English

• 1. INTRODUCTION

  Nanostructures have increased the electrical conductance and improved the capacity of metal-ion battery^[1-5]. The nanostructures have high area surfaces and beneficent electrical properties to use as electrode in metal-ion battery. The metal dioxides have been employed in electrochemistry and they have high capacity and performance than graphite^[6-9]. Researchers have described that nanotubes have great capacity as anode electrodes in metal-ion batteries^[10-13].

  The experimental researchers have demonstrated the carbon nanotubes have high application in industry due to excellent thermal, electrical and mechanical properties. The experimental researchers have used the composite structures of carbon nanotubes with metal oxides and metal dioxides in order to exploit the applications of carbon nanotubes^[14-16].

  The experimental researchers have considered the metal oxides and metal dioxides for energy storage devices due to particular physical and chemical properties. The experimental researchers have confirmed that metal oxides and metal dioxides have high electrical conductivities used in metal-ion batteries^[17-19].

  The experimental researchers have assembled the framework of metal oxides and metal dioxides on carbon nanotubes and these frameworks increased the heat conduction and surface. The experimental researchers confirmed that these frameworks enhanced the electron and ion transport from within and outside of carbon nanotubes which have applications in metal-ion batteries^[20-22].

  The experimental researchers have assayed to use layer-by-layer assembly to aid the growth of metal oxides and metal dioxides on carbon nanotubes. They have applied gel polymers to enforce the addition of various metals to create the composites of metal oxides and metal dioxides and carbon nanotubes^[23-26].

  In this study, potential of carbon nanotube (8, 0) and attached metal oxides (manganese oxide (MnO) and cadmium dioxide (CdO₂)) to carbon nanotube (8, 0) as materials of anode electrodes in metalion batteries are investigated. The main aims of this study are (a) to compare the potential of MnO and CdO₂ as anode electrodes in metal-ion batteries and (c) to compare the performance of LIB and KIB.

  2. COMPUTATIONAL DETAILS

  Geometries of CNT (8, 0), MnO-CNT (8, 0) and CdO₂-CNT (8, 0) are calculated via DFT/M06-2X and 6-311+G (2d, 2p) in GAMESS package. The frequency calculations of complexes (MnO-CNT (8, 0) and CdO₂-CNT (8, 0)) are done to confirm these optimized complexes are real minima structures^[27-32]. The Gibbs free energies of adsorption of metal oxides (MnO and CdO₂) on CNT (8, 0) are calculated as follows:

  $ \begin{aligned} & G_{\text {ad }}=G(\text { metal oxide-CNT }(8,0))- \\ & G(\text { metal oxide })-G(\operatorname{CNT}(8,0)) \end{aligned} $

  (1)

  The geometries of MnO-CNT (8, 0) and CdO₂-CNT (8, 0) with Li and K are calculated by DFT/M06-2X and 6-311+G (2d, 2p). The Gibbs free energies of adsorption of metals (Li and K) on surfaces of MnO-CNT (8, 0) and CdO₂-CNT (8, 0) are calculated as below:

  $ G_{\mathrm{ad}}=G\left(\mathrm{Li}-\mathrm{CdO}_2-\mathrm{CNT}(8,0)\right)-G(\mathrm{Li})-G\left(\mathrm{CdO}_2-\mathrm{CNT}(8,0)\right) $

  (2)

  $ G_{\mathrm{ad}}=G\left(\mathrm{~K}-\mathrm{CdO}_2-\mathrm{CNT}(8,0)\right)-G(\mathrm{~K})-G\left(\mathrm{CdO}_2-\mathrm{CNT}(8,0)\right) $

  (3)

  $ G_{\mathrm{ad}}=G(\mathrm{Li}-\mathrm{MnO}-\mathrm{CNT}(8,0))-G(\mathrm{Li})-G(\mathrm{MnO}-\mathrm{CNT}(8,0)) $

  (4)

  $ G_{\mathrm{ad}}=G(\mathrm{~K}-\mathrm{MnO}-\mathrm{CNT}(8,0))-G(K)-G(\mathrm{MnO}-\mathrm{CNT}(8,0)) $

  (5)

  The reactions in anode of Li-ion and K-ion batteries are:

  $ \mathrm{Li}-\mathrm{CdO}_2-\mathrm{CNT}(8,0) \leftrightarrow \mathrm{Li}^{+}-\mathrm{CdO}_2-\mathrm{CNT}(8,0)+e^{-} $

  (6)

  $ \mathrm{K}-\mathrm{CdO}_2-\mathrm{CNT}(8,0) \leftrightarrow \mathrm{K}^{+}-\mathrm{CdO}_2-\mathrm{CNT}(8,0)+e^{-} $

  (7)

  $ \mathrm{Li}-\mathrm{MnO}-\mathrm{CNT}(8,0) \leftrightarrow \mathrm{Li}^{+}-\mathrm{MnO}-\mathrm{CNT}(8,0)+e^{-} $

  (8)

