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Facile preparation of high performance degradation of HCHO catalyst from Li-MnO2 batteries
Materials Letters 260 (2020) 126958
Contents lists available at ScienceDirect
Materials Letters journal homepage: www.elsevier.com/locate/mlblue
Facile preparation of high performance degradation of HCHO catalyst from Li-MnO2 batteries Lingliang Xu a, Jianfei Fang b, Yao Tan c, Jiankang Xu b, Huijie Tang a, Zhe Han a, Ming Zhang a, Tianshou Yu a, Hongxiao Jin a, Hongliang Ge a, Xinqing Wang a, Dingfeng Jin a,d,⇑, Hui Lou d a
College of Materials Science and Engineering, China Jiliang University, Hangzhou 310018, China Quality and Technical Supervision Inspection Center of Yongkang, Yongkang, 321300, China Technology Center of Ningbo Customs, Ningbo, 315012, China d Department of Chemical, Zhejiang University, Hangzhou 310018, China b c
a r t i c l e
i n f o
Article history: Received 29 March 2019 Received in revised form 9 October 2019 Accepted 4 November 2019 Available online 6 November 2019 Keywords: Microstructure Oxidation Li-MnO2 battery Recycling Formaldehyde
a b s t r a c t Catalyst which effectively degraded low concentration of formaldehyde at room temperature is recovered from Li-MnO2 button cell by a simple washing-recovering method. The prepared samples were characterized by XRD, XPS and N2 adsorption-desorption. Compared with the original MnO2 (L0.00-MnO2), lithium MnO2 (Li1.00-MnO2) is gradually converted from Mn(IV) to Mn(III) due to the intercalation of Li+. The catalytic activity of catalyst is significantly increased after full discharge for higher specific surface area and surface oxygen species. Ó 2019 Elsevier B.V. All rights reserved.
1. Introduction Formaldehyde has become one of the most important indoor air pollutants, which was raised from a second-class carcinogen to a first-class of carcinogens by the International Agency for Research on Cancer at 2004. At present, the commonly used method for removing formaldehyde is physical adsorption, however this method is effective for only a short time for their limited adsorption capacity. The methods of photo-catalysis or thermo-catalysis degradation of formaldehyde indoor air have become popular. However, these catalyst processes have some disadvantage of irradiation with a light source and producing incomplete intermediates. Catalytic oxidation is regarded as a promising way for degradation HCHO at a low temperature. The most reported room-temperature catalysts for HCHO removal are supported noble metals, such as Pt/TiO2 [1], Pt/Fe2O3 [2], Pt/MnO2 [3], Au/CeO2 [4] and Au/Fe2O3 [5]. The high price of noble metals limits their wide application. Manganese oxide has been investigated to degrade many gaseous pollutants in the environment. Sekine [6] compared the removal efficiency of HCHO by Ag2O, MnO2, TiO2, CeO2, CoO, ⇑ Corresponding author. E-mail address: [email protected] (D. Jin). https://doi.org/10.1016/j.matlet.2019.126958 0167-577X/Ó 2019 Elsevier B.V. All rights reserved.
Mn3O4 and other catalysts. Sidheswaran [7] investigated the effect of MnOx materials on their activity for complete oxidation of HCHO. Miyawaki [8] loaded MnOx onto activated carbon fibers to mineralize formaldehyde to CO2. The lithium-containing transition metal oxides in the cathode materials of waste lithium batteries have encouraged us to investigate whether it could be directly utilized as catalysts. Herein, we present a simple washing-recycling process for efficiently recycling the MnO2 based catalysts from spent lithium batteries. Compared to the pristine MnO2, Li1.00MnO2 exhibits remarkably enhanced catalytic activity. The phase structure and structural factors are investigated in detail. The effect of the electrochemical lithiation degree on the catalytic activity of recycled MnO2 is studied. 2. Experimental The Li-MnO2 button-cell batteries (Panasonic 2032) were purchased from supermarket. The preparation and characterization showed in support information. 3. Results and discussion The XRD patterns of two battery positive electrode materials obtained before (Li0.00-MnO2) and after complete discharge
2
L. Xu et al. / Materials Letters 260 (2020) 126958
(Li1.00-MnO2) are shown in Fig. 1. For Li0.00-MnO2, the characteristic peaks of it at approximately 2h = 28.7°, 37.0°, 42.8°, 56.6°, 64.8° and 72.3°. It can be respectively indexed to the (110), (101), (111), (211), (002) and (112) planes of b-MnO2. With the continuous constant current discharge of the battery, Li+ is gradually intercalated into MnO2, and the tunnel structure of MnO2 changes with the slow migration of Li+. Many changes occurred in Li1.00-MnO2: (i) The peaks disappear at 2h of 28.7° and 56.6°; (ii) the intensity of peaks at 2h of 37.0°, 42.8°, 64.8°and 72.3° decreases and shifts; (iii) new peak (a) appeared at 2h of 19°, which indicates electrochemical embedding of Li+. XPS spectra of different degree of Lithiation were shown in Fig. 2 and the data summarized at support information. There is no peak appear in the 1s orbital of Li in Li0.00-MnO2, indicating that there is no Li+ in the positive electrode. The peak appears in Li1.00MnO2 indicated that Li+ enters the cathode. With the embedding of Li, Mn(IV) is gradually transformed into Mn(III) (Fig. 2b), and the 3s orbital of Mn gradually splits, due to the coupling of parallel spintronics in the 3s and 3d orbitals, with the decrease of 3d orbital electrons. The average oxidation state (AOS) of Mn can be calculated as the relationship (AOS = 8.95–1.13 DEs (eV)),DEMn 3s of Li0.00-MnO2 and Li1.00-MnO2 are 4.63 eV and 5.22 eV, respectively. The Li0.00-MnO2 with an AOS of 3.72 suggests that Mn cations possess an average valence close to 4. The AOS of Li1.00-MnO2 gradually decreases from approximately 4 to nearly 3. Fig. 2c shows the O 1s XPS spectra, which exhibited two peaks at binding energy 529.6 eV and 531.4 eV, corresponding to lattice oxygen (OLatt) and surface adsorbed oxygen (OSurf), respectively. The molar ratio of OSurf/OLatt increased with the increasing content of Li, which is consistent with the change of Mn3+/Mn4+ ratio. The surface Mn/O ratio continuously decreased with addition of Li. More surface hydroxyl groups generate to ensure the balance of Mn. The surface area, pore diameter, and pore volume of Li0.00-1.00MnO2 catalysts were shown in Table 1, Li1.00-MnO2 (45.86 m2/g) had larger specific surface areas than Li0.00-MnO2 (15.49 m2/g). The continuous discharge leads to the embedding of Li+, and the lattice distortion and lattice expansion increase the specific surface area of the positive electrode material. The larger surface area of Li1.00-MnO2 might be helpful for improving the catalytic activity for HCHO removal. The removal efficiency of Li0.00-MnO2 and Li1.00-MnO2 were shown in Fig. 3. The degradation efficiency of formaldehyde in Li0.00-MnO2 was gradually reduced to 50% within 10 h, while the
Fig. 2. XPS of Lix-MnO2 species (x = 0.00 is before complete discharge and = 1.00 is after complete discharge).
Fig. 1. XRD patterns of Lix-MnO2 species (x = 0.00 is before complete discharge and = 1.00 is after complete discharge).
Li1.00-MnO2 maintained nearly 100% at room temperature during 24 h. As mentioned above, the XPS results (Fig. 2) indicate that the amount of adsorbed surface oxygen species increased with Li+ is intercalated into MnO2. These results clearly showed the catalytic activity for HCHO decomposition is governed by the property
L. Xu et al. / Materials Letters 260 (2020) 126958
3
Samples
Surface area (m2/g)
Pore volume (cm3/g)
Pore size (nm)
100 % degradation efficiency of formaldehyde at room temperature in 24 h, which contributed to the increasing of specific surface area and surface oxygen species. This provides a new strategy for recycling used batteries.
Li0.00-MnO2 Li1.00-MnO2
15.94 45.86
0.05 0.07
10.53 5.80
Declaration of Competing Interest
Table 1 Textual parameters of Lix-MnO2 species (x = 0.00 is before complete discharge and = 1.00 is after complete discharge).
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. Acknowledgments The research was funded by Natural Science Foundation of Zhejiang Province (LY16B030006) and National Training Program of Innovation and Entrepreneurship for Undergraduates (201810356014). Appendix A. Supplementary data Supplementary data to this article can be found online at https://doi.org/10.1016/j.matlet.2019.126958. References
Fig. 3. Removing rate for formaldehyde of Lix-MnO2 species (x = 0.00 is before complete discharge and = 1.00 is after complete discharge).
and amount of adsorbed surface oxygen species, and the addition of Li greatly enhanced their amount. These results indicate that Li1.00-MnO2 has good activity of HCHO degrade in real environment, which can be ascribed to the enhanced activity of adsorbed surface oxygen species due to Li intercalated. 4. Conclusion In summary, the positive electrode material of the waste lithium manganese battery was recovered by simply disassembling, washing and drying steps. The Li1.00-MnO2 has a nearly
[1] C. Zhang, F. Liu, Y. Zhai, H. Ariga, N. Yi, Y. Liu, et al., Alkali-metal-promoted Pt/TiO2 opens a more efficient pathway to formaldehyde oxidation at ambient temperatures, Angew. Chem. Int. Ed. 51 (2012) 9628–9632. [2] N. An, Q. Yu, G. Liu, S. Li, M. Jia, W. Zhang, Complete oxidation of formaldehyde at ambient temperature over supported Pt/Fe2O3 catalysts prepared by colloiddeposition method, J. Hazard. Mater. 186 (2011) 1392–1397. [3] X. Yu, J. He, D. Wang, Y. Hu, H. Tian, Z. He, Facile controlled synthesis of Pt/MnO2 nanostructured catalysts and their catalytic performance for oxidative decomposition of formaldehyde, J. Phys. Chem. C 116 (2012) 851–860. [4] H. Li, N. Zhang, P. Chen, M. Luo, J. Lu, High surface area Au/CeO2 catalysts for low temperature formaldehyde oxidation, Appl. Catal. B 110 (2011) 279–285. [5] C. Li, Y. Shen, M. Jia, S. Sheng, M.O. Adebajo, H. Zhu, Catalytic combustion of formaldehyde on gold/iron-oxide catalysts, Catal. Commun. 9 (2008) 355–361. [6] Y. Sekine, Oxidative decomposition of formaldehyde by metal oxides at room temperature, Atmos. Environ. 36 (2002) 5543–5547. [7] M.A. Sidheswaran, H. Destaillats, D.P. Sullivan, J. Larsen, W.J. Fisk, Quantitative room-temperature mineralization of airborne formaldehyde using manganese oxide catalysts, Appl. Catal. B 107 (2011) 34–41. [8] J. Miyawaki, G.H. Lee, J. Yeh, N. Shiratori, T. Shimohara, I. Mochida, et al., Development of carbon-supported hybrid catalyst for clean removal of formaldehyde indoors, Catal. Today 185 (2012) 278–283.
Contents lists available at ScienceDirect
Materials Letters journal homepage: www.elsevier.com/locate/mlblue
Facile preparation of high performance degradation of HCHO catalyst from Li-MnO2 batteries Lingliang Xu a, Jianfei Fang b, Yao Tan c, Jiankang Xu b, Huijie Tang a, Zhe Han a, Ming Zhang a, Tianshou Yu a, Hongxiao Jin a, Hongliang Ge a, Xinqing Wang a, Dingfeng Jin a,d,⇑, Hui Lou d a
College of Materials Science and Engineering, China Jiliang University, Hangzhou 310018, China Quality and Technical Supervision Inspection Center of Yongkang, Yongkang, 321300, China Technology Center of Ningbo Customs, Ningbo, 315012, China d Department of Chemical, Zhejiang University, Hangzhou 310018, China b c
a r t i c l e
i n f o
Article history: Received 29 March 2019 Received in revised form 9 October 2019 Accepted 4 November 2019 Available online 6 November 2019 Keywords: Microstructure Oxidation Li-MnO2 battery Recycling Formaldehyde
a b s t r a c t Catalyst which effectively degraded low concentration of formaldehyde at room temperature is recovered from Li-MnO2 button cell by a simple washing-recovering method. The prepared samples were characterized by XRD, XPS and N2 adsorption-desorption. Compared with the original MnO2 (L0.00-MnO2), lithium MnO2 (Li1.00-MnO2) is gradually converted from Mn(IV) to Mn(III) due to the intercalation of Li+. The catalytic activity of catalyst is significantly increased after full discharge for higher specific surface area and surface oxygen species. Ó 2019 Elsevier B.V. All rights reserved.
