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Article
Spinel Li Co Ti O (0#x#0.5) for Lithium-Ion Batteries: Crystal
4–2x 3x 5–x 12

Structures, Material Properties and Battery Performances


Chunfu Lin, ManOn Lai, Li Lu, and Henghui Zhou
J. Phys. Chem. C, Just Accepted Manuscript • Publication Date (Web): 13 Jun 2014
Downloaded from http://pubs.acs.org on June 16, 2014

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The Journal of Physical Chemistry C is published by the American Chemical Society.


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However, no copyright claim is made to original U.S. Government works, or works
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Spinel Li4–2xCo3xTi5–xO12 (0≤x≤0.5) for Lithium-Ion
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12 Batteries: Crystal Structures, Material Properties and
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16 Battery Performances
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21 Chunfu Lin†, Man On Lai†, Li Lu†,*, Henghui Zhou‡,*
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Department of Mechanical Engineering, National University of Singapore, 9 Engineering Drive
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27 1, Singapore 117576, Singapore.
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College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, PR
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33 China.
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37 ABSTRACT
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41 Although disordered spinel Li4Ti5O12 with space group is an attracting anode material for
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43 lithium ion batteries, it suffers from its poor rate performance. Moreover, there are very limited
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46 studies of ordered spinel anode materials with P4332 space group. Here, spinel Li4–2xCo3xTi5–xO12
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48 materials with (0≤x≤0.2) or P4332 (0.25≤x≤0.5) space group have been synthesized. The
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lattice parameter and occupancy of Co2+ ions in tetrahedral 8a/8c sites quasi-linearly increase
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53 with the amount of Co2+ substitutes. Due to the increased lattice parameter and free 3d electrons
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55 in Co2+ ions, Co2+-substituted samples exhibit improved Li+ ion diffusion coefficients and
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58 electronic conductivities. The optimized sample, Li3.5Co0.75Ti4.75O12 with P4332 space group,
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shows the highest Li+ ion diffusion coefficient of 9.07×10–11 cm2 s–1 and electronic conductivity
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6 of 1.49×10–7 S cm–1. Consequently, Li3.5Co0.75Ti4.75O12 has the best rate performance with a large
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8 capacity of 158 mAh g–1 at a current density of 1000 mA g–1, while Li4Ti5O12 only possesses 70
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mAh g–1. Furthermore, the considerable occupancy of Co2+ ions in the tetrahedral sites tailors the
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13 shape of discharge profiles. Li3.5Co0.75Ti4.75O12 exhibits a much smaller plateau hysteresis than
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15 the previously developed spinel anode materials with the same space group.
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19 Keywords: anode; spinel lithium titanate · Co2+ substitution · electronic conductivity · Li+ ion
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diffusion coefficient · rate performance
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25 1. INTRODUCTION
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27 Due to the advantages of high energy output, long storage life and low maintenance, lithium-
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ion batteries (LIBs) are not only popular for portable electronic devices, but also promising for
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32 large-scale applications, such as electric vehicles (EVs) and hybrid electrical vehicles (HEVs).1
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34 However, the commonly used carbonaceous anodes cannot meet the requirement of high power
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37 density in EVs/HEVs due to the safety concerns arising from formation and growth of lithium
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39 dendrites on the surfaces of the anodes at high operating currents.2 To solve this safety problem,
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41 Li4Ti5O12 is being intensively investigated owing to its good cyclic stability and relatively high
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44 working potential avoiding the growth of lithium dendrites.3 Its structure can be described in a
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46 face-centered cubic spinel notation [Li3]8a[LiTi5]16d[O12]32e in space group, as sketched in
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Figure 1a.4 32e sites are fully occupied by O2– ions, tetrahedral 8a sites are exclusively taken up
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51 by Li+ ions, octahedral 16d sites are randomly filled by Li+ and Ti4+ ions with a molar ratio of
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53 1:5, while the remaining octahedral (16c) sites and tetrahedral (8b and 48f) sites are vacant. The
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56 three-dimensional 8a–16c–8a network has been identified as Li+ ion transportation pathways.
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During the lithiation process of Li4Ti5O12 at ~1.55 V (all the potentials in this study refer to
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6 Li/Li+), the three Li+ ions in the 8a sites together with three external Li+ ions cooperatively shift
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8 to the 16c sites to generate [Li6]16c[LiTi5]16d[O12]32e, and three of the five Ti4+ ions are reduced to
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Ti3+ ions. When the working potential is further decreased until ~0 V, additional two external Li+
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13 ions move to the 8a sites and the other two Ti4+ ions are reduced, leading to a final form of
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15 [Li2]8a[Li6]16c[LiTi5]16d[O12]32e and a theoretical capacity of 293 mAh g–1.5
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36 Figure 1. Schematic representations of spinel structures with (a) and (b) P4332 space
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39 groups.
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42 The drawbacks of Li4Ti5O12 are its intrinsically low electronic conductivity (˂1×10–13 S cm–1)6
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44 and sluggish Li+ ion diffusion coefficient (~10–12 cm2 s–1),7 which greatly limit its rate
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47 performance. To improve its rate performance, substitution by alien ions (in Li8a, Li16d, Ti16d or
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49 O32e sites),6,8–17 compositing a conductive phase18–25 and nanosizing particles26–35 have been
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51 used. The first method has drawn much attention since it can effectively modify the crystal
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54 structure and thus engineer the electronic conductivity and/or Li+ ion diffusion coefficient of
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56 Li4Ti5O12 particles. The effective ions include Mg2+,6 Ni2+,8 Al3+,9 Cu2+,10 Nb5+,11 Zr4+,12 V5+,13
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Yi3+,14 Zn2+,15 Fe2+,16 Cr3+,16 and Br– ions.17 However, Co2+-substituted Li4Ti5O12 has never been
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6 employed as the anode materials of LIBs.
