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Mater Renew Sustain Energy (2015) 4:40 DOI 10.1007/s40243-014-0040-7 OR IGINAL PAPER A new method of pretreatment of lithium manganese spinels and high-rate electrochemical performance of Li[Li Mn ]O 0.033 1.967 4 • • A. V. Potapenko S. I. Chernukhin S. A. Kirillov Received: 16 October 2014 / Accepted: 7 December 2014 / Published online: 19 December 2014 The Author(s) 2014. This article is published with open access at Springerlink.com Abstract Lithium manganese spinels tend to aggregate since that time attracts much attention of experimentalist upon annealing and do not allow for attaining high discharge [2]. Compared to currently employed LiCoO it is cheap, rates when used as cathodes in lithium-ion batteries. To non-toxic, has a high potential against lithium electrode -1 obtain spinel samples of lower aggregation and better high- (3.0–4.5 V) and the theoretical capacity of 148 mAh g rate properties, precursors synthesized by means of a citric [1, 3, 4]. Properties of this and related spinel compounds acid-aided route are suggested to be pyrolyzed in an inert and advances in their synthesis are reviewed in a recent atmosphere, instead of pyrolysis in air. The synthesis of paper [5]. nanosized Li[Li Mn ]O is described, and its char- LiMn O belongs to the cubic Fd3m space group, Z = 8 0.033 1.967 4 2 4 acteristics including X-ray diffraction, scanning electron [4, 6]. In this cubic structure, oxygen ions occupy the tet- microscopy, and porosity, as well as electrochemical test rahedral positions (32e) and form the cubic dense packing. results are presented. The particle size of the materials The octahedral positions (16d) are inhabited by manganese 3? 4? obtained is smaller, the degree of aggregation is lower, and ions (Mn /Mn ). Lithium ions hold the tetrahedral (8a) high-rate properties are better than for analogues pyrolyzed positions. Each of them is separated from four neighboring in air. In particular, sample Li||Li[Li Mn ]O cells ions by voids (16c). This means that three-dimensional 0.033 1.967 4 -1 -1 deliver *60 mAh g at the current loads of 4,000 mA g channels (8a–16c–8a–16c) exist for possible insertion and (30 C). After a sequence of 62 charge/discharge cycles with transport of lithium ions. the currents growing from 0.1 to 100 C the specific capacity Electrochemical intercalation/deintercalation of Li retains its initial value. into/from this material occurring in the potential range of 3.0–4.5 V can be expressed as Keywords Lithium battery Cathode material LiMn O þ 2 4 LiMn O $ Li Mn O þ xLi þ xe : ð1Þ 2 4 1x 2 4 spinel High-rate properties In the composition range of 0 B x B 0.5 and 0.5 B x B 1.0, reaction (1) occurs in two stages easily discernible in both galvanostatic and potentiodynamic regime, however, Introduction the spinel structure of LiMn O remains cubic keeping the 2 4 lattice parameter a close to ca. 8.248 A. Lithium manganese spinel LiMn O as a cathode material 2 4 Much work has been done so as to understand the nature for lithium-ion batteries has been suggested in 1983 [1] and of the Li Mn O phase and positioning of the lithium ions 0.5 2 4 in it. Careful electrochemical, X-ray and neutron diffrac- A. V. Potapenko S. I. Chernukhin S. A. Kirillov tion studies have shown that the charge/discharge process Joint Department of Electrochemical Energy Systems, occurs in three steps, hence up to three phases coexist in 38A Vernadsky Ave., Kiev 03142, Ukraine the 0 B x B 1 range [7–9]. The structure of Li Mn O has 0.5 2 4 S. A. Kirillov (&) been determined as belonging to the modulated R3m space Institute for Sorption and Problems of Endoecology, 2- group, Z = 6, with the O ions in the 6c and 18h posi- 13 Gen. Naumov St., Kiev 03164, Ukraine 3? 