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

doi:10.6023/A22110456

Abstract

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

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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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Fig. & Tab. 7

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

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

Figure 3. TGA curve of P-TiO2/C

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

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

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

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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基于P掺杂TiO2/C纳米管负极的高性能锂离子电容器