JP2019197649A - Nonaqueous electrolyte - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a non-aqueous electrolytic solution containing an ionic liquid, which is capable of improving input / output characteristics. A nonaqueous electrolytic solution disclosed herein contains a solvent component containing a difluoroacetic acid ester and an ionic liquid, and a lithium imide salt as a supporting salt. The ionic liquid is composed of a quaternary ammonium organic cation and an N (SO2F) 2 anion. The amount of the ionic liquid in the solvent component is 5% by volume or more and 20% by volume or less. The concentration of the lithium imide salt in the non-aqueous electrolyte is 1.5 mol / L or more and 2.5 mol / L or less. [Selection diagram] None

Description

  The present invention relates to a non-aqueous electrolyte solution.

  In recent years, non-aqueous secondary batteries such as lithium secondary batteries are portable power sources for personal computers, portable terminals, etc., and power sources for driving vehicles such as electric vehicles (EV), hybrid vehicles (HV), and plug-in hybrid vehicles (PHV). It is suitably used as a power storage power source.

  Non-aqueous electrolytes are used for non-aqueous secondary batteries such as lithium secondary batteries. With the spread of non-aqueous secondary batteries such as lithium secondary batteries, higher performance is desired. One of the measures for improving the performance is to improve the non-aqueous electrolyte. Specifically, for example, Patent Documents 1 and 2 propose that a non-aqueous electrolyte contains an ionic liquid. The organic solvent generally used for non-aqueous electrolytes is flammable, but the ionic liquid is a flame-retardant liquid. By using a non-aqueous electrolyte containing an ionic liquid, a non-aqueous secondary battery is used. Can improve the safety.

JP, 2015-026608, A JP 2009-070636 A

  However, as a result of intensive studies by the present inventors, it has been found that when the non-aqueous electrolyte containing the ionic liquid is used for a non-aqueous secondary battery, the input / output characteristics are insufficient.

  Accordingly, an object of the present invention is to provide a nonaqueous electrolytic solution containing an ionic liquid, which can improve input / output characteristics.

The non-aqueous electrolyte solution disclosed here contains a difluoroacetate ester, a solvent component containing an ionic liquid, and a lithium imide salt as a supporting salt. The ionic liquid is composed of a quaternary ammonium organic cation and an N (SO ₂ F) ₂ anion. The amount of the ionic liquid in the solvent component is 5% by volume or more and 20% by volume or less. The concentration of the lithium imide salt in the non-aqueous electrolyte is 1.5 mol / L or more and 2.5 mol / L or less.
According to such a configuration, it is possible to provide a non-aqueous electrolyte that can improve input / output characteristics.

It is sectional drawing which shows typically the internal structure of the lithium secondary battery using the non-aqueous electrolyte solution which concerns on one Embodiment of this invention. It is a schematic diagram which shows the structure of the winding electrode body of the lithium secondary battery of FIG.

  Embodiments according to the present invention will be described below. Note that matters other than the matters specifically mentioned in the present specification and necessary for the implementation of the present invention (for example, a general configuration and manufacturing process of a non-aqueous electrolyte that does not characterize the present invention) are as follows: It can be grasped as a design matter of a person skilled in the art based on the prior art in the field. The present invention can be carried out based on the contents disclosed in this specification and common technical knowledge in the field.

In the present specification, the “secondary battery” refers to a general power storage device that can be repeatedly charged and discharged, and is a term including a power storage element such as a so-called storage battery and an electric double layer capacitor.
Further, in the present specification, the “lithium secondary battery” refers to a secondary battery that uses lithium ions as a charge carrier and is charged and discharged by movement of charges accompanying the lithium ions between the positive and negative electrodes.

The nonaqueous electrolytic solution according to the present embodiment contains a difluoroacetic acid ester, a solvent component containing an ionic liquid, and a lithium imide salt as a supporting salt. Here, the ionic liquid is composed of a quaternary ammonium organic cation and an N (SO ₂ F) ₂ anion. The amount of the ionic liquid in the solvent component is 5% by volume or more and 20% by volume or less. The concentration of the lithium imide salt in the non-aqueous electrolyte is 1.5 mol / L or more and 2.5 mol / L or less.

  Examples of the difluoroacetic acid ester used as the solvent component of the non-aqueous electrolyte solution according to this embodiment include methyl difluoroacetate, ethyl difluoroacetate, propyl difluoroacetate, butyl difluoroacetate and the like. Of these, methyl difluoroacetate or ethyl difluoroacetate is preferable.

