Journal of Power Sources 379 (2018) 53–59
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Advanced and safer lithium-ion battery based on sustainable electrodes a
Xiang Ding , Xiaobing Huang , Junling Jin , Hai Ming
, Limin Wang , Jun Ming
Hunan Province Cooperative Innovation Center for the Construction & Development of Dongting Lake Ecological Economic Zone, College of Chemistry and Materials Engineering, Hunan University of Arts and Science, Changde, 415000, Hunan, P.R. China State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 215123, P.R. China c Research Institute of Chemical Defense, Beijing, 100191, P.R. China d King Abdullah University of Science & Technology, Thuwal, Saudi Arabia b
H I G H L I G H T S
G RA P H I C A L AB S T R A C T
new porous structured anatase TiO • Ananobundles (PTNBs) is synthesized. synthetics strategy is green and • The the formation mechanism is discussed. PTNBs exhibits high lithium sto• The rage capacity and better rate cap-
and safer Li-ion full bat• Sustainable tery of PTNBs/LiNi Mn O are prex
A R T I C L E I N F O
A B S T R A C T
Keywords: Lithium-ion battery Oxide Titania Anode Cathode Sustainability
Seeking advanced and safer lithium-ion battery with sustainable characteristic is signiﬁcant for the development of electronic devices and electric vehicles. Herein, a new porous TiO2 nanobundles (PTNBs) is synthesized though a scalable and green hydrothermal strategy from the TiO2 powders without using any high-cost and harmful organic titanium-based compounds. The PTNBs exhibits an extremely high lithium storage capacity of 296 mAh g−1 at 100 mA g−1, where the capacity can maintain over 146 mAh g−1 even after 500 cycles at 1000 mA g−1. To pursue more reliable Li-ion batteries, full batteries of PTNBs/LiNixMn1-xO4 (x = 0, 0.5) using spinel structured cathode are constructed. The batteries have the features of sustainability and deliver high capacities of 112 mAh gcathode−1 and 102 mAh gcathode−1 with stable capacity retentions of 99% and 90% over 140 cycles. Note that the energy densities can achieve as high as 267 and 270 Wh kgcathode−1 (535 and 540 Wh kganode−1) respectively, which is feasible to satisfy diverse requirements for energy storage products. We believe that the universal synthetic strategy, appealing structure and intriguing properties of PTNBs is applicable for wider applications, while the concept of sustainable strategy seeking reliable and safer Li-ion battery can attract broad interest.
1. Introduction The safety issue and sustainability of lithium-ion batteries (LIBs) has attracted more attention because it has become one bottle-neck in the
dramatically increased demand of grid energy storage system, electronic devices and electric vehicles [1–3]. To guarantee the durability of LIBs, the strategies of controlling inner thermal eﬀect , adding stabilizer in electrolyte [5,6], modifying battery conﬁguration [7,8],
∗ Corresponding author. State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 215123, P.R. China. ∗∗ Corresponding author. Research Institute of Chemical Defense, Beijing, 100191, P.R. China E-mail address: [email protected]
https://doi.org/10.1016/j.jpowsour.2018.01.027 Received 5 October 2017; Received in revised form 2 January 2018; Accepted 9 January 2018 0378-7753/ © 2018 Elsevier B.V. All rights reserved.
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ingredients of LiNixMn2-xO4 cathode, Super P, graphite and polyvinylidene diﬂuoride (PVDF) binder with the mass ratio of 8.5:0.5:0.5:0.5 was mixed to form a slurry in the N-Methyl-2-pyrrolidone (NMP). The slurry was casted on the aluminium foil and then dried at 120 °C for 12 h before punch. The mass density of LiMn2O4 and LiNi0.5Mn1.5O4 were controlled around at 4 mg cm−2.
