Synthesis of MnO 2 @TiO 2 composite electrodes via hydrolysis and calcination for high stability zinc ions batteries

doi:10.21203/rs.3.rs-4981525/v1

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Synthesis of MnO 2 @TiO 2 composite electrodes via hydrolysis and calcination for high stability zinc ions batteries

https://doi.org/10.21203/rs.3.rs-4981525/v1

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Aqueous Zn/MnO₂ batteries have been extensively attracted attentions for their superior comprehensive performance. However, the poor structural stability and dissolution of MnO₂ have seriously prevented its further development. Therefore, TiO₂ is introduced for coating MnO₂ to improve its electrochemical stability. Firstly, TiO₂ used as a protective layer could hamper the direct contact between the electrode and the electrolyte, and effectively inhibiting the dissolution of manganese. Secondly, TiO₂ has good mechanical strength to adapt to the volume change of MnO₂ during the charge/discharge processes, which consolidates the stability of the electrode material. Finally, TiO₂ could improve the electrical conductivity of the composite material, achieving lower polarization and good electron/ion transport. As a result, Zn/MnO₂@TiO₂-2 exhibits extraordinary electrochemical performance with a rate capacity of 245.16 mAh g^− 1 at 0.2 A g^− 1 and maintains a capacity of 137.09 mAh g^− 1 after 1000 cycles at 1 Ag^− 1. Even at a high current density of 3 A g^− 1, it has a capacity of 93.35 mAh g^− 1 after 1500 cycles, and the capacity retention rate is 97.47%. This work provides the inspiration and foundation method for designing high-performance Zn/MnO₂ batteries.

Zn/MnO 2 battery

MnO 2

TiO 2

structural stability

manganese dissolution

The evolution of renewable, green and clean energy is key for all humankind to achieve carbon neutrality and sustainable development.¹ The intermittent and fluctuating natural of renewable energy sources has inspired research on energy storage devices. Currently, lithium-ion batteries (LIBs) are widely used in various handheld electric devices and vehicles due to their great energy density, high average output voltage, and absence of memory effect.² However, the cost challenges caused by the scarcity of lithium resources and the inherent safety issues of organic electrolytes have seriously hindered their development.³ Therefore, the exploitation of new, more cost-effective and green energy storage devices is imminent. In contrast, aqueous zinc ion batteries (AZIBs) use a non-flammable and safe electrolyte, and having abundant zinc resources that are readily available and inexpensive.⁴ Thus, AZIBs have a large potential and are expected to be an alternative energy source to LIBs. In order to promote the practical application and commercialization of AZIBs, many cathode materials have been investigated, including manganese-based materials⁵, vanadium-based materials⁶, prussian blue analogues⁷ and organic compounds.⁸ Among them, manganese dioxide has the advantages of a sizable theoretical capacity (308 mAh g^− 1), high operating voltage (1.3 ~ 1.4 V vs. Zn/Zn²⁺), non-toxicity, and cheapness.^{9, 10} Unfortunately, manganese dioxide materials have poor rate performance due to the intrinsic poor electrical conductivity and the slow diffusion of the ions, and the Mn³⁺ ion disproportionation induced dissolution of Mn²⁺ and phase transition and structural collapse due to repeated ion inserting make the cycling stability poor and other problems prevent its wide application in AZIBs.^{11, 12} Thus, it is urgent to develop synthesis strategy for improving the performance of MnO₂.

Up to date, numerous measures such as ion doping¹³, pre-intercalation techniques¹⁴, defect engineering¹⁵ and surface coating¹⁶, have been taken to improve the electrochemical performance of MnO₂. Of them, surface coating is an effective way to enhance the cycling stability performance of MnO₂. Previous studies have shown that carbon-based materials, conductive polymers and derivatives, and metal oxides coating not only improve the conductivity of the materials and accelerate the rapid charge transfer, but also avoid direct contact between the electrode materials and the electrolyte, which effectively mitigates the volumetric change and dissolution of MnO₂.^17–20

