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Solid waste-derived carbon as anode for high performance lithium-ion batteries
Diamond & Related Materials 98 (2019) 107517
Contents lists available at ScienceDirect
Diamond & Related Materials journal homepage: www.elsevier.com/locate/diamond
Solid waste-derived carbon as anode for high performance lithium-ion batteries
T
⁎
Ravi Kali , Balaji Padya, T.N. Rao, P.K. Jain International Advanced Research Centre for Powder Metallurgy and New Materials (ARCI), Balapur P.O., Hyderabad 500005, India
A R T I C LE I N FO
A B S T R A C T
Keywords: Rubber tube soot Low-cost anode Li-ion batteries Electrochemical behaviour
A facile and inexpensive synthesis process is developed to derive carbonaceous nanomaterials from dumped bicycle's inner rubber tube as a novel anode material for lithium ion batteries. Rubber tube -derived carbon soot (RTS) has synthesized via controlled oxidation process from bicycle's rubber tube to prepare high quality carbon soot without any organic impurities. Phase evaluation and surface morphology, structure and purity of the resultant RTS are analysed by various characterization tools. RTS consist of concentric carbon shells with quasicrystalline nature. RTS exhibits stable Li-capacity of ~190 mAhg−1 at 2C-rate with 84% capacity retention continued after 1000 electrochemical cycles. This approach opens an innovative strategy to produce high quality carbonaceous nanomaterials from recycling of solid-waste bicycle's rubber tube, which can be used as electrodes for advanced electrochemical energy storage applications.
1. Introduction Rechargeable lithium ion batteries are undergoing rapid development and providing power to many modern portable electronic devices like mobile phones, laptops, and other electronic devices due to their high energy density and lightweight as compared to other rechargeable batteries [1–6]. The electrochemical performances such as cyclic stability and energy density of the rechargeable batteries depend on the properties of the anode materials. Currently, graphitic carbon is widely used as anode material in commercial lithium ion batteries because of its low and smooth charge/discharge potential, low cost and good cycle performance, but relatively low specific capacity (~372 mAhg−1) and Li-plating on the surface of the graphite electrode at high current density are disadvantages of graphite [7–10]. Therefore, research efforts are presently focussed on alternative anode materials for lithiumion batteries are essential to replace the commercial graphite includes elements, alloys, and metal oxides, which have much higher specific capacities as compared to graphite. Moreover, alloying reaction based electrodes are showing huge volume expansion/contraction during repeated electrochemical Li-alloying/dealloying cycles cause electrode pulverization which leads to the delamination of active materials from the current collector, resulting poor capacity fading upon Li-alloying/ dealloying, which is the main bottleneck towards the usage of alloying reaction based materials as anode material [5–16]. Similarly, focus of the researchers was back to development of high-performance electrode
⁎
materials based on carbonaceous anode materials, such as hard carbons, and disordered carbons as they demonstrated higher and stable Li-capacity as compared to pure graphitic carbon electrodes [17–20]. Though there are various routes to produce carbonaceous nanomaterials, their quality and unique properties are depending on kind of resources and processing parameters of the procedure to produce them effectively. Carbonaceous nanomaterials were derived from the dumped solid and biomass waste used as negative electrode materials for lithium-ion storage [21–24], and which performed the stable Licapacity of 200 mAhg−1 after 200 cycles at current density of 100 mAg−1. Candle soot-derived carbon nanoparticles used as binder-free anode materials for lithium-ion batteries reported by Kakunuri et al. [25] and which was stabilized at a specific capacity of 220 mAhg−1 after 1000 cycles at the high current rate (i.e.5C). Recently, reported high surface area carbon nanomaterials were used as anode for lithium ion storage, which derived from waste tire as precursor [26]. As an alternate to existing carbon materials, dumped bicycle's inner rubber tubes were used as resources for producing the carbonaceous nanomaterials which can be used as high performance anode materials for electrochemical energy storage. In the present work, we report a simple and economical process to produce carbonaceous nanomaterials in the form of carbon soot directly from the burning of dumped bicycle's rubber tube via controlled oxidation process, and successfully proved their use in rechargeable lithium-ion batteries as high-performance anode material without any
Corresponding author. E-mail address: [email protected] (R. Kali).
https://doi.org/10.1016/j.diamond.2019.107517 Received 15 May 2019; Received in revised form 26 July 2019; Accepted 14 August 2019 Available online 15 August 2019 0925-9635/ © 2019 Published by Elsevier B.V.