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8 P4332 space group, another member in the spinel family, on the other hand exists with 3:1
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cation ordering on the octahedral sites, as illustrated in Figure 1b.36 This ordering lowers the
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13 crystal symmetry accompanied with the following splits of Wyckoff positions: 8a→8c;
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15 16d→12d+4b; and 32e→8c+24e. Such ordered structure has rarely been studied. Up to date,
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18 only LiM0.5Ti1.5O4 (M=Mg, Zn, Co, Co0.5Zn0.5 and Mg0.5Zn0.5) have been used as the anode
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20 materials of LIBs.37–40 These materials exhibit a charge plateau of ~1.6 V and a fairly low
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22 discharge plateau of ~0.5 V. This large plateau hysteresis of ~1.1 V, however, inevitably limits
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25 their electrochemical performances. Thus, it is highly necessary to develop new ordered spinel
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27 anode materials with desirable performances in terms of small plateau hysteresis and high rate
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performance.
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32 Based on the considerations mentioned above, we select Li4–2xCo3xTi5–xO12 (0≤x≤0.5) as the
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34 research object. The Co2+ substituting is expected to improve the intrinsic (electronic and ionic)
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37 conductivity and thus the rate performance of Li4Ti5O12.41,42 On the other hand, since there is a
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39 transition from space group to P4332 space group when x is increased from 0 to 0.5,37,39,40
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41 some new ordered spinel anode materials with P4332 space group can be produced. In this work,
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44 Li4–2xCo3xTi5–xO12 (0≤x≤0.5) synthesized through a solid-state reaction method is systematically
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46 studied. The influences of crystal structures on material properties and electrochemical
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performances are intensively investigated.
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51 2. EXPERIMENTAL
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53 2.1. Material preparations. The Co2+ substitution is designed in such a way that one Ti4+ ion
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together with two Li+ ions is replaced by three Co2+ ions, following Equation 1:
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4 3Co = Co'Ti' + 2Co•Li (1)
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All the Li4–2xCo3xTi5–xO12 (x=0, 0.1, 0.2, 0.25, 0.35 and 0.5) samples were fabricated by a
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9 solid-state reaction method from Li2CO3 (Merck, 99.99%), CoO (Sigma–Aldrich, 99.99%) and
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11 TiO2 (Sigma–Aldrich, 99.9%). The chemicals were mixed at a predetermined molar ratio of
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14 Li:Co:Ti = 1.03(4–2x):3x:(5–x), ball-milled for 2 h by a ball-milling machine (SPEX 8000M),
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16 and calcined at 800 for 4 h in air. In all cases, the 3 mol% excessive Li2CO3 was used to
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18 compensate for the volatilization of Li at the high calcination temperature.
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21 2.2. Materials characterizations. Detailed crystal structures of the as-calcined powders were
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23 identified using X-ray diffractions combined with Rietveld refinements. Rietveld refinements
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were carried out using the GSAS program with the EXPGUI interface.43,44 X-ray diffraction
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28 patterns for the refinements were recorded in an angle interval of 10°–125° (2θ) with a step
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30 width of 0.03° and a counting time of 8 s per step using an X-ray diffractometer (Shimazu XRD-
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7000) with a Cu Kα radiation (λ = 0.1506 nm). During the refinements, the following
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35 instrumental and structural parameters were varied: background parameters, zero-shift, unit cell
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37 parameters, profile parameters, atomic fractional coordinates, atomic isotropic displacement
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40 parameters and atomic occupancies. Ex-situ X-ray diffraction patterns were collected between
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42 10° to 70° (2θ) at a scan speed of 2° min–1. Particle morphologies and sizes were observed using
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44 a field emission scanning electron microscopy (FESEM, Hitachi-4300). Nitrogen adsorption
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47 isotherms at 77 K were acquired in a surface area analyser (Quantachrome NOVA 2200e).
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49 Specific surface areas were calculated based on the Brunauer–Emmett–Teller (BET) model.
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Specimens used for electronic conductivity measurements were fabricated by pressing the same
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54 precursor powders in Section 2.1 into pellets with a diameter of 10.25 mm at a pressure of 500
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56 kg cm–2. The pressed pellets were then calcined at 650 for 5 h followed by sintering at 900
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for 48 h for densification. The thickness of these pellets was ~0.94 mm. Gold was sputtered to
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6 both sides of the pellets after the polishing of the surfaces using sand papers. Electronic
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8 conductivity tests were performed on the resultant pellets using a Solartron Analytical 1470E
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CellTest System under a constant voltage of 50 mV for 3 h until the currents became stabilized.
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13 2.3. Electrochemical tests. Electrochemical performances were examined in two-electrode
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15 coin-type half-cells using a multi-channel battery testing system (LANHE CT2001A). For the
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18 preparation of working electrodes, a mixture of Li4–2xCo3xTi5–xO12 powders, super P conductive
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20 carbon (TIMCAL Ltd.) and polyvinylidene fluoride (PVDF, Sigma–Aldrich) at a weight ratio of
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22 80:10:10 was ground in a mortar with an adequate amount of N-methylpyrrolidone (NMP,
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25 Sigma–Aldrich) to form uniform slurries. The slurries were cast on copper foils, which were
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27 subsequently dried in a vacuum oven at 120 overnight and rolled by a rolling machine. For the
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assembly of coin cells, the as-rolled working electrodes were incorporated into CR2016 coin
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32 cells (MTI Corporation) in a recirculating argon glove box having both O2 and H2O contents
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34 below 0.1 ppm. In these cells, Li foils were used as counter and reference electrodes, Celgard
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37 2400 as separators, and a mixed solvent of ethylene carbonate, dimethyl carbonate and
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39 diethylene carbonate (1:1:1 by weight) containing of 1 M LiPF6 (DAN VEC) as electrolyte.
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41 Cyclic voltammetry (CV) measurements were performed using the Solartron Analytical 1470E
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44 CellTest System. In order to prepare the electrodes for the ex-situ X-ray diffractions, the cells
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46 charged or discharged to different states were disassembled, and then the working electrodes
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were washed by dimethyl carbonate and dried at 80 .