and developing solid-state batteries  are being widely investigated. All these researches greatly improve the safety factors; however, more technologies and knowledges are still quested towards more reliable battery system particularly satisfying for the sustainable development . Based on the model of current LIBs (i.e., graphite vs. lithium layered metal oxide), several aspects can be further explored. For example, replace of graphite anode, because its low voltage for the lithium-ions intercalation may lead the formation of lithium dendrites, which can impale the separator and cause the short circuit . Besides, the ﬂammable properties of carbon anode and lithiated carbon (i.e., LixC6) , together with the side reactions of electrode and electrolyte beyond a high cut-oﬀ voltage (e.g., > 4.0 V) [13,14], always lead to an unsatisfactory safety, low Coulomb Eﬃciency (CE) and severe capacity decay. Thus herein, we choose sustainable TiO2 as anodic material considering its non-ﬂammable characteristic and the moderate voltage platform (i.e., ∼1.7 V) for the storage of lithium. Distinct from the previous researches preparing the TiO2-based composites via conductive compositions modiﬁcation [15–17], metal/non-metal elementsdoping [18–20], and/or surface coating/nitridation/hydronation [21–23], a scalable, green and convenient strategy was developed to synthesize a novel structured TiO2 nanobundles (PTNBs), which demonstrates extremely high and even better performances in lithium (ion) battery. To design the safer and sustainable LIBs, the cobalt-free, cost-effective and spinel structured LiNixMn2-xO4 (x = 0, 0.5) cathode is chosen instead of lithium layered metal oxide considering its higher stability . It is well known that the oxygen evolution reaction of lithium layered metal oxide as cycling remains challenging in current LIBs . Stimulated by the high capacity of PTNBs (e.g., 280 mAh g−1 at 100 mA g−1) available in industrial production, two kinds full batteries of PTNBs/LiNixMn2-xO4 with high CE and stability have been introduced. The constructed battery is reliable and has the advantages of improved safety, stability and sustainability, where the features can satisfy diverse requirements in sustainable energy storage products.
2.3. Characterizations and measurements The crystal information was acquired by X-ray powder diﬀraction (XRD) using a X‘Pert-ProMPD (Holand) D/max-γA X-ray diﬀractometer with Cu Kα radiation (λ = 0.154178 nm). The morphology of PTNBs was characterized by the scanning electron microscopy (SEM) on a FEIquanta 200 F scanning electron microscope with acceleration voltage of 30 kV. The distribution and crystalline structure of PTNBs was analysed by the transmission electron micrograph (TEM) with using the FEITecnai F20 (200 kV) transmission electron microscope (FEI). Nitrogen adsorption-desorption isotherms were measured by the instrument of ASAP2050 (Micromeritics Instrument Corporation) surface area & porosity Analyzer at 77 K. The electrochemical tests were carried out using the 2032-type coin cell and they were assembled in the glove box ﬁlled with pure argon, in which the moisture and oxygen were strictly controlled below 0.1 ppm. The half-cell has the conﬁguration of Li metal (−) | Microporous polypropylene separator | electrode (+) ﬁlled with the electrolyte of 1.0 M LiPF6, 1 wt% vinylene carbonate (VC) additive in the mixture of ethylene carbonate (EC)/diethyl carbonate (DEC) (w/w, 1/1). In the full battery, the electrodes of LiMn2O4 or LiNi0.5Mn1.5O4 were applied as cathode versus the anode of pre-lithiated PTNBs. The principle of designing full battery was followed by the description in recent literature . Before assembling the full battery, the PTNBs electrode is prelithiated ﬁrst to compensate the irreversibility. The prelithiation process is similar as the that in recent literature , in which the PTNBs electrode contacts with the electrolyte-wetted lithium foil and reacts for a certain time. The amount of lithium in anode after the prelithiation can be controlled by the reaction time and calculated by the discharged capacity diﬀerences in the ﬁrst cycle comparing to that of the pristine one. Generally, the prelithiation procedure is needed to get a good battery performance; otherwise the large irreversibility of anode (i.e., PTNBs) would consume a large part of lithium ions from cathode, leading to a low coulombic eﬃciency and inferior cycle ability. Galvanostatic charge-discharge was conducted by the TOSCAT-3100 at diﬀerent current densities, and the cyclic voltammetry was collected by the instrument of Biologic VMP3 under the scan rate of 0.1 mV s−1.
2. Experimental 2.1. Synthesis of PTNBs Typically, 1.0 g industrial-grade TiO2 powders were dispersed into 70 mL 10.0 M NaOH solution and stirred for 4 h. The solution was transferred into Teﬂon lined stainless steel autoclave and thermally treated at 180 °C for 24 h in oven. After cooling down to the room temperature, the powders were collected by ﬁltration and then washed by HCl (pH = 1) and water to neutral. The powders were re-dispersed into 70 mL 1.0 M acetic acid solution and kept stirring for 30 min; subsequently the solution was thermally treated at 180 °C for 4 h in the Teﬂon lined stainless steel autoclave. Finally, calcination of the powders at 500 °C for 4 h under a steady air gives rise to the product of PTNBs.
