硫化錫-硫化銻作為鋰離子電池負極材料之研究

SnS-Sb2S3 as Anode Materials for Li Ion Battery

郭怡汎(YU-FAN KUO)

指導教授 ： 李岱洲 ； 張仍奎

國立中央大學/工學院/化學工程與材料工程學系/碩士(2015年)

摘要

本實驗藉由溶劑熱法及物理混合法合成出SnS-Sb2S3粉末首次當作負極材料應用在鋰離子電池中，與Sb2S3及SnS做比較。本實驗有兩種不同比例的SnS-Sb2S3粉末：Sn(1)-Sb(2)-S(4)以及Sn(3)-Sb(2)-S(6)。Sn(1)-Sb(2)-S(4)是由溶劑熱法合成出來，分為無煅燒及煅燒兩種；Sn(3)-Sb(2)-S(6)是由溶劑熱法及物理混合法合成出來，也有分為無煅燒及煅燒，總共四種。這六種SnS-Sb2S3粉末與Sb2S3及SnS比較，其中以溶劑熱法製備Sn(3)-Sb(2)-S(6)煅燒後粉末電極在不同速率充放電中有較高的電容值以及在循環穩定性第一圈有較好的可逆電容值；以溶劑熱法製備Sn(1)-Sb(2)-S(4)煅燒後粉末電極於300 mA/g定電流下反覆充放電150圈有後有28 %的維持率。
藉由改變黏著劑以及電解液來提升電容值以及維持率，將黏著劑以及電解液改成polyimide DB100以及1 M LiPF6 in FEC/DEC，電容值以及維持率都提高很多。其中以Sn(1)-Sb(2)-S(4)煅燒後粉末電極在改變黏著劑與電解液之前的電容值是介於SnS與Sb2S3之間，改變之後電容值卻高於SnS與Sb2S3。以溶劑熱法製備Sn(3)-Sb(2)-S(6)煅燒後粉末電極於250 mA/g定電流下反覆充放電50圈後仍有高達92 %的維持率。

關鍵字

鋰離子電池 ； 負極 ； 硫化物

並列摘要

Lithium-ion batteries (LIBs) are the most widely used rechargeable batteries for powering electronic devices such as electric vehicles (EV), laptop computers and cellular phones due to their high energy density. We proposed to use ternary Sn-Sb-S metal sulfide as the active materials for LIBs. Specifically, Sn(1)-Sb(2)-S(4) and Sn(3)-Sb(2)-S(6) were first prepared and tested as anode. It is expected that the stepwise lithium insertion mechanism can alleviate volume changes and improve the mechanical stability of the electrode.
In this study, the Sn(1)-Sb(2)-S(4) and the Sn(3)-Sb(2)-S(6) powders are synthesized using solvothermal and physical mixture method. The as-prepared powders and annealed (500 oC) ones were tested. Noted that the as-prepared samples exhibited mixtures of SnS and Sb2S3. Depending on the preparation conditions, annealed samples show a major phase of SnSb2S4 and Sn3Sb2S6. Compare the Sn(1)-Sb(2)-S(4) and the Sn(3)-Sb(2)-S(6) with Sb2S3 and SnS, annealed Sn(3)-Sb(2)-S(6) powder provides the highest capacity of 829 mAh/g. However, anneaned Sn(1)-Sb(2)-S(4) powder has the best cycle stability with the reversible capacity of 164 mAh/g after 150 cycles at a constant current of 300 mA/g, corresponding to 28 % retention.
In a parallel experiment, binder and electrolyte were changed to improve the capacity and retention. Here, the binder, PVdF was replaced by polyimide DB100. The electrolyte was switched from commercial electrolyte (1 M LiPF6 in EC/DEC) to 1 M LiPF6 in FEC/DEC. The capacities of ternary metal sulfide (Sn-Sb-S) were significantly enhanced, even better than that of the Sb2S3 and SnS binary metal sulfide. At a constant current of 250 mA/g, Sn(3)-Sb(2)-S(6) powder exhibits a reversible capacity of 963 mAh/g after 50 cycles with the retention of 92 %.

並列關鍵字

Li-ion battery ； anode ； sulfide

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