Hydrothermal Synthesis of Mesoporous Co3O4 Nanorods as High Capacity Anode Materials for Lithium Ion Batteries

Hydrothermal Synthesis of Mesoporous Co3O4 Nanorods as High Capacity Anode Materials for Lithium Ion Batteries

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Energyonline Procedia 00 (2018) 000–000 Available onlineatat www.sciencedirect.com Available www.sciencedirect.com Energy Procedia 00 (2018) 000–000

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Energy Procedia 158 Energy Procedia 00(2019) (2017)5293–5298 000–000 www.elsevier.com/locate/procedia

10th International Conference on Applied Energy (ICAE2018), 22-25 August 2018, Hong Kong, 10th International Conference on Applied Energy China(ICAE2018), 22-25 August 2018, Hong Kong, China

Hydrothermal Synthesis of Mesoporous Co3O4 Nanorods as High Hydrothermal Synthesis ofSymposium Mesoporous CoHeating The 15th International on District and Coolingas High 3O4 Nanorods Capacity Anode Materials for Lithium Ion Batteries Capacity Anode Materials for Lithium Ion Batteries Assessing the feasibility of using the heat demand-outdoor Bin Wangbb, Shifeng Wangaa, Yuanyuan Tangcc, Yaxiong Jidd, Wei Liuaa, Xiao-Ying Lu aa* Bin Wang , Shifeng Wang , for Yuanyuan Tang , Yaxiong Ji ,heat Wei Liu , Xiao-Ying Lu * temperature function a long-term district demand forecast Faculty of Science and Technology, Technological and Higher Education Institute of Hong Kong, Hong Kong, China a a

b Faculty of Science and Kong Technology, and HigherResearch Education InstituteHong of Hong Kong, Hong Kong, China Hong AppliedTechnological Science and Technology Institute, Kong, China

a,b,c a a b c Hong Kong Applied Science and Technology Research Institute, Hong China of Environmental Science and Engineering, Southern University of.,Science and Kong, Technology, I. School Andrić *, A. Pina , P. Ferrão , J. Fournier B. Lacarrière , Shenzhen, O. Le China Correc c


d School of Environmental and Engineering, Southern University of Science and102249, Technology, College ofScience Science, China University of Petroleum (Beijing), Beijing, ChinaShenzhen, China a d College of Science, China University Petroleum (Beijing), Beijing, 102249, China Corresponding author. E-mail address: [email protected]; Tel: +852-21761453; Fax: +852-21761554. IN+ Center for*Innovation, Technology and Policy Research - of Instituto Superior Técnico, Av. Rovisco Pais 1, 1049-001 Lisbon, Portugal b * Corresponding E-mail address: [email protected]; Tel: +852-21761453; Fax: +852-21761554. Veoliaauthor. Recherche & Innovation, 291 Avenue Dreyfous Daniel, 78520 Limay, France c Département Systèmes Énergétiques et Environnement - IMT Atlantique, 4 rue Alfred Kastler, 44300 Nantes, France c

