One-pot synthesis of pure phase Mn3O4 at room temperature and probing its long-term supercapacitive performance
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Abstract
Present work deals with one-pot synthesis of pure phase mesoporous Mn3O4 nanoparticles by novel, easy, and cost-effective method at ambient conditions and probing its long-term supercapacitive performance. The co-precipitation-routed submicron MnCO3 particles (cp-MnCO3) and commercially available MnCO3 (cm-MnCO3) have been used as the precursor materials in the synthesis procedure. The nanoparticles of cp-Mn3O4 synthesized using cp-MnCO3 exhibits specific capacitance (Cs) of 290 (± 5) F g−1 at a current rate of 0.5 A g−1, whereas cm-Mn3O4 obtained from the chemical conversion of cm-MnCO3 shows Cs value of 204 (± 5) F g−1 at identical current rate. The better electrochemical behavior of cp-Mn3O4 is ascribed to its hierarchical pore size distribution and lower diffusion resistance, which facilitates an easy electrolytic ionic diffusion in the sample. cp-Mn3O4 also exhibits smaller relaxation time constant (τo = 140 ms), which allows it to deliver stored energy quickly at high power. Additionally, cp-Mn3O4 exhibits 71% capacitance retention after 15,000 cycles, 25 W h kg−1 energy density, and 202 W kg−1 power density at a current rate of 0.5 A g−1. Further, ex-situ XRD analysis demonstrates that cp-Mn3O4 retains its crystal structure to some extent even after prolonged cycles.
Keywords
Supercapacitor Mn3O4 Relaxation time Pore size distribution Cyclic stabilityNotes
Acknowledgements
Council of Scientific and Industrial Research (CSIR), Government of India is gratefully acknowledged for its financial support under project no. 22(0658)/14/EMR-II. One of the authors (A. K.) highly acknowledges CSIR, India, for the senior research fellowship (SRF, Grant number 19-12/2010(i)EU-IV). We are also very much thankful to Dr. Raju Gupta, Asst. Professor, Department of Chemical Engineering, IIT Kanpur for providing BET measurement facility.
Supplementary material
References
- 1.Zhang K, Han X, Hu Z, Zhang X, Tao Z, Chen J (2015) Nanostructured Mn-based oxides for electrochemical energy storage and conversion. Chem Soc Rev 44:699–728CrossRefGoogle Scholar
- 2.Dang TD, Le TTH, Hoang TBT, Mai TT (2015) Synthesis of nanostructured manganese oxides based materials and application for supercapacitor. Nanosci Nanotechnol 6:025011Google Scholar
- 3.Deng Y, Wan L, Xie Y, Qin X, Chen G (2014) Recent advances in Mn-based oxides as anode. RSC Adv 4:23914–23935CrossRefGoogle Scholar
- 4.Ortiz-vitoriano N, Drewett NE, Gonzalo E, Rojo T (2017) High performance manganese-based layered oxide cathodes : overcoming the challenges of sodium ion batteries. Energy Environ Sci 10:1051–1074CrossRefGoogle Scholar
- 5.Wang T, Peng Z, Wang Y, Zheng G (2013) MnO nanoparticle@mesoporous carbon composites grown on conducting substrates featuring high-performance lithium-ion battery, supercapacitor and sensor. Sci Rep 3:2693CrossRefGoogle Scholar
- 6.Li L, Liang J, Kang H, Fang J, Luo M, Jin X (2012) TEA-assisted synthesis of single-crystalline Mn3O4 octahedrons and their magnetic properties. Appl Surf Sci 261:717–721CrossRefGoogle Scholar
- 7.Yang Z, Mei Z, Xu F, Yao Y, Zhang W, Qi W, Song Q, Gao Z, Zhao T (2013) Different types of MnO2 recovered from spent LiMn2O4 batteries and their application in electrochemical capacitors. J Mater Sci 48:2512–2519CrossRefGoogle Scholar
- 8.Yuan Z, Chen S, Liu B (2017) Nitrogen-doped reduced graphene oxide-supported Mn3O4: an efficient heterogeneous catalyst for the oxidation of vanillyl alcohol to vanillin. J Mater Sci 52:164–172CrossRefGoogle Scholar
- 9.Wei W, Cui X, Chen W, Ivey DG (2011) Manganese oxide-based materials as electrochemical supercapacitor electrodes. Chem Soc Rev 40:1697–1721CrossRefGoogle Scholar
- 10.Sankar KV, Senthilkumar ST, Berchmans LJ, Sanjeeviraja C, Selvan RK (2012) Effect of reaction time on the synthesis and electrochemical properties of Mn3O4 nanoparticles by microwave assisted reflux method. Appl Surf Sci 259:624–630CrossRefGoogle Scholar
- 11.Suktha P, Phattharasupakun N, Dittanet P, Sawangphruk M (2017) Charge storage mechanism of electrospun Mn3O4 nanofibers for high-performance supercapacitors. RSC Adv 7:9958–9963CrossRefGoogle Scholar
- 12.Simon P, Gogotsi Y (2008) Materials for electrochemical capacitors. Nat Mater 7:845–854CrossRefGoogle Scholar
- 13.Bhagwan J, Sahoo A, Yadav KL, Sharma Y (2015) Porous, one dimensional and high aspect ratio Mn3O4 nanofibers: fabrication and optimization for enhanced supercapacitive properties. Electrochim Acta 174:992–1001CrossRefGoogle Scholar
- 14.Lin C, Chuang K, Lin C, Tsay C, Chen C (2007) Manganese oxide films prepared by sol–gel process for supercapacitor application. Surf Coat Technol 202:1272–1276CrossRefGoogle Scholar
- 15.Zhao J, Xu L, Xie T, Xie C (2015) Preparation of Mn3O4 from low-grade rhodochrosite ore by chemical bath deposition method. Chin J Geochem 34:55–61CrossRefGoogle Scholar
- 16.Liu Y, Liu Z, Wang G (2003) Preparation of Mn3O4 nanowires by calcining the precursor powders synthesized in a novel inverse microemulsion. Appl Phys A Mater Sci Process 76:1117–1120CrossRefGoogle Scholar
- 17.Ashoka S, Nagaraju G, Chandrappa GT (2010) Reduction of KMnO4 to Mn3O4 via hydrothermal process. Mater Lett 64:2538–2540CrossRefGoogle Scholar
- 18.Yang LX, Liang Y, Chen H, Meng Y, Jiang W (2009) Controlled synthesis of Mn3O4 and MnCO3 in a solvothermal system. Mater Res Bull 44:1753–1759CrossRefGoogle Scholar
- 19.Ahmed KAM, Zeng Q, Wu K, Huang K (2010) Mn3O4 nanoplates and nanoparticles: synthesis, characterization, electrochemical and catalytic properties. J Solid State Chem 183:744–751CrossRefGoogle Scholar
- 20.Chen B, Rao G, Wang S, Lan Y, Pan L, Zhang X (2015) Facile synthesis and characterization of Mn3O4 nanoparticles by auto-combustion method. Mater Lett 154:160–162CrossRefGoogle Scholar
- 21.Suzuki M, Kagawa M, Syono Y, Hirai T (1992) Synthesis of ultrafine single-component oxide particles by the spray-ICP technique. J Mater Sci 27:679–684CrossRefGoogle Scholar
- 22.Chang YQ, Xu XY, Luo XH, Chen CP, Yu DP (2004) Synthesis and characterization of Mn3O4 nanoparticles. J Cryst Growth 264:232–236CrossRefGoogle Scholar
- 23.Shen X, Ji Z, Miao H, Yang J, Chen K (2011) Hydrothermal synthesis of MnCO3 nanorods and their thermal transformation into Mn2O3 and Mn3O4 nanorods with single crystalline structure. J Alloys Compd 509:5672–5676CrossRefGoogle Scholar
- 24.Lei S, Peng X, Li X, Liang Z, Yang Y, Cheng B, Xiao Y, Zhou L (2011) Novel detached system to MnCO3 nanowires: a self-sacrificing template for. Mater Chem Phys 125:405–410CrossRefGoogle Scholar
- 25.Kumar A, Sharma Y (2017) In situ conversion of manganese carbonate to manganese oxide/hydroxide and its supercapacitive analysis in aqueous KOH solution. Inoics 23:3409Google Scholar
- 26.Nagamuthu S, Vijayakumar S, Muralidharan G (2013) Synthesis of Mn3O4/amorphous carbon nanoparticles as electrode material for high performance supercapacitor applications. Energy Fuel 27:3508–3515CrossRefGoogle Scholar
- 27.Chaturvedi P, Kumar A, Sil A, Sharma Y (2015) Cost effective urea combustion derived mesoporous-Li2MnSiO4 as a novel material for supercapacitors. RSC Adv 35:25156CrossRefGoogle Scholar
- 28.Fan Y, Liu P-F, Huang Z-Y, Jiang T, Yao K, Han R (2015) Porous hollow carbon spheres for electrode material of supercapacitors and support material of dendritic Pt electrocatalyst. J Power Sources 280:30–38CrossRefGoogle Scholar
- 29.Bhagwan J, Sivasankaran V, Yadav KL, Sharma Y (2016) Porous, one-dimensional and high aspect ratio nano fibric network of cobalt manganese oxide as a high performance material for aqueous and solid-state supercapacitor (2V). J Power Sources 327:29–37CrossRefGoogle Scholar
- 30.Dai Y-H, Kong L-B, Yan K, Shi M, Luo Y, Kang L (2016) Facile fabrication of manganese phosphate nanosheets for supercapacitor applications. Ionics 22:1461–1469CrossRefGoogle Scholar
- 31.Dong R, Ye Q, Kuang L, Lu X, Zhang Y, Zhang X, Tan G, Wen Y, Wang F (2013) Enhanced supercapacitor performance of Mn3O4 nanocrystals by doping transition-metal ions. ACS Appl Mater Interfaces 5:9508–9516CrossRefGoogle Scholar
- 32.Ghodbane O, Ataherian F, Wu N-L, Favier F (2012) In situ crystallographic investigations of charge storage mechanisms in MnO2-based electrochemical capacitors. J Power Sources 206:454–462CrossRefGoogle Scholar
- 33.Liu Y, He D, Wu H, Duan J, Zhang Y (2015) Hydrothermal self-assembly of manganese dioxide/manganese carbonate/reduced graphene oxide aerogel for asymmetric supercapacitors. Electrochim Acta 164:154–162CrossRefGoogle Scholar
- 34.Nagamuthu S, Vijayakumar S, Muralidharan G (2013) Biopolymer-assisted synthesis of λ-MnO2 nanoparticles as an electrode material for aqueous symmetric supercapacitor devices. Ind Eng Chem Res 52:18262–18268CrossRefGoogle Scholar
- 35.Sahoo A, Sharma Y (2015) Synthesis and characterization of nanostructured ternary zinc manganese oxide as novel supercapacitor material. Mater Chem Phys 149-150:721–727CrossRefGoogle Scholar
- 36.Sawangphruk M, Limtrakul J (2012) Effects of pore diameters on the pseudocapacitive property of three-dimensionally ordered macroporous manganese oxide electrodes. Mater Lett 68:230–233CrossRefGoogle Scholar
- 37.Zhu J, Shi W, Xiao N, Rui X, Tan H, Lu X, Hang HH, Ma J, Yan Q (2012) Oxidation-etching preparation of MnO2 tubular nanostructures for high-performance supercapacitors. ACS Appl Mater Interfaces 4:2769–2774CrossRefGoogle Scholar