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51 3. RESULTS AND DISCUSSION
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53 3.1. Crystal structure analysis. Figure 2 plots the observed, calculated and error X-ray
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56 diffraction patterns for Li4–2xCo3xTi5–xO12 (x=0, 0.1, 0.2, 0.25, 0.35 and 0.5), and their Rietveld
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refinement results are tabulated in Table 1 and Table 2. When 0≤x≤0.2, all the peaks in the
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6 patterns can be indexed as a face-centered cubic spinel structure with space group
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8 (JCPDS card No. 49-0207). When x is increased to 0.25, additional peaks (such as (110), (210)
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11 and (211) peaks) corresponding to the ordering on the octahedral sites start to appear.36 The
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xO12 possesses P4332 space group when 0.25≤x≤0.5, and that the border concentration for the
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18 order–disorder transition ( ↔P4332) is 0.2˂x˂0.25. The sharp diffraction peaks of all the
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detected, demonstrating that Co2+ ions have successfully substituted Ti4+ and Li+ ions in the
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25 crystal structure of Li4Ti5O12 according to Equation 1.
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43 Figure 2. X-ray diffraction patterns and Rietveld refinement results of Li4–2xCo3xTi5–xO12
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46 (0≤x≤0.5). For the sake of clarity, no all peaks in the patterns were indexed due to the large
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51 Table 1. Results of crystal structure analyses by Rietveld refinements in Li4–2xCo3xTi5–xO12 (x=0,
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0.1 and 0.2).
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4 spinel Li4–2xCo3xTi5–xO12 (0≤x≤0.2), space group: (cubic)
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6 composition x 0 0.1 0.2
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8 nominal [Li3.000]8a[Li1.000Ti5 [Li2.711Co0.289]8a[Li1. [Li2.408Co0.592]8a[Li1.1
16d
9 composition 16d
.000] [O12]
32e
089Co0.011Ti4.9] [O 92Co0.008Ti4.8]16d[O12]
10 32e 32e
12]
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lattice parameter a (Å) 8.36127(6) 8.36394(6) 8.36717(6)
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Li1 1.000(3) 0.904(2) 0.803(2)
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17 8a Co1 – 0.096(2) 0.197(2)
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19 Ti1 0.000(3) – –
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21 Li2 fa 0.167(1) 0.181(1) 0.199(1)
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23 16d Co2 – 0.002(1) 0.001(1)
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25 Ti2 0.833(1) 0.817(–) 0.800(–)
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27 32e O 1(–) 1(–) 1(–)
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29 Rwpb 0.1199 0.0999 0.0886
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31 Rp c 0.0891 0.0747 0.0670
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33 3.987 3.040 2.693
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35 Site occupancy. bWeighted profile residual. cProfile residual. dGoodness of fit.
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37 Table 2. Results of crystal structure analyses by Rietveld refinements in Li4–2xCo3xTi5–xO12
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(x=0.25, 0.35 and 0.5).
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43 spinel Li4–2xCo3xTi5–xO12 (0.25≤x≤0.5), space group: P4332 (cubic)
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45 composition x 0.25 0.35 0.5
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47 nominal [Li2.260Co0.740]8c[Li0.8 [Li1.959Co1.041]8c[Li1.2 [Li1.538Co1.462]8c[L
48 4b 4b 4b
composition 90Co0.010Ti0.600] [Li0. 54Co0.009Ti0.237] [Li0. i1.462Co0.038] [Ti4.
49 12d 8c 12d 8c
50 350Ti4.150] [O3] [O9 087Ti4.413] [O3] [O9 5] [O3] [O9]24e
12d 8c

51 ]24e ]24e
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53 lattice parameter a (Å) 8.36900(7) 8.37256(7) 8.37646(6)
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55 8c Li1 f 0.753(2) 0.653(2) 0.513(2)
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4 Co1 0.247(2) 0.347(2) 0.487(2)
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6 Li2 0.593(4) 0.836(3) 0.975(3)
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8 4b Co2 0.007(4) 0.006(3) 0.025(3)
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10 Ti2 0.400(7) 0.158(6) –
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12 Li3 0.078(2) 0.019(2) –
13 12d
14 Ti3 0.922(2) 0.981(2) 1(–)
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16 8c O1 1(–) 1(–) 1(–)
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18 24e O2 1(–) 1(–) 1(–)
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20 Rwp 0.0800 0.0754 0.0732
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22 Rp 0.0605 0.0577 0.0557
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24 2.325 2.210 2.339
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To get the details of the crystal structure, Rietveld refinements were carried out. In the
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31 refinements, the site occupancies were assumed to fulfill the stoichiometric compositions of Li4–
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33 2xCo3xTi5–xO12 (x=0, 0.1, 0.2, 0.25, 0.35 and 0.5). All isotropic temperature factors were fixed to
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36 be the same. The distributions of ions were fixed as follows. For space group, O2– ions
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38 were placed at the 32e sites, Li+ and Co2+ ions resided at the 8a sites, and Li+, Ti4+ and Co2+ ions
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occupied the 16d sites; for P4332 space group, O2– ions were distributed at the 8c and 24e sites,
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43 Li+ and Co2+ ions filled the 8c sites, Li+, Ti4+ and Co2+ ions shared the 4b sites, and Li+ and Ti4+
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45 ions stayed at the 12d sites.45 The total occupancies for all the sites were fixed to unity. The ion
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distributions listed in Table 1 and Table 2 are those give the best fits.
