2.2953 s
sSEI
e=s
el
e
sSEI
i=10s
el
i
-0.4 -0.2 0.0 0.2 0.40.0
0.2
0.4
0.6
0.8
1.0
sSEI
e=s
el
e
z/(
10
-6 m
)
x/(10-6 m)
0.0198 m, 0 s
0.1 m, 0.0091 s
0.3 m, 0.0355 s
0.6 m, 0.0772 s
1 m, 0.1348 s
sSEI
i=0.01s
el
i
-0.4 -0.2 0.0 0.2 0.40.0
0.2
0.4
0.6
0.8
1.0
z/(
10
-6 m
)
x/(10-6 m)
0.0198 m, 0 s
0.1 m, 0.0349 s
0.3 m, 0.1248 s
0.6 m, 0.2804 s
1 m, 0.4796 s
sSEI
e=s
el
e
sSEI
i=0.1s
el
i
Nonuniform SEI layer• The metallic lithium is
sharper with SEI of lower ionic conductivity, thickness effect is more significant.
Wang, Virkar, and Zhou, J. Electrochem. Soc., 168, 100503, 2021
Aspect Ratio, Sharpness of the Dendrite
h
w
• 𝐴𝑠𝑝𝑒𝑐𝑡 𝑅𝑎𝑡𝑖𝑜 =ℎ
𝑤
• Half sphere ℎ
𝑤= 0.5
• Sphere ℎ
𝑤= 1
0.0 0.1 0.2 0.3 0.4 0.5 0.6
0.5
0.6
0.7
0.8
0.9
1.0
Aspect R
atio
Dendrite Height (m)
sSEIi /sel
i
0.1
0.01
0.001
Uniform SEI
0.0 0.2 0.4 0.6 0.8 1.00
2
4
6
8
10
12
14
Asp
ect
Ra
tio
Dendrite Height (m)
sSEI
i/s
el
i
10
0.1
0.01
0.001
Nonuniform SEI
• 𝐴𝑠𝑝𝑒𝑐𝑡 𝑅𝑎𝑡𝑖𝑜 <1 • 𝐴𝑠𝑝𝑒𝑐𝑡 𝑅𝑎𝑡𝑖𝑜 grows slowly • Stay a spherical shape
• 𝐴𝑠𝑝𝑒𝑐𝑡 𝑅𝑎𝑡𝑖𝑜 can reach 12 • 𝐴𝑠𝑝𝑒𝑐𝑡 𝑅𝑎𝑡𝑖𝑜 increases fast at
initial stage, the one with
higher 𝜎𝑖SEI is smaller.
• Sharper cylindrical shape is formed - dendrite
Wang, Virkar, and Zhou, J. Electrochem. Soc., 168, 100503, 2021
23
Summaries
1. By applying local thermodynamic and chemical equilibrium and considering the electronic current, two measurable parameters, 𝜇𝐿𝑖 and 𝜑, are used to study the deposition kinetics of neutral species at quasi-steady state.
2. The high 𝜎𝑖𝑆𝐸𝐼 reduces the 𝜇𝐿𝑖 in the SEI layer and suppresses lithium precipitate formation. In addition, a
higher 𝜎𝑖𝑆𝐸𝐼 allows more homogeneous ion flux on the lithium metal surface and prevents lithium dendrite
formation. The high 𝜎𝑖𝑆𝐸𝐼 also leads to faster electrode kinetics, reduced charging time, and less energy loss
during cycling. As a result, durability and high performance could be achieved simultaneously through a proper choice of electrolyte/electrode materials that lead to SEI layer with low electronic conductivity and a high ionic conductivity rather than a tradeoff with the optimized properties of the SEI layer
3. The stretching of SEI layer during lithium electrodeposition could lead to nonuniform thickness or even cracks, which induces a nonuniform 𝐼𝑖 on the lithium electrode surface, which leads to a high aspect ratio over 10 and sharper dendrite geometry. Enhancing mechanical strength and the SEI formation kinetics can improve the stability of the lithium metal electrode.
4. Though the electronic current does not affect the ionic flux on the metal electrode surface, a highly electrically insulating SEI layer suppresses the formation and growth of lithium precipitate in the SEI layer during charging. Further reducing electronic conduction in the SEI layer would be a more efficient approach than developing an artificial SEI layer with higher ionic conductivity to achieve better durability.
Support
On the thermodynamic origin for
the formation of Li-dendrites
Institute for Materials Research and InnovationDepartment of Chemical EngineeringUniversity of Louisiana at Lafayette
Yudong Wang Anil VirkarXiao-Dong Zhou
LaSPACE Fall 2021 Council MeetingAnnual Meeting of the NASA Space Grant and ASA EPSCoR Programs in Louisiana on October 29, 2021
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