NASA’s Future Missions

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

mailto:[email protected]

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


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/

https://www.rochesterfirst.com/weather/weather-blog/winter-wonders-how-icicles-get-their-unique-shape/

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-fire

https://www.thedrive.com/news/28420/parked-teslas-keep-catching-on-fire-randomly-and-theres-no-recall-in-sight

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.


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.


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


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


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NASA’s Future Missions