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50 Figure 3 shows the variations of the lattice parameter a and occupancy of Co2+ ions in the
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52 tetrahedral 8a/8c sites f with the amount of Co2+ substitutes x. The pristine Li4Ti5O12 has a lattice
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55 parameter of 8.3613 Å, in good agreement with the values from previous reports.13 The lattice
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parameter is larger than those of Ni2+, Cu2+, Cr3+ and Fe2+-substituted Li4Ti5O12.8,10,16 Such
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6 increase can be interpreted by the ion-size effect. For instance, at x=0.2, Li3.6Co0.6Ti4.8O12 has a
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8 structure order of [Li2.408Co0.592]8a[Li1.192Co0.008Ti4.8]16d[O12]32e. Compared with the pristine
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Li4Ti5O12, in the tetrahedral 8a sites of Li3.6Co0.6Ti4.8O12, roughly 20% of Li+ ions (0.59 Å) are
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13 replaced by Co2+ ions (0.58 Å), which have a negative influence on the enhancement of the
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15 lattice parameter; conversely in the octahedral 16d sites, Li+ ions (0.76 Å) and Co2+ ions (0.745
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18 Å) substitute 4% of Ti4+ ions (0.605 Å),42 which can greatly benefit the increase in the lattice
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20 parameter. Since 0.592×(0.58–0.59)+(1.192–1.000)×(0.76–0.605)+0.008×(0.745–
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22 0.605)=0.02496>0, the latter effect plays the dominant role in increasing the lattice parameter,
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25 which results in an overall increased lattice parameter. In addition, the refinements show
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27 considerable inverse characteristics for Co2+-substituted Li4Ti5O12, as almost all the substituting
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Co2+ ions stay in the tetrahedral 8a/8c sites. With increasing the Co2+ substitutes, the occupancy
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32 of Co2+ ions in the 8a/8c sites is quasi-linearly increased, thereby the blockage of three-
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34 dimensional Li+ ion transportation pathways becomes gradually severer.
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52 Figure 3. Variations in lattice parameter a and occupancy of Co2+ ions in tetrahedral 8a/8c sites f
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54 with composition x in Li4–2xCo3xTi5–xO12 (0≤x≤0.5). Error bar represents one standard deviation
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3.2. Particle morphology and size. The morphologies and particle sizes of Li4–2xCo3xTi5–xO12
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6 (x=0, 0.1, 0.2, 0.25, 0.35 and 0.5) are presented in Figure 4a through Figure 4f. It is apparent that
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8 all the samples show similar morphologies with wide particle-size distributions ranging from less
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than 100 nm to more than 1000 nm. Their similar morphologies are further supported by their
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13 similar specific surface areas of ~3.6 m2 g–1. It can therefore be concluded that the Co2+
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15 substitution negligibly affected the morphology and particle size.
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39 Figure 4. FESEM images of Li4–2xCo3xTi5–xO12 with (a) x=0, (b) x=0.1, (c) x=0.2, (d) x=0.25, (e)
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42 x=0.35 and (f) x=0.5.
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45 3.3. Electronic conductivity. Figure 5 reveals the variation of the electronic conductivity as a
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47 function of the composition x. The electronic conductivity of the pristine Li4Ti5O12 is so low that
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50 it cannot be accurately measured using the Solartron Analytical 1470E CellTest System with a
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52 current limit of 1 nA. Actually, it was reported that it has a very low electronic conductivity of
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54 <1×10–13 S cm–1.6 Through the Co2+ substitution, the electronic conductivities are enhanced by at
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reaches a maximum value of 1.5×10–7 S cm–1 for Li3.5Co0.75Ti4.75O12 at x=0.25, but thereafter
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6 decreases. This value is significantly higher than those of Ni2+, Co3+, Al3+, Cu2+, Ta5+, Ga3+, and
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8 Cr3+, as well as Mg2+ and Al3+ co-substituted Li4Ti5O12 materials.8,10,16 It can be therefore
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concluded that the Co2+ substitution can greatly enhance the electronic conductivity of Li4Ti5O12.
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13 Previous research shows that electronic conduction in spinel oxides containing transition-metal
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15 ions originates from the hopping of free d electrons between octahedral cations.46–49 Therefore,
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18 the electronic conduction can be determined by (i) the amount of free d electrons, (ii) the
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20 distance between octahedral cations, and (iii) the amount of octahedral transition-metal ions in
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22 the crystal structure. A larger amount of free d electrons, smaller distance between the octahedral
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25 cations and larger amount of octahedral transition metal ions favour the electronic conduction.
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27 From the analyses of the crystal structures, more substituting Co2+ ions with the 3d electron
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configuration of t2g5 eg2 or t2g6 eg1 can supply more free 3d electrons;41 the larger lattice
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32 parameter implies the increased distance between octahedral cations; and the occupation of Co2+
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34 ions in the tetrahedral 8a/8c sites reduces the amount of octahedral transition metal (Ti4+ and
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37 Co2+) ions. Clearly, the first two parameters increase while the last one decreases with x. Due to
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39 the empty Ti4+ (t2g0 eg0) 3d orbitals,41 the pristine Li4Ti5O12 delivers the very disappointing
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41 electronic conductivity. When x is increased until 0.25, the increase of free 3d electrons in Co2+
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44 ions plays the dominant role in the electronic conduction, leading to the remarkably improved
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46 electronic conductivities. In contrast, when 0.25≤x≤0.5, the smaller amount of octahedral
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48 transition metal ions and the larger distance between the octahedral cations carry more weight,
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51 resulting in the subsequent decrease in the electronic conductivity.
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19 Figure 5. Variations in electronic conductivity and Li+ ion diffusion coefficient with
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21 composition x in Li4–2xCo3xTi5–xO12 (0≤x≤0.5).
