NaTiSi2O6/C复合材料用于锂离子电池负极材料

doi:10.3866/PKU.WHXB201912030

摘要/Abstract

摘要：

在本文中，我们首次报道了一种新型的硅酸盐负极材料NaTiSi₂O₆，由溶胶-凝胶法和固相烧结法合成而得。这种材料属于单斜晶系，空间群为C2/c。通过葡萄糖的高温裂解和碳化，NaTiSi₂O₆/C复合物被成功制备出来，其表面积为132 m²·g^-1。在0.1 A·g^-1的电流密度下其首圈放电和充电的比容量分别为542.9 mAh·g^-1和266.6 mAh·g^-1，首圈库伦效率为49.1%。在经过100圈循环后，其充电比容量为224.1 mAh·g^-1，容量保持率为84.1%。原位X射线衍射测试表明，其充放电机理为嵌入反应。这使得NaTiSi₂O₆成为硅酸盐负极材料家族中新的一员。

关键词: NaTiSi₂O₆, 锂离子电池, 负极材料, 硅酸盐电极材料

Abstract:

The development of human society and the continuously emerging environmental problems call for cleaner energy resources. Lithium-ion batteries, since their commercialization in the early 1990s, have been an important power source of mobile phones, laptops as well as other portable electronic devices. Their advantages include environment-friendliness, light weight, and no memory effect compared with lead-acid or nickel-cadmium batteries. Electrode materials play an important role in the performance of lithium-ion batteries. The traditional commercial anode material, graphite, has a theoretical specific capacity of 372 mAh·g^-1 and working potential close to 0 V (vs Li⁺/Li), making it prone to the formation of lithium dendrite, which may cause short circuit especially when large current is applied. Another commercial anode material Li₄Ti₅O₁₂, which also undergoes an intercalation reaction during lithiation process, has a theoretical specific capacity of 175 mAh·g^-1 along with three lithium-ion intercalations per formula unit. This is relatively small, and it has a relatively high working potential of 1.55 V (vs Li⁺/Li), which reduces its output voltage and specific energy when assembled in full battery. To overcome the shortcomings mentioned above, it is essential to search for new anode materials that are low-cost, environment-friendly, and easy to synthesize. Silicate materials have gained widespread attention owing to their low cost and facile synthesis. Herein, we report for the first time a novel titanosilicate, NaTiSi₂O₆, synthesized by sol-gel and solid sintering. It is isostructural to pyroxene jadeite NaAlSi₂O₆, belonging to monoclinic crystal system with a space group of C2/c. By in situ pyrolysis and carbonization of glucose, nanosized NaTiSi₂O₆ mixed with carbon was successfully obtained with a specific surface area of 132 m²·g^-1, calculated according to the Brunauer–Emmett–Teller formula. The specific charge/discharge capacity in the first cycle at current density of 0.1 A·g^-1 is 266.6 mAh·g^-1 and 542.9 mAh·g^-1, respectively, with an initial coulombic efficiency of 49.1%. After 100 cycles, it retains a specific charge capacity of 224.1 mAh·g^-1, corresponding to a capacity retention rate of 84.1%. The average working potential of NaTiSi₂O₆ is 1.2–1.3 V (vs Li⁺/Li), slightly lower than that of Li₄Ti₅O₁₂. The reaction mechanism while charging and discharging was determined by in situ X-ray diffraction test as well as selected area electron diffraction. The results showed that NaTiSi₂O₆ undergoes an intercalation reaction during lithiation process, with two lithium-ion intercalations per formula unit. This makes NaTiSi₂O₆ a new member of the silicate anode material family, and may provide insights into the development of new silicate electrode materials in the future.

Key words: NaTiSi₂O₆, Lithium-ion battery, Anode material, Silicate electrode material

刘昆, 刘瑶, 朱海峰, 董晓丽, 王永刚, 王丛笑, 夏永姚. NaTiSi₂O₆/C复合材料用于锂离子电池负极材料[J]. 物理化学学报, 2020, 36(11), 1912030. doi: 10.3866/PKU.WHXB201912030

Kun Liu, Yao Liu, Haifeng Zhu, Xiaoli Dong, Yonggang Wang, Congxiao Wang, Yongyao Xia. NaTiSi₂O₆/C Composite as a Novel Anode Material for Lithium-Ion Batteries[J]. Acta Physico-Chimica Sinica 2020, 36(11), 1912030. doi: 10.3866/PKU.WHXB201912030

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201912030

https://www.whxb.pku.edu.cn/CN/Y2020/V36/I11/1912030

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Atom	Wyckoff site	S.O.F.	x/a	y/b	z/c
Na1	4e	0.94	0	0.3030(5)	1/4
Ti1	4e	0.92	0	0.90204(28)	1/4
Si1	8f	0.932	0.29289(25)	0.0892(4)	0.2427(5)
O1	8f	0.999	0.1187(4)	0.0807(6)	0.1497(9)
O2	8f	1.041	0.3597(5)	0.2548(6)	0.3099(10)
O3	8f	1.043	0.3530(6)	0.0075(4)	0.0198(14)

Anode Material	Mass Loading/(mg·cm^?2)	Current Density/(A·g^?1)	Specific Capacity/(mAh·g^?1)	Reference
Li₂TiSiO₅	~3	0.02	308	44
Na₂Ti₂O₃SiO₄	1–6	0.02	750–40	45
Na₂TiOSi₄O₁₀	/	0.1	364	46
Na₂TiOSi₄O₁₀	0.9–1.6	C/10	67.6	47
Na₂TiSiO₅	~1	0.5	~200	48
NaTiSi₂O₆	~2	0.05	230	This Work

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NaTiSi₂O₆/C复合材料用于锂离子电池负极材料

NaTiSi₂O₆/C Composite as a Novel Anode Material for Lithium-Ion Batteries

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