  $ \mathrm{K}-\mathrm{MnO}-\mathrm{CNT}(8,0) \leftrightarrow \mathrm{K}^{+}-\mathrm{MnO}-\mathrm{CNT}(8,0)+e^{-} $

  (9)

  The reactions in cathode of Li-ion and K-ion batteries are: (Li⁺ + e⁻ ↔ Li and K⁺ + e⁻ ↔ K). The thorough reaction of Li-ion and K-ion batteries are:

  $ \mathrm{Li}^{+}+\mathrm{Li}-\mathrm{CdO}_2-\mathrm{CNT}(8,0) \leftrightarrow \mathrm{Li}^{+}-\mathrm{CdO}_2 \text {-CNT }(8,0)+\mathrm{Li}+\Delta G_{\text {cell }} $

  (10)

  $ \mathrm{K}^{+}+\mathrm{K}-\mathrm{CdO}_2-\mathrm{CNT}(8,0) \leftrightarrow \mathrm{K}^{+}-\mathrm{CdO}_2-\mathrm{CNT}(8,0)+\mathrm{K}+\Delta G_{\text {cell }} $

  (11)

  $ \mathrm{Li}^{+}+\mathrm{Li}-\mathrm{MnO}-\mathrm{CNT}(8,0) \leftrightarrow \mathrm{Li}^{+}-\mathrm{MnO}-\mathrm{CNT}(8,0)+\mathrm{Li}+\Delta G_{\text {cell }} $

  (12)

  $ \mathrm{K}^{+}+\mathrm{K}-\mathrm{MnO}-\mathrm{CNT}(8,0) \leftrightarrow \mathrm{K}^{+}-\mathrm{MnO}-\mathrm{CNT}(8,0)+\mathrm{K}+\Delta G_{\text {cell }} $

  (13)

  In metal-ion battery, cell voltage (V_cell) is: V_cell = − ΔG_cell/zF, where F as Faraday constant is 96, 500 C/mol, z is the charge on Li⁺ and K⁺ ions in electrolyte and ΔG_cell was the Gibbs free energy change of studied cells^[33-37]. The band gap energy (E_BG) of studied nanostructures is E_LUMO – E_HOMO^[38-40].

  3. RESULTS AND DISCUSSION

  The structures of CNT (8, 0), and MnO and CdO₂ on CNT (8, 0) are presented in Fig. 1. The top and bridge of carbon atoms are possible sites of adsorption of MnO and CdO₂ on CNT (8, 0). The G_ad of CNT (8, 0)-MnO and CNT (8, 0)-CdO₂ are reported in Table 1. The top positions of CNT (8, 0)-MnO and CNT (8, 0)-CdO₂ are more stable than bridge positions by 0.28 and 0.24 eV, respectively.

  Figure 1

  

  Figure 1.  Structures of CNT, CNT-MnO and CNT-CdO₂ and their complexes with metals

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  Table 1

  

  Table 1.  G_ad, Band Gap Energy, q and V_cell of CNT (8, 0), CNT (8, 0)-MnO and CNT (8, 0)-CdO₂

  DownLoad: CSV

  Complex	Type Interaction	Gad (eV)	Band gap energy (eV)
  CNT (8, 0)-MnO	Top	–3.63	0.05
  CNT (8, 0)-MnO	Bridge	–3.35	0.08
  CNT (8, 0)-CdO2	Top	–3.08	0.11
  CNT (8, 0)-CdO2	Bridge	–2.84	0.15
  Complex	Metal/metal ion	q (Electron)	Gad (eV)	Vcell (V)
  	Li	0.026	–0.18	1.97
  CNT (8, 0)	K	0.022	–0.16	1.71
  	Li+	0.311	–2.16
  	K+	0.269	–1.87
  	Li	0.062	–0.43	5.13
  CNT (8, 0)-MnO	K	0.058	–0.41	4.84
  	Li+	0.805	–5.59
  	K+	0.759	–5.27
  	Li	0.067	–0.46	5.99
  CNT (8, 0)-CdO2	K	0.064	–0.44	5.70
  	Li+	0.934	–6.48
  	K+	0.889	–6.17

  The CNT (8, 0)-MnO in top and bridge positions are more stable than CNT (8, 0)-CdO₂ by 0.55 and 0.51 eV, respectively. The top positions of CNT (8, 0)-MnO and CNT (8, 0)-CdO₂ have lower binding distance than bridge positions 0.13 and 0.12 Å, respectively. The CNT (8, 0)-MnO in top and bridge positions have lower binding distance than CNT (8, 0)-CdO₂ by 0.91 and 0.92 Å, respectively.

  The band gap energies of CNT (8, 0)-CdO₂ and CNT (8, 0)-MnO are calculated and reported in Table 1. The band gap energies of CNT (8, 0)-MnO and CNT (8, 0)-CdO₂ are 0.05~0.15 eV. The CNT (8, 0)-MnO in top and bridge positions have lower band gap energies than CNT (8, 0)-CdO₂ by 0.06 and 0.07 eV, respectively.