Abstract Abstract InAbstract this study, mesoporous Co3O4 nanorods were successfully fabricated via hydrothermal treatment with presence of In this study, mesoporouschloride Co3O4 (DDA) nanorods were successfully hydrothermal presence a high degree of diallyldimethylammonium as the structure directingfabricated agent. Theviaas-prepared Co3Otreatment 4 exhibitedwith District heating are commonly addressed in literature as oneThe of nm the inmost effective for decreasing the diallyldimethylammonium (DDA) as0.3~2.4 the structure as-prepared Co3Owing O4 solutions exhibited a high degree of crystallization andnetworks consistedchloride of nanorods with μmthe in directing length andagent. 100~150 diameter. to the unique properties gas from the building These require high investments are returned through the heat crystallization andemissions consisted of nanorods with sector. 0.3~2.4 μm insystems length and 100~150 nm in diameter. to the unique properties nanorods exhibited excellent ofgreenhouse one dimensional micro-/nano-architecture and mesoporous structure, the as-prepared Cowhich 3O4Owing Due to the changed climate conditions and building capacity renovation policies, heatg-1demand incapacity the future couldof decrease, exhibited excellent ofsales. one dimensional micro-/nano-architecture mesoporous structure, as-prepared Co3O 4 nanorods and high retention 74.7% electrochemical lithium storage capability. An and initial discharge of the 1343.8 mAh -1 and high capacity retention of 74.7% prolonging theatlithium investment return period. electrochemical storage capability. initial discharge capacity of 1343.8 mAh gperformances 200 cycles. These outstanding of the as-prepared Co3O4 were achieved a current density of 500 An mAh g-1 for The achieved maindemonstrated scope thistheir paper is topotentials assess using thematerials heat demand – outdoor temperature for heat demand for of 200 cycles. These outstanding performances offunction the as-prepared Co3O4 were at of a current density of 500the mAh g-1capacity nanorods great infeasibility high anode for lithium ion batteries. forecast.demonstrated The district their of Alvalade, locatedininhigh Lisbon (Portugal), was usedforaslithium a caseion study. The district is consisted of 665 nanorods great potentials capacity anode materials batteries. buildings ©that vary in both construction period and typology. Three weather scenarios (low, medium, high) and three district Copyright 2018 Elsevier Ltd. All rights reserved. ©renovation 2019 The Published by Elsevier Ltd. intermediate, deep). To estimate the error, scenarios wereLtd. developed (shallow, obtained heat demand on values were Copyright ©Authors. 2018 Elsevier Allresponsibility rights reserved. Conference Applied Selection and peer-review under of the scientific committee of the 10th International This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/) th International compared withpeer-review results fromunder a dynamic heat demand model, previously developed and10 validated by the authors. Conference on Applied Selection and responsibility of the scientific committee of the Energy (ICAE2018). Peer-review under responsibility of the scientific committee of ICAE2018 – The 10th International Conference on Applied Energy. The results showed that when only weather change is considered, the margin of error could be acceptable for some applications Energy (ICAE2018). (the errorCobalt in annual was lower than 20% for all weather scenarios considered). However, after introducing renovation Keywords: oxides;demand Nanorods; Mesoporous structure; Lithium ion batteries Keywords: oxides; Nanorods; Mesoporous structure; Lithium iononbatteries scenarios,Cobalt the error value increased up to 59.5% (depending the weather and renovation scenarios combination considered). The value of slope coefficient increased on average within the range of 3.8% up to 8% per decade, that corresponds to the in the number of heating hours of 22-139h during the heating season (depending on the combination of weather and 1.decrease Introduction scenarios considered). On the other hand, function intercept increased for 7.8-12.7% per decade (depending on the 1.renovation Introduction coupled scenarios). The values suggested could as be the usedkey to modify the function parameters the scenarios considered, and Lithium ion batteries (LIBs), recognized components of energy storageforsystems in various portable improve theion accuracy of heat demand estimations.as the key components of energy storage systems in various portable Lithium batteries (LIBs), recognized