The ionic liquid used as the solvent component of the non-aqueous electrolyte solution according to this embodiment is a component that imparts conductivity to the electrolyte solution. Moreover, since the ionic liquid is a flame retardant solvent, the safety of the lithium secondary battery using the electrolytic solution according to the present embodiment can be improved.
The ionic liquid contains a quaternary ammonium organic cation as a cation. Since the potential stability is high, the cation of the ionic liquid is preferably a saturated aliphatic cyclic quaternary ammonium organic cation. Examples of saturated aliphatic cyclic quaternary ammonium organic cation include N, N-dimethylpyrrolidinium cation, N-ethyl-N-methylpyrrolidinium cation, N-methyl-N-propylpyrrolidinium cation, N- Examples include butyl-N-methylpyrrolidinium cation, N-methyl-N-pentylpyrrolidinium cation, N-hexyl-N-methylpyrrolidinium cation, and N-methyl-N-octylpyrrolidinium cation. Among them, from N, N-dimethylpyrrolidinium cation, N-ethyl-N-methylpyrrolidinium cation, N-methyl-N-propylpyrrolidinium cation, and N-butyl-N-methylpyrrolidinium cation It is preferably at least one selected from the group consisting of
The ionic liquid contains an N (SO ₂ F) ₂ anion (that is, bis (fluorosulfonyl) imide anion: N (SO ₂ F) ₂ ⁻ ) as an anion.

  The solvent component of the non-aqueous electrolyte solution according to this embodiment may contain a solvent (for example, carbonates) other than difluoroacetate ester and ionic liquid within a range that does not significantly impair the effects of the present invention.

  The amount of the ionic liquid in the solvent component is 5% by volume or more and 20% by volume or less. If the amount of the ionic liquid is out of this range, the effect of improving input / output characteristics cannot be obtained. The amount of the ionic liquid in the solvent component is preferably 5% by volume to 15% by volume, more preferably 5% by volume to 10% by volume.

  Examples of the lithium imide salt used as the supporting salt of the non-aqueous electrolyte solution according to the present embodiment include lithium bis (fluorosulfonyl) imide (LiFSI), lithium bis (trifluoromethane) sulfonimide (LiTFSI), and the like. Lithium bis (fluorosulfonyl) imide is preferred.

  The concentration of the lithium imide salt in the non-aqueous electrolyte solution according to this embodiment is 1.5 mol / L or more and 2.5 mol / L or less. If the concentration of the lithium imide salt is out of this range, the input / output improvement effect cannot be obtained. The concentration of the lithium imide salt is preferably 1.7 mol / L or more and 2.3 mol / L or less, more preferably 1.85 mol / L or more and 2.15 mol / L or less.

  The non-aqueous electrolyte solution according to the present embodiment may contain other components within a range that does not significantly impair the effects of the present invention. For example, the nonaqueous electrolytic solution according to the present embodiment contains an unsaturated carboxylic anhydride compound represented by the following formula (1) as an additive (hereinafter also referred to as “unsaturated carboxylic anhydride compound (1)”). You may do it. When the non-aqueous electrolyte solution according to this embodiment contains the unsaturated carboxylic anhydride compound (1), the high-temperature cycle characteristics of a battery using the non-aqueous electrolyte solution are improved.

In formula (1), R ₁ and R ₂ are each independently a hydrogen atom, a fluorine atom, an aryl group, or an optionally substituted alkyl group, or R ₁ and R ₂ are bonded to each other, Form a ring structure.

Regarding Formula (1), the number of carbon atoms of the alkyl group optionally substituted by fluorine represented by R ₁ and R ₂ is preferably 1 to 3.
Examples of the aryl group represented by R ₁ and R ₂ include a phenyl group and a naphthyl group.
When R ₁ and R ₂ are bonded to form a ring structure, examples of the ring structure include an aromatic ring, and examples thereof include a benzene ring, a naphthalene ring, a pyridine ring, a furan ring, and a thiophene ring. Can be mentioned.
R ₁ and R ₂ are preferably a hydrogen atom, a methyl group, or a phenyl group, and more preferably a hydrogen atom. More specifically, the unsaturated carboxylic acid anhydride compound (1) is preferably maleic anhydride (R ₁ = H, R ₂ = H), citraconic anhydride (R ₁ = H, R ₂ = CH ₃ ). , Phenylmaleic anhydride (R ₁ = H, R ₂ = phenyl group), more preferably maleic anhydride.

