Enhanced ionic conductivity of sulfide-based solid electrolyte by incorporating lanthanum sulfide

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<ul><li><p>CERAMICSINTERNATIONAL</p><p>Available online at www.sciencedirect.comhttp://dx.doi.org/0272-8842/&amp; 20</p><p>nCorrespondinnnCorrespond</p><p>fax: 86 21 524E-mail addre</p><p>huangfq@mail.s(2014) 1549715501Ceramics International 40</p><p>www.elsevier.com/locate/ceramintEnhanced ionic conductivity of sulfide-based solid electrolyteby incorporating lanthanum sulfide</p><p>Zhanqiang Liu, Yufeng Tang, Xujie L, Guohao Renn, Fuqiang Huangnn</p><p>Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, PR China</p><p>Received 16 May 2014; received in revised form 2 July 2014; accepted 2 July 2014Available online 10 July 2014Abstract</p><p>Solid electrolyte is the key point for developing all-solid-state lithium-ion battery with good recyclability and no safety problem. Here, acrystalline phase of lanthanum sulfide (La2S3) was incorporated into glassy sulfide-based solid electrolytes (Li2SSiS2 or Li2SP2S5) to form twocomposite systems Li2SSiS2xLa2S3 and Li2SP2S5yLa2S3. The results demonstrated that La2S3 has the ability to suppress the crystallizationof Li2SSiS2 or Li2SP2S5 during the synthetic process. The lithium-ion conductivities of the designed composites can be improved by more thanone order of magnitude in comparison with the pristine samples. And both of these two composites have a wide electrochemical window of morethan 8 V vs. Li /Li.&amp; 2014 Elsevier Ltd and Techna Group S.r.l. All rights reserved.</p><p>Keywords: A. Powders: solid state reaction; B. Composites; C. Ionic conductivity; E. Batteries; Lanthanum sulfide1. Introduction</p><p>Traditional liquid electrolytes used in lithium-ion batterycontain toxic and flammable solvents, which bring seriousproblems such as leakage, inflammability and narrow operat-ing temperature range. For safety concerns and particularapplications, the next-generation lithium-ion batteries havebeen heading for replacing the traditional liquid electrolyteswith solid electrolytes [1]. However, the solid electrolytes havenot been widely used because their ionic conductivities are stillmuch lower than those of the liquid electrolytes. To meet therequirements of high performance solid-state batteries,advanced solid electrolytes having similar ionic conductivitywith the liquid electrolyte are highly required. Many inorganicsolid electrolytes have been investigated among which sulfide-based electrolytes show great promising prospects.10.1016/j.ceramint.2014.07.01114 Elsevier Ltd and Techna Group S.r.l. All rights reserved.</p><p>g author. Tel.: 86 21 69987741; fax: 86 21 5241 3903.ing author. Tel.: 86 21 5241 1620;1 6360.sses: rgh@mail.sic.ac.cn (G. Ren),ic.ac.cn (F. Huang).Sulfide-based electrolytes have much higher lithium-ion con-ductivity than oxide-based electrolytes owing to their higherpolarization ability of S2 than O2. Li2SP2S5 [25],Li2SSiS2 [68] and Li2SGeS2 [911] are currently themost studied sulfide-based electrolytes. In these systems,P2S5, SiS2 or GeS2 serve as network former and Li2S isnetwork modifier. It is well known that the lithium-ion conductiv-ities of these sulfide electrolytes can be improved by reducing thecrystallinity to form poorly-crystallized or amorphous phases.Unfortunately, these systems usually have low-melting pointsand are easy to form good crystalline phase. So it is very importantto develop strategies to stabilize the glassy phase of sulfide-basedelectrolytes. Although remarkable progress has been made in thepreparation of the glassy systems by doping oxides, sulfides,lithium halides or other chemical materials to improve ionicconductivities, an effective strategy still represents a big challenge[6,1219]. In this paper, we propose a facile route to improve theionic conductivities of Li2SSiS2 and Li2SP2S5 systems byincorporating lanthanum sulfide (La2S3). The La2S3 in thecomposites can suppress the crystallization of Li2SSiS2 orLi2SP2S5, and the ionic conductivities of these compositescan be significantly enhanced.