Electronic Supplementary Material (ESI) for Sustainable Energy & Fuels.

This journal is © The Royal Society of Chemistry 2022

Gradient distribution of functional components in PAN-based electrolyte

endowing solid-state lithium sulfur battery with long cycle life

Jizong Zhang a,b, Yu Si a,b, Qiumi Huang a,b, Ting Yang a,b, Chengyang Wang a,b, Kemeng Ji a,b, Jin

Wang c and Mingming Chen a,b*

a Key Laboratory for Green Chemical Technology of MOE, School of Chemical Engineering and Technology,

Tianjin University, Tianjin 300072, P. R. China

b Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin University, Tianjin

300072, P. R. China
c Sichuan Best Graphite New Energy Co., Ltd, Suining 629000, Sichuan, P. R. China

* E-mail: [email protected] (Mingming Chen)

Experimental section

1 Materials and methods

The synthesis of MoP/MoS2@C

MoP/MoS2@C is synthesized according to the previous paper [1].

The preparation of PAN-based solid electrolyte

PAN, PMMA and other solid materials were dried at 80oC vacuum oven for over

24 h. Then, 0.1 g PMMA was dispersed into 10.0 g DMF at 50oC with continuous but

slow stirring. About 3 h later, PAN (MW = 150,000) powder and 0.03 g super-P were

added to the above solution subsequently. Until the uniform light-black solution was

achieved, the as-obtained MoP/MoS2@C was placed into. After stirring overnight, the

thick solution was coated onto a clean glass pane with a doctor blade. The solid

electrolyte layer could be obtained by experiencing a phase conversion process, that

is, in detail, immersing the glass pane with electrolyte solution into water, then

standing a few minutes, the electrolyte layer was automatically separated from the

glass base. To condense such an electrolyte layer, it would be rolled immediately once

fished out. There were four components in the solid electrolyte, naming PMMA,

PAN, carbon (super-P), MoP/MoS2@C. According to the distribution of each

component in the electrolyte (from negative to positive electrode side), the electrolyte

was named as p-PPCM (here p representing phase conversion). The control

electrolyte is obtained by the similar method, without one or several components.

They were p-PAN, p-PPm, p-PPmC, and p-PPmCMo. Besides, another control

sample was prepared by coating PAN-based slurry onto glass pane and dried directly,
which was named as c-PAN and c-PPmCMo. Finally, the layer did not use as solid

electrolyte until it sucked up a typical amount LiTFSI solution and evaporating all the

solvents, named as p-PAN/Li, p-PPmLi, p-PPmCLi, p-PPmCMoLi and c-PAN/Li, p-

PPmCMoLi.

2 Physical characterization

The field-emission scanning microscope (FESEM, S4800, Hitachi, Japan) with

EDX was employed to exhibit the morphology and element distribution of the solid-

state composite polymer electrolyte (CPE). The SSEs were conducted by X-ray

diffraction (XRD) using a Bruker D8 Advanced X-ray diffractometer with Cu Kα

radiation (at scanning step of 5o min-1) to get the crystallization behavior. Beyond

XRD, polarizing microscope (Nikon Eclipse E600 Pol, Japan) and photograph of

SSEs gave the detailed and visualized information. Differential scanning calorimetry

(DSC, 200 F3, Netzsch, Germany, 5°C min-1) and thermogravimetric analysis (TGA,

TA-50 instrument) were performed in an N2 atmosphere at 5°C min-1 to ensure the

phase change and thermostability of SSEs. The BET specific surface area and pore

structure of the SSEs were examined by a Tristar-3000 at 77 K. To get the content of

sulfur species at the SSE surface next to either cathode or anode, X-ray photoelectron

spectroscopy (PHI-1600 ESCA spectrometer) was performed.

3 Electrochemical measurements of the solid-state electrolyte

The ionic conductivity (σ)

The σ can be got by, firstly confirming the value of bulk resistance R of the cell that

sandwiched the CPE between two stainless sheel sheets (SS, the diameter was 16
mm), then calculating by the following formula:

σ=L/SR

here the L and S represent the thickness (cm) and the area (cm2) of the SS,

respectively. As for the R values, they were obtained by the electrochemical

impedance spectroscopy (EIS) test with an amplitude voltage of 10 mV in the

frequency range from 106 to 10-1 Hz at temperatures from 30 to 70°C, which was

conducted on CHI660E electrochemical work stations.