Titanium dioxide is a non-toxic, non-hazardous, widely available semiconductor material.²¹ It plays an important role in photocatalysis, sensors, solar cells, lithium batteries, and supercapacitors.²² With good electrochemical corrosion resistance and stability of electrochemical reactions²³, TiO₂ also possesses good mechanical strength (about five times that of amorphous carbon),^{24, 25} making it one of the preferred choices as a surface coating material. In this paper, MnO₂@TiO₂ materials were synthesized by hydrolysis and calcination. For one hand, the TiO₂ coating can improve the electrical conductivity of composite material and promote the rapid and uniform transmission of Zn²⁺. And another hand, the coating TiO₂ with good mechanical strength can adapt to the volume change of the electrode, which protects the structural stability of the material. Furthermore, the coating TiO₂ blocks the direct contact between the electrolyte and the electrode material, effectively inhibiting manganese dissolution. When MnO₂@TiO₂ is used as the cathode, the results exhibit an excellent rate capacity of 245.16 mAh g^− 1 at 0.2 A g^− 1, and maintains a capacity of 137.09 mAh g^− 1 after 1000 cycles at 1 A g^− 1. Even at a high current density of 3 A g^− 1, it has a capacity of 93.35 mAh g^− 1 after 1500 cycles, with a capacity retention rate of 97.47%.

2.1 Preparation of MnO₂@TiO₂ and MnO₂ samples:

Firstly, 0.005 mol of KMnO₄ dissolved in 35 mL of deionized water. 1 mL of hydrochloric acid was slowly dripped into the above solution and stirred for 30 min, and then the solution was transferred to a sealed reactor and stored in an oven at 120 ℃ for 6 h. After that, the product MnO₂ was collected by filtration and washed with deionized water and ethanol for several times, and then dried overnight.

MnO₂ (0.2g) was dispersed in anhydrous ethanol (45mL), and then 1 mL of ammonia and 1.5 mL of n-tetrabutyl titanate were added slowly and stirred in a water bath at 50 ℃ for 10 h. After the reaction was completed, the product was collected by filtration and washed with deionized water and ethanol. The product was dried and then calcinated in a tube furnace at 500 ℃ for 2 h under Ar atmosphere. The MnO₂@TiO₂ composites were finally obtained. The MnO₂@TiO₂ materials were prepared by using 1 mL, 1.5 mL and 2 mL of n-tetrabutyl titanate, which were named as MnO₂@TiO₂-1, MnO₂@TiO₂-2 and MnO₂@TiO₂-3, respectively.

2.2 Material characterization.

In order to determine the crystal structure and chemical composition of the materials, a Bruker D8 Advance diffractometer equipped with Cu-Kα radiation (λ = 0.15406 nm) was used at 40 kV and 40 mA and XRD patterns were obtained in the 2θ range from 5 to 80°. Scanning electron microscopy (SEM, FEI FEG250), energy dispersive spectroscopy (EDS) and transmission electron microscopy (TEM, Talos F200S) were used to observe the morphology and microscopic features of the samples.

2.3 Electrochemical measurements.

The synthesized samples (70 mg), acetylene black (20 mg) and PVDF (10 mg) were mixed in n-methyl-2-pyrrolidone (NMP) and thoroughly milled to form a homogeneous and viscous slurry, which was then coated on a stainless steel foil and vacuum dried at 80°C overnight. Glass fibers (GF/A) dripping with 1.5 M Zn(CF₃SO₃)₂ + 0.1 M MnSO₄ electrolyte were placed between the prepared cathode and the zinc foil anode to assemble a model 2025 coin cell. Constant current charge/discharge tests with the voltage range of 0.8 ~ 1.8 V were performed on a Neware (CT-4008 Tn) system. Cyclic voltammetry (CV) tests with a voltage range of 0.8 ~ 1.8 V and a scan rate of 0.2 ~ 1.0 mV s^− 1 and electrochemical impedance spectroscopy (EIS) tests with frequencies ranging from 0.01 to 100k Hz were performed on a Donghua (DH7000C) electrochemical workstation.