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24 3.4. Li+ ion diffusion coefficient. Li+ ion diffusion coefficients of Li4–2xCo3xTi5–xO12 (x=0, 0.1,
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27 0.2, 0.25, 0.35 and 0.5) were determined using the CV technique. The Li4–2xCo3xTi5–xO12/Li cells
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29 were tested at a sweep rate of 0.1 mV s–1 for four cycles and then successively at 0.3, 0.5 and 0.7
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mV s–1 for one cycle each (Figure 6a through Figure 6f). It was found that the peak currents of
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34 the anodic reaction Ip were in proportional to the square root of the sweep rate ν0.5, as illustrated
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36 in Figure 6g. Thus, the Li+ ion diffusion coefficient DLi can be calculated based on Equation 2:
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39 Ip=0.4463n1.5F1.5CLiSR–0.5T–0.5DLi0.5ν0.5 (2)
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41 where n is the number of electrons involved in the electrochemical reaction, F, the Faraday’s
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44 constant, CLi, the concentration of Li+ ions, S, the electrode surface area of contact between the
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46 active materials and electrolyte, R, the molar gas constant, and T, the absolute temperature.50 The
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48 calculated values are also summarized in Figure 5. A volcano-type curve is observed, similar to
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51 that of the electronic conductivity. The improvement of the Li+ ion diffusion coefficient can also
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53 be ascribed to the crystalline characteristics of the Co2+-substituted samples. It is well known that
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Li+ ions transport in three-dimensional pathways in the spinel structure with /P4332 space
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group during lithiation and delithiation processes.51 Li+ ions have to pass through the O2– ion
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6 planes located between the octahedral and tetrahedral sites, which form the Li+ ion transportation
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8 bottlenecks. Consequently, the Li+ ion diffusion coefficient in this study can be determined by
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the distance between the neighbouring O2– ions and occupancy of Co2+ ions in the tetrahedral
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13 8a/8c sites. Compared with the pristine Li4Ti5O12 with no blockage of Li+ ion transportation
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15 pathways (Table 1), Co2+-substituted samples show considerable blockages, which is
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18 unfavourable for the diffusion of Li+ ions. However, the increased lattice parameter implies the
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20 increase in the distance between the neighbouring O2– ions, thereby benefits the diffusion and
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22 may play the dominant role in the entire Li+ ion diffusion coefficient. In fact, previous reports
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25 showed that the Li+ ion diffusion coefficient is very sensitive to the lattice parameter.52–54 Thus,
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27 the significantly improved Li+ ion diffusion coefficients were obtained. The highest Li+ ion
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diffusion coefficient is 9.07×10–11 cm2 s–1 also achieved in Li3.5Co0.75Ti4.75O12, which is ~20
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32 times larger than that of the pristine Li4Ti5O12 (4.45×10–12 cm2 s–1). This result can be explained
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34 by its best combination of the lattice parameter and occupancy of Co2+ ions in the tetrahedral
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37 sites. Therefore, Li3.5Co0.75Ti4.75O12 has the best material properties in terms of the electronic
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39 conductivity and Li+ ion diffusion coefficient.
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48 Figure 6. CVs of Li4–2xCo3xTi5–xO12/Li cells with (a) x=0, (b) x=0.1, (c) x=0.2, (d) x=0.25, (e)
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50 x=0.35 and (f) x=0.5; and (g) relationship between peak current of anodic reaction Ip and square
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53 root of sweep rate ν0.5. The loading density of the active materials in the cells was ~2.0 mg cm–2.
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3.5. Electrochemical performances. As shown in Figure 6a through Figure 6f, there is a pair
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6 of cathodic/anodic peaks centered at ~1.3 V/1.7 V in the first cycle of each sample, which can
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8 correspond to the lithiation/delithiation in octahedral vacancies, such as the 16c vacancies.
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Moreover, the cathodic/anodic peaks below 0.6 V are caused by the lithiation/delithiation in
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13 tetrahedral vacancies, such as the 8a vacancies.5,55–58 For instance, the pair at ~1.3 V/1.7 V for
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15 the pristine Li4Ti5O12 represents the two-phase reaction between [Li3]8a[LiTi5]16d[O12]32e and
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18 [Li6]16c[LiTi5]16d[O12]32e, and that below 0.6 V is attributed to the reaction between
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20 [Li6]16c[LiTi5]16d[O12]32e and [Li2]8a[Li6]16c[LiTi5]16d[O12]32e.5 The shapes and intensities of these
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22 peaks in the first cycle differ from those in the following cycles. This finding together with the
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25 peaks at ~0.7 V in the first cathodic branches can be interpreted by the formation of solid-
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27 electrolyte interface (SEI) films during the first cycle.58 From the second cycle, the area of the
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cathodic peak at ~1.4 V is comparable to that of the anodic peak at ~1.7 V when x=0 and 0.1, but
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32 becomes smaller and smaller with increasing x from 0.2 to 0.5 while the area of the cathodic
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34 peak below 0.6 V becomes larger and larger. This observation suggests that less and less Li+ ions
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37 intercalate into/de-intercalate from the octahedral vacancies while more and more Li+ ions act on
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39 the tetrahedral vacancies with increasing x. This result can also be rooted in the crystalline
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41 characteristics of the Co2+-substituted samples. The occupancy of Co2+ ions in the tetrahedral
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44 sites makes some octahedral vacancies blocked and thus inaccessible for Li+ ions. The larger
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46 occupancy at larger x results in more inaccessible octahedral vacancies, and thus less Li+ ions
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48 acting on the octahedral vacancies while more on the tetrahedral vacancies. Besides the 8a/8c
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51 vacancies, the accessible tetrahedral vacancies can include some other tetrahedral vacancies
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53 (such as the 8b vacancies in space group) since the total number of the tetrahedral sites is
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twice that of the octahedral sites in the spinel structure. In addition, it is worth noting that the
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potential difference of Li3.5Co0.75Ti4.75O12 between the cathodic and anodic peaks is the smallest
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6 among all the samples, implying its smallest polarization, largest mixed (electronic and ionic)
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8 conductivity, highest reactivity and best rate performance.
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The further confirm the electrochemical reaction mechanism of the Co2+-substituted samples,
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13 electrodes recovered from the cells discharged or charged to selected potentials were subjected to
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15 ex-situ X-ray diffraction analysis. Figure 7 displays the X-ray diffraction patterns of
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18 LiCo0.5Ti1.5O4 electrodes after as-fabricated, first-discharged to 0.02 V, first-charged to 3 V, and
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20 charged to 3 V in the 8th cycle. It is clear that the four patterns only show some variations in peak
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22 intensity and not possible impurities (such as Co, CoO, Co2O3, Co3O4 or TiO2) were detected,
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25 demonstrating that the basic crystal structure of LiCo0.5Ti1.5O4 was not destroyed and thereby its
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27 structure is stable during the repeated discharge (lithiation) and charge (delithiation) processes.