4? tions, the Mn ions in the 3b positions, the Mn ions in e-mail: kir@i.kiev.ua 123 40 Page 2 of 8 Mater Renew Sustain Energy (2015) 4:40 the 9e positions, and the Li ions partially filling 6c sites. the first place) as precursors [21–27]. High homogeneity of In a cubic setting, this cell has a = 8.142 A. Its remarkable final products and lower thermal treatment temperatures feature is an opportunity to derive superlattices corre- decrease the probability of particle growth and are con- sponding to the two ‘‘missing’’ phases having the predicted sidered to be advantages of such approaches. Li Mn O and Li Mn O compositions [9]. In a previous paper [28], we have described the high- 0.25 2 4 2/3 2 4 If x exceeds 1.0, i.e. at potentials of *3.0 V against Li/ rate properties of the lithium substituted spinel of the Li , a tetragonal LiMnO phase with a slightly increased Li[Li Mn ]O composition with the lithium to 2 0.033 1.967 4 ˚ ˚ unit volume (a = 8.007 A, c = 9.274 A) appears, manganese ratio equal to 1.05:2 and the theoretical -1 capacity of 133 mAh g . It has been obtained according Li þ LiMn O $ 2LiMnO : ð2Þ 2 4 2 to the aforementioned directions by means of an optimized Furthermore, tetragonal distortions in lithium–manganese citric acid-aided route. In terms of Paulsen and Dahn [15], spinels are favored by the Jahn–Teller effect which facilitates this composition is structurally stable and does not tend to lowering the symmetry of the structure if more than 50 % of lose oxygen upon heating. As follows from Ref. [28], 3? Mn is accumulated in the product of reaction (2) [10]. sample cells with cathodes made of the material in question An effect of solid state synthesis conditions and evidence the absence of discharge capacity fading within annealing of LiMn O on its stoichiometry and electro- 100 cycles and the capability to be discharged with great 2 4 chemical properties is studied in detail [11, 12]. It is found currents. In particular, at the current density of -1 that annealing at temperatures not exceeding 850 C and 1,480 mA g (*11 C) the discharge capacity equals to -1 slow cooling ensure the minimal loss of oxygen and the 58 mAh g or almost the half of the theoretical capacity maximal specific capacity. However, major drawbacks of of the material, and at the highest current load of -1 the material are inability to gain the theoretical capacity 2,220 mA g (*16.5 C) applied, the capacity of -1 values and a significant capacity fading on cycling (up to 33 mAh g has been retained. 10 % after 50 cycles). On the other hand, the data presented in Ref. [15] and There are at least two possible directions in improving our practice have shown that even being synthesized at the electrochemical properties of the lithium manganese mild conditions, these and other lithium manganese spinel spinel electrode materials. One of them is based on the samples demonstrate a clear trend to the fast aggregation of replacement of a part of the manganese ions in the 16d particles upon the thermal treatment of a pyrolyzed mate- positions by excess lithium ions and obtaining substituted rial. This trend levels the advantages of the citric acid- spinels of a general formula Li[Li Mn ]O [13, 14]. It aided route where pyrolysis gives nanosized powders with q 2-q 4 should be mentioned that annealing in air often leads to an crystallites of *15 nm size. oxygen loss and to a non-stoichiometricity of the spinels To avoid this obstacle and to obtain spinel samples of whose formula can be written as Li[Li Mn ]O .A the lower degree of aggregation and better high-rate q 2-q 4-d detailed investigation by Paulsen and Dahn [15] reveals properties the following idea is suggested in this paper. that between 400 and 880 C only the mentioned spinel is Instead of the pyrolysis in air (a ‘standard’ scheme), citrate stable having a negligible oxygen nonstoichiometric range, precursors are pyrolyzed in an inert atmosphere (a pro- d \ 0.02. The lithium stoichiometry can vary from posed scheme). In this case, two circumstances are con- 0.05 \ q \ 0.13 and increases with decreasing tempera- sidered to favor the smaller degree of aggregation of the ture and increasing oxygen partial pressure. Upon the target product. First of all, no chemical reactions between 3? substitution, the fraction of Mn decreases and the lithium carbonate and manganese-II oxide obtained in the specific capacity diminishes (e.g., to 117 mAh/g for course of pyrolysis shall occur. Second, a great amount of Li Mn O [13] and to 98 mAh/g for Li Mn O carbon shall be formed covering the products of pyrolysis. 