The XRD profiles are shown in Fig. 1a, and all the samples presented similar diffraction peaks. The diffraction peaks of MnO₂@TiO₂ located at 12.78°, 18.12°, 28.84°, 37.52°, 41.97°, 49.86°, 60.27°, and 69.71° corresponded to the diffraction peaks (110), (200), (310), (211), (301), (411), (521), and (541) crystal planes of α-MnO₂ (JCPDS NO. 44–0141)²⁶, but the peak intensities decreased with the increase of the addition of n-tetrabutyl titanate, which may be due to the excessive addition of n-tetrabutyl titanate resulting in the generation of a thick TiO₂ coating that the X-rays failed to detect the MnO₂ crystals sufficiently. In comparison with MnO₂, six diffraction peaks were also observed at 25.35°, 37.78°, 48.08°, 53.92°, 55.11°, 62.73°, and 75.09°, with pronounced sharp intensities of the diffraction peaks, which respectively corresponded to the (101), (004), (200),( 105), (211), (204) and (215) crystal planes of anatase TiO₂ (JCPDS NO.04-0477).²⁷ In addition, no other obvious impurity peaks existed in the XRD, which implies that TiO₂ was successfully coated on the surface of MnO₂.

The morphological features of MnO₂ and MnO₂@TiO₂ were compared via SEM. Figures (1b, c) show the SEM images of MnO₂, which has a nanorod-like structure with a length of about 1.0 ~ 2.0 µm and a diameter of about 50 ~ 100 nm. Figures (S1a, b), Figures (1d, e) and Figures (S1c, d) show the SEM images of MnO₂@TiO₂-1, MnO₂@TiO₂-2, and MnO₂@TiO₂-3, respectively, which have a similar nanorod-like structure, except that the nanorods are surrounded by some block structures of TiO₂. From the figures, it can be seen that the introduction of TiO₂ coating improves the dispersion of MnO₂ nanorods, which can provide a large number of active sites for electrochemical reactions. In addition, the large voids between the nanorods and nanoblocks are favorable for the infiltration of the electrolyte, which can provide a rapid insertion/extraction path for ions and alleviate the volume change of MnO₂. The elemental mapping of MnO₂@TiO₂-2 is shown in Fig. 1f, which intuitively shows that MnO₂@TiO₂-2 consists of Mn, O, and Ti elements with uniform distribution and no other impurity elements are present. The TEM maps (Figures (1g, h)) further demonstrate the microstructure of MnO₂@TiO₂-2, which can be obviously observed to be composed of smooth nanorods and nanoblocks. HR-TEM image (Fig. 1i) clearly visualized the lattice spacing of 0.48 nm and 0.35 nm, which respectively corresponded to the (200) lattice plane of α-MnO₂²⁸and the (101) lattice plane of anatase-type TiO₂²⁹, and thus the MnO₂@TiO₂-2 could easily accommodate Zn²⁺ (with the size of about 0.074 nm)³⁰, which was conducive to the insertion and extraction of Zn²⁺.

The electrochemical performances of MnO₂@TiO₂ composites were tested at 1 A g^− 1, and the results are shown in Fig. 2a. The cycling capacities of MnO₂ with TiO₂ coating are higher than that of MnO₂, and the capacity of MnO₂ gradually improves with the increase of the thickness of the TiO₂ coating. When 1.5 mL of n-tetrabutyl titanate is added, the capacity and stability of the MnO₂@TiO₂-2 electrode material is superior, and the discharge specific capacity can be maintained at 137.09 mAh g^− 1 after 1000 cycles. The capacity of MnO₂@TiO₂-1 is higher than that of MnO₂ before 500 cycles, but it starts to decrease from the 250th cycle, and the specific capacity of discharge is lower than that of MnO₂ after 561 cycles, which is due to the small amount of TiO₂ coating, providing a weaker protective effect. The discharge specific capacity of MnO₂@TiO₂-3 is lower than MnO₂@TiO₂-2, but higher than MnO₂@TiO₂-1. This could be attributed to the increased mass of active material due to the excessive amount of TiO₂ coating, which decreases the discharge specific capacity, leading to the overall poorer performance. Therefore, in the subsequent experiments, the amount of n-tetrabutyl titanate added was fixed at 1.5 mL to achieve the optimal electrochemical performance.