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The variations in peak intensity indicate the lithiation/delithiation in the octahedral and
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32 tetrahedral vacancies.5 Furthermore, since no X-ray diffraction peaks responding to Co can be
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34 detected after the first lithiation process, Co2+ ions could not be reduced to Co while only Ti4+
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37 ions were reduced to Ti3+ ions during this process. In addition, in the anodic branch of the CV
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39 curve, apart from the peak related to the Ti3+/Ti4+ redox couple, no other peaks can be found,
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41 inferring that the Co2+/Co3+ redox couple is inactive in the potential range of 3–0.02 V.
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44 Therefore, it can be concluded that Co2+ is stable in the Co2+-substituted samples and only the
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46 Ti3+/Ti4+ redox couple is active between 3 and 0.02 V. These results are in good agreement with
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48 the CV analysis.
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19 Figure 7. Ex-situ X-ray diffraction patterns of LiCo0.5Ti1.5O4 electrodes after (a) as-fabricated,
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21 (b) first-discharged to 0.02 V, (c) first-charged to 3 V, and (d) charged to 3 V in the 8th cycle.
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Identical discharge–charge rates were used. The loading density of the active materials in the
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26 cells was ~6.5 mg cm–2.
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29 Figure 8 plots the second galvanostatic discharge–charge profiles of the Li4–2xCo3xTi5–xO12/Li
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31 cells (x=0, 0.1, 0.2, 0.25, 0.35 and 0.5) at different current densities from 62.5 to 1000 mA g–1 in
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34 a potential range between 3 and 0.02 V. Although all the samples show similar capacities (~220
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36 mAh g–1) at the low current density of 62.5 mA g–1, their discharge profiles vary in shape. The
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pristine Li4Ti5O12 exhibits long discharge plateau at ~1.5 V presenting the insertion of Li+ ions
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41 into the octahedral vacancies, and a slope below 1 V corresponding to the insertion of Li+ ions
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43 into the tetrahedral vacancies. It delivers a large discharge capacity of 162 mAh g–1 in 3–1 V and
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46 a small value of 77 mAh g–1 in 1–0.02 V. These results are in accordance with those previously
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48 reported.58 However, the discharge capacity within 3–1 V becomes slightly smaller with
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50 increasing x until 0.25 and significantly smaller after x=0.25, and that within 1–0.02 V has the
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53 reverse trend, as displayed in Figure 9. A discharge plateau at ~0.5 V appears and becomes
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55 longer when x increases from 0.25 to 0.5. For LiCo0.5Ti1.5O4 (x=0.5), the discharge plateau at
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57 ~0.5 V contributes most of the discharge capacity. It can be therefore concluded that more and
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more Li+ ions act on the tetrahedral vacancies rather than the octahedral vacancies with
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6 increasing x at 62.5 mA g–1. Interestingly, the discharge–charge profiles with short (x=0.25) and
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8 long (x=0.5) discharge plateaus at ~0.5 V are respectively similar to those of slightly and
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severely Li+-excessive Li4Ti5O12 with less octahedral vacancies reported by Hsieh and co-
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Figure 8. Second discharge–charge profiles of Li4–2xCo3xTi5–xO12/Li cells (0≤x≤0.5) at (a) 62.5,
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54 (b) 125, (c) 250, (d) 500 and (e) 1000 mA g–1. Identical discharge–charge rates were used. The
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Figure 9. Variations in second discharge capacities within 3–1 V and 1–0.02 V at 62.5 mA g–1
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21 with composition x in Li4–2xCo3xTi5–xO12/Li cells (0≤x≤0.5). The loading density of the active
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23 materials in the cells was ~2.0 mg cm–2.
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26 It was also found that the ratio of the discharge capacity within 1–0.02 V to 3–0.02 V
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29 increased with the current density, as shown in Figure 10. An exception is that the ratio kept
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31 roughly constant at ~83% in LiCo0.5Ti1.5O4, because the ratio is so large that it cannot be
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obviously varied. The increased ratio indicates that the tetrahedral vacancies become more
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36 favorable for the lithiation/delithiation at high current densities. Meanwhile, the hysteresis
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38 becomes larger since the hysteresis is largely ascribed to the lithiation/delithiation in the
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41 tetrahedral vacancies.55 It is worth noting that the ratio of the pristine Li4Ti5O12 increases fairly
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43 fast. At 62.5 and 125 mA g–1, its ratios are smaller than those of the Co2+-substituted samples.
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45 With increasing the current density to 500 and 1000 mA g–1, however, its ratios become larger
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48 than those of Li3.8Co0.3Ti4.9O12, Li3.6Co0.6Ti4.8O12 and Li3.5Co0.75Ti4.75O12, suggesting that these
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50 three Co2+-substituted samples have smaller hystereses than the pristine Li4Ti5O12 at the high
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current densities. In contrast, the heavily Co2+-substituted samples (Li3.3Co1.05Ti4.65O12 and
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55 LiCo0.5Ti1.5O4) show large hystereses at all current densities.
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19 Figure 10. Variations in ratio of second discharge capacity within 1–0.02 V to 3–0.02 V with
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21 current density (62.5–1000 mA g–1) in Li4–2xCo3xTi5–xO12/Li cells (0≤x≤0.5). The loading density
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of the active materials in the cells was ~2.0 mg cm–2.