3. Results and discussion 3.1. Features of PTNBs The PTNBs has a high crystallization belonging to the anatase TiO2 (JCPDS Card No. 89-4921) (Fig. 1a). The features of PTNBs including the morphology of uniform nanobundles, high length/dimeter ratio (e.g., average length of 1–5 μm with the diameter of 200 nm) and rich porosity were demonstrated in SEM and TEM images (Fig. 1b–c). The nanobundle consists of connected nanocrystals, where numerous pores and crystalline boundaries were constructed, giving rise to a rough surface. The building block of nanocrystals has the lattice fringe with a spacing of 0.35 nm as observed under HRTEM (Fig. 1d), which is consistence with and correspond to the (001) planes of crystalline TiO2. The porosity and external structure were measured by BET analysis (Fig. 1e–f), where the N2 adsorption-desorption isotherm can be categorized as type III isotherm considering the absence of the typical distinct hysteresis loop . The result is in accordance with the structural observations. The pore volume of PTNBs is moderate around 0.057 cm3 g−1 because of the ultrathin thickness (Fig. 1b). The speciﬁc structure of PTNBs could be ascribed to the formation mechanism,
2.2. Electrode preparation The active materials of PTNBs, conductive carbon of Super P, and binders of polyacrylic acid/carboxymethyl cellulose (PAA-CMC)  with the mass ratio of 7.5:1.5:0.5:0.5 were homogeneously mixed in water to form a slurry, which was then casted on the copper foil by doctor blade. After vacuum drying at 80 °C overnight, the foil was punched into circular electrode with a diameter of 14 mm (alternatively Ø16 for full battery). The mass density of active materials is about 2 mg cm−2 with the thickness around at 40–50 μm. Note that a rough comparative lithium storage capability of TiO2 is listed and discussed as one of the reference considering the mass density and thickness of TiO2 is diﬀerent or lack in diﬀerent literature. For the preparation of cathodic electrode, the cathodic powders of LiNixMn2-xO4 (x = 0, 0.5) were synthesized ﬁrst by the sol-gel method . And then, the 54
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Fig. 1. (a) XRD pattern, (b) SEM images, (c) TEM and (d) HRTEM images of PTNBs. Insert of (a) is the typical crystalline structure of anatase TiO2. (e) Nitrogen adsorption-desorption isotherm and (f) pore size distribution of the PTNBs.
1.75 V caused by the surface reactions; (ii) a plateau region around 1.75 V, corresponding to the Li+ intercalation into the crystalline channel of TiO2 (xLi+ + xe− + TiO2 → LixTiO2); (iii) a gradual decayed tail after the voltage plateau region, resulting from the deposition of lithium on electrode surface (Li+ + e− → Li) (Fig. 2a) . An extremely high capacity around 296 mAh g−1 can be achieved in initial hundreds cycles (Fig. 2b), which is much higher than most TiO2 reported before [16–23,32–41], as summarized in Fig. 2c. Furthermore, the capacity retention can maintain around 98.5% after 450 cycles and the CE is almost 100%, indicating the excellent cycle stability of PTNBs. Besides, the CV results also conﬁrm the characteristics and stability of PTNBs (Fig. S1). Note that the observed capacity variation with the “S” curve against cycle number should be ascribed to three combined reasons: i) irreversible reaction (i.e., irreversibility) in initial cycles which is similar as most oxide-based anode; ii) the unique properties of PTNBs (vs. normal TiO2 powders, Fig. S2); iii) the activation of PTNBs-based electrode by PAA/CMC binder (vs. PVDF binder, Fig. S3). Thus, the PTNBs-based electrode experiences a capacity decay in initial cycles, an increased capacity trend as activation and then a ﬁnal stabilization with a decreased capacity ﬁnally. The robust rate capability of PTNBs is further conﬁrmed. High capacities over 272, 243, 219, 187, 149 and 90 mAh g−1 were obtained at the current densities of 50, 100, 200, 400, 800, 1600 and 3200 mA g−1, respectively, where the capacity can recover to 265 mAh g−1 at
where the industrial-grade TiO2 can react with NaOH to form Na2Ti3O7 ﬁrst, and then it ions-exchange with HAc to form H2Ti3O7 intermediates and ﬁnally give rise to anatase TiO2. The ions-exchange reaction is beneﬁcial to construct the porosity and connected small nanocrystals, and the HAc may further facilitate the formation of nanobundles . Note that the new structured TiO2 nanobundles has an interesting phenomenon, where the BJH surface area of pores around 25.2 m2 g−1 is close to the BET surface area of 25.5 m2 g−1, indicating that an open and connection of pores . The unique structure of PTNBs with high surface area, rich porosity and grain boundaries, and moderate pore volume can demonstrate intrinsic unique properties for the wide applications in the ﬁelds of photo-catalysis, electrochemistry, sensor, energy storage and environmental science. 3.2. Lithium storage capability of PTNBs The lithium-ions storage ability of PTNBs was evaluated in LIBs versus metallic lithium. An extremely high stability was demonstrated in the galvanostatic charge-discharge curves, in which the voltage vs. capacity proﬁles associated Ti4+/Ti3+ redox couple (i.e., 1.75 V vs. 2.0 V) almost remains constant over 450 cycles, demonstrating the highly reversible reaction of lithium and TiO2 (Fig. 2a). The reaction in the discharge process can be divided into three main stages: (i) a fast decrease in potential starting from the open-circuit voltage (OCV) to 55
