Sulfurized-polyacrylonitrile in lithium-sulfur batteries: Interactions between undercoordinated carbons and polymer structure under low lithiation

doi:10.1016/j.jechem.2021.08.070

Journal of Energy Chemistry

Volume 66, March 2022, Pages 587-596

https://doi.org/10.1016/j.jechem.2021.08.070 Get rights and content

Abstract

Lithium-sulfur battery (LSB) represents an important candidate to be used in energy storage applications, due to its high specific capacities. Sulfurized-polyacrylonitrile (SPAN) is a candidate as a host material in LSB to replace graphite, due to its ability to chemisorb polysulfides (PSs). The sulfur chains attached to the polymer can reversibly form Li₂S, and SPAN indicates to have a good cyclability and better performance than graphite, thus, SPAN acts partially as an active and also as a host material. In this study, we investigated the capacity of the solvent or the SPAN to lose a hydrogen atom from the backbone, to predict possible anodic reactions between solvent and host material. The simulation suggests that the photophilic salts may preferentially react with the solvent, and possibly building a cathode electrolyte interphase (CEI). We observed that an undercoordinated carbon (C_uc) can be thermodynamically created, due to lithiation. The C_uc can react with the solvent on the polymer backbone through different mechanisms, however, the simulations indicated that the reaction should be affected by the interaction between the solvent and C_uc, according to SPAN’s configuration. Moreover, C_uc reacts with long sulfur chains attached to SPAN, capturing sulfur and forming a C-S bond. A sulfur chain from one SPAN can connect to another polymer backbone, however, this process is affected by lithiation and vice-versa. Therefore, this work also investigates the formation of interconnected SPAN structures and the multiple C_uc effects.

Graphical abstract

Sulfur chain interconnecting two sulfurized polyacrylonitrile backbone (left), and formation of polysulfide surrounding a disulfide attached to the polymer backbone (right).

Section snippets

1. Introduction

Many different applications need energy storage devices, which normally use lithium-ion batteries (LIBs) to convert chemical into electrical energy, such as electric vehicles, laptops, and solar panels [1], [2]. However, there is an increasing demand for denser energy capacities and LSBs are promising candidates to replace LIBs, because LSBs have a theoretical specific capacity of 1672 mAh/g vs. 300 mAh/g of LIBs. Nevertheless, LSBs still have some challenges to overcome [3], [4].

LSBs currently

2. Computational methods

In this work, we used Vienna Ab-initio Simulation Package (VASP) [62], [63] code to perform the density functional theory calculations. The projector-augmented-wave (PAW) pseudopotentials and plane-wave basis were set with an energy cut-off of 400 eV to describe the electrons distribution [64], [65]. Generalized gradient approximation (GGA) functional proposed by Perdew, Burke, and Ernzerhof (PBE) describes contributions from exchange and correlation energies. Van der Waals (vdW) dispersion

3.1. Interactions between a second C_uc and an absorbed PS in the same backbone

Considering in SPAN that the same sulfur chain can be attached to the backbone in multiple carbon sites, the sulfur chain can have different sizes [48], and C_uc can exist during the synthesis and be produced during cycles [56], [57]. We investigated the interaction of different PS in C_uc sites and the possibility to form a closed-ring structure by forming a C–S bond, without breaking a S–S bond.

In the presence of a S₆ chain (models a.I and b.I), there is no exchange of S between C_uc and the

4 Conclusion

In this study, we observed that in small chains (Li₂S₆), the sulfur chain attached to the SPAN does not exchange sulfur with nearby C_uc or form a close-ring structure by bounding to the C_uc. However, the reactions with the solvent can take place, decomposing the solvent due to reactions with the C_uc. In contrast, long sulfur chains (Li₂S₈) can exchange sulfur when a C_uc is close enough to the sulfur chain attached to the SPAN backbone. Additionally, long sulfur chains indicate to improve

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgment

Support from the Deutsche Forschungsgemeinschaft (DFG) through Project ID 390874152 (POLiS Cluster of Excellence) as well as the Schwerpunktprogramm (priority program) SPP- 2248 (polymer-based batteries) is gratefully acknowledged. The authors also acknowledge the computer time supported by the state of Baden-Württemberg through the HPC project 511 and the Deutsche Forschungsgemeinschaft (DFG) through Grant Number INST40/467-1 FUGG.