1.063 1.932 4 1.12 1.88 4 [14]). However, in this case, the mean degree of oxidation This means that upon further annealing, carbon-coated of manganese exceeds 3.5 and thus prevents of arising the Li CO and MnO will react, and the coating, even being 2 3 Jahn–Teller effect and capacity-fading phenomena. burnt, will prevent the rapprochement of the spinel parti- Another way for improving the electrochemical prop- cles. In what follows, we describe the physicochemical and erties of electrode materials is obtaining them in the form electrochemical properties of the lithium-substituted spinel of nanosized crystals. Decreasing the size of particles leads of the Li[Li Mn ]O composition supporting this 0.033 1.967 4 to their better cycling ability and makes it possible to idea. Its particle size is smaller, the degree of aggregation discharge lithium ion batteries with higher currents, i.e. is lower, and high-rate properties are better that for its increases their rate [16]. To do so, significant efforts are analogue pyrolyzed in air. In particular, model Li||Li[- -1 undertaking in the field of sol–gel synthesis of electrode Li Mn ]O cells deliver *60 mAh g at the cur- 0.033 1.967 4 -1 materials with improved electrochemical parameters rent loads of 4,000 mA g (30 C); at the highest current -1 -1 [17–26], in particular, using oxyacid metal salts (citrates on load of 13,300 mA g (100 C), the capacity 11 mAh g 123 Mater Renew Sustain Energy (2015) 4:40 Page 3 of 8 40 is retained; after a sequence of 62 charge/discharge cycles % of the studied material, 10 wt. % of a conductive addi- with the currents varied from 0.1 to 100 C the specific tive (soot) and 8 wt. % of a binder (poly (vinyliden) capacity returns at its initial value. difluoride). A 20 lm layer of the slurry has been put on an aluminum foil with a doctor blade and then dried at 120 C for 18-21 h under an IR radiator. The quantity of Experimental Li[Li Mn ]O in a dried remainder was of 0.033 1.967 4 -2 3–8 mg cm . The electrodes were rolled so as to decrease Citrate precursors have been obtained in the following way the thickness of the layer from 70–80 to 25–35 lm. Sample [27–31]. Solutions of lithium nitrate, manganese-II nitrate, coin-type cells have been assembled in 2016 cases with and citric acid (all of analytical grade) of approx. 1 M Celgard 2500 separators and an electrolyte containing the concentration have been analyzed with the four significant 1 M solution of LiPF in a mixture of ethylene carbonate digits accuracy, mixed using calibrated pipettes in the and dimethyl carbonate taken in the 1:1 mass ratio. The 1.05:2:6 ratio, and evaporated up to a resin state (80 C). reference and counter electrode has been made of lithium The resins have been dried at 120 C giving the precursors metal. Potentiodynamic tests have been performed within for all further operations. the voltage range of 3.4–4.5 V at the scanning speed of -1 According to the ‘standard’ scheme, the precursors have 0.1 mV s . High rate tests have been carried out in a been pyrolyzed and annealed in air. By the proposed galvanostatic mode within the same voltage range using a scheme, pyrolysis has been performed in the argon atmo- CCCV regime with the charge current of 1C and a trickle sphere and after that, pyrolyzed samples have been charge at 0.1 C; discharge currents varied from 0.1C to annealed in air. The temperature of pyrolysis in both cases 100C. As noticed above, the theoretical specific capacity of has been equal to 400 C; the duration of pyrolysis has the compound studied, Li[Li Mn ]O is 0.033 1.967 4 -1 -1 been taken equal to 0.5 h. Subsequent operations with the 133 mAh g , therefore, 1C = 133 mA g . samples pretreated in air have been made according to Ref. [28] and consisted of 24 h annealing in air at 700 C with -1 heating and cooling rates taken equal to 5 and 2 Cmin , Results