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diﬀusion constant and highly active TiO2 beneﬁting from the short diﬀusion path within nanocrystals, porosity and ultrathin thickness of PTNBs. 3.3. Sustainable full batteries PTNBs is competent as a sustainable and reliable anode because of the rich abundance of elements, non-ﬂammable properties, suitable voltage and particularly the extremely high capacity. Thus, sustainable lithium-ion full batteries were conﬁgured though matching the spinel structured LiNixMn1-xO4 (x = 0, 0.5), which is a cobalt-free, cost-effective, more reliable and higher voltage cathode comparing to the layered lithium metal oxide . Cycled charge-discharge curves of PTNBs/LiMn2O4 battery were demonstrated in Fig. 4. A high capacity of 224 mAh ganode−1 (i.e., 112 mAh gLiMn2O4−1) was delivered after a charged capacity of 260 mAh ganode−1 (i.e., 130 mAh gLiMn2O4−1) in the ﬁrst cycles, giving rise to an initial CE of 85.6% (Fig. 4a, black curve). Later, the following CE can achieve 100%, demonstrating the reversible reaction of lithium-ions within the battery. In detail, the cathodic oxidation of Mn3+/Mn4+ and the reduction of Ti4+/Ti3+ in anode take place via the reaction of LiMn2O4 + TiO2 → 2λ-MnO2 + 2Li0.5TiO2 in the charge process. And then, the discharged long plateau at 2.05 V is ascribed to the extraction of Li+ from the PTNBs (∼1.90 V) and the intercalation of Li+ into the λ-MnO2 lattice (∼3.95 and 4.08 V). This process was conﬁrmed more clearly by the dQ/dv-V curve (Inset of Fig. 4b), in which the pair of redox peaks located at around 2.05/2.18 V are consistence with the voltage diﬀerence of LiMn2O4 (i.e., 3.95 and 4.08 V) vs. 1.90 V of PTNBs (Fig. 4a). Note that the PTNBs/LiMn2O4 full cell can deliver a reversible capacity of 223 mA h ganode−1 at 100 mA g−1 with a capacity retention of 99% after 140 cycles (vs. the 10th cycle), where the energy density is as high as 535 Wh kganode−1 (i.e., 267 Wh kgcathode−1). To seek higher energy density, the full battery of PTNBs/ LiNi0.5Mn1.5O4 with the high work voltage of 2.75 V was further demonstrated in Fig. 5. The voltage is about 0.7 V higher that of PTNBs/ LiMn2O4 due to the high Ni4+/Ni3+ redox couple around 4.66 V in LiNi0.5Mn1.5O4 (Fig. 5a). The dQ/dV-V curve exhibits the pair of redox peak located at 2.75/2.95 V (insert in Fig. 5b), which is consistence with the high working voltage characteristic of LiNi0.5Mn1.5O4 . The CE can achieve 90.6% in the ﬁrst cycle even a dynamic balance existed in battery between anode and cathode, and particularly it can maintain around 99.1% fast as cycling. The battery can deliver a high capacity of 204 mAh ganode−1 (i.e., 102 mAh gcathode−1) at the cut-oﬀ voltage of 4.0 V, under which the cycle performance of LiNi0.5Mn1.5O4
Fig. 2. (a) Voltage vs. capacity proﬁles and (b) cycle performance, coulombic eﬃciency of PTNBs in lithium battery. (c) A rough comparative capacity of TiO2-based anode in previous literature at the rate of 0.5C.
100 mA g−1 (Fig. 3a). Even further cycling under a hash current density of 1000 mA g−1 (∼6C), the capacity can still be persevered as high as 146 mAh g−1 over 500 cycles with a capacity retention of 80% (Fig. 3b–c). Although the TiO2 have been widely studied as anode in LIB, the performances of such pristine PTNBs, including the capacity (Fig. 2c) and rate capabilities (Fig. 3d), are much better than most TiO2based electrode [32–41], particularly without any elemental doping and modiﬁcation. The reason should be ascribed to the fast Li+
Fig. 3. Voltage vs. capacity proﬁles of PTNBs (a) under the current densities of 100–3200 mA g−1 and (b) at the 1000 mA g−1. (c) Corresponding rate capability and cyclic performance of PTNBs in lithium battery. (d) A rough comparative rate capacity of TiO2-based anode in previous literature.
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Fig. 4. (a) Voltage vs. capacity proﬁles of PTNBs/LiMn2O4 full battery and (b) its cycle performance at 100 mA ganode−1. Inset of (b) is the typical dQ/dV-V curve of PTNBs/LiMn2O4 within the work voltage of 1.5–4.0 V.
