基于P掺杂TiO2/C纳米管负极的高性能锂离子电容器

doi:10.6023/A22110456

摘要/Abstract

以磷酸二氢钠(NaH₂PO₄)为磷源, 通过溶剂热法制备了P掺杂的TiO₂/C (P-TiO₂/C)纳米管以改善TiO₂的储锂性能. 电化学测试表明: P-TiO₂/C负极具有高的比容量(在0.1 A•g^-1的电流密度下达到335 mAh•g^-1)、优异的倍率性能(在2.0 A•g^-1的电流密度下为92 mAh•g^-1)及循环性能(在1.0 A•g^-1的电流密度下经过1000次循环后放电比容量仍维持在135 mAh•g^-1). 并且, P-TiO₂/C在2 mV•s^-1时的赝电容贡献约为96%. 由P-TiO₂/C负极和活性炭正极组装的锂离子电容器在250 W•kg^-1的功率密度下能量密度能够达到74.7 Wh•kg^-1. 此外, 该锂离子电容器在10000次循环后比电容保持率约为43%. 此外, 该器件在1.0 A•g^-1下循环10000次后充满电仍可点亮18只红色的LED灯组成的“LIC”字样. 该工作为高性能锂离子电容器TiO₂负极材料的设计提供了思路.

关键词: 二氧化钛, 磷掺杂, 负极, 锂离子电容器

As an anode material for Li-ion capacitors (LICs), TiO₂ exhibits pseudocapacitive behavior, low sodium storage potential and small structural changes in lithium storage process. However, poor conductivity and slow ion diffusion lead to sluggish lithium storage kinetics. Using sodium dihydrogen phosphate (NaH₂PO₄) as a phosphorus source, P-doped TiO₂/C (P-TiO₂/C) nanotubes are prepared by a simple solvothermal method to improve the lithium storage performance of TiO₂. The P-TiO₂/C nanotubes composed of nanosheets grown vertically on the surface can provide effective contact areas between electrolyte and active materials. And the C and P in P-TiO₂/C are derived from the carbonization of alcohols and decomposition of NaH₂PO₄. P-doping easily causes P—O—Ti bond formed in TiO₂ by P⁵⁺ replacing part of Ti⁴⁺, which can effectively improve the conductivity of TiO₂. Electrochemical tests show that the P-TiO₂/C anode for Li-ion batteries exhibits a high specific capacity (335 mAh•g^-1 at a current density of 0.1 A•g^-1), excellent rate capability (92 mAh•g^-1 at a current density of 2.0 A•g^-1) and long cycle performance (135 mAh•g^-1 at a current density of 1.0 A•g^-1 after 1000 cycles). In addition, the pseudocapacitive contribution of P-TiO₂/C anode is about 96% at a scan rate of 2 mV•s^-1. The superior lithium storage performance of P-TiO₂/C nanotubes is derived from the P-doping in TiO₂, which can change the electron structure of TiO₂, which facilitates the electrons transport and lithium diffusion kinetics. The LICs assembled by P-TiO₂/C anodes and activated carbon cathodes have a high energy density of 74.7 Wh•kg^-1 at a power density of 250 W•kg^-1, which are higher than some LICs based on titanic-based compound anodes. And the capacity retention of the LICs is about 43% after 10000 cycles at a current density of 1.0 A•g^-1. In addition, after 10000 cycles test, a fully charged LICs can still light up the “LIC” model composed of 18 red LED lights. This work provides an idea for the design of TiO₂ anode materials for high-performance LICs.

Key words: titanium dioxide, P-doping, anode, Li-ion capacitors

引用此文

张国强, 霍京浩, 王鑫, 郭守武. 基于P掺杂TiO₂/C纳米管负极的高性能锂离子电容器[J]. 化学学报, 2023, 81(1): 6-13.