Diamond & Related Materials 98 (2019) 107517
R. Kali, et al.
confocal micro-Raman spectrometer (Alpha 300 of Witec, Germany) near field scanning optical microscope with a 514 nm laser. Surface morphology and structure of the as-derived samples were observed by scanning electron microscopy (SEM, Carl-Geiss microscopy, Gemini500, Germany) and high-resolution transmission electron microscopy (HRTEM, JEM-2100F. The thermogravimetry (TG) experiments were conducted using STA 449 F3 Jupiter (Netzsch, Germany) thermal analyzer with alumina crucibles in oxygen (O2) atmosphere to measure thermal stability. The specific surface area and pore size distribution were carried out from nitrogen adsorption–desorption measurement (ASAP2020 physisorption analyzer).
treatment. 2. Experimental 2.1. Materials A bicycle's rubber tube was purchased from local market in Hyderabad, India to collect carbon soot. All chemicals related electrode assembling including battery grade Lithium foil and electrolyte were purchased from Sigma Aldrich, India and thin copper foil (9 μm thick, battery grade) was purchased from Ranga Techno Impex Pvt. Ltd., India.
2.4. Electrochemical measurements 2.2. Synthesis of the rubber tube-derived soot (RTS) The electrochemical characterizations of as-derived carbonaceous nanomaterials were evaluated in a half-cell configuration with lithium foil as reference electrode. Electrochemical testing of RTS electrodes were fabricated using active materials (RTS), conductive additive (Super P carbon) and binder (PVDF) in the weight ratio of 80:10:10 with few drops of N-methyl 2-pyrrolidone (NMP) as a solvent for slurry preparation. As prepared slurry was coated on a copper foil (current collector) and dried at 80 °C for overnight using vacuum oven to evaporate residual solvent and then, pressed at 6 MPa using a hydraulic press for better connectivity. The half- cell was assembled using CR2032-type coin cells with RTS as working electrode and lithium foil as reference electrode in an argon-filled glove box and 1 M LiPF6 dissolved in 1:1 wt/wt mixture of ethylene carbonate and diethyl carbonate used as electrolyte with glass microfiber filter (Whatman) as the separator. The electrochemical analysis of resulting half-cells were performed using Bio-Logic Science instruments (BCS-805) in a voltage window between 0.01 V and 2.0 V at different current rates and the current rates were calculated based on the weight of coated active material. Electrochemical impedance spectroscopy (EIS) was carried out in a frequency range of 10 mHz to 10 kHz before and after
The dumped bicycle's rubber tube was cut into fine pieces and cleaned with copious amount of DI water to remove unwanted organic and dirt particles which could affect the quality of final product. The cleaned pieces were dried at 80 °C using a hot air oven for overnight to remove moisture content before burning in a fume hood. A custommade set-up was designed to collect the carbon soot which consists of a quartz tube and a burner. The dried rubber tube pieces were burnt in a controlled way by maintaining appropriate atmosphere in the fume hood and the soot was collected. Then, the soot was ground in a mortarpestle and annealed at 900 °C for 5 h in an argon atmosphere at 10 °C/ min using a tubular furnace. The final product was called rubber tubederived soot (RTS). The schematic procedure implemented for the preparation of RTS was shown in Fig. 1. 2.3. Material characterizations As-derived carbonaceous nanomaterials were investigated by X-ray diffraction (XRD) (Bruker D8 Advance) using Cu Kα (λ = 1.5418 Å) with step size of 0.02° min−1. Raman spectra were recorded with a
Soot collector
Exhaust
Exhaust Membrane filter
Membrane filter
Rubber tube pieces
Burner Fig. 1. Schematic diagram for collection setup of RTS. 2
Diamond & Related Materials 98 (2019) 107517
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Fig. 2. (a) XRD pattern of RTS and corresponding Raman spectrum (b), thermogravimetric analysis of RTS (c) and N2 adsorption-desorption isotherms of RTS sample (d).
shift value means stacking of concentric layers in RTS [31]. Fig. 2c shows the thermo-gravimetric curves of RTS. RTS undergone weight losses in multiple stages comprising 3 regimes are < 400 °C, 400–600 °C and > 600 °C corresponding to Regime I, Regime II and Regime III, respectively. RTS shown considerable weight loss of 5.52, 91.80 and 2.68% in Regime I, Regime II, and Regime III, respectively, ascribed to desorption of water molecules and organic volatile vapours, decomposition of network in rubber and oxidation of high molecular weight disintegration, respectively. The noticeable weight loss was noticed in Regime II as the lower molecular weight rubber network would be disintegrated. DTG curve presented maximum temperature peak for high rate of decomposition for thermal degradation around 550 °C located in Regime II. The residue remained in TG crucible was negligible indicates that entire carbonaceous material were decomposed and converted into flue gases. The TG data confirms that RTS does not contain any metallic contaminants. Surface area analysis was carried out at −196.24 °C by N2 adsorption to measure the specific surface area and pore size distribution of RTS sample. N2 adsorption-desorption isotherms of RTS sample as shown in Fig. 2d and its looks like type (IV) isotherm with H3/H4 hysteresis loop indicating micro and mesoporous material. Moisture in the RTS sample was removed by degassing the sample at 300 °C for 8 h in a vacuum chamber and obtained specific surface area and pore volume were 115.63 m2/g and 0.176 cm3/g, respectively. Surface morphology and microstructure of RTS was investigated by FESEM and HRTEM respectively. Fig. 3a shows SEM image of RTS, composed of uniform spherical particles with diameters are in the size
electrochemical cycling. 3. Results and discussion 3.1. Phase evaluation & surface morphology In order to assess the presence of various impurities, XRD measurement was performed. The XRD pattern of RTS was depicted in Fig. 2a. The pattern consists an intense broad peak at θ = 23.7° corresponding to (002) plane which is lower side of actual graphite peak (θ = 26.6°) and another broad diffraction peak at θ = 43.6° corresponding to (101) plane, which is due to the presence of hexagonal structure of graphite. Therefore, the XRD pattern suggests that RTS has amorphous carbon structures [27,28]. The interlayer spacing of RTS was calculated to be to 0.375 nm, which is higher than that of crystalline graphitic carbon (0.334 nm). Raman spectroscopy is a versatile tool intensively deployed for qualitative analysis of carbon-based materials. Generally, the Raman spectra of any carbon-based material shows two significant peaks positioned at 1350 cm−1 and 1584 cm−1, which are conforming to Dband and G-band, respectively [29,30]. Fig. 2b shows the Raman spectra of RTS, which is consist of peaks at 1350, 1588 and 2837 cm−1 denote the disordered (D), graphitic (G) carbon phases, and 2D respectively. The ratio between the relative intensities of the D band to the G band (ID/IG) is about to be 0.9, which means high value of ID/IG ratio indicating the presence of tangled carbon in the RTS. 2D peak indicates the multilayer structure of RTS and it shifted towards higher 3
Diamond & Related Materials 98 (2019) 107517
R. Kali, et al.
Fig. 3. (a) Surface morphology of RTS, TEM images of RTS (b, c,) and (d) SAED pattern of RTS.
a current density of 100 mAg−1 are shown in Fig. 4b. It can be seen that in first discharge curve exhibits plateau at 1.4 and 0.77 V, which is associated with the electrolyte decomposition and solid electrolyte interface (SEI), the plateaus are not observed in the 2nd cycle, consistency with the above cyclic voltammograms (CV). Specific capacity of first discharge and charge cycles were about 520 and 267.09 mAhg−1, respectively with 31.9% initial coulombic efficiency. The electrochemical cycling stability of RTS was observed to be about 200 mAhg−1 at a current density of 100 mAg−1 after 100 discharge-charge cycles as shown in Fig. 4c. and, the resulting the capacity fade by ~20% from the second cycle. The electrochemical behavior of RTS was observed by the impedance spectroscopy in frequency range of 10 KHz to 10 mHz at the end of the 100 cycles at the current density of 100 mAg−1 and before cycling and the Nyquist plot was shown in Fig. 4d. The Nyquist plots of RTS electrodes depict a semicircle, which corresponding to the charge transfer resistance (Rct) at high frequency and a sloping line at low frequency, which corresponding to the diffusion or Ohmic resistance [36]. The Rct of the RTS electrode before and after 100 cycles were about 27.2 Ω and 32.5 Ω, respectively. This suggests that there was a negligible increase in the charge transfer resistance after 100 electrochemical cycles for RTS electrode. Based on the above EIS results, it can be concluded that RTS material perform a suitable anode for lithium ion storage application. The rate performance or capacity obtained with different current rates of C/10, C/5, C/2, and 1C for 10 discharge/charge cycles each and corresponding discharge capacities of ~300 mAhg−1, ~250 mAhg−1, ~200 mAhg−1 and ~185 mAhg−1, respectively as depicted in Fig. 5a. Another significant reflection from Fig. 5a is that, at high current rates (i.e., up to C-rate) in the middle cycles, specific capacity of RTS sample ~280 mAhg−1 is obtained even at the end of the 70th cycle, upon ‘returning’ to C/10. This indicates excellent stability even at the high
range of 50–60 nm. Most of the RTS particles were found as agglomerated structures with well interconnected to each other. Such structures could aid in providing a continuous electronic path to enhance electronic conductivity of RTS. The HRTEM image of RTS reveals that the spherical particles with diameters are in nanometres was illustrated in Fig. 3b. The insight into the microstructure of RTS was explored extensively by HRTEM to notice the structural changes and d-spacing. It revealed that the RTS was in spherical structure consist of layered concentric-shelled structures as shown Fig. 3c. The SAED pattern (Fig. 3d) of the RTS sample confirmed that the amorphous nature of the material which indicates that RTS was not fully graphitized (i.e. crystalline) but its looks like semi-crystalline material. Therefore, rubber tube soot (RTS) has porous structure which can enhance the electrochemical performance with high surface area, resulting RTS as an excellent choice in energy storage as anode material. 3.2. Electrochemical performance The basic electrochemical behaviour of RTS as working electrode material for lithium-ion batteries were investigated using CR2032 type coin cells assembled in Ar filled glovebox with lithium foil used as a counter/reference electrode. Fig. 4a shows the cyclic voltammetry recorded with voltage sweep rate of 0.05 mVs−1 with potential range from 0.01 to 2.0 V (against Li/Li+). Overall, two cathodic peaks were observed at 1.4 V and 0.73 V during first cathodic scan, which are related to the electrolyte decomposition or SEI layer formation, respectively [32–35]. No cathodic peak related to electrolyte decomposition or SEI layer formation could be observed during the second cathodic scan (Fig. 4a). The galvanostatic discharge-charge cycles (chronopotentiograms) of RTS electrode were performed between 0.01 and 2.0 V against Li/Li+ at 4
Diamond & Related Materials 98 (2019) 107517
R. Kali, et al.
Fig. 4. (a) Cyclic voltammogram of RTS at scan rate of 0.05 mV/s (b) galvanostatic voltage profile of RTS sample at current density of 100 mA g−1 (c) cycling performance of the RTS at current density of 100 mA g−1 and (d) Nyquist plot of RTS sample before and after 100 cycles at 100 mA g−1.
RTS materials as provided in Table 1.
current rates, which is likely to be considerably superior anode for lithium ion storage. The cycling stability of RTS was confirmed by charging/discharging at high current rate of 2C (~1.339 mA) (Fig. 5b). After 1000 charging/discharging cycles, the specific charge capacity as high as 190 mAhg−1 is maintained at 2C current-rate for the RTS and corresponding capacity retention was about 84% of the initial charge capacity (from the 2nd cycle). The good cycling stability indicates that RTS plays a fundamental role in ensuring their performance in high energy density lithium-ion batteries. Capacity comparison of different carbonaceous materials derived from dumped solid and bio-waste with
4. Conclusions In summary, we have reported here the electrochemical characterization of rubber tube soot for lithium ion batteries and successfully prepared through a simple and inexpensive way of a waste bicycle's inner rubber tube and explored them as anode materials for lithium-ion storage. Reversible lithium capacity of RTS was recorded to be ~190 mAhg−1 at the high current rate (i.e., 2C) after 1000 electrochemical
Fig. 5. (a) Rate performance of the RTS at current rates: C/10, C/5, C/2, and C. and (b) cycling performance of the RTS at high current rate of 2C. 5
Diamond & Related Materials 98 (2019) 107517
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Table 1 A comparison of electrochemical performance of carbon derived from solid or bio-waste. Carbon soot source
Micro structure
Capacity (mAh/g)
Capacity retention (%)
Reference
Sulfonated tire rubber Recycle waste soot from ships Waste plastic bags Waste tires (Activated) Waste tire
Fused particles with irregular shapes Chain-like morphologies Sheet/flake architectures Interconnected porous network Cross-sectional layer
– – – 80 (after 100 cycles) –
[21] [22] [23] [26] [37]
Bicycle's rubber tube
Concentric shell
390 260 200 670 360 432 190
84 (after 1000 cycles)
This work
cycles against lithium. Therefore, based on the above results suggests that recycling of solid waste like bicycle's inner tube and tyre are sources for producing carbonaceous nanomaterials, which can be enhance the performance of the lithium ion batteries and new strategy to develop new materials with modification of surface morphology of the produce carbon materials.
(at C/10) (at 1C) (C/5) (50 mA g−1) (at C/3-without carbon coating) (at C/10-with carbon coating) (at high rate i.e., 2C)
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Acknowledgments The authors are grateful to Dr. G. Padmanabham, Director, ARCI for his constant support and providing necessary research facilities. Authors are acknowledging University of Hyderabad for enabling of Raman spectroscopy facility. Dr. R.K. acknowledge DST-INSPIRE Faculty award (IFA17-ENG235) research grant for financial support. References [1] M. Winter, R.J. Brodd, What are batteries fuel cells, and supercapacitors, Chem. Rev. 104 (2004) 4245–4269. [2] J.M. Tarascon, M. Armand, Issues and challenges facing rechargeable lithium batteries, Nature 414 (2001) 359–367. [3] A.S. Arico, P. Bruce, B. Scrosati, J.M. Tarascon, W. van Schalkwijk, Nanostructured materials for advanced energy conversion and storage devices, Nat. Mater. 4 (2005) 366–377. [4] P.G. Bruce, B. Scrosati, J.M. Tarascon, Nanomaterials for rechargeable lithium batteries, Angew. Chem. Int. Ed. 47 (2008) 2930–2946. [5] N. Nitta, G. Yushin, High-capacity anode materials for lithium-ion batteries: choice of elements and structures for active particles, Part. Part. Syst. Charact. 31 (2013) 317–336. [6] S. Goriparti, E. Miele, F.D. Angelis, E.D. Fabrizio, R.P. Zaccaria, C. Capiglia, Review on recent progress of nanostructured anode materials for Li-ion batteries, J. Power Sources 257 (2014) 421–443. [7] N.A. Kaskhedikar, J. Maier, Lithium storage in carbon nanostructures, Adv. Mater. 21 (25–26) (2009) 2664–2680. [8] M. Pumera, Graphene based nanomaterials for energy storage, Energy Environ. Sci. 4 (2011) 668–674. [9] H. Azuma, H. Imoto, S. Yamada, K. Sekai, Advanced carbon anode materials for lithium ion cells, J. Power Sources 81 (1999) 1–7. [10] H. Fujimoto, Development of efficient carbon anode material for a high-power and long-life lithium ion battery, J. Power Sources 195 (2010) 5019. [11] A. Mukhopadhyay, B.W. Sheldon, Deformation and stress in electrode materials for Li-ion batteries, Prog. Mater. Sci. 63 (2014) 58–116. [12] M.V. Reddy, G.V. Subba Rao, B.V.R. Chowdari, Metal oxides and oxysalts as anode materials for Li ion batteries, Chem. Rev. 113 (2013) 5364–5457. [13] J.O. Besenhard, J. Yang, M. Winter, Will advanced lithium-alloy anodes have a chance in lithium-ion batteries? J. Power Sources 68 (1997) 87–90. [14] L.Y. Beaulieu, S.D. Beattie, T.D. Hatchard, J.R. Dahn, The electrochemical reaction of lithium with tin studied by in situ AFM, J. Electrochem. Soc. 150 (2003) A419–A424. [15] A. Mukhopadhyay, R. Kali, S. Badjate, A. Tokranov, B.W. Sheldon, Plastic deformation associated with phase transformations during lithiation/delithiation of Sn, Scr. Mater. 92 (2014) 47–50. [16] R. Kali, Y. Krishnan, A. Mukhopadhyay, Effects of phase assemblage and microstructure-type for Sn/intermetallic ‘composite’ films on stress developments and cyclic stability upon lithiation/delithiation, Scr. Mater. 130 (2017) 105–109.
6
Contents lists available at ScienceDirect
Diamond & Related Materials journal homepage: www.elsevier.com/locate/diamond
Solid waste-derived carbon as anode for high performance lithium-ion batteries
T
⁎
Ravi Kali , Balaji Padya, T.N. Rao, P.K. Jain International Advanced Research Centre for Powder Metallurgy and New Materials (ARCI), Balapur P.O., Hyderabad 500005, India
A R T I C LE I N FO
A B S T R A C T
Keywords: Rubber tube soot Low-cost anode Li-ion batteries Electrochemical behaviour
A facile and inexpensive synthesis process is developed to derive carbonaceous nanomaterials from dumped bicycle's inner rubber tube as a novel anode material for lithium ion batteries. Rubber tube -derived carbon soot (RTS) has synthesized via controlled oxidation process from bicycle's rubber tube to prepare high quality carbon soot without any organic impurities. Phase evaluation and surface morphology, structure and purity of the resultant RTS are analysed by various characterization tools. RTS consist of concentric carbon shells with quasicrystalline nature. RTS exhibits stable Li-capacity of ~190 mAhg−1 at 2C-rate with 84% capacity retention continued after 1000 electrochemical cycles. This approach opens an innovative strategy to produce high quality carbonaceous nanomaterials from recycling of solid-waste bicycle's rubber tube, which can be used as electrodes for advanced electrochemical energy storage applications.
1. Introduction Rechargeable lithium ion batteries are undergoing rapid development and providing power to many modern portable electronic devices like mobile phones, laptops, and other electronic devices due to their high energy density and lightweight as compared to other rechargeable batteries [1–6]. The electrochemical performances such as cyclic stability and energy density of the rechargeable batteries depend on the properties of the anode materials. Currently, graphitic carbon is widely used as anode material in commercial lithium ion batteries because of its low and smooth charge/discharge potential, low cost and good cycle performance, but relatively low specific capacity (~372 mAhg−1) and Li-plating on the surface of the graphite electrode at high current density are disadvantages of graphite [7–10]. Therefore, research efforts are presently focussed on alternative anode materials for lithiumion batteries are essential to replace the commercial graphite includes elements, alloys, and metal oxides, which have much higher specific capacities as compared to graphite. Moreover, alloying reaction based electrodes are showing huge volume expansion/contraction during repeated electrochemical Li-alloying/dealloying cycles cause electrode pulverization which leads to the delamination of active materials from the current collector, resulting poor capacity fading upon Li-alloying/ dealloying, which is the main bottleneck towards the usage of alloying reaction based materials as anode material [5–16]. Similarly, focus of the researchers was back to development of high-performance electrode
⁎
materials based on carbonaceous anode materials, such as hard carbons, and disordered carbons as they demonstrated higher and stable Li-capacity as compared to pure graphitic carbon electrodes [17–20]. Though there are various routes to produce carbonaceous nanomaterials, their quality and unique properties are depending on kind of resources and processing parameters of the procedure to produce them effectively. Carbonaceous nanomaterials were derived from the dumped solid and biomass waste used as negative electrode materials for lithium-ion storage [21–24], and which performed the stable Licapacity of 200 mAhg−1 after 200 cycles at current density of 100 mAg−1. Candle soot-derived carbon nanoparticles used as binder-free anode materials for lithium-ion batteries reported by Kakunuri et al. [25] and which was stabilized at a specific capacity of 220 mAhg−1 after 1000 cycles at the high current rate (i.e.5C). Recently, reported high surface area carbon nanomaterials were used as anode for lithium ion storage, which derived from waste tire as precursor [26]. As an alternate to existing carbon materials, dumped bicycle's inner rubber tubes were used as resources for producing the carbonaceous nanomaterials which can be used as high performance anode materials for electrochemical energy storage. In the present work, we report a simple and economical process to produce carbonaceous nanomaterials in the form of carbon soot directly from the burning of dumped bicycle's rubber tube via controlled oxidation process, and successfully proved their use in rechargeable lithium-ion batteries as high-performance anode material without any
Corresponding author. E-mail address: [email protected] (R. Kali).
https://doi.org/10.1016/j.diamond.2019.107517 Received 15 May 2019; Received in revised form 26 July 2019; Accepted 14 August 2019 Available online 15 August 2019 0925-9635/ © 2019 Published by Elsevier B.V.
Diamond & Related Materials 98 (2019) 107517
R. Kali, et al.
confocal micro-Raman spectrometer (Alpha 300 of Witec, Germany) near field scanning optical microscope with a 514 nm laser. Surface morphology and structure of the as-derived samples were observed by scanning electron microscopy (SEM, Carl-Geiss microscopy, Gemini500, Germany) and high-resolution transmission electron microscopy (HRTEM, JEM-2100F. The thermogravimetry (TG) experiments were conducted using STA 449 F3 Jupiter (Netzsch, Germany) thermal analyzer with alumina crucibles in oxygen (O2) atmosphere to measure thermal stability. The specific surface area and pore size distribution were carried out from nitrogen adsorption–desorption measurement (ASAP2020 physisorption analyzer).
treatment. 2. Experimental 2.1. Materials A bicycle's rubber tube was purchased from local market in Hyderabad, India to collect carbon soot. All chemicals related electrode assembling including battery grade Lithium foil and electrolyte were purchased from Sigma Aldrich, India and thin copper foil (9 μm thick, battery grade) was purchased from Ranga Techno Impex Pvt. Ltd., India.
2.4. Electrochemical measurements 2.2. Synthesis of the rubber tube-derived soot (RTS) The electrochemical characterizations of as-derived carbonaceous nanomaterials were evaluated in a half-cell configuration with lithium foil as reference electrode. Electrochemical testing of RTS electrodes were fabricated using active materials (RTS), conductive additive (Super P carbon) and binder (PVDF) in the weight ratio of 80:10:10 with few drops of N-methyl 2-pyrrolidone (NMP) as a solvent for slurry preparation. As prepared slurry was coated on a copper foil (current collector) and dried at 80 °C for overnight using vacuum oven to evaporate residual solvent and then, pressed at 6 MPa using a hydraulic press for better connectivity. The half- cell was assembled using CR2032-type coin cells with RTS as working electrode and lithium foil as reference electrode in an argon-filled glove box and 1 M LiPF6 dissolved in 1:1 wt/wt mixture of ethylene carbonate and diethyl carbonate used as electrolyte with glass microfiber filter (Whatman) as the separator. The electrochemical analysis of resulting half-cells were performed using Bio-Logic Science instruments (BCS-805) in a voltage window between 0.01 V and 2.0 V at different current rates and the current rates were calculated based on the weight of coated active material. Electrochemical impedance spectroscopy (EIS) was carried out in a frequency range of 10 mHz to 10 kHz before and after
The dumped bicycle's rubber tube was cut into fine pieces and cleaned with copious amount of DI water to remove unwanted organic and dirt particles which could affect the quality of final product. The cleaned pieces were dried at 80 °C using a hot air oven for overnight to remove moisture content before burning in a fume hood. A custommade set-up was designed to collect the carbon soot which consists of a quartz tube and a burner. The dried rubber tube pieces were burnt in a controlled way by maintaining appropriate atmosphere in the fume hood and the soot was collected. Then, the soot was ground in a mortarpestle and annealed at 900 °C for 5 h in an argon atmosphere at 10 °C/ min using a tubular furnace. The final product was called rubber tubederived soot (RTS). The schematic procedure implemented for the preparation of RTS was shown in Fig. 1. 2.3. Material characterizations As-derived carbonaceous nanomaterials were investigated by X-ray diffraction (XRD) (Bruker D8 Advance) using Cu Kα (λ = 1.5418 Å) with step size of 0.02° min−1. Raman spectra were recorded with a
Soot collector
Exhaust
Exhaust Membrane filter
Membrane filter
Rubber tube pieces
Burner Fig. 1. Schematic diagram for collection setup of RTS. 2
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Fig. 2. (a) XRD pattern of RTS and corresponding Raman spectrum (b), thermogravimetric analysis of RTS (c) and N2 adsorption-desorption isotherms of RTS sample (d).