and Discussion respectively. The samples pretreated in argon have been annealed in air at two different regimes: for 24 h at 700 C As follows from Refs. [29–31], citrate precursors after and for 10 h at 800 C; the heating and cooling rates have drying at 120 C (dried resins) consist of stoichiometric been kept as the same as in the case of the samples pre- hydrous citrates and upon pyrolysis, decompose giving the treated in air. target products. In the case of lithium manganese spinels, Since the content of lithium and manganese is crucial the precursors contain the mixture of dihydrates of lithium for the correct comparison of the properties of the samples citrate, manganese-II citrate, and two excess moles of citric pretreated at different conditions, it has been controlled by acid, and their decomposition in air is described by the means of atomic absorption spectrophotometry (AA-8500, following reaction [28], Nippon Jarrell–Ash, Japan). The mean Li:2Mn ratio of LiC H O 2H O þ 2MnC H O 2H O þ 2C H O 6 7 7 2 6 6 7 2 6 8 7 1.0503 has been determined for thermally treated samples þ 23:25O ! LiMn O þ 30CO þ 23:5H O: with standard deviation of 0.00082 and standard error of 2 2 4 2 2 0.00033 thus signifying that no lithium loss occurs. This ð3Þ Li:2Mn ratio perfectly matches the title composition, Unlike pyrolysis in air, the decomposition of the spinel Li[Li Mn ]O . To check the thermal decomposition 0.033 1.967 4 precursor in argon atmosphere should proceed according process, the differential thermal analysis has been the following scheme, employed (Q-1500 D, MOM, Hungary). Porosity studies have been utilized on an ASAP 2000 device (Micromeri- LiC H O 2H O þ 2MnC H O 2H O þ 2C H O 6 7 7 2 6 6 7 2 6 8 7 tics, USA). The phase composition of the samples, their 1 ! = Li CO þ 2MnO þ 15:5C þ 23:5H O þ 14CO: 2 2 3 2 morphology and the particle size have been studied by ð4Þ means of X-ray diffraction (DRON-4-07, LOMO, Russia, In this case, the reaction products are lithium carbonate CoR and CuR radiation) and scanning electron a a and manganese-II oxide. On further annealing in air, the microscopy (JSM 6700F, JEOL, Japan). To qualitatively excess carbon should serve as a coating preventing the determine the phase composition of samples JCPDS-ICDD aggregation of the spinel particles. The calculated mass database has been used. loss in reaction (4) is 60.9 %. In accord with this estimate, Electrochemical tests have been performed in sample pyrolysis at 400 C for 0.5 h leads to the experimental Li||Li[Li Mn ]O cells on a home-made versatile 0.033 1.967 4 workstation. Working electrodes have consisted of 82 wt. mass loss of 62.0 %. X-ray diffraction data evidence the 123 40 Page 4 of 8 Mater Renew Sustain Energy (2015) 4:40 formation of MnO. A diffraction pattern obtained (Fig. 1a) well agrees with existing data (JCPDS 07-0230). The lithium salt formed is not recognizable due to low scattering abilities of lithium, carbon and oxygen. Upon heating the mixture of Li CO , MnO and carbon 2 3 in air, the following reaction accompanied by the mass loss of 51.0 % should occur, Li CO þ 4MnO þ 31C þ 32:5O 2 3 2 ! 2LiMn O þ 32CO : ð5Þ 2 4 2 Respective thermal analysis data are given in Fig. 2. The mass loss of 47.0 % registered is in a good agreement with the calculations by reaction (5). On the other hand, the burning of carbon and accompanying exothermic effect Fig. 1 X-ray diffraction pattern of the decomposition products of the makes any attempts to interpret the DTA data difficult. An precursor treated in argon atmosphere (a) and the spinel obtained X-ray analysis proves that the product obtained is the upon further thermal treatment (b) lithium manganese spinel (Fig. 2b). To determine the crystallite size d of spinels the Scherrer formula has been employed [32], d ¼ 0:9k=ðB cos hÞ; ð6Þ where k is the wavelength of X-ray radiation, B is the line width at the half maximum of the diffraction peak, and h is the angle of diffraction. The lattice parameters a (A) for the spinel samples have been calculated by the Holland-Red- fern method using