electronic devices and electric vehicles, have attracted a large amount of attention in the scientific research and electronic devices and electric vehicles, haveanode attracted a large attention in the of scientific research and industries [1]. Graphite as one conventional material has amount a typicalofspecific capacity 372 mAh g-1, which © 2017 The Authors. Published by Elsevier Ltd. -1 , which industries [1]. Graphite as one conventional anode material has a typical specific capacity of 372 mAh g cannot satisfy the responsibility growing demand high lithium storage capacity. Recently, Symposium transition metal oxides (TMOs) Peer-review under of theof Scientific Committee of The 15th International on District Heating and have cannot satisfy the as growing demand of high lithium storage capacity. Recently, transition metal oxides (TMOs) have O was regarded as one of the most competitive been considered potential alternatives, among which Co 3 4 Cooling. -1 O was regarded as one of the most competitive been considered as potential alternatives, among which Co 3 4 mAh g [2, 3]. However, Co3O4 usually suffered candidates because of its high theoretical specific capacity of 890 -1 candidates because ofForecast; its highClimate theoretical Keywords: Heat demand; change specific capacity of 890 mAh g [2, 3]. However, Co3O4 usually suffered 1876-6102 Copyright © 2018 Elsevier Ltd. All rights reserved. 1876-6102 Copyright © 2018 Elsevier Ltd. All of rights reserved. committee of the 10th International Conference on Applied Energy (ICAE2018). Selection and peer-review under responsibility the scientific Selection and peer-review under responsibility of the scientific committee of the 10th International Conference on Applied Energy (ICAE2018). 1876-6102 © 2017 The Authors. Published by Elsevier Ltd. Peer-review under responsibility of the Scientific Committee of The 15th International Symposium on District Heating and Cooling. 1876-6102 © 2019 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/) Peer-review under responsibility of the scientific committee of ICAE2018 – The 10th International Conference on Applied Energy. 10.1016/j.egypro.2019.01.646

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from poor cycling stability and inferior rate capability, due to the poor conductivity and severe volume expansion. The volume change of Co3O4 was reported to be about 100% during charge-discharge processes [4]. To overcome such drawbacks, various strategies have been adopted, such as nanostructure design, surface modification and dopant manipulation [5]. Rational nanostructuring has been proven as one of the effective routes to improve battery performances. A variety of structures have been examined for LIBs, like nanosheets [6], nanotubes [7], hollow spheres [8], nanorod-assembled hexapods [9] and snow-flaked shaped Co3O4 [10] etc. Recently, design of micro/nano-architecture has been considered as a promising approach for addressing the above challenges, due to the combined benefits from both microscale and nanoscale [11]. In this study, a facile one-pot hydrothermal method was adopted to synthesize mesoporous Co3O4 nanorods with multi-scale dimensions by applying diallyldimethylammonium chloride (DDA) as structure controlling agent. To the best of our knowledge, this is the first report on the utilization of DDA for synthesizing mesoporous Co3O4 nanorods and their structure tailoring. The excellent electrochemical performances of the as-prepared Co3O4 nanorods demonstrated their great potential as high capacity anode materials for LIBs. 2. Experimental Details 2.1. Material fabrication Mesoporous Co3O4 nanorods were prepared by hydrothermal treatment with DDA. In a typical process, 1.24 g CoCl2•6H2O (≥98.0%, Sigma-Aldrich) was first dissolved in 55 mL deionized water, accompanied with addition of 3 g urea (99.5%, Acros Organics) and 5 g DDA (20 wt. %, Sigma-Aldrich). The resulting solution was mixed and transferred to a Teflon-lined hydrothermal reactor at 120°C for 12 hours. The as-prepared precursors were harvested by vacuum filtration, followed by rinsing with sufficient deionized water and ethanol. Finally, the precursors were calcined in air at 450°C for 2 hours to yield mesoporous Co3O4 nanorods. 2.2. Structural characterizations The crystal phases of the as-prepared products were studied by employing X-ray diffractometer (XRD, Bruker) with Cu Kα12 X-ray radiation at wavelength of 0.15418 nm and a LynxEye detector. Field emission scanning electron microscopy (FE-SEM, Hitachi S4800) and transmission electron microscope (TEM, FEI Tecnai G2 20 scanning) were used to examine the morphologies and micro-structures. Thermo-gravimetric analysis (TGA, Perkin Elmer) equipped with EXSTAR TG/DTA 6300 instrument (SII Nanotechnology, Tokyo, Japan) was adopted to evaluate the thermal conversion from precursors into products from room temperature to 800°C with a ramping rate of 10°C min-1. 2.3. Electrochemical performance tests LAND CT2001 battery testing system (Wuhan Jinnuo Electronics, Ltd., China) in 2025 type coin cell with a cutoff voltage range from 0.01 V to 3.0 V versus Li+/Li was applied to assess the battery performance of mesoporous Co3O4 anode. The working electrodes consisted of 70 wt% active anode materials (Co3O4), 15 wt% carbon black (SuperP®) and 15 wt% polyvinylidene fluoride (PVDF) mixed in N-methyl-2-pyrrolidinone (NMP, Sigma-Aldrich) solvent. The resultant slurry was uniformly coated on Cu foil by an automatic film applicator (AFAII, Shanghai Pushen Chemical Machinery Co. Ltd, China) and were dried in a vacuum oven at 120°C for 12 h. The mesoporous Co3O4 anode disc was fabricated by cutting coated Cu foil with a compact and precision disc cutter (MSK-T-10, MTI Corporation). For the fabrication of a 2025 type coin cell, the as-prepared Co3O4 disc was used as the anode, lithium metal as the counter electrode and a polypropylene microporous membrane (Celgard 2400) was employed as the separator. Electrolyte was composed of 1 mol L-1 LiPF6 in ethylene carbonate (EC) and diethyl carbonate (DEC) with a volume ratio of 1:1. The assembly of coin cell was accomplished by a compact hydraulic crimping machine (MSK-110, MTI Corporation) in an argon-filled glove-box (MBRAUN) with <0.5 ppm of oxygen and water.