1. Introduction Formaldehyde has become one of the most important indoor air pollutants, which was raised from a second-class carcinogen to a first-class of carcinogens by the International Agency for Research on Cancer at 2004. At present, the commonly used method for removing formaldehyde is physical adsorption, however this method is effective for only a short time for their limited adsorption capacity. The methods of photo-catalysis or thermo-catalysis degradation of formaldehyde indoor air have become popular. However, these catalyst processes have some disadvantage of irradiation with a light source and producing incomplete intermediates. Catalytic oxidation is regarded as a promising way for degradation HCHO at a low temperature. The most reported room-temperature catalysts for HCHO removal are supported noble metals, such as Pt/TiO2 [1], Pt/Fe2O3 [2], Pt/MnO2 [3], Au/CeO2 [4] and Au/Fe2O3 [5]. The high price of noble metals limits their wide application. Manganese oxide has been investigated to degrade many gaseous pollutants in the environment. Sekine [6] compared the removal efficiency of HCHO by Ag2O, MnO2, TiO2, CeO2, CoO, ⇑ Corresponding author. E-mail address: [email protected] (D. Jin). https://doi.org/10.1016/j.matlet.2019.126958 0167-577X/Ó 2019 Elsevier B.V. All rights reserved.
Mn3O4 and other catalysts. Sidheswaran [7] investigated the effect of MnOx materials on their activity for complete oxidation of HCHO. Miyawaki [8] loaded MnOx onto activated carbon fibers to mineralize formaldehyde to CO2. The lithium-containing transition metal oxides in the cathode materials of waste lithium batteries have encouraged us to investigate whether it could be directly utilized as catalysts. Herein, we present a simple washing-recycling process for efficiently recycling the MnO2 based catalysts from spent lithium batteries. Compared to the pristine MnO2, Li1.00MnO2 exhibits remarkably enhanced catalytic activity. The phase structure and structural factors are investigated in detail. The effect of the electrochemical lithiation degree on the catalytic activity of recycled MnO2 is studied. 2. Experimental The Li-MnO2 button-cell batteries (Panasonic 2032) were purchased from supermarket. The preparation and characterization showed in support information. 3. Results and discussion The XRD patterns of two battery positive electrode materials obtained before (Li0.00-MnO2) and after complete discharge
2
L. Xu et al. / Materials Letters 260 (2020) 126958
(Li1.00-MnO2) are shown in Fig. 1. For Li0.00-MnO2, the characteristic peaks of it at approximately 2h = 28.7°, 37.0°, 42.8°, 56.6°, 64.8° and 72.3°. It can be respectively indexed to the (110), (101), (111), (211), (002) and (112) planes of b-MnO2. With the continuous constant current discharge of the battery, Li+ is gradually intercalated into MnO2, and the tunnel structure of MnO2 changes with the slow migration of Li+. Many changes occurred in Li1.00-MnO2: (i) The peaks disappear at 2h of 28.7° and 56.6°; (ii) the intensity of peaks at 2h of 37.0°, 42.8°, 64.8°and 72.3° decreases and shifts; (iii) new peak (a) appeared at 2h of 19°, which indicates electrochemical embedding of Li+. XPS spectra of different degree of Lithiation were shown in Fig. 2 and the data summarized at support information. There is no peak appear in the 1s orbital of Li in Li0.00-MnO2, indicating that there is no Li+ in the positive electrode. The peak appears in Li1.00MnO2 indicated that Li+ enters the cathode. With the embedding of Li, Mn(IV) is gradually transformed into Mn(III) (Fig. 2b), and the 3s orbital of Mn gradually splits, due to the coupling of parallel spintronics in the 3s and 3d orbitals, with the decrease of 3d orbital electrons. The average oxidation state (AOS) of Mn can be calculated as the relationship (AOS = 8.95–1.13 DEs (eV)),DEMn 3s of Li0.00-MnO2 and Li1.00-MnO2 are 4.63 eV and 5.22 eV, respectively. The Li0.00-MnO2 with an AOS of 3.72 suggests that Mn cations possess an average valence close to 4. The AOS of Li1.00-MnO2 gradually decreases from approximately 4 to nearly 3. Fig. 2c shows the O 1s XPS spectra, which exhibited two peaks at binding energy 529.6 eV and 531.4 eV, corresponding to lattice oxygen (OLatt) and surface adsorbed oxygen (OSurf), respectively. The molar ratio of OSurf/OLatt increased with the increasing content of Li, which is consistent with the change of Mn3+/Mn4+ ratio. The surface Mn/O ratio continuously decreased with addition of Li. More surface hydroxyl groups generate to ensure the balance of Mn. The surface area, pore diameter, and pore volume of Li0.00-1.00MnO2 catalysts were shown in Table 1, Li1.00-MnO2 (45.86 m2/g) had larger specific surface areas than Li0.00-MnO2 (15.49 m2/g). The continuous discharge leads to the embedding of Li+, and the lattice distortion and lattice expansion increase the specific surface area of the positive electrode material. The larger surface area of Li1.00-MnO2 might be helpful for improving the catalytic activity for HCHO removal. The removal efficiency of Li0.00-MnO2 and Li1.00-MnO2 were shown in Fig. 3. The degradation efficiency of formaldehyde in Li0.00-MnO2 was gradually reduced to 50% within 10 h, while the
Fig. 2. XPS of Lix-MnO2 species (x = 0.00 is before complete discharge and = 1.00 is after complete discharge).