The electrochemical stability windows

The electrochemical stability window is exhibited as the stable voltage range of the

cell assembled with stainless steel sheet, CPE and Li anode (SS|CPE|Li) in a linear

scanning voltammetry (LSV) test at 50°C. The LSV curves had a voltage range of

1.0~6.0 V (vs. Li+/Li) and a scanning rate of 1 mV s-1. Note that the cells were

assembled in the glove box.

The lithium ion migration number (tLi+)

The tLi+ can be calculated according to the following equation proposed by Vincent

et al,

where I0 and It were the initial and steady (terminal) currents during the direct-current

(DC) polarization (with a DC voltage of 10 mV) at 50°C, and the test object was

Li|SSE|Li symmetric cells. The R0 and Rt were the resistance values before and after

the polarization measurement with the same system, but the technique is AC

impedance in the frequency range from 106 to 10-1 Hz at temperature of 50°C, and
with an amplitude voltage of 10 mV.

The voltage polarization measurements

The polarization curves of various CPEs were generated with Li|CPE|Li cells on

Land 2001A battery testing system by using galvanostatic charge/discharge technique.

And the current density was 0.1 mA cm-2.

4 Batteries assembly and electrochemical tests

Laboratory-scale all-solid-state cells were constructed by employing sublimed

sulfur in combination with Super-P, binder and additive as the cathode, together with

a lithium anode and a solid electrolyte located between the cathode and the anode. For

composite cathode electrodes, it was prepared by mixing the slurry consisted of 70

wt.% sublimed sulfur, 20 wt.% super-P and 10 wt.% poly (vinylidene difluoride)

(PVDF), then coating it onto an aluminum foil with a doctor blade. The mass loading

of cathode is about 2.5~3.0 mg cm-2, corresponding to a sulfur loading of 1.5~1.8 mg

cm-2 in cathode. All the processes were performed in an argon filled glove box.

Electrochemical performances the all-solid-state lithium batteries (SSLSB) were

investigated by galvanostatic charge/discharge tests at different C rate (1 C = 1675

mA g-1) by using a multichannel battery test system (LAND CT-2001A, Wuhan

Rambo Testing Equipment Co., Ltd.) under a cut-off voltage of 1.5~3.0 V. The

temperature was controlled in a constant temperature oven. The specific capacities

were calculated based on the mass of sulfur. CV and EIS were recorded on a

CHI660E electrochemical work station.

 Figure S1 The elements/substances distribution of (A) p-PPm; (B) p-PPmCMo and (C) p-

PPmCMoLi along c-axis.

Figure S2 (A) FESEM image of the surface of c-PPmCMo membrane; (B) the

elements/substances distribution of c-PPmCMo along c-axis; (D) cross-sectional micrographs of

c-PPmCMo; (C) and (E) the enlarged and different areas of c-PPmCMo section.

The characterization of the ab- and c-axis section of the ungraded c-PPmCMo is

shown in Figure S2. The composition is uniformly distributed. Compared with non-

graded electrolytes, Grad-CPE exhibits different component distributions and

functions at the cathode/electrolyte and anode/electrolyte interfaces, benefiting for

both reaction and mass transfer.

 Figure S3 (A~F) XRD patterns; (G~L) polarizing microscope (POM) images and electronic

photos of c-PAN, p-PAN, p-PPm, p-PPmC, p-PPmCMo and p-PPmcMoLi, respectively.