  The top positions of CNT (8, 0)-MnO and CNT (8, 0)-CdO₂ have lower band gap energies bridge positions 0.03 and 0.04 eV, respectively. The addition of MnO and CdO₂ molecules to the surface of CNT (8, 0) can decrease the band gap energies of CNT (8, 0) from 1.23 to 0.05~0.15 eV.

  The potentials of CNT (8, 0), CNT (8, 0)-MnO and CNT (8, 0)-CdO₂ as anode in metal-ion batteries (Li-ion and K-ion battery) are investigated. In Fig. 1, the binding distances of metal ions and CNT (8, 0), CNT (8, 0)-MnO and CNT (8, 0)-CdO₂ are 1.55, 1.67 and 1.74 Å, respectively.

  The charge (q) values of metal atoms on CNT (8, 0), CNT (8, 0)-MnO and CNT (8, 0)-CdO₂ surfaces are reported in Table 1. The q of CNT (8, 0)-MnO and CNT (8, 0)-CdO₂ of Li and K atoms/ions are higher than CNT (8, 0). The CNT (8, 0)-CdO₂ has higher charges than CNT (8, 0)-MnO and CNT (8, 0).

  The Gibbs free energy (G_ad) values of metal atoms on CNT (8, 0), CNT (8, 0)-MnO and CNT (8, 0)-CdO₂ are reported in Table 1. The cell voltages (V_cell) of CNT (8, 0), CNT (8, 0)-MnO and CNT (8, 0)-CdO₂ as anode electrodes are calculated and reported in Table 1. The |G_ad| of CNT (8, 0)-MnO and CNT (8, 0)-CdO₂ for Li and K atoms/ions are higher than CNT (8, 0). The |G_ad| of CNT (8, 0)-CdO₂ for Li and K atoms/ions are higher than CNT (8, 0)-MnO.

  The V_cell values of CNT (8, 0), CNT (8, 0)-MnO and CNT (8, 0)-CdO₂ as anode electrodes in LIB are 1.97, 5.13 and 5.99 V, respectively, while those in KIB are 1.71, 4.84 and 5.70 V correspondingly.

  The V_cell of CNT (8, 0)-MnO and CNT (8, 0)-CdO₂ as anode electrodes in KIB are higher than CNT (8, 0) 3.13 and 4.00 V, respectively. The CNT (8, 0)-CdO₂ has the best potential as an anode electrode in LIB and KIB and it can be proposed as a novel material in electricity storage machines.

  4. CONCLUSION

  The top positions of CNT (8, 0)-MnO and CNT (8, 0)-CdO₂ have higher binding distances than bridge positions by 0.13 and 0.12 Å, respectively. The top positions of CNT (8, 0)-MnO and CNT (8, 0)-CdO₂ are 0.28 and 0.24 eV more stable than the bridge ones, respectively. The CNT (8, 0)-MnO on top and bridge positions are more stable than CNT (8, 0)-CdO₂ by 0.55 and 0.51 eV, respectively. The CNT (8, 0)-CdO₂ can have higher charges than CNT (8, 0)-MnO and CNT (8, 0). The V_cell of CNT (8, 0)-MnO and CNT (8, 0)-CdO₂ as anode electrodes in LIB and KIB are higher than CNT (8, 0) by 3.15 and 4.01 V, respectively. The V_cell values of CNT (8, 0)-CdO₂ as an anode electrode in LIB and KIB are higher than CNT (8, 0)-MnO by 0.85 and 0.86 V, respectively. Finally, the CNT (8, 0)-CdO₂ has the best potential as an anode electrode in LIB and KIB and it can be proposed as a novel material in electricity storage machines.

  
  
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• 

  Figure 1  Structures of CNT, CNT-MnO and CNT-CdO₂ and their complexes with metals

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  Table 1.  G_ad, Band Gap Energy, q and V_cell of CNT (8, 0), CNT (8, 0)-MnO and CNT (8, 0)-CdO₂

  Complex	Type Interaction	Gad (eV)	Band gap energy (eV)
  CNT (8, 0)-MnO	Top	–3.63	0.05
  CNT (8, 0)-MnO	Bridge	–3.35	0.08
  CNT (8, 0)-CdO2	Top	–3.08	0.11
  CNT (8, 0)-CdO2	Bridge	–2.84	0.15
  Complex	Metal/metal ion	q (Electron)	Gad (eV)	Vcell (V)
  	Li	0.026	–0.18	1.97
  CNT (8, 0)	K	0.022	–0.16	1.71
  	Li+	0.311	–2.16
  	K+	0.269	–1.87
  	Li	0.062	–0.43	5.13
  CNT (8, 0)-MnO	K	0.058	–0.41	4.84
  	Li+	0.805	–5.59
  	K+	0.759	–5.27
  	Li	0.067	–0.46	5.99
  CNT (8, 0)-CdO2	K	0.064	–0.44	5.70
  	Li+	0.934	–6.48
  	K+	0.889	–6.17

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•