Fabrication of Lithium-sulfur Battery Cathode with Radiation Crosslinked Low Molecular Weight of Polyacrylonitrile and the Mechanism of Sulfur Storage

doi:10.7503/cjcu20210632

Abstract

Abstract:

By the method of γ-ray irradiation cross-linking heteromorphic polyacrylonitrile（PAN）fibers， the pro? blem of melt collapse in the semi-carbonization of low-molecular-weight polyacrylonitrile was solved and the semi- carbonization stability of PAN was impoved. The irradiation cross-linking mechanism was first determined by Fourier transform infrared spectra， elemental analysis and nuclear magnetic resonance spectra. At the same time， according to the relationship between the different degree of crosslinking produced by irradiation and the change of sulfur load after PAN vulcanization， the sulfur storage mechanism of vulcanized polyacrylonitrile（SPAN） for lithium-sulfur battery cathode material was discussed. Using Raman spectra， X-ray photoelectron spectra and other analytical methods， from the perspective of cross-linking， the reaction position of S in SPAN was demonstrated， and the tertiary carbon on the PAN main chain was the active site for chemical bonding with S. It provides a new basis for exploring the SPAN structure. The increase in the degree of cross-linking promotes the electrochemical stability of the SPAN cathode material formed after vulcanization， and the capacity retention rate can be increased to 98%.

Key words: Sulfurized polyacrylonitrile, Cathode material of lithium-sulfur battery, γ-Ray irradiation cross- linking, Sulfur storage mechanism

CLC Number:

O646

TrendMD:

ZHANG Shiyu, HE Runhe, LI Yongbing, WEI Shijun, ZHANG Xingxiang. Fabrication of Lithium-sulfur Battery Cathode with Radiation Crosslinked Low Molecular Weight of Polyacrylonitrile and the Mechanism of Sulfur Storage[J]. Chem. J. Chinese Universities, 2022, 43(3): 20210632.

Figures/Tables 15

Fig.1 SEM image of the profiled PAN fiberInset: cross?sectional image.

Fig.2 Morphology(A) and gel fraction diagram(B) Irradiation under different irradiation doses

Fig.3 Polarizing optical microscopy images of profiled PAN fibers at different temperatures and under different irradiation dosesIrradiation dose/kGy: (A1—A5) 0; (B1—B4) 200; (C1—C4) 250; (D1—D4) 300; (E1—E4) 350.Temperature/℃: (A1—E1) r.t.; (A2—E2) 220; (A3—E3) 250; (A4—E4) 270; (A5) 290.

Table 1 Elemental analysis of profiled PAN fibers with different cross-linking degrees

Sample	C（%）	H（%）	N（%）	C/H molar ratio	C/N molar ratio
PAN	65.90	5.82	24.35	0.94	3.16
PAN?IR200	66.08	5.42	24.40	1.02	3.17
PAN?IR300	66.17	5.30	24.42	1.14	3.17

Fig.4 FTIR(A) and 13C NMR(B) spectra of PAN fibers with different cross?linking degreesa. PAN； b. PAN?IR200； c. PAN?IR300.

Scheme 1 Possible reaction sites and structures during PAN cross?linking

Table 2 Elemental analysis of SPAN with different cross-linking degrees

Sample	C（%）	H（%）	N（%）	S（%）	C/H molar ratio	C/S molar ratio	N/S molar ratio
SPAN	57.37	1.70	19.19	16.43	2.81	9.37	2.69
SPAN?IR200	61.74	1.52	19.63	12.09	3.39	13.55	3.68
SPAN?IR300	62.18	1.10	19.59	11.13	4.71	14.80	4.00

Fig.5 SEM images(A1—C1) and corresponding elemental mappings(A2—A4, B2—B4, C2—C4) of SPAN with different cross?linking degrees

Fig.6 XRD patterns of SPAN with different cross?linking degrees

Fig.7 FTIR(A) and Raman(B) spectra of SPAN with different cross?linking degrees

Fig.8 S2p (A—C) and N1s (D—F) XPS spectra of SPAN with different cross?linking degrees(A, D) SPAN?IR300; (B, E) SPAN?IR200; (C, F) SPAN.

Scheme 2 Structure diagram of cross?linking and vulcanization reaction

Fig.9 Cycling performance(A) and electrochemical impedance spectra(B) of SPAN electrodes with different cross?linking degrees

Fig.10 Rate performance curves(A) and charge?discharge curves in the second cycle(B) of the SPAN cathode with different cross?linking degrees

Fig.11 CV curves of the SPAN cathode with different cross?linking degrees(A) SPAN; (B) SPAN?IR200; (C) SPAN?IR300.

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