Fig. 1. XRD patterns of Lix-MnO2 species (x = 0.00 is before complete discharge and = 1.00 is after complete discharge).
Li1.00-MnO2 maintained nearly 100% at room temperature during 24 h. As mentioned above, the XPS results (Fig. 2) indicate that the amount of adsorbed surface oxygen species increased with Li+ is intercalated into MnO2. These results clearly showed the catalytic activity for HCHO decomposition is governed by the property
L. Xu et al. / Materials Letters 260 (2020) 126958
3
Samples
Surface area (m2/g)
Pore volume (cm3/g)
Pore size (nm)
100 % degradation efficiency of formaldehyde at room temperature in 24 h, which contributed to the increasing of specific surface area and surface oxygen species. This provides a new strategy for recycling used batteries.
Li0.00-MnO2 Li1.00-MnO2
15.94 45.86
0.05 0.07
10.53 5.80
Declaration of Competing Interest
Table 1 Textual parameters of Lix-MnO2 species (x = 0.00 is before complete discharge and = 1.00 is after complete discharge).
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. Acknowledgments The research was funded by Natural Science Foundation of Zhejiang Province (LY16B030006) and National Training Program of Innovation and Entrepreneurship for Undergraduates (201810356014). Appendix A. Supplementary data Supplementary data to this article can be found online at https://doi.org/10.1016/j.matlet.2019.126958. References
Fig. 3. Removing rate for formaldehyde of Lix-MnO2 species (x = 0.00 is before complete discharge and = 1.00 is after complete discharge).
and amount of adsorbed surface oxygen species, and the addition of Li greatly enhanced their amount. These results indicate that Li1.00-MnO2 has good activity of HCHO degrade in real environment, which can be ascribed to the enhanced activity of adsorbed surface oxygen species due to Li intercalated. 4. Conclusion In summary, the positive electrode material of the waste lithium manganese battery was recovered by simply disassembling, washing and drying steps. The Li1.00-MnO2 has a nearly
[1] C. Zhang, F. Liu, Y. Zhai, H. Ariga, N. Yi, Y. Liu, et al., Alkali-metal-promoted Pt/TiO2 opens a more efficient pathway to formaldehyde oxidation at ambient temperatures, Angew. Chem. Int. Ed. 51 (2012) 9628–9632. [2] N. An, Q. Yu, G. Liu, S. Li, M. Jia, W. Zhang, Complete oxidation of formaldehyde at ambient temperature over supported Pt/Fe2O3 catalysts prepared by colloiddeposition method, J. Hazard. Mater. 186 (2011) 1392–1397. [3] X. Yu, J. He, D. Wang, Y. Hu, H. Tian, Z. He, Facile controlled synthesis of Pt/MnO2 nanostructured catalysts and their catalytic performance for oxidative decomposition of formaldehyde, J. Phys. Chem. C 116 (2012) 851–860. [4] H. Li, N. Zhang, P. Chen, M. Luo, J. Lu, High surface area Au/CeO2 catalysts for low temperature formaldehyde oxidation, Appl. Catal. B 110 (2011) 279–285. [5] C. Li, Y. Shen, M. Jia, S. Sheng, M.O. Adebajo, H. Zhu, Catalytic combustion of formaldehyde on gold/iron-oxide catalysts, Catal. Commun. 9 (2008) 355–361. [6] Y. Sekine, Oxidative decomposition of formaldehyde by metal oxides at room temperature, Atmos. Environ. 36 (2002) 5543–5547. [7] M.A. Sidheswaran, H. Destaillats, D.P. Sullivan, J. Larsen, W.J. Fisk, Quantitative room-temperature mineralization of airborne formaldehyde using manganese oxide catalysts, Appl. Catal. B 107 (2011) 34–41. [8] J. Miyawaki, G.H. Lee, J. Yeh, N. Shiratori, T. Shimohara, I. Mochida, et al., Development of carbon-supported hybrid catalyst for clean removal of formaldehyde indoors, Catal. Today 185 (2012) 278–283.