Fig. 5. (a) Voltage vs. capacity proﬁles of PTNBs/LiNi0.5Mn1.5O4 full battery and (b) its cycle performance at 100 mA ganode−1. Inset of (b) is the typical dQ/dV-V curve of PTNBs/LiNi0.5Mn1.5O4 within the work voltage of 2.0–4.0 V.
Fig. 6. Voltage vs. capacity proﬁles and rate capabilities of (a, b) PTNBs/LiMn2O4 and (c, d) PTNBs/LiNi0.5Mn1.5O4 full batteries at the current densities of 100–1600 mA ganode−1.
210, 182, 145 and 105 mAh ganode−1 at the current densities of 100, 200, 400, 800 and 1600 mA g−1, which can recover to 230 mAh g−1 at 100 mA ganode−1 (Fig. 6a–b). While the capacities of PTNBs/LiNi0.5Mn1.5O4 battery are 203, 172, 130, 50 and 0.2 mAh ganode−1 under the same variation of current densities, and then it can recover to 202 mAh g−1 at 100 mA ganode−1 (Fig. 6c–d). One interesting phenomena is that the rate capability of PTNBs/LiNi0.5Mn1.5O4 battery is a bit inferior comparing to that of PTNBs/LiMn2O4, which should be ascribed to the crystalline channel diﬀerence in the spinel structured LiNixMn1-xO4 (x = 0, 0.5) . Nevertheless, the capacities of both full batteries can recover once the current density is reduced, demonstrating the durability of battery system even it is performed under a high current impulse. Note that the working potential of 2.05 and 2.75 V in the presented conﬁguration are comparable or even much higher than current commercial battery systems of Pb-Acid (2.0 V) , Ni-Cd (1.5 V) , Ni-MH (0.9 V) , as well as most aqueous battery system (< 1.5 V) . Comparing to the aforementioned systems involving harmful metallic-ions, the concept of using sustainable, nonﬂammable and carbon-free PTNBs versus low-cost, cobalt-free spinel structured cathode towards green and advanced battery can satisfy the safety and sustainability issues in rechargeable batteries.
can be persevered well while maximally avoiding the serious structural deterioration and reducing the side reactions (e.g., electrolyte decomposition, Mn2+ dissolution and migration, reconstruction of SEI ﬁlm). Generally, the structural deterioration and the side reactions of the cathode can be suppressed by using PTNBs comparing to that using carbon anode, because the carbon is not stable as that expected when the battery was charged to a high voltage over 4.0 V . The parasitic reaction products can be created at carbon anode and then induce the “electrode-electrode interactions” , under which the deterioration and the side reaction of LiNi0.5Mn1.5O4 would become severe. Note that, the parasitic reaction products created on LiNi0.5Mn1.5O4 can also aggravate the side reactions on carbon anode in turn. By contrast, the PTNBs is more stable than carbon and then the parasitic reaction is reduced, therefore the LiNi0.5Mn1.5O4 can cycle better versus PTNBs. An average capacity of 195 mAh ganode−1 with the capacity retention of 90% (vs. the 10th cycle) was obtained over 140 cycles (Fig. 5a), where the energy density can reach to 540 Wh kganode−1 (e.g., 270 Wh kgcathode−1). Note that the attained capacity is close to 200 mAh g−1 of graphite (vs. LiNi0.4Mn1.6O4) , but its safety factor was signiﬁcantly improved. In the rate test, the capacities of PTNBs/LiMn2O4 battery are 216, 57