  If the concentration of the unsaturated carboxylic anhydride compound (1) in the non-aqueous electrolyte solution according to this embodiment is too small, the effect of improving the high-temperature cycle characteristics cannot be sufficiently obtained. On the other hand, if the concentration of the unsaturated carboxylic anhydride compound (1) is too large, the effect of improving the input / output characteristics is adversely affected. Therefore, the concentration of the unsaturated carboxylic anhydride compound (1) is preferably 0.05% by mass or more and less than 5% by mass, more preferably 0.1% by mass or more and 3% by mass or less, and further preferably 0%. It is 5 mass% or more and 2 mass% or less.

  Examples of other components that may be contained in the nonaqueous electrolytic solution according to the present embodiment include gas generating agents such as biphenyl (BP) and cyclohexylbenzene (CHB); dispersants; thickeners and the like. Can be mentioned.

  By using the non-aqueous electrolyte solution according to the present embodiment for a non-aqueous secondary battery (particularly a lithium secondary battery), the input / output characteristics of the secondary battery can be enhanced. In addition, the high-temperature cycle characteristics of the secondary battery can be improved.

The non-aqueous electrolyte solution according to the present embodiment can be used for a non-aqueous secondary battery (particularly, a lithium secondary battery) according to a known method.
Thus, as an example, an outline of a configuration example of a lithium secondary battery using the nonaqueous electrolytic solution according to the present embodiment will be described below with reference to the drawings. In the following drawings, members / parts having the same action are described with the same reference numerals. In addition, the dimensional relationships (length, width, thickness, etc.) in each drawing do not reflect actual dimensional relationships.

  A lithium secondary battery 100 shown in FIG. 1 is a sealed battery constructed by accommodating a flat wound electrode body 20 and an electrolytic solution 80 in a flat rectangular battery case (that is, an exterior container) 30. is there. The battery case 30 is provided with a positive terminal 42 and a negative terminal 44 for external connection, and a thin safety valve 36 set so as to release the internal pressure when the internal pressure of the battery case 30 rises above a predetermined level. Yes. Further, the battery case 30 is provided with an inlet (not shown) for injecting the electrolytic solution 80. The positive terminal 42 is electrically connected to the positive current collector 42a. The negative electrode terminal 44 is electrically connected to the negative electrode current collector plate 44a. As the material of the battery case 30, for example, a light metal material having good thermal conductivity such as aluminum is used.

  As shown in FIGS. 1 and 2, the wound electrode body 20 has a positive electrode active material layer 54 formed along the longitudinal direction on one side or both sides (here, both sides) of an elongated positive electrode current collector 52. The positive electrode sheet 50 and the negative electrode sheet 60 in which the negative electrode active material layer 64 is formed along the longitudinal direction on one side or both sides (here, both sides) of the long negative electrode current collector 62 are two long shapes. The separator sheet 70 is overlapped and wound in the longitudinal direction. The positive electrode active material layer non-formed portion 52a (that is, the positive electrode active material) formed so as to protrude outward from both ends of the wound electrode body 20 in the winding axis direction (that is, the sheet width direction orthogonal to the longitudinal direction). The portion where the positive electrode current collector 52 is exposed without forming the material layer 54) and the negative electrode active material layer non-forming portion 62a (that is, the portion where the negative electrode current collector 62 is exposed without forming the negative electrode active material layer 64). The positive electrode current collector plate 42a and the negative electrode current collector plate 44a are joined to each other.

  As the positive electrode sheet 50 and the negative electrode sheet 60, the same ones used in conventional lithium secondary batteries can be used without particular limitation. One typical embodiment is shown below.

Examples of the positive electrode current collector 52 constituting the positive electrode sheet 50 include aluminum foil. Examples of the positive electrode active material included in the positive electrode active material layer 54 include lithium transition metal oxides (eg, LiNi _1/3 Co _1/3 Mn _1/3 O ₂ , LiNiO ₂ , LiCoO ₂ , LiFeO ₂ , LiMn ₂ O). ₄ , LiNi _0.5 Mn _1.5 O ₄ etc.), lithium transition metal phosphate compounds (eg, LiFePO ₄ etc.) and the like. The positive electrode active material layer 54 can include components other than the active material, such as a conductive material and a binder. As the conductive material, for example, carbon black such as acetylene black (AB) and other (eg, graphite) carbon materials can be suitably used. As the binder, for example, polyvinylidene fluoride (PVDF) can be used.