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27 The rate performances of the six samples are compared in Figure 11 besides Figure 8. As can
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29 be seen in Figure 8, with increasing the current density, the capacities gradually decrease, all
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31 discharge plateaus monotonically drop and their corresponding charge plateaus monotonically
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34 rise due to the increasing polarization. Among all the samples, Li3.5Co0.75Ti4.75O12 exhibits the
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36 smallest polarization. The six samples show diverse capacities at the current densities of 125–
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1000 mA g–1 although they deliver similar capacities of ~220 mAh g–1 at the low current density
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41 of 62.5 mA g–1. For instance, at 250 mA g–1, the capacities of Li4Ti5O12, Li3.5Co0.75Ti4.75O12 and
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43 LiCo0.5Ti1.5O4 are 167, 208 and 195 mAh g–1 respectively; at 500 mA g–1, they are 113, 191 and
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46 161 mAh g–1; and at 1000 mA g–1, Li3.5Co0.75Ti4.75O12 and LiCo0.5Ti1.5O4 respectively present
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48 158 and 108 mAh g–1 while Li4Ti5O12 only has 70 mAh g–1.
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19 Figure 11. Rate performances of Li4–2xCo3xTi5–xO12/Li cells (0≤x≤0.5). Identical discharge–
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21 charge rates were used. The loading density of the active materials in the cells was ~2.0 mg cm–
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.
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27 The above results indicate that the Co2+ substitution can obviously improve the rate
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29 performance of Li4Ti5O12. During the lithiation/delithiation process, electrons and Li+ ions
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simultaneously conduct in the active material particles in order to achieve charge balance. In this
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34 study, since all the six samples have similar morphologies and particle sizes, their rate
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36 performances can be determined by their electronic conductivities and Li+ ion diffusion
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coefficients. At the low current density, the capacities are less sensitive to the conductivities of
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41 the active materials since electrons and Li+ ions have adequate time to conduct and to diffuse
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43 respectively, which minimizes the capacity difference at this rate. However, electrons and Li+
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46 ions cannot effectively transport to the centers of the particles once the current density is overly
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48 high. Consequently, the improvements of the electronic conductivity and Li+ diffusion
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50 coefficient in the Co2+-substituted materials can facilitate the electrochemical reactions, leading
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53 to their good rate performances. Li3.5Co0.75Ti4.75O12 exhibits the best rate performance with a
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55 large capacity of 158 mAh g–1 at 1000 mA g–1, which is 126% larger than that of the pristine
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Li4Ti5O12 (70 mAh g–1). This result can be attributed to the highest electronic conductivity and
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Li+ ion diffusion coefficient of Li3.5Co0.75Ti4.75O12. It is worth noting that Li3.5Co0.75Ti4.75O12 is
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6 comprehensively superior to LiCo0.5Ti1.5O4 since Li3.5Co0.75Ti4.75O12 shows not only better rate
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8 performance but also a much smaller hysteresis. These analyses of the discharge–charge profiles,
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polarization and rate performance are well consistent with the CV results.
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13 3.6. P4332 space group vs. space group. Based on the results of Rietveld refinements,
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15 it is clear that the structure differences among Li4–2xCo3xTi5–xO12 (x=0, 0.1, 0.2, 0.25, 0.35 and
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18 0.5) are (i) the occupancies of ions in crystal sites, (ii) the lattice parameter, (iii) the amount of
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20 Co2+ ions and (iv) the space group. The first one, two and three factors are respectively
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responsible for the variations of the lithiation–delithiation behaviour (Section 3.5), Li+ ion
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25 diffusion coefficient (Section 3.4) and electronic conductivity (Section 3.3). Compared with
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27 space group, P4332 space group exhibits 3:1 cation ordering on the octahedral sites
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30 (Figure 1b). However, there is no clear evidence showing such ordering has obvious influences
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32 on the material properties in terms of the electronic conductivity and Li+ ion diffusion coefficient
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34 and thus on the electrochemical performances. In particular, both the lattice parameter and
35
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37 occupancy of Co2+ ions in the tetrahedral 8a/8c sites have a quasi-linear relationship with the
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39 composition x throughout the whole range of 0–0.5 (Figure 3), inferring the minor influences of
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the space-group difference. Therefore, spinels with P4332 space group can possess desirable
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44 material properties and electrochemical performances. As a good example, Li3.5Co0.75Ti4.75O12
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46 with P4332 space group, exhibits the best electronic conductivity, Li+ ion diffusion coefficient
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and rate performance among all the six spinels as well as a much smaller hysteresis than the
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51 previously developed LiM0.5Ti1.5O4 (M=Mg, Zn, Co, Co0.5Zn0.5 and Mg0.5Zn0.5).37–40
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53 4. CONCLUSIONS
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Li4–2xCo3xTi5–xO12 materials have been prepared through a facile solid-state reaction method.
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6 These materials possess a disordered spinel structure with space group (0≤x≤0.2) or
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8 ordered spinel structure with P4332 space group (0.25≤x≤0.5). With increasing the amount of
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11 Co2+ substitutes, the lattice parameter and occupancy of Co2+ ions in the tetrahedral 8a/8c sites
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13 increase while the amount of octahedral transition-metal ions decreases. As a result, both the
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15 electronic conductivity and Li+ ion diffusion coefficient are enhanced, leading to the
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18 improvement of the rate performance; and more Li+ ions act on the tetrahedral vacancies but less
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20 on the octahedral vacancies, resulting in the shape change of the discharge profiles. However, the
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space-group difference does not obviously affect the material properties and electrochemical
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25 performances. Li3.5Co0.75Ti4.75O12, with P4332 space group, exhibits the best rate performance
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27 due to its highest electronic conductivity and Li+ ion diffusion coefficient. It delivers a high
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capacity of 158 mAh g–1 between 3 and 0.02 V at 1000 mA g–1, ~1.3 times larger than that of the
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32 pristine Li4Ti5O12. In addition, it shows a significantly smaller hysteresis than the previously
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34 developed anode materials with ordered spinel structures. These findings indicate that the
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37 material structures decisively determine the material properties and LIB performances, which
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39 may benefit future material design for LIBs.
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44 AUTHOR INFORMATION
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46 Corresponding Author
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* Prof. Li Lu. Tel.: +65 65162236; Fax: +65 67791459. E-mail address: luli@nus.edu.sg.
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51 Address: Department of Mechanical Engineering, National University of Singapore, 9
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53 Engineering Drive 1, Singapore 117576, Singapore; Prof. Henghui Zhou. Tel.: +86 10
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62757908. Fax: +86 10 62757908. E-mail address: hhzhou@pku.edu.cn. Address: College of
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6 Chemistry and Molecular Engineering, Peking University, Beijing 100871, PR China.
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9 Notes
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12 The authors declare no competing financial interest.
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15 ACKNOWLEDGMENT
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This research is supported by Agency for Science, Technology and Research, Singapore
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21 through Singapore–China Joint Research programme (R265-000-442-305 and
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23 No.2012DFG52130).
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25
26 REFERENCES
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29 (1) Armand, G.; Tarascon, J. M. Building Better Batteries. Nature 2008, 451, 652–657.
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32 (2) Zheng, S. S. The Effect of the Charging Protocol on the Cycle Life of a Li-Ion Battery. J.
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34 Power Sources 2006, 161, 1385–1391.
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38 (3) Chen, Z. H.; Belharouak, I.; Sun, Y. K.; Amine, K. Titanium-based Anode Materials for
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40 Safe Lithium-Ion Batteries. Adv. Funct. Mater. 2013, 23, 959–969.
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43 (4) Goodenough, J. B.; Kim, Y. Challenges for Rechargeable Li Batteries. Chem. Mater. 2010,
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22, 587–603.
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49 (5) Ge, H.; Li, N.; Li, D. Y.; Dai, C. S.; Wang, D. L. Study on the Theoretical Capacity of
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51 Spinel Lithium Titanate Induced by Low-Potential Intercalation. J. Phys. Chem. C 2009, 113,
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6324–6326.
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29 Figure 4. FESEM images of Li4–2xCo3xTi5–xO12 with (a) x=0, (b) x=0.1, (c) x=0.2, (d) x=0.25, (e) x=0.35
30 and (f) x=0.5.
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29 Figure 4. FESEM images of Li4–2xCo3xTi5–xO12 with (a) x=0, (b) x=0.1, (c) x=0.2, (d) x=0.25, (e) x=0.35
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Figure 5. Variations in electronic conductivity and Li+ ion diffusion coefficient with composition x in Li4–
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2xCo3xTi5–xO12 (0≤x≤0.5).
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Figure 6. CVs of Li4–2xCo3xTi5–xO12/Li cells with (a) x=0, (b) x=0.1, (c) x=0.2, (d) x=0.25, (e) x=0.35
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and (f) x=0.5; and (g) relationship between peak current of anodic reaction Ip and square root of sweep
32 rate ν0.5.
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Figure 6. CVs of Li4–2xCo3xTi5–xO12/Li cells with (a) x=0, (b) x=0.1, (c) x=0.2, (d) x=0.25, (e) x=0.35
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and (f) x=0.5; and (g) relationship between peak current of anodic reaction Ip and square root of sweep
32 rate V0.5.
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Figure 6. CVs of Li4–2xCo3xTi5–xO12/Li cells with (a) x=0, (b) x=0.1, (c) x=0.2, (d) x=0.25, (e) x=0.35
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and (f) x=0.5; and (g) relationship between peak current of anodic reaction Ip and square root of sweep
32 rate V0.5.
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Figure 6. CVs of Li4–2xCo3xTi5–xO12/Li cells with (a) x=0, (b) x=0.1, (c) x=0.2, (d) x=0.25, (e) x=0.35
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and (f) x=0.5; and (g) relationship between peak current of anodic reaction Ip and square root of sweep
32 rate V0.5.
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Figure 6. CVs of Li4–2xCo3xTi5–xO12/Li cells with (a) x=0, (b) x=0.1, (c) x=0.2, (d) x=0.25, (e) x=0.35
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and (f) x=0.5; and (g) relationship between peak current of anodic reaction Ip and square root of sweep
32 rate V0.5.
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Figure 6. CVs of Li4–2xCo3xTi5–xO12/Li cells with (a) x=0, (b) x=0.1, (c) x=0.2, (d) x=0.25, (e) x=0.35
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and (f) x=0.5; and (g) relationship between peak current of anodic reaction Ip and square root of sweep
32 rate V0.5.
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Figure 6. CVs of Li4–2xCo3xTi5–xO12/Li cells with (a) x=0, (b) x=0.1, (c) x=0.2, (d) x=0.25, (e) x=0.35
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and (f) x=0.5; and (g) relationship between peak current of anodic reaction Ip and square root of sweep
32 rate V0.5.
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Ex-situ X-ray diffraction patterns of LiCo0.5Ti1.5O4 electrodes after (a) as-fabricated, (b) first-discharged to
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0.02 V, (c) first-charged to 3 V, and (d) charged to 3 V in the 8th cycle. Identical discharge–charge rates
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Second discharge–charge profiles of Li4–2xCo3xTi5–xO12/Li cells (0≤x≤0.5) at (a) 62.5, (b) 125, (c) 250,
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(d) 500 and (e) 1000 mA g–1. Identical discharge–charge rates were used. The loading density of the active
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Variations in second discharge capacities within 3–1 V and 1–0.02 V at 62.5 mA g–1 with composition x in
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Li4–2xCo3xTi5–xO12/Li cells (0≤x≤0.5). The loading density of the active materials in the cells was ~2.0
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Variations in ratio of second discharge capacity within 1–0.02 V to 3–0.02 V with current density (62.5–1000
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mA g–1) in Li4–2xCo3xTi5–xO12/Li cells (0≤x≤0.5). The loading density of the active materials in the cells
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Rate performances of Li4–2xCo3xTi5–xO12/Li cells (0≤x≤0.5). Identical discharge–charge rates were used.
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The loading density of the active materials in the cells was ~2.0 mg cm–2.
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