The CV curves are shown in Fig. 2b, and the CV curves are highly overlapped each other, indicating the excellent electrochemical reversibility of the MnO₂@TiO₂-2 electrode material.^{31, 32} In the first cycle, two reduction peaks corresponding to the insertion of H⁺ and Zn²⁺ and the reduction reaction of Mn⁴⁺→Mn³⁺ appeared at 1.17 V and 1.36 V, and two oxidation peaks corresponding to the extraction of H⁺ and Zn²⁺ and the oxidation reaction of Mn³⁺→Mn⁴⁺ appeared at 1.59 V and 1.63 V.^{16, 33, 34} The oxidation peaks in the second cycle appeared at 1.58 V and 1.62 V. The oxidation peaks in the third cycle appeared at 1.56 V and 1.62 V. The oxidation peaks were shifted to lower potentials compared to the first cycle, indicating that the difficulty of the material reaction was reduced, which suggests that the MnO₂@TiO₂-2 needs less voltage motivation process. It is noteworthy that the area of the CV curve gradually increases as the reaction proceeds, which means that MnO₂@TiO₂-2 is activated and accompanied by a rise in specific capacity.^{26, 35} The GCD curves of MnO₂ and MnO₂@TiO₂-2 at 1 A g^-1 are shown in Fig. 2c. The charge-discharge plateau of the GCD curve of MnO₂@TiO₂-2 corresponds to the two pairs of redox peaks in the CV curve. In Furthermore, it is visually evident that the potential difference of the charging and discharging platforms of MnO₂@TiO₂-2 is smaller than that of MnO₂, which may be attributed to the reduction of the polarization of MnO₂ by the TiO₂ coating. More interestingly, the charge/discharge platforms of TiO₂ at 1.61 V and 1.20 V are much longer than those of MnO₂, which suggests that the TiO₂ coating increases the conductivity of MnO₂, achieving lower polarization and good electron/ion transport, which helps the insertion and extraction of H⁺/Zn²⁺.^{36, 37}

Figure 2d shows the rate performance of MnO₂ and MnO₂@TiO₂-2 at current densities ranging from 0.2 to 5 A g^-1. The discharge specific capacities for MnO₂@TiO₂-2 are 161.82, 166.07, 151.72, 136.79, 116.68, 99.95, and 76.82 mAh g^-1 at 0.2, 0.5, 1, 2, 3, 4, and 5 A g^-1, respectively, and the discharge specific capacity was not decayed or even increased to 245.16 mAh g^-1 when the current returned to 0.2 A g^-1. The discharge specific capacities of MnO₂ at 0.2-5 A g^-1 are all lower than those of MnO₂@TiO₂-2, and at high current density, their discharge specific capacities are almost zero. In addition, when the current density is returned to 0.2 A g^-1, its discharge-specific capacity is 130.64 mAh g^-1, and there is a serious capacity decay. In comparison, the MnO₂@TiO₂-2 exhibits more excellent rate performance. Figure 2e shows the GCD curves of MnO₂@TiO₂-2 at different current densities, from which it can be intuitively seen that the voltage and the discharge specific capacity of the first discharge platform decrease slowly with the increase of the current density, and the voltage and the discharge specific capacity of the second discharge platform also decrease, but with a much larger decrease. This indicates that there are different reaction kinetics rates between the two platforms, and the reaction kinetics of the first discharge platform is faster.³⁸ It might be attributed to the different insertion mechanisms of H⁺ and Zn²⁺.³⁹ And the first discharge platform is dominated by H⁺ insertion, while the second discharge platform is led from Zn²⁺ insertion, corresponding to the two reduction peaks in the CV curves, respectively. With the gradual increase of current density, the turning point between the two platforms gradually disappeared, and the second discharge platform also disappeared, which was attributed to the fact that the diffusion of Zn²⁺ was slower at high current densities, and its capacity contribution mainly came from the insertion/extraction of H⁺.⁴⁰