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3. Results and discussion Fig. 1 showed typical XRD patterns of precursors and products before and after heat treatment. The diffraction peaks obtained from the precursors confirmed the existence of Co(CO3)0.5(OH)•0.11H2O phase (JCPDS No. 480083), while the peaks originating from the products were well indexed to Co3O4 phase (JCPDS No. 43-1003). No other impurities were detected, suggesting high purity of precursors and products. Sharp peaks in the XRD pattern of the products implied high crystallinity of the prepared Co3O4. The formation of Co(CO3)0.5(OH) •0.11H2O was due to the precipitation reaction between Co2+ and by-products of urea decomposition. Urea could be decomposed into CO32- and OH-, as indicated in Eq. (1)-(3) [12].

Fig. 1 XRD patterns of precursors and products.

NH2CONH2 + H2O  2 NH3 + CO2 CO2 + H2O  CO32- + 2 H+ NH3 + H2O  NH4+ + OH3 Co(CO3)0.5(OH) •0.11H2O  Co3O4 + 1.5 CO2 + 1.83 H2O

(1) (2) (3) (4)

Fig. 2 revealed thermos-gravimetric (TGA) and differential thermal analysis (DTA) of precursors and products. When the precursors were heated from room temperature to 500oC in air, a total weight loss of 28.8% was observed, which was consistent with the theoretically calculated weight loss of 25.7%, based on the decomposition reaction of precursors in Eq. (4). The obvious DTG peaks located at 326°C and 360°C were ascribed to thermal decomposition of precursors and removal of DDA. No obvious weight change was found at temperature over 450oC, implying complete conversion from precursors to Co3O4. Additionally, the as-prepared Co3O4 products were highly stable under thermal conditions, indicated by no apparent weight loss up to 500oC. Fig. 3 (a) and 3 (b) showed FE-SEM images of precursors. Note that, urchin-like structures consisting of numerous nanorods were observed, revealing that 1D structure was the building unit of precursors. The nanorods with a dimension of about 5 μm in length and 230 nm in diameter were connected to each other at the tails, thus exhibiting urchin-like structure. The aspect ratio (L/D ratio) of precursors were deduced to be around 22. However, as shown in Fig. 3 (c) and 3 (d), when the temperature increased to 450oC, the urchin-like structures disassembled upon calcination and only individual nanorods with a length of 0.3 ~2.4 μm and a diameter of 100-150 nm left. The aspect ratio of Co3O4 products was reduced in the range of 3~16, compared with that of the as-prepared precursors.


Binname Wang/ et al. / Energy Procedia 158000–000 (2019) 5293–5298 Author Energy Procedia 00 (2018)

Fig. 2 TGA and DTA curves of precursors and products.