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 M.M. Ottakam Thotiyl, S.A. Freunberger, Z. Peng, P.G. Bruce, The carbon electrode in nonaqueous Li-O2 cells, J. Am. Chem. Soc. 135 (2013) 494–500.  H. Ming, J. Ming, S.-M. Oh, E.-J. Lee, H. Huang, Q. Zhou, J. Zheng, Y.K. Sun, High dispersion of TiO2 nanocrystals within porous carbon improves lithium storage capacity and can be applied batteries to LiNi0.5Mn1.5O4, J. Mater. Chem. A 2 (2014) 18938–18945.  Y. Chen, X.Q. Ma, X.L. Cui, Z.Y. Jiang, In situ synthesis of carbon incorporated TiO2 with long-term performance as anode for lithium-ion batteries, J. Power Sources 302 (2016) 233–239.  Y. Cai, H.E. Wang, X. Zhao, F. Huang, C. Wang, Z. Deng, Y. Li, G.Z. Cao, B.L. Su, Walnut-like porous core/shell TiO2 with hybridized phases enabling fast and stable lithium storage, ACS Appl. Mater. Interfaces 9 (2017) 10652–10663.  M. Fehse, S. Cavaliere, P.E. Lippens, I. Savych, A. Iadecola, L. Monconduit, D.J. Jones, J. Roziere, F. Fischer, C. Tessier, L. Stievanot, Nb-doped TiO2 nanoﬁbers for lithium ion batteries, J. Phys. Chem. C 117 (2013) 13827–13835.  M. Lubke, I. Johnson, N.M. Makwana, D. Brett, P. Shearing, Z.L. Liu, J.A. Darr, High power TiO2 and high capacity Sn-doped TiO2 nanomaterial anodes for lithium-ion batteries, J. Power Sources 294 (2015) 94–102.  H. Usui, Y. Domi, S. Yoshioka, K. Kojima, H. Sakaguchi, Electrochemical lithiation and sodiation of Nb-Doped rutile TiO2, ACS Sustain. Chem. Eng. 4 (2016) 6695–6702.  J.Y. Shin, J.H. Joo, D. Samuelis, J. Maier, Oxygen-deﬁcient TiO2-delta nanoparticles via hydrogen reduction for high rate capability lithium batteries, Chem. Mater. 24 (2012) 543–551.  J.X. Qiu, S. Li, E. Gray, H.W. Liu, Q.F. Gu, C.H. Sun, C. Lai, H.J. Zhao, S.Q. Zhang, Hydrogenation synthesis of blue TiO2 for high-performance lithium-ion batteries, J. Phys. Chem. C 118 (2014) 8824–8830.  J. Zheng, L. Liu, G.B. Ji, Q.F. Yang, L.R. Zheng, J. Zhang, Hydrogenated anatase TiO2 as lithium-ion battery anode: size-reactivity correlation, ACS Appl. Mater. Interfaces 8 (2016) 20074–20081.  X.H. Ma, B. Kang, G. Ceder, High rate micron-sized ordered LiNi0.5Mn1.5O4, J. Electrochem. Soc. 157 (2010) A925–A931.  A. Konarov, S.T. Myung, Y.K. Sun, Cathode materials for future electric vehicles and energy storage systems, ACS Energy Lett. 2 (2017) 703–708.  J. Ming, H. Ming, W.J. Kwak, C. Shin, J.W. Zheng, Y.K. Sun, The binder eﬀect on an oxide-based anode in lithium and sodium-ion battery applications: the fastest way to ultrahigh performance, Chem. Commun. 50 (2014) 13307–13310.  H. Ming, Y.R. Yan, J. Ming, J. Adkins, X.W. Li, Q. Zhou, J.W. Zheng, Gradient V2O5 surface-coated LiMn2O4 cathode towards enhanced performance in Li-ion battery applications, Electrochim. Acta 120 (2014) 390–397.  J. Ming, W.J. Kwak, S.J. Youn, H. Ming, J. Hassoun, Y.K. Sun, Lithiation of an iron oxide-based anode for stable, high-capacity lithium-ion batteries of porous carbonFe3O4/Li[Ni0.59Co0.16Mn0.25]O2, Energy Technol. 2 (2014) 778–785.  K.S.W. Sing, D.H. Everett, R.A.W. Haul, L. Moscou, R.A. Pierotti, J. Rouquerol, T. Siemieniewska, Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity, Pure Appl. Chem. 57 (1985) 603–619.  J. Zhou, B. Song, G.L. Zhao, G.R. Han, Eﬀects of acid on the microstructures and properties of three-dimensional TiO2 hierarchical structures by solvothermal method, Nanoscale Res. Lett. 7 (2012) 217.  J. Ming, Y. Wu, S. Nagarajan, D.J. Lee, Y.K. Sun, F. Zhao, Fine control of titania deposition to prepare [email protected]
composites and TiO2 hollow particles for photocatalysis and lithium-ion battery applications, J. Mater. Chem. 22 (2012) 22135.  Z.Y. Wang, X.W. Lou, TiO2 Nanocages: fast synthesis, interior functionalization and improved lithium storage properties, Adv. Mater. 24 (2012) 4124–4129.  H. Ren, J.J. Sun, R.B. Yu, M. Yang, L. Gu, P.R. Liu, H.J. Zhao, D. Kisailus, D. Wang, Controllable synthesis of mesostructures from TiO2 hollow to porous nanospheres with superior rate performance for lithium ion batteries, Chem. Sci. 7 (2016) 793–798.  Y. Li, S. Wang, Y.B. He, L.K. Tang, Y.V. Kaneti, W. Lv, Z.Q. Lin, B.H. Li, Q.H. Yang, F.Y. Kang, Li-ion and Na-ion transportation and storage properties in various sized TiO2 spheres with hierarchical pores and high tap density, J. Mater. Chem. A 5 (2017) 4359–4367.  