The crystallinity of the polymer segment in Grad-CPE is significantly reduced. The

XRD peak intensity of p-PAN is only half of that of c-PAN, that is, it decreases from

705 a.u. to 352 a.u. (Figure S3A and S3B). The reduced intensity can be ascribed to
the following aspects: (1) The film forming temperature of p-PAN and c-PAN are

different. Beyond the rigid and asymmetric structure, the high glass transition

temperature (~94°C) and decomposition temperature (275°C) of PAN (Figure S4)

make p-PAN have almost no rearrange and crystallize at the film forming temperature

of 25°C; while the film formation of c-PAN occurs at 80°C, the generated energy

enhances the possibility of polymer-chain movement, thus the crystallization ability

increases. (2) The film forming speeds of p-PAN and c-PAN are different. The film

formation of p-PAN is faster (about 40 s), but the movement speed of the polymer is

so slow that the polymer cannot rearrange and crystallize in time during the film

formation process, resulting in low crystallinity [2]; it takes above 2 h to get c-PAN.

The crystallinity increases because long time makes the movement of polymer-chain

possible. The addition of functional components basically maintains the crystallinity

of Grad-CPE at the same or even smaller level (Figure S3C~F). The crystallinity of

the p-PPmCMoLi is the lowest. Decrease in crystallinity means an increase in non-

crystalline areas in polymer electrolytes, which is the main place for ion transfer and

S8 ↔ Li2S conversion.

The isotropy of the electrolyte membrane also benefits ion transport. As shown in

Figure S3J~L, compared with other PAN-based electrolyte (Figures S3G and 4H), p-

PPmCMoLi has the most uniform response to polarized light, indicating the most

obvious isotropic characteristics on the ab surface of the membrane. The isotropic

nature of the electrolyte on the ab plane means that its dielectric constant is scalar and

has no directionality. Therefore, under the action of electric field force (during charge
and discharge), there is no restriction on the transmission direction of ions, and there

are more transmission channels. Therefore, p-PPmCMoLi makes ions transport

uniform and avoids local accumulation of ions, thus leading to excessive charge

density and breakdown of the electrolyte. In addition, the diffuse reflectance of the p-

PPmCMoLi film is enhanced, and the opacity increases (Figure 5-4M~R), indicating

that (1) the arrangement of the polymer segments inside the electrolyte is irregular,

the crystallinity is reduced, and (2) the surface/interface is rough, small pores appear.

Both provide convenience for the transmission of ions [3]. Therefore, the reaction

kinetics is increased from the perspective of increasing ion transport.

 Figure S4 (A) DSC curves and (B) TG plots of c-PAN, p-PAN and p-PPmCMoLi.

Figure S5 Raman spectra of (A) c-PAN/Li, (B) p-PAN/Li and (C) p-PPmCMoLi electrolyte.
Figure S6 EIS spectrum of SS|p-PPmCMoLi|SS cell at a temperature range of 30~70°C.
 Figure S7 (A) Arrhenius plots of the c-PAN/Li and p-PAN/Li electrolytes; (B) LSV curves of

Li|c-PAN/Li|SS and Li|p-PAN/Li|SS at 10 mV s-1; Chronoamperometry profiles of (C) Li|c-

PAN/Li|Li and (D) Li|p-PAN/Li|Li cells at 50°C (insets are the Nyquist impedance curves of the

cells in their initial and stable polarization states). Galvanostatic cycling profiles (50°C) of (E)

Li|c-PAN/Li|Li and (F) Li|p-PAN/Li|Li cells at 0.1 mA cm-2 and (G and H) the detail information

of the selected regions in E and F, respectively.

 In p-PAN/Li and c-PAN/Li symmetric cells (Li|CPE|Li), the ions at the

electrode/CPE interfaces both transfer and react slowly, which is insufficient to

maintain the fluent and complete Li+ deposition/decomposition. In this case, the

PAN-based electrolytes are subjected to a shock of aggregated ions and high voltage,

they are much more vulnerable to experience short cycling life. As a consequence, the

life span of p-PAN/Li cell comes to an end at only 45th hour (Figure S7E~H).

Figure S8 CV curves of Li|p-PPmCMoLi|S cell with a small amount (E/S = 2.1 μL mg-1) of

electrolyte be added or without electrolyte.

Figure S9 (A) Rate performances and cycling stabilities of Li|c-PAN/Li|S and Li|p-PAN/Li|S cells,

the cycling of the two cells were tested at 0.5 mA cm-2 before 5-cycle activation at 0.1 mA cm-2.