Guoqiang Zhang, Jinghao Huo, Xin Wang, Shouwu Guo. P-doped TiO₂/C Nanotubes as Anodes for High-performance Li-ion Capacitors[J]. Acta Chimica Sinica, 2023, 81(1): 6-13.

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图/表 7

图1. P-TiO2/C的（A~C) SEM，(D, E) TEM 和(F) 元素mapping 图

Figure 1. (A~C) SEM, (D, E) TEM and (F) element mapping of P-TiO2/C

图2. (A) P-TiO2/C和P-TiO2/C的XRD图, (B) P-TiO2/C的XPS全谱图以及(C) C 1s, (D) Ti 2p, (E) O 1s和(F) P 2p的XPS谱图

Figure 2. (A) XRD patterns of TiO2/C and P-TiO2/C, (B) XPS survey scan and XPS spectra of (C) C 1s, (D) Ti 2p, (E) O 1s and (F) P 2p of P-TiO2/C

图3. P-TiO2/C的TGA曲线

Figure 3. TGA curve of P-TiO2/C

图4. (A) TiO2/C和(B) P-TiO2/C 在0.1 mV?s-1扫速下的前四次CV曲线, (C) TiO2/C和(D) P-TiO2/C 在0.1 A?g-1电流密度下的前三次充放电曲线, (E) TiO2/C和P-TiO2/C的倍率性能和P-TiO2/C相应的库伦效率, (F) TiO2/C和P-TiO2/C循环前以及P-TiO2/C在1.0 A?g-1电流密度下循环1000次的Nyquist图, (G) P-TiO2/C在1.0 A?g-1电流密度下的1000次循环性能和相应的库伦效率

Figure 4. The initial four cycles of CV curves for TiO2/C (A) and P-TiO2/C (B) at a scan rate of 0.1 mV?s-1, the initial three galvanostatic discharge/charge profiles of TiO2/C (C) and P-TiO2/C (D) at a current density of 0.1 A?g-1, (E) rate capability of TiO2/C and P-TiO2/C and corresponding coulombic efficiency of P-TiO2/C, (F) Nyquist plots of TiO2/C and P-TiO2/C before cycling and P-TiO2/C after 1000 cycles at 1.0 A?g-1, (G) cycling capability and corresponding coulombic efficiency of P-TiO2/C at 1.0 A?g-1

图5. P-TiO2/C负极: (A) 不同扫速下的CV曲线, (B)氧化还原峰对应的log i-log v曲线, (C) 2 mV?s-1扫速下的表面电容电流贡献和(D) 不同扫速下表面电容占比

Figure 5. The P-TiO2/C anode: (A) CV curves at different scan rates, (B) the corresponding log i-log v plots at redox peaks, (C) the estimated surface- controlled capacitive current contribution at 2 mV?s-1 and (D) the ratio of surface-controlled capacitive at different sweep rates

图6. AC的(A) CV曲线, (B) GCD曲线, (C) 倍率性能和(D) 1000次循环性能曲线

Figure 6. (A) CV curves, (B) GCD curves, (C) rate capability and (D) cycle performance for AC

图7. AC//P-TiO2/C型LICs的(A)结构示意图, (B) CV曲线和 (C) GCD曲线, (D) Ragone图与其他工作的对比, (E) 10000次GCD曲线, 插图为最后10次GCD曲线和一个LIC在10000次循环后充满电点亮18只红色的LED灯组成的“LIC”字样

Figure 7. (A) The construction, (B) CV curves and (C) GCD curves of AC//P-TiO2/C LIC, (D) Ragone plot of this work and other previously reported LICs, (E) GCD test over 10000 cycles, last 10 GCD cycle curves and after 10000 cycles, a LIC was fully charged and lighted up the word “LIC” composed of 18 red LED lights (inset)

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基于P掺杂TiO₂/C纳米管负极的高性能锂离子电容器

P-doped TiO₂/C Nanotubes as Anodes for High-performance Li-ion Capacitors

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