shift value means stacking of concentric layers in RTS [31]. Fig. 2c shows the thermo-gravimetric curves of RTS. RTS undergone weight losses in multiple stages comprising 3 regimes are < 400 °C, 400–600 °C and > 600 °C corresponding to Regime I, Regime II and Regime III, respectively. RTS shown considerable weight loss of 5.52, 91.80 and 2.68% in Regime I, Regime II, and Regime III, respectively, ascribed to desorption of water molecules and organic volatile vapours, decomposition of network in rubber and oxidation of high molecular weight disintegration, respectively. The noticeable weight loss was noticed in Regime II as the lower molecular weight rubber network would be disintegrated. DTG curve presented maximum temperature peak for high rate of decomposition for thermal degradation around 550 °C located in Regime II. The residue remained in TG crucible was negligible indicates that entire carbonaceous material were decomposed and converted into flue gases. The TG data confirms that RTS does not contain any metallic contaminants. Surface area analysis was carried out at −196.24 °C by N2 adsorption to measure the specific surface area and pore size distribution of RTS sample. N2 adsorption-desorption isotherms of RTS sample as shown in Fig. 2d and its looks like type (IV) isotherm with H3/H4 hysteresis loop indicating micro and mesoporous material. Moisture in the RTS sample was removed by degassing the sample at 300 °C for 8 h in a vacuum chamber and obtained specific surface area and pore volume were 115.63 m2/g and 0.176 cm3/g, respectively. Surface morphology and microstructure of RTS was investigated by FESEM and HRTEM respectively. Fig. 3a shows SEM image of RTS, composed of uniform spherical particles with diameters are in the size
electrochemical cycling. 3. Results and discussion 3.1. Phase evaluation & surface morphology In order to assess the presence of various impurities, XRD measurement was performed. The XRD pattern of RTS was depicted in Fig. 2a. The pattern consists an intense broad peak at θ = 23.7° corresponding to (002) plane which is lower side of actual graphite peak (θ = 26.6°) and another broad diffraction peak at θ = 43.6° corresponding to (101) plane, which is due to the presence of hexagonal structure of graphite. Therefore, the XRD pattern suggests that RTS has amorphous carbon structures [27,28]. The interlayer spacing of RTS was calculated to be to 0.375 nm, which is higher than that of crystalline graphitic carbon (0.334 nm). Raman spectroscopy is a versatile tool intensively deployed for qualitative analysis of carbon-based materials. Generally, the Raman spectra of any carbon-based material shows two significant peaks positioned at 1350 cm−1 and 1584 cm−1, which are conforming to Dband and G-band, respectively [29,30]. Fig. 2b shows the Raman spectra of RTS, which is consist of peaks at 1350, 1588 and 2837 cm−1 denote the disordered (D), graphitic (G) carbon phases, and 2D respectively. The ratio between the relative intensities of the D band to the G band (ID/IG) is about to be 0.9, which means high value of ID/IG ratio indicating the presence of tangled carbon in the RTS. 2D peak indicates the multilayer structure of RTS and it shifted towards higher 3
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Fig. 3. (a) Surface morphology of RTS, TEM images of RTS (b, c,) and (d) SAED pattern of RTS.