</p><p>www.sciencedirect.com/science/journal/02728842http://dx.doi.org/10.1016/j.ceramint.2014.07.011http://crossmark.crossref.org/dialog/?doi=10.1016/j.ceramint.2014.07.011&amp;domain=pdfwww.elsevier.com/locate/ceraminthttp://dx.doi.org/10.1016/j.ceramint.2014.07.011http://dx.doi.org/10.1016/j.ceramint.2014.07.011http://dx.doi.org/10.1016/j.ceramint.2014.07.011mailto:rgh@mail.sic.ac.cnmailto:huangfq@mail.sic.ac.cn</p></li><li><p>Fig. 1. X-ray diffraction patterns for the samples 3Li4SiS4xLa2S3.</p><p>Fig. 2. Complex impedance plots for 3Li4SiS4xLa2S3 with x0.3.(a) Complex impedance plots. (b) Enlarged plots from 0 to 500 .</p><p>Z. Liu et al. / Ceramics International 40 (2014) 1549715501154982. Experimental details</p><p>La2S3, SiS2, P2S5 and Li2S were used as the startingmaterials. All the raw materials were stoichiometricallysynthesized in our lab, and the purities were confirmed byX-ray diffraction. For the incorporation of La2S3 intoLi2SSiS2, the molar ratio of Li2S, SiS2 and La2S3 was controlledas 6: 3: x (x=0, 0.1, 0.3, 0.5, 0.75 and 1.0). For the additionof La2S3 into Li2SP2S5, the molar ratio of Li2S, P2S5 andLa2S3 was controlled as 4: 1: y (y=0, 0.1, 0.2, 0.3 and 0.5).The fully mixed precursors were loaded into evacuated andsealed silica tubes. The tubes were placed into the furnace,heated at 750 1C for 10 h and then quenched in water. Thefinal products were collected and ground into fine powders.</p><p>X-ray diffraction (XRD) analysis was carried out with anX-ray diffractometer (Rigaku D/Max 2550V, 40 kV 40 mA)with CuK radiation in the 2 range from 201 to 601.</p><p>For ionic conductivity measurement, powder sample wascold-pressed into a 10 1 mm pellet and both sides of thepellet were attached with indium plates as current collectors.Then the measurement was conducted in a dry argon flow bycomplex impedance on an impedance analyzer (Chenhua660B) in the frequency range of 0.1 Hz and 0.1 MHz overthe temperature range from 30 to 210 1C.</p><p>DC polarization measurement was carried out to determinethe electronic conductivity. Indium foil was used as blockingelectrode and lithium plate as unblocking electrode. Timedependence of the electrical current was measured under aconstant voltage 1 V for 1600 s.</p><p>Cyclic voltammogram (CV) of the asymmetric Li/sample/Ptcell was performed on Chenhua 660B to evaluate the electro-chemical stability of the electrolytes at the scan rate of 10 mV s1.The Lithium plate and Pt plate in the cell are serve as thereference/counter and working electrodes, respectively.</p><p>3. Results and discussion</p><p>XRD patterns of 6Li2S3SiS2xLa2S3 with various La2S3contents are shown in Fig. 1. It can be seen that Li4SiS4 wasobtained at x0 [8]. With the increasing of La2S3, the peaksindexed to La2S3 appear and become stronger gradually. Theunchanged phase of La2S3 before and after the syntheticprocess indicates that there is no reaction between La2S3 andLi2S or SiS2. Since the melting temperature of Li4SiS4 isaround 750 1C, the quenching process should result in the poorcrystallinity of Li4SiS4. And it can be observed that the peaksindexed to Li4SiS4 become relatively weaker with the increas-ing of x and almost disappeared at x1.0. The poor-crystalLi4SiS4 transforms into amorphous state step by step, implyingthat the added La2S3 can efficiently suppress the crystallizationof Li4SiS4 during the preparation process.</p><p>Usually, the coordination number of La3 is six to nine,while Si4 is 4-coordinated in Li4SiS4. Considering otherconditions, such as the reaction temperature, reaction time andespecially the big difference of atomic radius between La3</p><p>and Si4 , the possibility of substitution of Si4 by La3 isvery low. So it can be concluded that the final samples can berecognized as a kind of composite, poor-crystallized Li4SiS4/well-crystallized La2S3 (3Li4SiS4xLa2S3).Ionic conductivities of the obtained samples were examined</p><p>through the AC impedance spectroscopy. Fig. 2 shows theimpedance plots of 3Li4SiS4xLa2S3 with x0.3 at varioustemperatures. A semicircle in the high-frequency range with aspike in the low frequency range was observed at 30 1C.As typical ionic conductor, the semicircle is interpreted as a</p></li><li><p>Figofcon</p><p>Z. Liu et al. / Ceramics International 40 (2014) 1549715501 15499parallel combination of a resistance and a capacitance, whichare attributed to the bulk and grain boundary contribution,respectively. The spike is caused by the electrode contribution,where Warburg impedance exists. By increasing the measure-ment temperatures over 60 1C, no semicircle can be observedbut only spikes left. The total resistance at each temperaturecan be calculated from the intersection of the semicircle withthe real axis at the lower frequency side. Then the totallithium-ion conductivity at each temperature can be derived.</p><p>Fig. 3 shows the temperature dependences of conductivitiesfor the series of 3Li4SiS4xLa2S3. The plots of log(T) vs.103/T indicate that the conductivities of these composites in thetemperature range from 30 to 210 1C follow the Arrheniusequation: T0exp(Ea/RT), where 0 is the pre-exponentialfactor, Ea the activation energy for conduction, R the gasconstant and T the absolute temperature. So it can be inferredthat the system of 3Li4SiS4xLa2S3 is a good lithium-ionconductor. Then the corresponding activation energies werecalculated based on the Arrhenius equation.</p><p>To further demonstrate the effect of the amount of La2S3 onthe Li4SiS4 system. The composition dependences of the con-ductivity and the activation energy for are shown in Fig. 3(the inset figure). The ionic conductivity and activation energy ofthe obtained Li4SiS4 are calculated to be 3.3 106 S cm1 and0.43 eV, respectively. As reported, however, the ionic conductiv-ity and activation energy of the fine crystalline Li4SiS4 are5.0 108 S cm1 and 0.60 eV, respectively [20]. The reasonfor the big differences is the poor crystallinity of the obtainedLi4SiS4, which is caused by the quenching process. So the aboveresult demonstrates that poor crystallinity is benefit for the lithiumion diffusion in Li4SiS4. The XRD analysis has disclosed that thepoor crystallinity will turn into amorphous gradually with theincreasing of La2S3, suggesting the ionic conductivity might befurther enhanced. As shown in Fig. 3, the conductivities ofLi4SiS4xLa2S3 increase initially and then decrease as the La2S3content increasing from x0 to 1.0. The corresponding activationenergy almost follows the reverse trend. Apparently, the contentof La2S3 was optimized to be x0.3. And the correspondingconductivity and activation energy were calculated to be. 3. Temperature dependences of the electrical conductivities for the samples3Li4SiS4xLa2S3. The inset depicts the composition dependence of theductivities and the activation energies for the samples 3Li4SiS4xLa2S3.</p><p>Figaft3.4 105 S cm1 and 0.38 eV, respectively. The optimizedconductivity is ten times higher than that of the pristine Li4SiS4after La2S3 added. Since La2S3 is ionic-insulating, heavy additionwill block the lithium ions and subsequently reduce the ionicconductivity of the composite.Fig. 4 shows the time dependence of the DC conductivity</p><p>obtained from current after applying a constant 1 V DCvoltage on sample 3Li4SiS40.3La2S3 at room temperature.When using lithium as nonblocking electrode, the DC con-ductivity is almost constant with time and the value, around2.8 105 S cm1, is in good agreement with the numberobtained from AC impedance shown above. When usingindium as blocking electrode, a large decrease of DC con-ductivity, resulted from the accumulation of lithium atoms onthe electrode, can be observed initially and then the conduc-tivity become almost constant. The constant conductivity of1.80 108 S cm1 is about three orders of magnitude lowerthan that obtained using the nonblocking electrode. Therefore,it can be concluded that the electronic conduction in the totalconductivity is almost negligible.Electrochemical stabilities of the obtained samples were also</p><p>studied by cyclic voltammetry with a potential range from0.50 to 10.0 V vs. Li /Li. Fig. 5 shows the cyclicvoltammogram of the sample 3Li4SiS43La2S3. A cathodiccurrent due to lithium deposition (Lie-Li) is observedat around 0 V on the cathodic sweep up to 0.50 V, and thenan anodic current due to lithium dissolution (Li-Li e) isobserved at around 0.2 V on the an anodic sweep. There is nosignificant anodic current in the potential up to 10 V, whichmeans the sample of 3Li4SiS40.3La2S3 has a wide electro-chemical window up to 10 V vs. Li /Li.In order to verify our statement on the effects of La2S3</p><p>addition, La2S3 was also introduced into the Li2SP2S5system. As shown in Fig. 6, the phases of the series of4Li2SP2S5yLa2S3 were examined by X-ray powder dif-fraction. At the point of y0, the main peaks are indexed toLi30.55P10.11S4 [21]. Similar to Li4SiS4, the peaks ofLi30.55P10.11S4 also become weaker and weaker graduallywith La2S3 adding, which implies the crystallinity ofLi30.55P10.11S4 is becoming weaker. Interestingly, with. 4. Time dependence of DC conductivity for the sample 3Li4SiS40.3La2S3er applying a constant DC voltage of 1 V at room temperature.</p></li><li><p>Fig. 6. X-ray diffraction patterns for the samples 2.25Li30.55P10.11S4yLa2S3.</p><p>Fig. 7. Temperature dependences of the electrical conductivities for thesamples 2.25Li30.55P10.11S42yLaS2.</p><p>Fig. 8. Cyclic voltammogram of the sample 2.25Li30.55P10.11S40.2LaS2at room temperature with scanning rate of 10 mV s1.</p><p>Fig. 5. Cyclic voltammogram of the sample 3Li4SiS40.3La2S3 at roomtemperature with scanning rate of 10 mV s1.</p><p>Z. Liu et al. / Ceramics International 40 (2014) 154971550115500increasing y up to 0.5, new peaks of LaS2 come up graduallyrather than the originally added La2S3. The conversion ofLa2S3 to LaS2 should be resulted from the high vapor pressureof P2S5 [1,22]. Consequently, the final products should be acomposite in the form of poor-crystallized Li30.55P10.11S4and well-crystallized LaS2 (2.25Li30.55P10.11S42yLaS2).</p><p>The conductivities and the corresponding activity energiesof 2.25Li30.55P10.11S42yLaS2 were also measured by ACimpedance spectroscopy. The temperature dependences ofconductivities are shown in Fig. 7. Just as the former studiedLi4SiS4xLa2S3 system, the plots of log(T) against 103/Tindicate that the conductivities of these composite samples inthe temperature range from 30 to 210 1C also follow theArrhenius equation. The reported data for Li30.55P10.11S4 isalso displayed in Fig. 7 as reference. It can be seen that for thesample with y0 at 30 1C, both of the conductivity,1.82 105 S cm1 and the activity energy, 0.43 eV aresimilar with the reported data. With LaS2 existed, theconductivity of 2.25Li30.55P10.11S42yLaS2 reached amaximum value of 7.41 105 S cm1 at y0.1. Then theconductivity decreased gradually with the increase of LaS2 dueto its insulating nature.The DC conductivity was studied on 2.25Li30.55P10.11S40.2LaS2. As shown in Fig. 4, the DC conductivitieswith nonblocking or blocking electrodes were measured to be6.07 105 or 3.40 108 S cm1, respectively. Therefore, theelectronic conduction in the total conductivity is almost negli-gible. And the o...</p></li></ul>

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