a UnitCell 1997 software [33]. The values of d and a are summarized in Table 1. As follows from these data, the samples consist of nanosized crystal- lites of comparable dimensions. Scanning electron microscopy supports a conclusion regarding the nanosized nature of the spinels under investi- gation (Fig. 3). Comparing the micrographs one easily Fig. 2 Thermal analysis data for the mixture of Li CO , MnO and 2 3 reassures that the particle size d in the sample pyrolyzed part. carbon obtained in the course of its heating in air in argon is at least twice smaller than in the sample pyrolyzed in air (50–70 nm against 70–100 nm, respectively). More- Table 1 X-ray diffraction and scanning electron microscopy data for over, the former sample demonstrates a less significant ten- Li[Li Mn ]O 0.033 1.967 4 dency to aggregation. Combining these data with the ˚ ˚ crystallite size d obtained by means of X-ray diffraction, Sample treatment d (400), nm a,A V,A d ,nm part. Table 1, one can speculate that the particles in the argon- Air 30 8.2356 559 70–100 pyrolyzed samples are single crystals, whereas the particles Argon 65 8.2405 560 50–70 in the air-pyrolyzed samples are aggregates of single crystals. Unlike lithium manganese spinels obtained by means of nanochemistry routes [14, 34] and showing high surface areas and clear hysteresis loops on nitrogen adsorption/ stationary voltammetric curves corresponding to the 3rd desorption curves, porosity data for our samples are much cycle for sample Li||Li[Li Mn ]O cells are pre- 0.033 1.967 4 simpler (Fig. 4). They reveal low surface areas (*11 m /g) sented. The term ‘stationary’ means the complete repro- and do not enable one to perform the calculation of pore size ducibility of voltammetric data in preceding and following distributions. This means that the materials obtained have measurements. Peaks in the cathodic and anodic regions no micro- and mesopores, and their porosity, as follows reflect processes occurring upon insertion/deinsertion of from SEM micrographs, is determined by voids between lithium ions into/from the lithium manganese spinel in the particles. composition range of 0 B x B 0.5 and 0.5 B x B 1.0. It After physico-chemical characterization the samples should be mentioned that the low-voltage insertion and have been subjected to electrochemical tests. In Fig. 5, deinsertion peaks are clearly asymmetric possibly 123 Mater Renew Sustain Energy (2015) 4:40 Page 5 of 8 40 Fig. 3 Scanning electron micrographs (9100,000) of Li[Li Mn ]O treated in air (left) and in argon (right) 0.033 1.967 4 Fig. 4 Nitrogen adsorption/desorption isotherm for Li[Li 0.033 Mn ]O treated in argon Fig. 6 Discharge curves for sample Li||Li[Li Mn ]O cells at 1.967 4 0.033 1.967 4 various discharge current densities: a Li[Li Mn ]O treated in 0.033 1.967 4 air; b Li[Li Mn ]O treated in argon 0.033 1.967 4 Discharge curves for sample Li||Li[Li Mn ]O 0.033 1.967 4 cells at various discharge current densities are given in Fig. 6, and dependences of specific capacities on current densities are shown in Fig. 7. At minimal current loads, the specific capacities of materials under investigation are lower than the theoretical values. For the samples fired in max: air discharge capacities Q at minimal discharge currents -1 I = 0.1C are equal to 103 mAh g ; for those fired in min. max: -1 argon Q = 113 mAh g . As follows from Figs. 6 and Fig. 5 Stationary voltammetric characteristics of Li[Li Mn ]O – 0.033 1.967 4 7, the cells with the cathode materials fired in argon retain based electrodes. Scanning speed 0.1 mV/s. a Thin black curve their working ability at the currents growing from 14.8 to Li[Li Mn ]O treated in air. b Thick red curve Li[Li 0.033 1.967 4 0.033 -1 14,800 mA g (from 0.1 to 100 C). After heavy-duty tests Mn ]O treated in argon 1.967 4 during 62 charge/discharge cycles their specific capacity returns to its initial value. The materials treated in air signifying the presence of a third phase, as described in remain stable at much lower current loads and do not retain Introduction. These features, as well as an analysis of their initial capacity after loading. diffusion coefficients in Li[Li Mn ]O spinels (0 B q B q 2-q 4 It is tempting to compare these results with those 0.065) determined from voltammetric and impedance existing in the literature. Since the rate capability of Li- measurements will be described elsewhere. substituted spinels has not been widely studied we present 123 40 Page 6 of 8 Mater Renew Sustain Energy (2015) 4:40 Fig. 7 Dependences of discharge capacity on cycle number for Li||Li[Li Mn ]O cells. 