Y. Cai, H.E. Wang, S.Z. Huang, M.F. Yuen, H.H. Cai, C. Wang, Y. Yu, Y. Li, W.J. Zhang, B.L. Su, Porous TiO2 urchins for high performance Li-ion battery electrode: facile synthesis, characterization and structural evolution, Electrochim. Acta 210 (2016) 206–214.  X.G. Han, X. Han, L.Q. Sun, P. Wang, M.S. Jin, X.J. Wang, Facile preparation of hybrid anatase/rutile TiO2 nanorods with exposed (010) facets for lithium ion batteries, Mater. Chem. Phys. 171 (2016) 11–15.  W.J. Yu, Y.M. Liu, N. Cheng, B. Cai, K.K. Kondamareddy, S. Kong, S. Xu, W. Liu, X.Z. Zhao, Ultra-thin anatase TiO2 nanosheets with admirable structural stability for advanced reversible lithium storage and cycling performance, Electrochim. Acta 220 (2016) 398–404.  H.Q. Xie, L.F. Hu, F.L. Wu, M. Chen, L.M. Wu, Self-templated synthesis of ultrathin nanosheets constructed TiO2 hollow spheres with high electrochemical properties, Adv. Sci. 3 (2016) 1600162.  M.G. Fischer, X. Hua, B.D. Wilts, I. Gunkel, T.M. Bennett, U. Steiner, Mesoporous titania microspheres with highly tunable pores as an anode material for lithium ion batteries, ACS Appl. Mater. Interfaces 9 (2017) 22388–22397.  H. Ming, P. Kumar, W. Yang, Y. Fu, J. Ming, W.J. Kwak, L.J. Li, Y.K. Sun, J. Zheng, Green strategy to single crystalline anatase TiO2 nanosheets with dominant (001) facets and its lithiation study toward sustainable cobalt-free lithium ion full battery, ACS Sustain. Chem. Eng. 3 (2015) 3086–3095.  Y. Li, S.A. Wang, D.N. Lei, Y.B. He, B.H. Li, F.Y. Kang, Acetic acid-induced preparation of anatase TiO2 mesocrystals at low temperature for enhanced Li-ion
A green and convenient hydrothermal strategy starting from the industrial TiO2 powders was developed to synthesis a porous structured anatase TiO2 nanobundles (PTNBs), and it successfully avoids the using of high-cost and harmful organic titanium compounds, which is feasible for a large-scalable production. The PTNBs can be used as a sustainable anode in lithium (ion) battery, and it exhibits an extremely high lithium storage ability of 296 mAh g−1 at 100 mA g−1, stable cycle performance over 500 cycles and robust rate capability better than most TiO2based materials. Besides, sustainable and safer full LIBs of PTNBs/ LiNixMn1-xO4 (x = 0, 0.5) were conﬁgured. The designed batteries have the characteristic of sustainability, and it can deliver high energy capacities satisfying diverse requirements in energy storage systems. The convenient strategy, unique structure and properties of PTNBs have high potential for wider applications, while the concept using sustainable electrodes and seeking reliable system is attractive in energy storages for developing advanced and safe batteries towards commercialization. Acknowledgements This work was supported by the construct program of the key discipline in Hunan province (Applied Chemistry), Hunan Provincial Natural Science Foundation of China (2016JJ3094), Scientiﬁc Research Fund of Hunan Provincial Education Department (15C0933, 16C1082) and Startup Foundation for Doctors of Hunan University of Arts and Science. J. Ming is grateful for the support from the King Abdullah University of Science & Technology (Kingdom of Saudi Arabia). H. Ming is grateful for the support from the Natural Science Foundation of China (NSFC: 21703285). Appendix A. Supplementary data Supplementary data related to this article can be found at http://dx. doi.org/10.1016/j.jpowsour.2018.01.027. References  J.M. Tarascon, M. Armand, Issues and challenges facing rechargeable lithium batteries, Nature 414 (2001) 359–367.  N.S. Choi, Z.H. Chen, S.A. Freunberger, X.L. Ji, Y.K. Sun, K. Amine, G. Yushin, L.F. Nazar, J. Cho, P.G. Bruce, Challenges facing lithium batteries and electrical double-layer capacitors, Angew. Chem. Int. Ed. 51 (2012) 9994–10024.  