a current density of 100 mAg−1 are shown in Fig. 4b. It can be seen that in first discharge curve exhibits plateau at 1.4 and 0.77 V, which is associated with the electrolyte decomposition and solid electrolyte interface (SEI), the plateaus are not observed in the 2nd cycle, consistency with the above cyclic voltammograms (CV). Specific capacity of first discharge and charge cycles were about 520 and 267.09 mAhg−1, respectively with 31.9% initial coulombic efficiency. The electrochemical cycling stability of RTS was observed to be about 200 mAhg−1 at a current density of 100 mAg−1 after 100 discharge-charge cycles as shown in Fig. 4c. and, the resulting the capacity fade by ~20% from the second cycle. The electrochemical behavior of RTS was observed by the impedance spectroscopy in frequency range of 10 KHz to 10 mHz at the end of the 100 cycles at the current density of 100 mAg−1 and before cycling and the Nyquist plot was shown in Fig. 4d. The Nyquist plots of RTS electrodes depict a semicircle, which corresponding to the charge transfer resistance (Rct) at high frequency and a sloping line at low frequency, which corresponding to the diffusion or Ohmic resistance [36]. The Rct of the RTS electrode before and after 100 cycles were about 27.2 Ω and 32.5 Ω, respectively. This suggests that there was a negligible increase in the charge transfer resistance after 100 electrochemical cycles for RTS electrode. Based on the above EIS results, it can be concluded that RTS material perform a suitable anode for lithium ion storage application. The rate performance or capacity obtained with different current rates of C/10, C/5, C/2, and 1C for 10 discharge/charge cycles each and corresponding discharge capacities of ~300 mAhg−1, ~250 mAhg−1, ~200 mAhg−1 and ~185 mAhg−1, respectively as depicted in Fig. 5a. Another significant reflection from Fig. 5a is that, at high current rates (i.e., up to C-rate) in the middle cycles, specific capacity of RTS sample ~280 mAhg−1 is obtained even at the end of the 70th cycle, upon ‘returning’ to C/10. This indicates excellent stability even at the high
range of 50–60 nm. Most of the RTS particles were found as agglomerated structures with well interconnected to each other. Such structures could aid in providing a continuous electronic path to enhance electronic conductivity of RTS. The HRTEM image of RTS reveals that the spherical particles with diameters are in nanometres was illustrated in Fig. 3b. The insight into the microstructure of RTS was explored extensively by HRTEM to notice the structural changes and d-spacing. It revealed that the RTS was in spherical structure consist of layered concentric-shelled structures as shown Fig. 3c. The SAED pattern (Fig. 3d) of the RTS sample confirmed that the amorphous nature of the material which indicates that RTS was not fully graphitized (i.e. crystalline) but its looks like semi-crystalline material. Therefore, rubber tube soot (RTS) has porous structure which can enhance the electrochemical performance with high surface area, resulting RTS as an excellent choice in energy storage as anode material. 3.2. Electrochemical performance The basic electrochemical behaviour of RTS as working electrode material for lithium-ion batteries were investigated using CR2032 type coin cells assembled in Ar filled glovebox with lithium foil used as a counter/reference electrode. Fig. 4a shows the cyclic voltammetry recorded with voltage sweep rate of 0.05 mVs−1 with potential range from 0.01 to 2.0 V (against Li/Li+). Overall, two cathodic peaks were observed at 1.4 V and 0.73 V during first cathodic scan, which are related to the electrolyte decomposition or SEI layer formation, respectively [32–35]. No cathodic peak related to electrolyte decomposition or SEI layer formation could be observed during the second cathodic scan (Fig. 4a). The galvanostatic discharge-charge cycles (chronopotentiograms) of RTS electrode were performed between 0.01 and 2.0 V against Li/Li+ at 4
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Fig. 4. (a) Cyclic voltammogram of RTS at scan rate of 0.05 mV/s (b) galvanostatic voltage profile of RTS sample at current density of 100 mA g−1 (c) cycling performance of the RTS at current density of 100 mA g−1 and (d) Nyquist plot of RTS sample before and after 100 cycles at 100 mA g−1.
RTS materials as provided in Table 1.
current rates, which is likely to be considerably superior anode for lithium ion storage. The cycling stability of RTS was confirmed by charging/discharging at high current rate of 2C (~1.339 mA) (Fig. 5b). After 1000 charging/discharging cycles, the specific charge capacity as high as 190 mAhg−1 is maintained at 2C current-rate for the RTS and corresponding capacity retention was about 84% of the initial charge capacity (from the 2nd cycle). The good cycling stability indicates that RTS plays a fundamental role in ensuring their performance in high energy density lithium-ion batteries. Capacity comparison of different carbonaceous materials derived from dumped solid and bio-waste with
4. Conclusions In summary, we have reported here the electrochemical characterization of rubber tube soot for lithium ion batteries and successfully prepared through a simple and inexpensive way of a waste bicycle's inner rubber tube and explored them as anode materials for lithium-ion storage. Reversible lithium capacity of RTS was recorded to be ~190 mAhg−1 at the high current rate (i.e., 2C) after 1000 electrochemical
Fig. 5. (a) Rate performance of the RTS at current rates: C/10, C/5, C/2, and C. and (b) cycling performance of the RTS at high current rate of 2C. 5
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Table 1 A comparison of electrochemical performance of carbon derived from solid or bio-waste. Carbon soot source
Micro structure
Capacity (mAh/g)
Capacity retention (%)
Reference
Sulfonated tire rubber Recycle waste soot from ships Waste plastic bags Waste tires (Activated) Waste tire
Fused particles with irregular shapes Chain-like morphologies Sheet/flake architectures Interconnected porous network Cross-sectional layer
– – – 80 (after 100 cycles) –
[21] [22] [23] [26] [37]
Bicycle's rubber tube
Concentric shell
390 260 200 670 360 432 190
84 (after 1000 cycles)
This work
cycles against lithium. Therefore, based on the above results suggests that recycling of solid waste like bicycle's inner tube and tyre are sources for producing carbonaceous nanomaterials, which can be enhance the performance of the lithium ion batteries and new strategy to develop new materials with modification of surface morphology of the produce carbon materials.
(at C/10) (at 1C) (C/5) (50 mA g−1) (at C/3-without carbon coating) (at C/10-with carbon coating) (at high rate i.e., 2C)
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