0.033 1.967 4 Left Li[Li Mn ]O 0.033 1.967 4 treated in air. Right Li[Li Mn ]O treated in 0.033 1.967 4 argon. Numeric values mean discharge current densities in C units Table 2 Parameters of materials obtained by various routes and demonstrating good high-rate properties Route Initial dQ /dI References capacity min: Q , -1 mAh g Literature data Resorcinol- 137 0.6 (60 C) [20] formaldehyde Solid state 105 1.9 (10 C) [35] Solid state 119 1.45 (20 C) [36] Sol–gel 100 2.1 (20 C) [17] Sol–gel 115 0.8 (40 C) [18] Fig. 8 Capacities retained by Li||Li[Li Mn ]O cells upon 0.033 1.967 4 Hydrothermal 108 0.12 (90 C) [37] various current loads. Squares, black Li[Li Mn ]O treated in 0.033 1.967 4 air. Circles, red Li[Li Mn ]O treated in argon Hydrothermal 118 0.23 (95 C) [38] 0.033 1.967 4 Nanowires 120 0.22 (135 C) [39] -1 -1 (130–133 mAh g [19, 41], 135 mAh g [42–45], Pechini 120 0.8–2.1 (60 C) [40] -1 145 mAh g [46]) have never been treated at high current This work loads. On the other hand, it is well-seen that pyrolyzing the Pechini/air 103 4.2 (16.7 C) – citrate precursor in argon one can attain better high-rate Pechini/argon 113 2.3 (40 C)–1.2 (100 C) – capabilities and significantly improve the initial capacity of the spinel material. Table 2 where selected latest data on LiMn O are sum- In our opinion, this promising result is bound not only to 2 4 marized. This seems appropriate because the lithium excess a decrease in the size and degree of aggregation of the in the sample is very small. More detailed structural and spinel particles, but to the nature of the crystallites in the electrochemical information about these and other argon-treated sample, each of which, according to XRD LiMn O samples demonstrating good high-rate proper- 2 4 and SEM data, can be considered as a separate single ties can be found in Ref. [5]. For the sake of compari- crystal. As follows from Ref. [5], just the perfectness of the son, the high-rate parameters are characterized by the particles, together with their size and degree of aggrega- minimal capacity losses per the unit current rate, tion, is crucial for the accessibility of theoretical capacities max: min: max: dQ =dI ¼ðQ Q Þ=ðI I Þ, where Q and and high speed of discharge of lithium batteries. d max: min: d d d min: Q are the discharge capacities at the minimal and maximal discharge currents applied, I and I . For our min. max. Conclusion samples these values have been determined from Fig. 8. The inspection of Table 2 reveals that electrode mate- In this paper, we have synthesized two samples of the rials demonstrating good high-rate properties have low nanosized lithium-doped lithium manganese spinel, initial capacities, except the sample obtained by means of a Li[Li Mn ]O using a citric acid-aided route, per- resorcinol-formaldehyde route and exhibiting exceptional 0.033 1.967 4 formed their characterization by means of X-ray diffrac- results. It should be mentioned parenthetically that, to our tion, scanning electron microscopy, and porosity studies, surprise, numerous materials with high initial capacities 123 Mater Renew Sustain Energy (2015) 4:40 Page 7 of 8 40 13. Xia, Y., Yoshio, M.: An investigation of lithium ion insertion into and carried out their electrochemical tests in Li||Li[- spinel structure Li-Mn-O compounds. J. Electrochem. Soc. 143, Li Mn ]O cells. 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Materials for Renewable and Sustainable Energy – Springer Journals
Published: Dec 19, 2014
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