S.T. Myung, F. Maglia, K.J. Park, C.S. Yoon, P. Lamp, S.-J. Kim, Y.K. Sun, Nickelrich layered cathode materials for automotive lithium-ion batteries: achievements and perspectives, ACS Energy Lett. 2 (2017) 196–223.  Q.S. Wang, P. Ping, X.J. Zhao, G.Q. Chu, J.H. Sun, C.H. Chen, Thermal runaway caused ﬁre and explosion of lithium ion battery, J. Power Sources 208 (2012) 210–224.  A.M. Haregewoin, A.S. Wotango, B.J. Hwang, Electrolyte additives for lithium ion battery electrodes: progress and perspectives, Energy Environ. Sci. 9 (2016) 1955–1988.  J. Ming, M. Li, P. Kumar, A.Y. Lu, W. Wahyudi, L.J. Li, Redox species-based electrolytes for advanced rechargeable lithium ion batteries, ACS Energy Lett. 1 (2016) 529–534.  M.A. Hannan, M.M. Hoque, A. Mohamed, A. Ayob, Review of energy storage systems for electric vehicle applications: issues and challenges, Renew. Sustain. Energy Rev. 69 (2017) 771–789.  J. Ming, M. Li, P. Kumar, L.J. Li, Multilayer approach for advanced hybrid lithium battery, ACS Nano 10 (2016) 6037–6044.  S. Xin, Y. You, S. Wang, H.-C. Gao, Y.-X. Yin, Y.G. Guo, Solid-state lithium metal batteries promoted by nanotechnology: progress and prospects, ACS Energy Lett. 2 (2017) 1385–1394.  J. Groenewald, T. Grandjean, J. Marco, Accelerated energy capacity measurement of lithium-ion cells to support future circular economy strategies for electric vehicles, Renew. Sustain. Energy Rev. 69 (2017) 98–111.  R. Zhang, N.W. Li, X.B. Cheng, Y.X. Yin, Q. Zhang, Y.G. Guo, Advanced micro/ nanostructures for lithium metal anodes, Adv. Sci. 4 (2017) 1600445.  P. Roy, S.K. Srivastava, Nanostructured anode materials for lithium ion batteries, J. Mater. Chem. A 3 (2015) 2454–2484.  J. Ming, Y. Wu, G. Liang, J.-B. Park, F. Zhao, Y.K. Sun, Sodium salt eﬀect on hydrothermal carbonization of biomass: a catalyst for carbon-based nanostructured materials for lithium-ion battery applications, Green Chem. 15 (2013) 2722.
Journal of Power Sources 379 (2018) 53–59
X. Ding et al.
 Y.Y. Xia, Y.H. Zhou, M. Yoshio, Capacity fading on cycling of 4 V Li/LiMn2O4 cells, J. Electrochem. Soc. 144 (1997) 2593–2600.  J.E. Jin, D. Jin, J. Shim, W. Shim, Enhancing reversible sulfation of PbO2 nanoparticles for extended lifetime in lead-acid batteries, J. Electrochem. Soc. 164 (2017) A1628–A1634.  M.J. Kim, J.Y. Seo, Y.S. Choi, G.H. Kim, Bioleaching of spent Zn-Mn or Ni-Cd batteries by Aspergillus species, Waste Manag. 51 (2016) 168–173.  S.G. Real, M.G. Ortiz, E.B. Castro, Electrochemical characterization of nickel hydroxide nanomaterials as electrodes for Ni-MH batteries, J. Solid State Electrochem. 21 (2017) 233–241.  J.O.G. Posada, A.J.R. Rennie, S.P. Villar, V.L. Martins, J. Marinaccio, A. Barnes, C.F. Glover, D.A. Worsley, P.J. Hall, Aqueous batteries as grid scale energy storage solutions, Renew. Sustain. Energy Rev. 68 (2017) 1174–1182.
storage, J. Mater. Chem. 5 (2017) 12236–12242.  K. Zhang, X.P. Han, Z. Hu, X.L. Zhang, Z.L. Tao, J. Chen, Nanostructured Mn-based oxides for electrochemical energy storage and conversion, Chem. Soc. Rev. 44 (2015) 699–728.  C. Zhan, J. Lu, A. Jeremy Kropf, T. Wu, A.N. Jansen, Y.K. Sun, X. Qiu, K. Amine, Mn (II) deposition on anodes and its eﬀects on capacity fade in spinel lithium manganate-carbon systems, Nat. Commun. 4 (2013) 2437.  S.R. Li, C.H. Chen, X. Xia, J.R. Dahn, The impact of electrolyte oxidation products in LiNi0.5Mn1.5O4/Li4Ti5O12 cells, J. Electrochem. Soc. 160 (2013) A1524–A1528.  C. Arbizzani, F. De Giorgio, L. Porcarelli, M. Mastragostino, V. Khomenko, V. Barsukov, D. Bresser, S. Passerini, Use of non-conventional electrolyte salt and additives in high-voltage graphite/LiNi0.4Mn1.6O4 batteries, J. Power Sources 238 (2013) 17–20.