Figure S10 Galvanostatic cycling profiles of Li|p-PPmCMoLi|Li cells at 0.2 mA cm-2 and 50°C
 Table S1 The solubility of different components in DMF and water.

Solubility (mg mL-1) in different solvents

Dissolved form
DMF (50°C) Water (25°C)

PAN (MW = 150,000) Swelling ~220 < 20

PMMA
Swelling ~90 < 10
(MW = 150,000)

Super P Dispersion - -

MoP/MoS2@C Dispersion - -

Table S2 The ionic-conductivity values of c-PAN/Li, p-PAN/Li, c-PPmcMoLi and p-PPmCMoLi

electrolyte at a temperature range of 30~70°C.

Temperature Ionic Conductivity (S cm-1)

(oC) c-PAN/Li p-PAN/Li c-PPmCMoLi p-PPmCMoLi

30 4.36 × 10-5 6.23 × 10-5 5.38 × 10-5 8.73 × 10-5

35 5.62 × 10-5 7.11 × 10-5 6.39 × 10-5 1.11 × 10-4

40 7.26 × 10-5 9.12 × 10-5 7.45 × 10-5 1.52 × 10-4

45 1.13 × 10-4 1.35 × 10-4 9.24 × 10-5 2.62 × 10-4

50 1.76 × 10-4 2.43 × 10-4 1.30 × 10-4 4.40 × 10-4

55 2.79 × 10-4 3.39 × 10-4 1.59 × 10-4 6.23 × 10-4

60 3.98 × 10-4 4.60 × 10-4 2.09 × 10-4 8.28 × 10-4

65 5.04 × 10-4 5.59 × 10-4 3.04 × 10-4 9.76 × 10-4

70 6.48 × 10-4 6.90 × 10-4 3.98 × 10-4 1.15 × 10-3

 Table S3 The relavent current and impendence values and the calculated t Li+.

I0 (μA) It (μA) R0 (Ω) Rt(Ω) tLi+

c-PAN/Li 36.89 26.29 162.3 150.9 0.17

p-PAN/Li 51.23 45.83 179.1 74.6 0.26

c-PPmCMoLi 32.30 19.51 116.2 113.5 0.17

p-PPmCMoLi 77.93 71.06 110.9 109.2 0.65

Note: I0 and It represent the current at initial and steady state during polarization. R0
and Rt are the impedance before and after polarization

Table S4 The comparison of all solid-state LSBs electrolytes with their abbreviations

Abbreviation Components

c-PAN or p-PAN PAN

c-PAN/Li or p-PAN/Li PAN + LiTFSI
p-PPm PAN + PMMA
p-PCa PAN + Super-P
p-PPmLi PAN + PMMA + LiTFSI
p-PPmC PAN + PMMA + Super-P
p-PPmCLi PAN + PMMA + Super-P + LiTFSI
c-PPmCMo or p-PPmCMo PAN + PMMA + Super-P + MoP/MoS2@C
c-PPmCMoLi or p-PPmCMoLi PAN + PMMA + Super-P + MoP/MoS2@C + LiTFSI

Note: The prefix c represents the preparation method of the electrolyte membrane is coating-
drying method, and p represents the phase inversion
 Table S5 A performance comparison of symmetric solid-state battery tests

Temperatur
Current Cycle time Polarization voltage-
Solide electrolyte e Reference
(mA cm-2) (h) Final (mV)
(oC)

PEO-1%LSPS 0.1 600 60 25 S4

Vr/PEO-LCSE 0.05 200 60 14 S5

0.1 200 26

0.2 200 47

PLO 0.1 350 35 60 S6

PEO+Li3N 0.1 650 70 16 S7

SPE-LATP-SPE 0.25 220 75 50 S8

LiG3-LGPS 0.1 300 RT 43 S9

PLALF 0.05 200 60 9 S10

0.1 200 16

0.2 200 34

GPE@FEC 0.1 980 25 80 S11

LHB 0.1 1000 60 <100 S12

LEC 0.1 400 60 20 S13

p-PPmCMoLi 0.1 1000 50 30 This work

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