References (75)

A.F. Hofmann et al.
J. Power Sources
(2014)
L. Yuan et al.
J. Power Sources
(2009)
C. Barchasz et al.
J. Power Sources
(2012)
J. Balach et al.
J. Power Sources
(2016)
W. Zheng et al.
Electrochim. Acta
(2006)
B. Zhang et al.
Electrochim. Acta
(2009)
L. Yuan et al.
J. Power Sources
(2009)
F. Wu et al.
Nano Energy
(2017)
S.-C. Zhang et al.
Synth. Met.
(2010)
H. Peng et al.
J. Nanoparticle Res.
(2017)

J. Li et al.

J. Power Sources

(2014)

L. Wang et al.

Electrochim. Acta

(2012)

T.N.L. Doan et al.

J. Power Sources

(2013)

E.P. Kamphaus et al.

ChemPhysChem

(2020)

A. Marzouk et al.

J. Phys. Chem. C

(2018)

S. Sharifi-Asl et al.

Adv. Funct. Mater.

(2019)

Y. Zheng et al.

J. Mater. Chem. A

(2019)

Y.-X. Chen et al.

Nanoscale

(2014)

Y. Yang et al.

Chem. Soc. Rev.

(2013)

H. Schneider et al.

J. Electrochem. Soc.

(2014)

Y. Yang et al.

J. Am. Chem. Soc.

(2012)

J.C. Burgos et al.

J. Phys. Chem. C

(2013)

M.-S. Song et al.

J. Electrochem. Soc.

(2004)

Y. Zhang et al.

J. Mater. Chem. A

(2013)

Y. Choi et al.

Phys. Scr.

(2007)

X. Ji et al.

Nat. Commun.

(2011)

S. Evers et al.

J. Phys. Chem. C

(2012)

J. Song et al.

Angew. Chem. Int.

(2015)

K. Han et al.

ChemSusChem

(2014)

Y. Yang et al.

ACS Nano

(2011)

W. Li et al.

Proc. Natl. Acad. Sci.

(2013)

B. Zhang et al.

Energy Environ. Sci.

(2010)

X. Li et al.

J. Mater. Chem.

(2011)

C. Liang et al.

Chem. Mater.

(2009)

Y.-S. Su et al.

Phys. Chem. Chem. Phys.

(2012)

A. Manthiram et al.

Google Patents

(2015)

G. Zheng et al.

Nano Lett.

(2011)

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Journal of Energy Chemistry

Sulfurized-polyacrylonitrile in lithium-sulfur batteries: Interactions between undercoordinated carbons and polymer structure under low lithiation

Abstract

Graphical abstract

Section snippets

1. Introduction

2. Computational methods

3.1. Interactions between a second Cuc and an absorbed PS in the same backbone

4 Conclusion

Declaration of Competing Interest

Acknowledgment

J. Power Sources

J. Power Sources

J. Power Sources

J. Power Sources

Electrochim. Acta

Electrochim. Acta

J. Power Sources

Nano Energy

Synth. Met.

J. Nanoparticle Res.

J. Power Sources

Electrochim. Acta

J. Power Sources

ChemPhysChem

J. Phys. Chem. C

Adv. Funct. Mater.

J. Mater. Chem. A

Nanoscale

Chem. Soc. Rev.

J. Electrochem. Soc.

J. Am. Chem. Soc.

J. Phys. Chem. C

J. Electrochem. Soc.

J. Mater. Chem. A

Phys. Scr.

Nat. Commun.

J. Phys. Chem. C

Angew. Chem. Int.

ChemSusChem

ACS Nano

Proc. Natl. Acad. Sci.

Energy Environ. Sci.

J. Mater. Chem.

Chem. Mater.

Phys. Chem. Chem. Phys.

Google Patents

Nano Lett.

3.1. Interactions between a second C_uc and an absorbed PS in the same backbone