The long cycling performance of MnO₂@TiO₂-2 was analyzed and evaluated at high current density (Fig. 2g). The initial capacity of MnO₂ is 186.34 mAh g^-1, which is higher than that of MnO₂@TiO₂-2. However, its capacity starts to decrease from the first cycle, and the capacity is only 43.42 mAh g^-1 after 1500 cycles, with a capacity retention rate of 21.93%. Although the initial capacity of MnO₂@TiO₂-2 is low, its capacity tends to increase with cycling, indicating that MnO₂@TiO₂-2 is gradually activated. The specific capacity of MnO₂@TiO₂-2 exceeds that of MnO₂ at the 77th cycle, and after 1500 cycles, the specific capacity of MnO₂@TiO₂-2 remains at 93.35 mAh g^-1, with the retention is 97.64%. The capacity value and stability performance of MnO2@TiO2-2 are both improved, and better than those of the previously reported MnO₂ (Table S1). The improved electrochemical properties of MnO₂@TiO₂-2 are responsible for the protective effect of TiO₂ coating. The TiO₂ protective layer avoids the direct contact between MnO₂ and the electrolyte, which effectively inhibits the dissolution of Mn²⁺. At the same time, TiO₂ with better mechanical properties can adapt to the volume change of the material in the charging and discharging process, alleviating the problem of structural collapse of the electrode material and improving the structural stability of the material. In addition, the coin cell battery using MnO₂@TiO₂-2 material as the cathode successfully lights up the electronic watch (Figure S2a).

Electrochemical impedance tests were performed on MnO₂ and MnO₂@TiO₂-2 under the same conditions, and the corresponding Nyquist plots and equivalent circuits for the two electrodes are shown in Fig. 2f. The impedance curves consisting of semicircular arcs in the high-frequency region and straight lines in the low-frequency region can be obtained by fitting the EIS data of MnO₂ and MnO₂@TiO₂-2, respectively, using the equivalent circuits in the inset. In the equivalent circuit, Rs is the internal resistance generated between the electrolyte, the diaphragm and the electrical contacts, Rct is the charge transfer impedance, and Zw is the Warburg impedance to ion diffusion. The semicircular arc of MnO₂@TiO₂-2 is smaller than that of MnO₂. Therefore, MnO₂@TiO2-₂ has a smaller Rct value, and the fitting gets the Rct of 121.7 Ω for MnO₂@TiO₂-2 and 176.5 Ω for MnO₂, which suggests that the TiO₂ coating improves the electron transfer kinetics of the material, accelerates the charge transfer at the electrode/electrolyte interface, and improves the electrochemical performance.¹¹ In the low-frequency region, it was fitted to obtain straight line slopes of 3.63 and 3.34 for MnO₂@TiO₂-2 and MnO₂, respectively. Obviously, the slope of MnO₂@TiO₂-2 is larger, demonstrating that the ions diffuse faster in the MnO₂@TiO₂-2 electrode.⁴¹ To further investigate the reaction kinetics, we tested the CV curves of the MnO₂@TiO₂-2 cathode at different scanning rates. As shown in Fig. 3a, the CV curves have similar shapes when the scanning rate is increased from 0.2 mV s^− 1 to 1 mV s^− 1, which indicates that the electrochemical reaction of MnO₂@TiO₂-2 is highly reversible. It is noteworthy that the oxidation peak is shifted toward a higher potential and the reduction peak is shifted toward a lower potential with increasing scanning rate, which is due to the polarization resulting from the decrease of the effective interaction between the electrolyte and the electrode. The peak current (i) and scan rate (v) have the following linear relationship⁴²:

$$\:i=a{v}^{b}$$

log ($\:i)$=log ($\:a)$ + $\:b$ log ($\:\nu\:)$(2)

where a, b are variable parameters, and usually, the range of b values is 0.5 to 1. The electrochemical energy storage of the battery is controlled by ionic diffusion when the b value is equal to 0.5, and by capacitive behavior when the b value is equal to 1. As shown in Figs. 2b and S2c, MnO₂@TiO₂-2 has peaks 1, 2, 3, and 4 of 0.659, 0.868, 0.611, and 0.762, respectively, and MnO₂ has peaks 1, 2, 3, and 4 of 0.617, 0.885, 0.689, and 0.809, respectively. This shows that the electrochemical kinetics of MnO₂@TiO₂-2 and MnO₂ are related to diffusive behavior and capacitive behavior. To further obtain the contribution of the capacitance effect to the total electrode capacity, we calculate it using the following Eq. 4³:

