Experimental and Theoretical Investigation of Lithium

Polysulfide Solubility on Capacity of Li-S Batteries

Chao Shen, Petru Andrei, and Jim P. Zheng
Department of Electrical and Computer Engineering, Florida A&M University and Florida State University

Jianxin Xie and Mei Zhang

Department of Industrial and Manufacturing Engineering, Florida A&M University and Florida State University

Mary Hendrickson and Edward J. Plichta

Army Power Division, RDER-CCA

Li-SM3 2018 conference, Chicago, IL

 Outline

• Introduction
• Material and Synthesis Method
• Study of Polysulfide Solubility Effect
• Modeling of Li-S Batteries
• Conclusion

2
E/S Ratio Introduction

• Many parameters have profound influence on the specific

energy of Li-S batteries:
 carbon/sulfur (C/S) ratio
 excess mass of lithium
 electrolyte/sulfur (E/S) ratio
• Use of high E/S ratios:
 fully dissolve the intermediate LiPS products
 alleviate performance degradation and electrolyte consumption from
side reaction
 avoid the gradual etching of Li metal at high LiPS concentrations

3
 Solid Deposition Process Introduction

• 75% of the theoretical specific

2.4
capacity (1,254 mAh g−1) is from the
lower plateau
• The capacity difference is mainly
Voltage (V)

2.2
caused by incomplete Li2S
2.0 deposition process
• Li2S is an insulating material to
terminate the reaction prematurely
1.8

0% 25% 50% 75% 100%

X. Zhang et al., Mater. Sci. Eng. R Reports, 121, 1–29 (2017).
Depth of discharge

4
Presentation Highlight Introduction

2.5
Limit 1: In the upper plateau, the
2.4
use of a low E/S ratio could
2.3 severely degrade the battery
performance.
Voltage (V)

2.2
LiPS solubility
2.1
Liquid phase Solid phase Limit 2: in the lower plateau, the
2.0 insulating solid product could
1.9 terminate the discharge reaction
1.8
before the full capacity is reached.
0 200 400 600 800 1000 1200
Specific capacity (mAh/gS)
1400
Rate-dependent solid deposition

5
CNT Foams Material and Synthesis Method

Disperse CNTs in Add PMMA Mix PMMA Remove solvent Remove polymer
PAN/DMF/IPA template spheres and CNTs and dry sample spheres by
solution by sonication thermal treatment
Advantages:
 High conductivity
 Good electrolyte wetting
 High pore volume
 High surface area
 Freestanding structure
Y. Cui and M. Zhang, ACS Appl. Mater. Interfaces, 5, 8173–8178 (2013)
. Chem. A, 1, 13984 (2013)
Y. Cui and M. Zhang, J. Mater.
6
LiPS solubility & E/S ratio Study of Polysulfide Solubility Effect

• LiPS solubility is directly related to the concept of E/S ratios

• The E/S ratio sets an upper bound for LiPS dissolution
• The E/S ratios of Li-S cells are well above 10 ml g-1
E/S ratio (ml g-1) Note
Cheng et al. 2014 28 optimized value to suppress polysulfide
shuttle effect
Zheng et al. 2013 20 optimal value for cell performance
Chung et al 2018 4.2 achieve high areal capacity at low E/S ratios
Pang et al. 2017 3.5
Cheng et al. 2016 3-4 state-of-the-art performance for practical
Li-S batteries
C. Shen et al., J. Electrochem. Soc., 164, A1220–A1222 (2017).

7
Specific Energy vs. E/S Ratio Study of Polysulfide Solubility effect

100

)
-1
Li 1400

Theoretical specific energy (W h kg

Sulfur
80 Electrolyte
1200
W eight percentage (% )

60 1000

800
40
469 Wh kg-1
600
20
400

0 200
1 3 5 7 9 0 2 4 6 8 10
-1 -1
E/S ratio (mL g ) E/S ratio (mL g )
Assumptions:
The maximum solubility of LiPS species ([S]=~ 6 M)
The density of the electrolyte is 1.2 g ml-1.
corresponds to an E/S ratio of 5.2 mL g-1.
The average discharge voltage is 2.15 V.
C. Shen et al., Electrochim. Acta, 248, 90–97 (2017). J. W. Dibden, J. W. Smith, N. Zhou, N. Garcia-Araez, and J. R. Owen, Chem. Commun., 52,
12885–12888 (2016).

8
Specific Energy vs. E/S Ratio Study of Polysulfide Solubility effect

LiPS is not fully dissolved at these E/S ratios

E/S= 4 ml g-1 E/S= 3 ml g-1

600 600
Specific energy (W h kg )

Specific energy (W h kg )
-1

-1
500
DOE target 500
DOE target

50% S 50% S
60% S 60% S
400 70% S 400 70% S
80% S 80% S
90% S 90% S
100% S 100% S
300 300

1300 1350 1400 1450 1500 1550 1600 1650 800 900 1000 1100 1200 1300 1400 1500 1600
-1 -1
Discharge capacity (mAh g ) Discharge capacity (mAh g )

9
LiPS Solubility Limit Study of Polysulfide Solubility Effect

Does LiPS have to be dissolved in electrolyte?

Can LiPS precipitate after saturation?
Will LiPS solubility be an intrinsic
Can precipitated limit reduced?
LiPS be further for cell capacity?

2.4 Regular electrolyte 0

High Li salt electrolyte
Regular electrolyte 2.2
-1
1 M LiTFSI and 0.1 M -2
LiNO3 in DME:DOL

C urrent (m A )
2.0
V oltage (V )

-3
1.8 -4
High Li salt electrolyte
-5
5 M LiTFSI and 0.1 M 1.6
Low LiPS solubility
LiNO3 in DME:DOL 1.4 due to common ion
-6
Regular electrolyte
effect -7 High Li salt electrolyte
Rate: 0.5 mA 1.2 -8
0 200 400 600 800 1000 1200 1.4 1.6 1.8 2.0 2.2 2.4
-1
Discharge capacity (m Ah g ) Voltage (V)

10
Two Reaction Pathways Study of Polysulfide Solubility Effect

Assumptions:
1. LiPS is generated in solution
exclusively before saturation.
2. Upon saturation, LiPS forms
continuously and precipitates.
3. The electrochemical reactions
occur in both soluble and
insoluble pathways.
4. Some solid-state LiPS could enter
liquid phase once LiPS is
consumed in solution reactions.

C. Shen et al., Electrochim. Acta, 248, 90–97 (2017).

11
Results Study of Polysulfide Solubility Effect

2.4
cathode: 2.4 C-only
#1 C/S
C-only or C/S (~4 , #2 C/S
2.3
2, 1 mg S loading 2.2
[S]= 5 M
#3 C/S

V oltage (V )
for #1, #2, #3,
2.2
respectively)
2.0

electrolyte: 2.1

Li2S8 [S=5 M], 0.5 M 1.8

LiTFSI and 0.1 M 0 1 2 3 4 5
2.0
0.0 0.5 1.0 1.5 2.0
LiNO3 in DME:DOL Discharge capacity (mAh)

• Upper plateau capacities increase with • The increased capacities are from
sulfur loading sulfur reduction in cathode
• Overall capacities of C/S cathodes is • Full utilization of newly generated
lower than that of a sulfur-free cathode LiPS is prohibited

12
Results Study of Polysulfide Solubility Effect

A new type of cathode: C/LiPS 2.4 C-only

#1 C/LiPS
• Upper plateau and overall
2.3 #2 C/LiPS
#3 C/LiPS
capacities increase with LiPS
[S]= 1 M
2.2 loading

V oltage (V )
#2 C/S 2.1
2.4 Starting from S #2 C/LiPS
2.0

1.9

2.2
V oltage (V )

1.8

0 1 2 3 4 5
Discharge capacity (mAh)
2.0 Starting from Li2S8 • Upper plateau and overall
2.4 C-only
#1 C/LiPS capacities do not increase
#2 C/LiPS
with LiPS loading
2.3
[S]= 5 M #3 C/LiPS
1.8 2.2
• The addition of LiPS does not

V oltage (V )
0 200 400 600 800 1000 1200
2.1
further contribute to
-1 2.0 capacity once saturation
Discharge capacity (m Ah g )
1.9 condition is reached
1.8

0 1 2 3 4 5
Discharge capacity (mAh)

13
Results Study of Polysulfide Solubility Effect

2.4
Same configurations 2.4 C -only
Rate: 0.05 mA #1 C /S
#2 C /S
instead of 0.5 mA 2.3
[S]= 5 M #3 C /S
2.3
2.2

Voltage (V) 2.1 2.2

2.0
2.1
1.9

1.8
2.0
0 2 4 6 8 10 12 0.0 0.5 1.0 1.5 2.0
Discharge capacity (mAh)

• Upper plateau capacities increase with • The increased capacities are from
sulfur loading both sulfur and LiPS reduction
• Overall capacities of C/S cathodes also • Newly generated LiPS can be further
increase compared to that of a sulfur- reduced
free cathode

14
Summary Study of Polysulfide Solubility Effect

Does LiPS have to be dissolved in electrolyte?

No, there exist both LiPS soluble and insoluble pathways.

Can LiPS precipitate after oversaturation?

Yes, initial sulfur reduction still occurs in LiPS-saturated condition.

Can precipitated PS be reduced in subsequent electrochemical reactions?

No, at sufficiently high rate the subsequent reactions occur exclusively in liquid phase
and can be limited by LiPS solubility.

15
Modeling of Li-S Batteries
Anode

Lithium oxidation: Li  Li + +e 

Sulfur dissolution: S8s   S8

1 1
Reduction of S8 to S82  : S8 +e   S82  Precipitation of Li2S8: 2Li  +S82   Li 2S8(s)
2 2
3 2 
Reduction of S82  to S62  : S8 +e  2S62  Precipitation of Li2S6: 2Li  +S62   Li 2S6(s)
Cathode

2
3
Reduction of S62  to S24  : S62  +e  S42  Precipitation of Li2S4: 2Li  +S24   Li 2S4(s)
2
1 2 
Reduction of S24  to S22  : S4 +e  S22  Precipitation of Li2S2: 2Li  +S22   Li 2S2(s)
2
1 2 
Reduction of S22  to S2  : S2 +e  S2  Precipitation of Li2S: 2Li  +S2   Li 2S(s)
2

Electrochemical reactions only take places on cathode surface.

Chemical precipitations can occur in both cathode and separator.

16
Equations Modeling of Li-S Batteries

• Growth
 k 
 Vk  rk 
t
• Transport
 ci
     zi uici   Dici   a 1    Ri    i ,k  rk   0    V    R j  0
t k
j

• Kinetics
1  
i0 j 
si , j   si , j
 ci  VT  ci  
 
 c 
 i ,k 
R j     ref  e    ref  e VT  rk  kk  k   K sp ,k  
F  i , si , j  0  ci  i , si , j  0  ci    i
   i 
1  A 
i0, Li   cLi  A

RA   ref e VT  e VT 
F  cLi 

17
Surface Coverage Modeling of Li-S Batteries

Low discharge current

•The driving force of the initial nucleation
High
process is the surface oversaturation
•The nucleation rate depends on the current of
Deposition S2 − S2 −

of
2 discharge since the surface oversaturation is
rate-dependent

Li2S(s) Li2S(s )
•The surface coverage is written in the form of
Li2S(s) Li2S(s)
S differential equations:
 k
Electrons Electrochemical reaction  K k S k 1    Fk
t
Fk
 S k Gk
t
Gk
P. Andrei, C. Shen, J. P. Zheng, under review, 2018.
t
 
 M k Sk Nk  1

18
Results Modeling of Li-S Batteries

Number of nuclei per unit area (normalized)

100
1.0
1C
Average surface coverage, 

1C
-2
0.1 C 10
0.8
0.1 C
-4
10
0.6
Precipitation of Li2S 0.1 C
10-6
0.1 C 0.2 C
0.4 0.2 C 0.25 C
0.25 C 10-8 0.33 C
0.33 C 0.5 C
0.2 0.5 C 1C
10-10
1C Reg.
Region 1 2 Region 3
-12
0.0 10
0 200 400 600 800 1000 1200 1400 0 200 400 600 800 1000 1200 1400
Dissolution of S Specific capacity (mAh/gS) Specific capacity (mAh/gS)

Region 1 : initial sulfur dissolution

Region 2: oversaturation of Li2S molecules
Region 3: solid product precipitation

19
Results Modeling of Li-S Batteries

Experimental results: Simulation results:

2.5

0.1C
2.5

0.1 C
• The model describes correctly the
2.4 2.4

2.3
0.2C
0.25C
0.33C 2.3
0.2 C
0.25 C features of:
the two voltage dips (A and B);
0.33 C
0.5C

Voltage (V)
0.5 C
Voltage (V)

1C 0.1 C
2.2 0.1 C 2.2 1C
the specific capacity of the cells as a
A A

2.1 2.1

2.0 1C 2.0 function of the discharge rates

B B
1.9 1.9 1C

1.8 1.8
0 200 400 600 800 1000 1200 1400 0 200 400 600 800 1000 1200 1400
Specific capacity (mAh/gS)
Specific capacity (mAh/gS)

0.2C
• The voltage from “F” to “G” do not
2.4 1C
overlap with the curve at 0.2 C
0.2C 2.4
SC2 = 482 mAh/gs 0.2 C
SC2

• The capacity from “B” to “C” (SC1) is

Voltage (V)

2.2
Voltage (V)

D E 0.2C 2.2
A A D E 0.2 C

1C
smaller than that from “E” to “F”
(SC2)
2.0 0.2 C
2.0
B 1C
B
1C
C
1.8 SC1=414 mAh/gs F
SC1 C
G 1.8 F G
0 200 400 600 800 1000 1200 1400 0 200 400 600 800 1000 1200 1400
Specific capacity (mAh/gs)
Specific capacity (mAh/g)

20
Indications from Modeling Modeling of Li-S Batteries

• Large oversaturation is required to initiate the precipitation of

solid product:
It is better to artificially introduce a small number of catalyst
particles as nucleation seeds.

• The dissolution rate of solid species is much slower than their

precipitation rate:
It is essential to avoid the solid formation of intermediate LiPS.

21
Conclusion
1. Study of Polysulfide Solubility Effect
• LiPS soluble reaction pathway dominates in a liquid electrolyte environment
• Reduction of sulfur to Li2S8 is not inhibited by high Li2S8 concentration
• Subsequent LiPS electrochemical reactions are restricted by LiPS solubility

2. Modeling of Li-S Batteries

• Surface coverage of solid product is modeled in the form of differential equations
• Features including the rate-dependent discharge capacity are modeled correctly

Work supported by :
US Army Power Division (grant No. GTS-S-15-014)
National Science Foundation (grant No. 1609860)
22