Fig. 3 FE-SEM images of (a, b) Co(CO3)0.5(OH) •0.11H2O precursors and (c, d) Co3O4 final products.

The micro-sized length and nano-sized diameter of 1D electrode materials were highly beneficial for enhancing electron transport and Li+ diffusion at microscale and nanoscale. Tang et al. reported that the battery performance was significantly improved at high charge-discharge rate with the increase of aspect ratio [13]. Thus, high aspect ratio of 1D materials (e.g. nanorods, nanotubes, nanowires) was a crucially important factor while developing electrode materials. Notably, the formation of 1D architecture of Co3O4 was accomplished by the aid of morphology tailoring using DDA, which was endowed with positively charged groups (-N+) in the molecules. By virtue of electrostatic interaction, DDA molecules could be selectively adsorbed onto the surface of crystal nucleus at the beginning of precipitation reaction, thus controlling the crystal growth along a preferred direction. Here, DDAassisted hydrothermal route was reported for the first time and will have great potentials in developing metal oxides with micro-/nanostructures for LIBs. The microstructures of Co3O4 nanorods were further investigated by TEM. As shown in Fig. 4 (a), the 1D architecture with mesoporous structure of Co3O4 nanorods could be distinctly identified. The diameter of Co3O4

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nanorods was in the range between 100 nm and 150 nm, in good agreement with the SEM observations. Small nanoparticles of 10 nm were interconnected with each other, leaving mesopores in between, thus forming mesoporous structure. Fig. 4 (b) presented a high resolution TEM image taken from the edge of a nanorod. The presence of lattice fringes verified high crystallinity of the fabricated Co3O4, consistent with XRD result. The interplaner spacing of 0.28 nm was associated with the (220) crystal plane of Co3O4, and the pore size estimated from TEM image was about 20 nm. Mesopores in Co3O4 nanorods were beneficial for enhancing electrolyte diffusion and alleviating volume expansion during charge-discharge processes, because of the enlarged specific surface area.

Fig. 4 Typical TEM images of the as-prepared Co3O4 products.

The cycling performance of the mesoporous Co3O4 nanorods was displayed in Fig. 5. The initial discharge and charge capacities were about 1343.8 mAh g-1 and 982 mAh g-1, respectively, suggesting Coulombic efficiency of 73.1% in the first cycle. The irreversible capacity loss was due to the irreversible formation of a solid electrolyte interface (SEI) and electrolyte decomposition [14]. Afterwards, Coulombic efficiency of ~100% was achieved, revealing highly reversible electrochemical processes in charge-discharge cycles. When tested for 100 cycles, mesoporous Co3O4 nanorods exhibited a specific discharge capacity of 1059.2 mAh g-1. After 200 cycles, the discharge capacity could still maintain at 733.9 mAh g-1, indicating a high capacity retention of 74.7%. In addition, the unique structure of mesoporous Co3O4 nanorods could still be found in the electrode layer after the cycling test, indicative of excellent structure integrity and stability. The lithium storage capability in this study was comparable to or better than previously reported Co3O4-based materials (e.g. foam-like nanosheets, single-crystal nanomesh and nanobelts etc). The long-term cycling stability of mesoporous Co3O4 nanorods was attributed to the unique 1D micro-/nano-architecture and mesoporous structure, thus demonstrating potential applications in LIBs.

Fig. 5 Cycling performance and Coulombic efficiency of mesoporous Co3O4 nanorods at current density of 500 mAh g-1.