  Examples of the negative electrode current collector 62 constituting the negative electrode sheet 60 include copper foil. As the negative electrode active material contained in the negative electrode active material layer 64, for example, a carbon material such as graphite, hard carbon, or soft carbon can be used. Of these, graphite is preferable. The negative electrode active material layer 64 can include components other than the active material, such as a binder and a thickener. As the binder, for example, styrene butadiene rubber (SBR) can be used. As the thickener, for example, carboxymethyl cellulose (CMC) can be used.

As the separator 70, a porous sheet (film) made of polyolefin such as polyethylene (PE) or polypropylene (PP) is preferably used. Such a porous sheet may have a single-layer structure or a laminated structure of two or more layers (for example, a three-layer structure in which PP layers are laminated on both sides of a PE layer). A heat resistant layer (HRL) may be provided on the surface of the separator 70.
The air permeability obtained by the Gurley test method of the separator 70 is preferably 350 seconds / 100 cc or less.

  As the electrolytic solution 80, the non-aqueous electrolytic solution according to the above-described embodiment is used. FIG. 1 does not strictly indicate the amount of the electrolytic solution 80 injected into the battery case 30.

  The lithium secondary battery 100 configured as described above can be used for various applications. Suitable applications include driving power sources mounted on vehicles such as electric vehicles (EV), hybrid vehicles (HV), and plug-in hybrid vehicles (PHV). The lithium secondary battery 100 can also be used in the form of a battery pack typically formed by connecting a plurality of lithium secondary batteries 100 in series and / or in parallel.

  As an example, the prismatic lithium secondary battery 100 including the flat wound electrode body 20 has been described. However, the lithium secondary battery can also be configured as a lithium secondary battery including a stacked electrode body. The lithium secondary battery can also be configured as a cylindrical lithium secondary battery, a laminated lithium secondary battery, or the like. In addition, a non-aqueous secondary battery other than a lithium secondary battery can be constructed using the non-aqueous electrolyte solution according to the present embodiment.

  EXAMPLES Examples relating to the present invention will be described below, but the present invention is not intended to be limited to those shown in the examples.

<Preparation of electrolyte>
Solvents of the types shown in Table 1 were mixed at the volume ratio shown in Table 1. To this, the supporting salt described in Table 1 is dissolved at the concentration shown in Table 1, and when it is added, the additive described in Table 1 is dissolved at the concentration shown in Table 1 and the electrolytic solutions A1 to A10 and B1 to B13 were obtained.

Supporting salt LiFSI: lithium bis (fluorosulfonyl) imide LiPF ₆ : lithium hexafluorophosphate Organic solvent MDFA: methyl difluoroacetate EDFA: ethyl difluoroacetate EC: ethylene carbonate DMC: dimethyl carbonate EMC: ethyl methyl carbonate MTFP: 3, Methyl 3,3-trifluoropropionate ionic liquid: cation PYR13: N-methyl-N-propylpyrrolidinium PYR14: N-butyl-N-methylpyrrolidinium EMIm: 1-ethyl-3-methylimidazolium -Ionic liquid: Anion FSI: Bis (fluorosulfonyl) imide TFSI: Bis (trifluoromethanesulfonyl) imide- Additive MA: Maleic anhydride CA: Citraconic anhydride PMA: Phenylma Inn acid anhydride

<Preparation of lithium secondary battery for evaluation>
LiNi _1/3 Co _1/3 Mn _1/3 O ₂ (LNCM) as a positive electrode active material powder, acetylene black (AB) as a conductive material, and polyvinylidene fluoride (PVdF) as a binder are LNCM: A slurry for forming a positive electrode active material layer was prepared by mixing with N-methylpyrrolidone (NMP) at a mass ratio of AB: PVdF = 87: 10: 3. The slurry was applied to an aluminum foil and dried to prepare a positive electrode sheet.
As a negative electrode active material, natural graphite carbon material (C) having an average particle size of 20 μm, styrene butadiene rubber (SBR) as a binder, and carboxymethyl cellulose (CMC) as a thickener, C: SBR: CMC = The slurry for negative electrode active material layer formation was prepared by mixing with ion exchange water at a mass ratio of 98: 1: 1. The slurry was applied to a copper foil and dried to prepare a negative electrode sheet.
In addition, a polyolefin porous membrane having a three-layer structure of PP / PE / PP having an air permeability of 300 seconds / 100 cc obtained by the Gurley test method was prepared as a separator.
The produced positive electrode sheet and the negative electrode sheet were opposed to each other through a separator to produce an electrode body.
A current collector was attached to the produced electrode body, and it was housed in a laminate case together with the electrolyte and sealed. As the electrolytic solutions, electrolytic solutions A1 to A10 and B1 to B13 shown in Table 1 were used, respectively, and thus lithium secondary batteries for evaluation A1 to A10 and B1 to B13 were produced.