- 38.Ujjain SK, Sahu V, Sharma RK, Singh G (2015) High performance, all solid state, flexible supercapacitor based on ionic liquid functionalized graphene. Electrochim Acta 157:245–251CrossRefGoogle Scholar
- 39.Singh A, Chandra A (2016) Enhancing specific energy and power in asymmetric supercapacitors—a synergetic strategy based on the use of redox additive electrolytes. Nat Publ Gr 6:25793Google Scholar
- 40.Messaoudi B, Joiret S, Keddam M, Takenouti H (2001) Anodic behaviour of manganese in alkaline medium. Electrochim Acta 46:2487–2498CrossRefGoogle Scholar
- 41.Qi Z, Younis A, Chu D, Li S (2016) A facile and template-free one-pot synthesis of Mn3O4 nanostructures as electrochemical supercapacitors. Ionics 8:165Google Scholar
- 42.Raj BGS, Ramprasad RNR, Asiri AM, jj W, Anandan S (2015) Ultrasound assisted synthesis of Mn3O4 nanoparticles anchored graphene nanosheets for supercapacitor applications. Electrochim Acta 156:127–137CrossRefGoogle Scholar
- 43.Raj BGS, Asiri AM, Wu JJ, Anandan S (2015) Synthesis of Mn3O4 nanoparticles via chemical precipitation approach for supercapacitor application. J Alloys Compd 636:234CrossRefGoogle Scholar
- 44.Fan Y, Zhang X, Liu Y, Cai Q, Zhang J (2013) One-pot hydrothermal synthesis of Mn3O4/graphene nanocomposite for supercapacitors. Mater Latt 95:153–156CrossRefGoogle Scholar
- 45.Ssankar KV, Kalpana D, Selvan RK (2012) Electrochemical properties of microwave-assisted reflux-synthesized Mn3O4 nanoparticles in different electrolytes for supercapacitor applications. J Appl Electrochem 42:463–470CrossRefGoogle Scholar
- 46.Ning X, Wang X, Yu X, Zhao J, Wang M, Li H, Yang Y (2016) Outstanding supercapacitive properties of Mn-doped TiO2 micro/nanostructure porous film prepared by anodization method. Nat Publ Gr 6:22634Google Scholar
- 47.Saha D, Li Y, Bi Z, Chen J, Keum JK, Hensley DK, Grappe HA, Meyer HM, Dai S, Paranthaman MP, Naskar AK (2014) Studies on supercapacitor electrode material from activated lignin-derived mesoporous carbon. Langmuir 30:900–910CrossRefGoogle Scholar
- 48.Li Y, Jian J, Xiao L, Wang H, Yu L, Cheng G, Zhou J, Sun M (2016) Synthesis of NiMoO4 nanosheets on graphene sheets as advanced supercapacitor electrode materials. Mater Lett 184:21–24CrossRefGoogle Scholar
- 49.Miller JR (1998) Pulse power performance of electrochemical capacitors: technical status of present commercial devices. In: Proceedings of the 8th International Seminar on double-layer capacitors and similar energy storage devices, Deerfield Beach, FL, Dec 7–9Google Scholar
- 50.Ujjain SK, Ahuja P, Sharma RK (2015) Graphene nanoribbon wrapped cobalt manganite nanocubes for high performance all-solid-state fl exible supercapacitors. J Mater Chem A 3:9925–9931CrossRefGoogle Scholar
- 51.Kumar N, Kumar A, Huang G-M, Wu W (2018) Facile synthesis of mesoporous NiFe2O4/CNTs nanocomposite cathode material for high performance asymmetric pseudocapacitors. Appl Surf Sci 433:1100–1112CrossRefGoogle Scholar
- 52.Saravanakumar B, Purushothaman KK, Muralidharan G (2012) Interconnected V2O5 nanoporous network for high-performance supercapacitors. ACS Appl Mater Interfaces 4:4484–4490CrossRefGoogle Scholar