Improvement of Sulfur Cathode Reversibility by Specific Chemical Lithium Pre-doping Method
Authors: Kuroda Masato , Okuno Morihiko , Okuda Daisuke , Ishikawa Masashi 
Published: November 2022

1.Intoroduction
Recently, lithium-ion batteries (LIBs) have been required in terms of a high energy density for large-scale applications such as power supplies for electric vehicles. Lithium-sulfur (Li-S) batteries are, therefore, expected as next generation batteries because of their high energy density.
Sulfur is utilized as cathode material for Li-S batteries because of a high specific capacity. However, sulfur has a low electric conductivity and a risk of dissolution into an electrolyte during a charge-discharge process [1]. L. Nazar et al. applied activated carbon as substrate for sulfur to help electric conduction and prevent dissolution of sulfur [2]. The activated carbon allows Li-S batteries to show high specific capacity with high reversibility. Even if these problems are solved, however, Li-S batteries have a further problem of excessive initial irreversible capacity during the first discharge process. Li pre-doping is a useful technique to cancel the large irreversible capacity in actual LIBs. Abe et al. reported a chemical lithium pre-doping method for a graphite using lithium naphthalenide [3]. Studies have been reported on the use of such pre-doping to improve the performance of Li-S batteries, for instance, with a sulfur-Ketjenblack composite cathode [4]. In our previous study, we have applied that method to a sulfur cathode composed of microporous activated carbon and sulfur before cell assembly and developed a Li2S cathode that suppressed the initial irreversible capacity during the first discharge process. However, the Li2S cathode showed an unignorable initial irreversible capacity and poor cycle life [5].
This work attempts to improve the reversible capacity of the Li2S cathode by a specialized chemical lithium pre-doping method. Our report would lead to the proposal of novel cathode and anode options in Li-S batteries.

Method

2-1. Fabrication of lithium naphthalenide solution
As Li metal and Li2S are both sensitive to moisture in air, all the following synthesis processes were carried out in an Ar-filled glove box. Lithium naphthalenide, a dark green solution was prepared by mixing an equal mol amount of Li metal with naphthalene in a cyclic ether solvent.
2-2. Fabrication of Li2S-AC cathodes
Each sulfur cathode was prepared by mixing the S-AC (a composite of microporous activated carbon and sulfur), acetylene black, carboxymethyl cellulose, and styrene butadiene rubber at a respective weight ratio of 93: 3: 2: 2 and coating the resulting aqueous slurry on a carbon paper.
The 1M lithium naphthalenide solution was dropped on the sulfur cathode. After 20 min reaction, the cathode was rinsed several times with 2–dimethoxyethane (DME) to remove the residues of reagents. The cathode was then dried under reduced pressure for 12 h. After that, the resulting Li2S cathode was impregnated with a mixture of vinylene carbonate (VC) and fluoroethylene carbonate (FEC) (VC: FEC = 1: 1 by weight). After 20 min impregnation, the cathode was dried under reduced pressure for 12 h.
2-3. Assembling of cells
Cells were assembled with the Li2S electrode and Li metal foil as an anode. Lithium bis(trifluorosulfonyl)imide (LiTFSI): tetraglyme (G4): 1,1,2,2–tetrafluoroethyl–2,2,3,3–tetrafluoropropyl ether (D2) at a respective ratio of 10: 8: 40 (by mol) was used as the electrolyte.
3.Major results and discussion
The Li2S cathode without the VC/FEC impregnation showed an initial charge capacity of 1791 mAh g-1 and an initial discharge capacity of 1298 mAh g-1, indicating a large irreversible capacity. In contrast, the Li2S cathode with the VC/FEC impregnation showed 1446 mAh g-1 and 1422 mAh g-1, respectively. Thus, the impregnation with VC/FEC reduced the initial irreversible capacity and improved the initial charge capacity. According to these results, Li remaining in the sulfur cathode would be partially consumed to form a film by the impregnation with VC/FEC. In addition, the capacity retention of the Li2S cathode with and without the VC/FEC impregnation was 73 % and 64 % at the 30th cycle, respectively. This suggests that the Li2S cathode with the film leads to better cycle performance than that without the film.
We will also report the results of surface composition analysis of the Li2S cathode with and without the VC/FEC impregnation by Hard X-ray Photoelectron Spectroscopy (HAXPES).
References
[1] M. Wild et al., Energy & Environ. Sci., 8 (2015) 3477.
[2] X. Ji et al., Nat. Mater., 8 (2009) 500.
[3] T. Abe et al., J. Power Sources, 68 (1997) 216.
[4] Y. Wu et al., J. Power Sources, 366 (2017) 65.
[5] M. Okuno et al., The 60th Battery Symposium in Japan (2019) Abstract [3D01].