$$\:i（v）={k}_{1}v+{k}_{2}{v}^{1/2}$$

Where $\:{k}_{1}v$ and $\:{k}_{2}{v}^{1/2}$ correspond to the control of capacitive behavior and diffusion process, respectively. Figure S2d demonstrates that the percentage of capacitive contribution of MnO₂ is 75%, 77%, 79%, 83% and 87% at 0.2, 0.4, 0.6, 0.8 and 1 mV s^− 1, respectively. The percentage of capacitive contribution of MnO₂@TiO₂-2 increases to 76%, 78%, 81%, 84% and 88%. The results show that the MnO₂@TiO2-2 electrode has a higher capacitance contribution with the increase of scanning rate, which indicates that the TiO₂ coating facilitates the insertion and extraction of Zn²⁺ and plays a good protective role, so that the MnO₂@TiO₂-2 can withstand the impact of a higher density current, which can effectively alleviate the problem of the volumetric change caused by the dissolution of manganese.

To summarize, the introduction of TiO₂ coating improves the electrochemical performance of MnO₂@TiO₂ composite. Firstly, TiO₂ can be used as a protective layer, obstructing the direct contact between the electrolyte and the electrode material, and effectively inhibiting manganese dissolution. Secondly, TiO₂ has good mechanical properties, which can adapt to the volume change of the electrode material during the charging and discharging process and avoid the structural collapse, thus consolidating the structural stability of the material. In addition, the TiO₂ coating improves the conductivity of the material, achieving lower polarization and good electron/ion transport. When MnO₂@TiO₂-2 was used as the cathode, the battery exhibited outstanding electrochemical performance. It has an excellent rate capacity of 245.16 mAh g^− 1 at 0.2 A g^− 1 and maintains 137.09 mAh g^− 1 after 1000 cycles at 1 A g^− 1. Even at the high current density of 3 A g^− 1, it retains at 93.35 mAh g^− 1 after 1500 cycles, and the capacity retention rate is 97.47%. This work provides inspiration and foundation to develop high performance AZIBs cathode materials.

Author Contribution

Jun Zhu: Project administration. Hongwei Shi: Investigation and writing original draft. Chengcheng Liu: Methodology. Wenzhu Ouyang: Writing original draft. Yuling Liu: Data curation. Xiaoling Li: Formal analysis, data curation, review and editing.

Acknowledgement

This work was supported by the Key projects of natural science research in Universities of Anhui Province (KJ2018A0454).

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You are reading this latest preprint version

Synthesis of MnO 2 @TiO 2 composite electrodes via hydrolysis and calcination for high stability zinc ions batteries

Status:

Version 1

Abstract

Figures

1. INTRODUCTION

2. EXPERIMENTAL SECTION

2.1 Preparation of MnO₂@TiO₂ and MnO₂ samples:

2.2 Material characterization.

2.3 Electrochemical measurements.

3. RESULTS AND DISCUSSION

4. CONCLUSION

Declarations

Author Contribution

Acknowledgement

References

Additional Declarations

Supplementary Files

Status:

Version 1

Synthesis of MnO 2 @TiO 2 composite electrodes via hydrolysis and calcination for high stability zinc ions batteries

Status:

Version 1

Abstract

Figures

1. INTRODUCTION

2. EXPERIMENTAL SECTION

2.1 Preparation of MnO2@TiO2 and MnO2 samples:

2.2 Material characterization.

2.3 Electrochemical measurements.

3. RESULTS AND DISCUSSION

4. CONCLUSION

Declarations

Author Contribution

Acknowledgement

References

Additional Declarations

Supplementary Files

Status:

Version 1

2.1 Preparation of MnO₂@TiO₂ and MnO₂ samples: