Polyhedral oligomeric silsesquioxane containing gel polymer electrolyte based on a PMMA matrix

Abstract

The present research is based on two expectations: a polyhedral oligomeric silsesquioxane (POSS) nano-cage can endow gel polymer electrolyte (GPE) with similar properties as can be accomplished with other inorganic nanoparticles; and the organic substituents at the cage corners of POSS are more compatible with GPEs. Therefore, POSS, as a hybrid modification filler, was added into GPE within a polymethyl methacrylate (PMMA) matrix. The results indicated that the amount of POSS addition was a critical factor for the ionic conductivity of prepared GPEs. When the POSS content was 7.5 wt%, the thermal stability was sufficient at the elevated temperature; the ionic conductivity of GPE reached 2.0 × 10⁻³ S cm⁻¹; the mechanism of conductivity followed typical Arrhenius behavior; the lithium ion transference number reached up to 0.33; the deposition/dissolution of lithium was highly reversible; the electrochemical stability window was high enough at 5.25 V and the compatibility with lithium electrolyte was satisfactory.

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1. Introduction

Lithium ion batteries (LIBs) have attracted considerable attention in the last decade for their wide application in digital devices and vehicles.^1–6 At present, the electrolyte commonly used in LIBs is a liquid electrolyte that has its own advantages such as low cost, high ionic conductivity and better compatibility with electrodes.⁷ However, it also has some shortcomings such as liquid leakage, flammability and explosiveness,⁸ which compels many researchers to develop novel electrolytes to improve application performance in batteries.^9–15 Gel polymer electrolyte (GPE) is one type of potential electrolyte and provides high ionic conductivity, better compatibility with electrodes, free shape flexibility and safety.^16–23 GPE is considered the optimal electrolyte and the key to further improve properties of LIBs. But there still exists one fatal problem for GPE: increased mechanical stability and better membrane self-standing are usually are based on the sacrifice of ionic conductivity. Therefore, considerable research has to be carried out to improve the comprehensive properties of GPE while questing to achieve these following basic requirements at the same time:^24–27 (i) ionic conductivity higher than 10⁻⁴ S cm⁻¹ at room temperature, (ii) good thermal stability, (iii) adequate electrochemical properties, (iv) suitably high mechanical strength, (v) and the self-standing property. Many effective methods and research directions have been adopted to accomplish the targeted goal. The most outstanding advance in this field has been the incorporation of inorganic nanoparticle fillers into GPE.^28–35 The obtained results reveal that inorganic nano-particle fillers usually improve GPE performances through the following micro-effects: the capillary action produced by nano-particles can tightly capture the plasticizer in GPE and evidently increase ionic conductivity and electrochemical stability of GPE;³⁶ the Lewis acid and base action existing between nanoparticles and the lithium salt in GPE can promote the extent of lithium salt dissociation and enhance the conductivity;³⁷ the tremendous surface area of nanoparticles endows GPE with improved mechanical strength and leads to easier membrane formation.³⁸ However, the high surface energy from the large surface area of all inorganic nanoparticles usually leads to particle agglomeration, which negates any benefits obtained from nano-particles.³⁹ In order to overcome the aforementioned drawback and at the same time retain all advantages of nano-particles, a facile and efficient route to incorporate an organic–inorganic hybrid particle of polyhedral oligomeric silsesquioxane (POSS) into GPE is presented here.

The POSS nanoparticle is a class of discrete, 3-dimensional, polycyclic compound and has received widespread interest due to their cage-like molecular structure. The empirical formula of POSS is (RSiO_1.5)_n, where ‘n’ is an integer that can be 8, 10 or 12 and R can be a variety of organic substituents.⁴⁰ The POSS nano-cage is surrounded by eight organic groups and is highly soluble in organic/inorganic materials.^41,42 The POSS nano-cage can endow GPE with similar modification that inorganic nanoparticles have achieved. Simultaneously, the organic substituents at the cage corners of POSS make it hydrophobic and more compatible with GPE when compared with other inorganic nanoparticles.

To date, related publications about POSS modified GPE have not been reported. The present work is the first to introduce a POSS containing GPE based on a polymethyl methacrylate (PMMA) matrix in the field of electrolytes used in LIBs. The following objectives were targeted: synthesize and characterize a POSS particle from vinyl trismethoxy silane (VTMS); prepare a POSS modified GPE with PMMA, a propylene carbonate (PC) plasticizer, and lithium perchlorate (LiClO₄) and investigate the comprehensive performance of the GPE obtained. In this research, we report a preliminary study demonstrating the feasibility of POSS modified GPE.

2. Experimental

2.1. Materials

Polymethyl methacrylate (PMMA) with an average molecular weight in the range of 10⁵ g mol⁻¹, ethyl acetate (EA, AR), hydrochloric acid (AR), anhydrous lithium perchlorate (LiClO₄, AR), and propylene carbonate (PC, AR) were obtained from Chengdu Kelong Company. Vinyl trismethoxy silane (VTMS, CP) was obtained from Nanjing UP Chemical.

2.2. Synthesis of POSS

200 mL EA and 20 mL VTMS were mixed in a 3 neck glass reactor equipped with a reflux condenser, an addition funnel and a mechanical stirrer under stirring at room temperature for 10 min. A solution containing 30 mL HCl and 70 mL deionized water was added dropwise through the addition funnel into the glass reactor within 30 min. The reaction was carried out under vigorous stirring for 4 days. The reaction solution was filtrated and the solid white product was recrystallized from acetone. Scheme 1 presents the synthesis reaction.

Scheme 1 The synthesis reaction of POSS.

2.3. Preparation of GPE films

PMMA (1.000, 0.990, 0.975, 0.950, 0.925 or 0.900 g) was dissolved in acetone at 70 °C in a sealed glass cup for about 1 hour, and then a certain corresponding amount of POSS (0.000, 0.010, 0.025, 0.050, 0.075 or 0.100 g) was dispersed in the resulting mixture for 2 hours under the same temperature. The resulting solution was cast onto a PTFE plate to allow acetone to evaporate slowly at room temperature. Two days later, this procedure yielded a mechanically stable and free standing transparent dry film of uniform thickness. Liquid electrolyte was prepared by dissolving LiClO₄ in plasticizer PC to obtain a 1 mol L⁻¹ solution. The dry film was then immersed into this liquid electrolyte to soak the plasticizer. The final plasticizer saturated film was the expected GPE. Table 1 lists the prepared GPEs with different POSS amounts.

Table 1 The GPEs with different POSS content

GPE	GPE-0	GPE-1	GPE-2.5	GPE-5	GPE-7.5	GPE-10
POSS/g	0.000	0.010	0.025	0.050	0.075	0.100
PMMA/g	1.000	0.990	0.975	0.950	0.925	0.900

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The liquid electrolyte uptake (A) of a membrane is determined by immersing it in a liquid electrolyte for enough time and is calculated by eqn (1):

where W₁ is the mass of dry membrane and W₂ is the mass of the wet membrane.

2.4. Characterization

The composition and structure of POSS was characterized by Fourier transform infrared spectroscopy (FTIR) (Perkin Elmer Spectrum 2000 series spectrometer) in the range of 4000–400 cm⁻¹ with a nominal resolution of 2 cm⁻¹. The Spectrum 2000 spectrometer was equipped with a DGTS detector and a Perkin Elmer MIR-IR source and used a conventional short-pathway IR gas cell (Wilmad) (New Jersey, USA), 10 cm path length and 60 mL internal volume, and equipped with 32 mm × 2 mm circular SeZn windows. The sample of POSS was mixed with potassium bromide (KBr) in a ratio of 1 : 100 and was ground into fine particles using an agate mortar and pestle prior to FTIR analysis. The sample was transferred into a micro-quartz tube for extensive drying. The resulting powder was compressed into a thin disk using a pelletizer under 100 kg cm⁻² of pressure for 2 min.

Differential scanning calorimetry (DSC) was conducted using a METTLER TOLEDO Star DSC 822^e model equipped with an automatic sampler (TSO801RO) in sealed Al pans (40 mL) with a dry air flow rate of 20 mL min⁻¹ to survey the thermal properties of POSS and GPEs in air at a heating rate of 10 °C min⁻¹; the error of temperature measurement was 0.2 K. Thermogravimetric analysis (TGA) was conducted using a METTLER TOLEDO TGA/SDTA851^e/LF/1100 °C equipped with an automatic sampler (TSO801RO) and METTLER TOLEDO Scale (MT5) with a heating rate of 10 °C min⁻¹ under air.

X-ray diffraction (XRD) patterns were obtained by a Rigaku miniflex diffractometer (CuKα radiation source, λ = 0.154 nm) at a generator voltage of 40 kV and a current of 40 mA at room temperature.

The ionic conductivity of GPE was characterized by electrochemical impedance spectra (EIS) measurements (CHI-660D electrochemical work station, Shanghai CH Instruments Co., China) in an ordinary cell composed of a Teflon tube with two identical stainless steel electrodes (diameter = 1 cm). The frequency range of the signal was from 0.1 Hz to 100 kHz, and the amplitude of the alternative signal was 10 mV. The GPE was sandwiched between two stainless steel (SS) rectangles (length of a side = 1 cm). The ionic conductivity measurement of GPE was obtained from the complex EIS curve according to eqn (2).

where L (cm) is the thickness of GPE, R_b (Ω) is the electrolyte bulk resistance and S (cm²) is the contact area between GPE and SS square.

The lithium ion transference number was measured using a symmetric cell of Li/GPE/Li by the DC polarization method combined with the EIS method. It can be obtained according to the following equation:⁴³

where I₀ and I_s are the initial and steady current, respectively; R₀ and R_s are the initial interfacial and steady-state resistance, respectively; ΔV is the DC voltage applied.

The electrochemical stability test (cyclic voltammetry) was conducted in a Li/GPE/SS cell using the CHI-660D instrument in the voltage range of −1.0–5.0 V at a scan rate of 5.0 mV s⁻¹. The oxidative stability of GPE was determined using the electrochemical instrument (CHI-660D) by linear sweep voltammetry (LSV) using the Li/GPE/SS cell, in which the SS was used as the working electrode and lithium was used as both the reference and counter electrodes. The scanning rate was 5.0 mV s⁻¹ over the range of 3.0–6.0 V at room temperature.

Time dependent interfacial resistance (R_i) between the lithium electrode and GPE was evaluated by monitoring the complex impedance response in the Li/GPE/Li cell over a period of 28 days at room temperature. The test was conducted using the CHI-660D instrument in the frequency range from 0.1 Hz to 100 kHz and with an amplitude of 10.0 mV.

3. Results and discussion

3.1. POSS characterization

3.1.1. FTIR spectrum analysis. Fig. 1 presents the POSS FTIR spectrum. From Fig. 1, the characteristic peaks of POSS are at 1621 cm⁻¹ for the C=C bond and at 1115 cm⁻¹ for the symmetric stretching vibrations of the siloxane (Si–O–Si) group and are the characteristic absorption peaks for silsesquioxane cages.^44,45 The peak at 778 cm⁻¹ is the stretching vibration of the Si–C–H functional group,⁴⁶ and the absorption peaks of the Si–C=CH₂ bending vibration are at 1411 cm⁻¹, 973 cm⁻¹, 1279 cm⁻¹ and 1007 cm⁻¹. Therefore, it can be concluded that POSS was successfully synthesized.

Fig. 1 FTIR spectrum of POSS.

3.1.2. XRD analysis. From Fig. 2, it can be observed that the POSS is a highly crystalline material and has characteristic dominant diffraction peaks at 19.1°, 20.9°, 22.5°, 23.3°, 27.9°, 29.2° and 30.5°.

Fig. 2 XRD spectrum of POSS.

3.1.3. Thermal analysis. The thermal stability of POSS was examined by TGA, as shown in Fig. 3(a). The thermal degradation curve displays decomposition starting at 250 °C. The decomposition behavior between 250 °C and 500 °C shows a two-step mass loss process: the first stage of degradation from 250 °C to 320 °C with the sharp mass loss should be assigned to the decomposition of the alkyl side chains on the corners of the POSS cage; the second stage from 320 °C to 500 °C with the little and slow mass loss should be ascribed to the disintegration of the POSS cage. In addition, it can be observed that during thermal degradation, the residual mass percent was always comparatively high, and even at temperatures beyond 500 °C the residual mass percent was still high (68.8 wt%). This can be attributed to three reasons: first, POSS contains a large number of high energy bonds such as Si–O bonds and Si–C bonds that endows POSS with excellent thermal stability; second, the cage inorganic structure of POSS is relatively stable and difficult to collapse; third, in POSS the inorganic component content of silicon becomes solid SiO₂ during the TGA test and is massive.

Fig. 3 (a) TGA and (b) DSC curves of POSS.

Fig. 3(b) shows the DSC profile for the synthesized POSS and there are three characteristic peaks. The endothermic peak at the lower temperature of 121 °C is indicative of organic phase chain movement. Therefore, 121 °C should be the glass transition temperature (T_g) of organic phase formed by the large number of alkyl groups at the corners of the POSS cage structure. At 213 °C, a slight broad endothermic peak is present and indicative of crystalline melting processes, and 213 °C should be the melting temperature (T_m) of POSS. The very strong exothermic peak at 300 °C corresponds to the degradation of POSS, which has been proved from the TGA.

3.2. GPE performances

3.2.1. Thermal stability of GPE. The thermal stability of GPE was examined by TGA and the results are presented in Fig. 4(a). For all of the GPEs, the trends for thermal decomposition are similar. Considering the application temperature of lithium ion batteries, the temperature of 100 °C is comparatively enough. From the enlarged inset, as the temperature reaches 100 °C, a mass loss resulted from the volatilization of the plasticizer (PC) in GPE and is very small (less than 5 wt%). Therefore, it can be concluded that all of the prepared GPEs are thermally stable. However, there is one very evident influence of the amount of POSS addition on thermal stability. Comparing all of the GPEs, the lowest mass loss was observed from GPE-0. This can be explained by the capillary action produced by POSS containing GPEs as they can adsorb higher amounts of the liquid electrolyte,³⁶ which will be proved in the discussion of ionic conductivity. When temperature increases, these GPEs release more plasticizer of PC. For the five modified GPEs, there is an optimum amount of POSS addition and it appears that GPE-5 and GPE-7.5 have better thermal stability. In addition, all GPEs appear massive and quick mass losses occur at 225 °C and around 300 °C, respectively. Therefore, the POSS containing GPEs have sufficient thermal stability, even at elevated temperatures.

Fig. 4 (a) TGA and (b) DSC curves of GPEs.

DSC was used to measure GPE for further application towards LIB applications. The DSC curves of GPE are shown in Fig. 4(b). Before 100 °C, the vertical fluctuation range of DSC curves is very weak, which is evidence for the non-existence of any evident endothermic peak. This is further proof that the five types of POSS containing GPE systems are stable in the temperature range from 30 °C to 100 °C and satisfy the upper temperature requirements for actual production applications.

The TGA and DSC analysis demonstrate that the obtained membranes can withstand temperatures of up to 100 °C without undergoing thermal decomposition and meet the practical application requirements of for flexible lithium ion batteries.

3.2.2. Ionic conductivity. EIS was carried out on the SS/GPE/SS cell to determine the ionic conductivity. Fig. 5 presents the Nyquist plots of electrochemical impedance at room temperature and depicts the experimentally obtained ionic conductivities of GPEs as a function of POSS addition content. It can be seen from Table 2 that the ionic conductivity is increased from GPE-0 to GPE-7.5 as the POSS filling amount increased. Then, the ionic conductivity of GPE-10 decreases as POSS content further increases. Thus, the maximum ionic conductivity is obtained by GPE-7.5. For GPE membranes, the liquid electrolyte uptake is usually one of the most important factors to improve ionic conductivity. The reason is that the more amount of plasticizer endows the charge carriers of lithium ions in GPE with the easier movement ability. Although the uptake of liquid electrolyte for GPE-10 is maximized, the POSS in GPE maintains a crystalline structure and is not good for ionic conductivity, which is evident in the discussion of XRD analysis of GPEs.

Fig. 5 EIS spectra of GPEs.

Table 2 The uptake value and ionic conductivity of GPEs

Samples	Uptake A (wt%)	Ionic conductivity (×10^−4 S cm^−1)
GPE-0	61	2.7
GPE-1	100	3.5
GPE-2.5	104	9.5
GPE-5	108	10.9
GPE-7.5	120	13.3
GPE-10	126	10.1

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It can also be seen from the inset of Fig. 5 that the imaginary part of the impedance curve is almost linearly related to its real counterpart and the imaginary part increases more quickly than the real part as the frequency becomes lower, which demonstrates the equivalent characteristics of a resistor and a capacitor in series, corresponding to the resistance of the polymer electrolyte and the double capacitance of the cell in this case.

3.2.3. The relationship between ionic conductivity and temperature. The relationship between temperature and ionic conductivity is used to analyze the mechanism of ionic conduction in the six types of GPE membrane between the temperature ranges from 30 °C to 55 °C, which are shown in Fig. 6. From (a) to (f), the electrolyte bulk resistance R_b (Ω) continuously decreases with temperature, which means the ionic conductivity is increased correspondingly. In GPE systems, the ionic conductivity of all samples increase with rises in temperature. This well-known phenomenon results from faster ion movement when the temperature increases and as a consequence leads to higher ionic conductivity. In addition, the movements of the polymer chains are the driving force of the current carriers of lithium ion, and the higher temperature endows the polymer chain with more flexibility and enhances segmental mobility, which undoubtedly and ultimately is beneficial for improving ionic conductivity. The ionic conductivity is determined by the Arrhenius equation⁴⁷ and can be written as follows:

σ = A exp(−E_a/κT) (4)

where σ is the ionic conductivity; A is the pre-exponential factor; E_a is the activation energy; κ is the Boltzmann constant and T is the absolute temperature.

Fig. 6 EIS of (a) GPE-0, (b) GPE-1, (c) GPE-2.5, (d) GPE-5, (e) GPE-7.5 and (f) GPE-7.5 at different temperatures.

The dependence of ionic conductivity on temperature is shown in Fig. 7. From (a) to (f), the corresponding linear relationship between lg σ and 1/T follows typical Arrhenius behavior.

Fig. 7 The dependence of ionic conductivity of (a) GPE-0, (b) GPE-1, (c) GPE-2.5, (d) GPE-5, (e) GPE-7.5 and (f) GPE-10 on temperature.

Considering the ionic conductivity and self-standing property of GPE-7.5, it was chosen for further investigation.

3.2.4. XRD analysis. XRD patterns of GPE membranes with different POSS/PMMA ratios are shown in Fig. 8. The XRD spectrum of lithium salt indicates LiClO₄ is crystalline; however, in the XRD curves of all GPEs, there are no evident peaks indicative of LiClO₄, which means LiClO₄ is completely dissociated. This type of dissociation produces the charge carriers of lithium ions in GPE. The pure PMMA XRD curve shows two evident peaks, which hints that the purchased PMMA is a type of crystalline polymer and must have been synthesized by isotactic polymerization. From GPE-1 to GPE-7.5, there are very weak peaks of POSS in the XRD patterns, indicating that the crystallinity of POSS was almost destroyed. In contrast, there are evident peaks in the GPE-10 XRD pattern, which means that POSS exists in a crystalline form. Combining the abovementioned investigations of liquid electrolyte uptakes and ionic conductivity of GPEs with different POSS addition amount, it can be concluded that whether the POSS is still crystalline and its modification effects on the GPE stays intact. For example, with increasing amount of POSS, the liquid electrolyte uptake is enhanced. However, when POSS addition amount is high (up to 10 wt%), the crystallinity obtained is not favorable for the movement of lithium ions and leads to decreases in the ionic conductivity. In addition, compared to GPE-1 and GPE-2.5, GPE-5 shows a little more crystalline structure and higher ionic conductivity. This can be explained as follows: when added POSS content is low, the ionic conductivity is mainly determined by the liquid electrolyte uptake, and the uptake value of GPE-5 is the highest in these three GPE systems.

Fig. 8 XRD spectra of LiClO₄, PMMA, POSS, GPE-1, GPE-2.5, GPE-5, GPE-7.5 and GPE-10.

3.2.5. Transference number. The lithium ion transference number, t_Li⁺, is an important parameter for lithium ion batteries. The t_Li⁺ of GPE-7.5 was calculated to be 0.33 (Fig. 9), which is considerably higher than or near to that of many commercial separators and GPEs reported in ref. 48 and 49.

Fig. 9 Impedance spectra of the Li/GPE/Li cell measured before and after polarization.

3.2.6. Electrochemical stability. As a prerequisite and important step to characterize electrochemical performance of GPE, its electrochemical stability is elucidated by cyclic voltammogram (CV), as shown in Fig. 10. A pair of cathodic and anodic peaks appeared at around 0 V, corresponding to lithium redox processes.⁵⁰ On scanning the electrode in the negative direction, a cathodic peak is observed at about −0.35 V, which corresponds to the plating of lithium onto the stainless steel electrode. Reversing the scanning direction, the stripping of lithium is observed at about 0.30 V. In addition, the voltammograms ascribed to lithium deposition/dissolution is highly reversible, because the peak currents retain fairly considerable symmetry.⁵¹ This type of high reversibility is favorable for the application of GPE in lithium ion batteries.

Fig. 10 Cyclic voltammogram of the Li/GPE/SS cell.

3.2.7. Electrochemical stability window. For practical battery applications, the electrochemical stability of electrolyte within the operation voltage of the battery system is very important. Linear sweep voltammetry (LSV) has been used in this study to investigate the electrochemical stability window (ESW).⁵² The electrochemical stability of GPE was evaluated by LSV measurements, as shown in Fig. 11. The current flow appears flat when the voltage is below 5.25 V (vs. Li/Li⁺). The current onset at 5.25 V in the anodic voltage range results from a decomposition process associated with the electrolyte and such an onset voltage is considered as the upper limit of the electrolyte stability range. This can be assigned to the electrochemical decomposition voltages of GPE-7.5 and is a key parameter for lithium ion batteries with high working voltages. Therefore, GPE-7.5 has the electrochemical stability suitable for allowing the use of high-voltage electrode materials.

Fig. 11 Linear sweep voltammogram of the Li/GPE/SS cell.

3.2.8. Compatibility with anode. The compatibility of GPE with a lithium anode is very important for safety and cycle performance when an electrolyte is considered for application in lithium ion batteries, which can be evaluated by the interfacial resistance between a lithium metal electrode and GPE.⁵³ The interfacial resistance is related to the passive layer and the charge transfer resistances on the lithium metal electrode.^38,54 The EIS plots for the Li/GPE-7.5/Li symmetric cell over different storage times are demonstrated in Fig. 12, which can clearly and directly reflect the compatibility between GPE and a lithium anode.^23,55 Combined with the amplified figure, all plots include two semicircular curves. The first high-frequency trough is associated with ion transport resistance (R_p) in the passive layer formed on the lithium electrode surface through the chemical reaction between lithium and PC. The second semicircle at low frequencies is associated with charge transfer resistance (R_ct) of the Li⁺ + e⁻ ↔ Li reaction. The summation of these two types of resistance is the interfacial resistance (R_i) of the electrode/electrolyte. For all EIS plots, both parts of semicircles are present. Examining the entire change trend, the interfacial resistance of the symmetrical Li/GPE-7.5/Li cell, as shown in Fig. 12, decreases from day 1 to day 28. However, it is known that R_p must increase because the thickness and structure of the formed passive layer changes with storage time. Here, it can be concluded that R_ct decreases with a larger magnitude. The tremendous decrease of R_ct within 28 days is due to the activation of the lithium electrode surface through the iterative process of Li⁺ + e⁻ ↔ Li reaction during the electrochemical impedance test. Therefore, GPE-7.5 shows wonderful compatibility with the lithium anode.

Fig. 12 Electrochemical impedance spectra of Li/GPE/Li cell.

4. Conclusion

The suitability of the membrane of POSS containing GPE with PMMA as host matrix for lithium ion battery applications was explored. The amount of POSS addition was a key influencing factor for GPE performance. These performances of ionic conductivity, thermal stability, lithium ion transference number, electrochemical stability window and compatibility with lithium metal electrode of GPE-7.5 evidently indicate that it can be used in lithium ion batteries as one type of potential electrolyte candidate.

Acknowledgements

The authors gratefully acknowledge the financial support from the Key Fund Project of Sichuan Provincial Department of Education (15ZA0050), Open Fund for the Oil and Gas Materials Key Laboratory of Higher Education of Sichuan Province (x151514kc104) and the Innovative Research Team of Sichuan Provincial Department of Education (14TD0005).

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