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4. Conclusion Mesoporous Co3O4 nanorods were successfully synthesized by hydrothermal treatment with DDA-assisted structural tailoring. The as-prepared Co3O4 products with high crystallinity possessed 1D micro-/nano-architecture and mesoporous structure. This unique micro-/nano-architecture was highly favorable for boosting electron transport at microscale and reducing lithium ion diffusion length to nanoscale. In addition, mesoporous structure was also beneficial for mitigating the volume variation. The as-prepared mesoporous Co3O4 nanorods showed excellent lithium storage capability by delivering an initial capacity of 1343.8 mAh g-1 at current density of 500 mA g-1, and achieve prominent long-term cycling stability, which was reflected by a high capacity retention of 74.7% after 200 cycles. Importantly, DDA-assisted hydrothermal route will offer a facile and effective way to develop advanced energy storage materials with micro-/nano-architectures for LIBs applications. Acknowledgements This research was financially supported by Hong Kong Competitive Research Funding for Faculty Development Scheme (No.: UGC/FDS25/E07/16). References [1] Goodenough JB, Park KS, Am J. The Li-ion rechargeable battery: A perspective. J Am Chem Soc 2013; 135 (4): 1167–1176. [2] Poizot P, Laruelle S, Grugeon S, Dupont L, Tarascon JM. Nano-sized transition-metal oxides as negative-electrode materials for lithium-ion batteries. Nature 2000; 407:496–499. [3] Fang F, Bai L, Liu YG, Cheng SB, Sun HY. Facile synthesis of Co3O4 mesoporous nanosheets and their lithium storage properties. Mater Lett 2014;125: 103–106. [4] Wen W, Wu JM, Cao MH. Facile synthesis of a mesoporous Co3O4 network for Li-storage via thermal decomposition of an amorphous metal complex. Nanoscale 2014; 6:12476–12481. [5] Tang Y, Zhang Y, Li W, Ma B, Chen X. Rational material design for ultrafast rechargeable lithium-ion batteries. Chem Soc Rev 2015; 44(17):5926-40. [6] Wang X, Guan H, Chen S, Li H, Zhai T, Tang D, Bando Y, Golberg D. Self-stacked Co3O4 nanosheets for high-performance lithium ion batteries. Chem Commun 2011; 47:12280–12282. [7] Lou X, Deng D, Lee J, Feng J, Archer LA. Self-supported formation of needlelike Co3O4 nanotubes and their application as lithium-ion battery electrodes. Adv Mater 2008; 20:258–262. [8] Rui X, Tan H, Sim D, Liu W, Xu C, Hng HH, Yazami R, Lim TM, Yan Q. Template-free synthesis of urchin-like Co3O4 hollow spheres with good lithium storage properties. J Power Sources 2013; 222:97–102. [9] Wang L, Liu B, Ran S, Huang H, Wang X, Liang B, Chen D, Shen G. Nanorod-assembled Co3O4 hexapods with enhanced electrochemical performance for lithium-ion batteries. J Mater Chem 2012; 22:23541–23546. [10] Wang B, Lu XY, Tang Y. Synthesis of snowflake-shaped Co3O4 with a high aspect ratio as a high capacity anode material for lithium ion batteries. J Mater Chem A 2015; 3:9689–9699. [11] Cao H, Zhou X, Zheng C, Liu Z. Two-dimensional porous micro/nano metal oxides templated by graphene oxide. ACS Appl Mater Interfaces 2015; 7(22):11984–11990. [12] Chen H, Zhang Q, Wang J, Xu D, Li X, Yang Y, Zhang K. Improved lithium ion battery performance by mesoporous Co3O4 nanosheets grown on self-standing NiSix nanowires on nickel foam. J Mater Chem A 2014; 2:8483–8490. [13] Tang Y, Zhang Y, Deng J, Qi D, Leow WR. Wei J, Yin S, Dong Z, Yazami R, Chen Z, Chen X, Unravelling the correlation between the aspect ratio of nanotubular structures and their electrochemical performance to achieve high‐rate and long‐life lithium‐ion batteries. Angew Chem Int Edit 2014; 53:13488–13492. [14] Ge D, Geng H, Wang J, Zheng J, Pan Y, Cao X, Gu H. Porous nano-structured Co3O4 anode materials generated from coordination-driven self-assembled aggregates for advanced lithium ion batteries. Nanoscale 2014; 6:9689–9694.