<Activation and initial characteristic evaluation>
Each of the prepared lithium secondary batteries for evaluation was placed in a constant temperature bath at 25 ° C. and charged for the first time. In the initial charging, each evaluation lithium secondary battery was charged with a constant current up to 4.10 V at a current value of 0.3C. Then, constant current discharge was performed to 3.0V with the current value of 0.3C.
Further, each evaluation lithium secondary battery was subjected to constant current-constant voltage charging (constant voltage charging until the current value reached 1/50 C after constant current charging to 4.10 V at a current value of 0.2 C). The battery was fully charged. Thereafter, constant current discharge was performed to 3.0 V at a current value of 0.2 C. The discharge capacity at this time was measured and used as the initial capacity.
In addition, assuming that the initial capacity is SOC 100%, each evaluation lithium secondary battery was charged in a constant temperature bath at 25 ° C. with a current value of 0.3 C until the depth of charge (SOC) reached 30%. Next, discharging was performed at a current value of 5C, 15C, 30C, and 45C for 10 seconds in a thermostatic bath at 25 ° C., and the battery voltage after discharging at each current value was measured. Each current value and each battery voltage were plotted to determine the IV characteristics during discharge, and the IV resistance (Ω) during discharge was determined as the initial resistance from the slope of the obtained straight line. The ratio of the initial resistances of the other evaluation lithium secondary batteries to the evaluation lithium secondary battery B1 when the initial resistance of the evaluation lithium secondary battery B1 was 1.00 was determined. The results are shown in Table 2.

<High temperature cycle characteristics evaluation>
Subsequently, each evaluation lithium secondary battery was placed in a constant temperature bath at 60 ° C. For each lithium secondary battery for evaluation, charging / discharging was repeated 200 cycles at a constant current charge of 2 C up to 4.1 V and a constant current discharge of 2 C up to 3.0 V. Thereafter, the discharge capacity was measured by the same method as described above, and the discharge capacity at this time was determined as the battery capacity after 200 cycles of charge and discharge. The capacity retention rate (%) was determined as (battery capacity after 200 cycles of charge / discharge / initial capacity) × 100. Further, the resistance was measured in the same manner as the initial resistance, and the rate of increase in resistance (%) was determined as {1- (battery resistance after 200 cycles of charge / discharge) / * 100. The results are shown in Table 2.

In the lithium secondary battery B1, an electrolytic solution B1 having a conventional general composition (that is, containing a mixed solvent of EC, DMC, and EMC as a solvent and LiPF ₆ as a supporting salt) was used.
As shown in the results of Table 2, the difluoroacetate ester, the solvent component containing the ionic liquid, and the lithium imide salt as the supporting salt are contained, and the ionic liquid contains the quaternary ammonium organic cation, N (SO ₂ F) ₂ anions, the amount of the ionic liquid in the solvent component is in the range of 5% by volume or more and 20% by volume or less, and the concentration of the lithium imide salt is 1.5 mol / L or more and 2.5 mol / L or less. The lithium secondary batteries A1 to A10 using the electrolytic solutions A1 to A10 within the range of the battery resistance were lower than those of the lithium secondary battery B1 using the electrolytic solution B1 having a conventional general composition. In addition, the lithium secondary batteries A1 to A10 had a capacity retention rate after 200 cycles of charge / discharge higher than that of the lithium secondary battery B1 and a low resistance increase rate. That is, the lithium secondary batteries A1 to A10 were superior in high-temperature cycle characteristics than the lithium secondary battery B1.

Lithium secondary batteries B2 to B4 are reference examples in which no ionic liquid is used as the solvent of the electrolytic solution. From these results, it can be seen that the addition of MA increases the initial resistance. It can also be seen that MDFA is a component that contributes to lowering the resistance. In addition, since electrolyte solution B2-B4 did not contain an ionic liquid, compared with lithium secondary battery electrolyte solution A1-A10, high temperature cycling characteristics were bad.
In the lithium secondary battery B5, although the electrolytic solution contains an ionic liquid, DMC was used as an organic solvent, so that the initial resistance was high and the high-temperature cycle characteristics were also poor.
In the lithium secondary battery B6, since the concentration of LiFSI in the supporting salt was as low as 1 mol / L, the initial resistance was high and the high-temperature cycle characteristics were also poor.
In the lithium secondary battery B7, the initial resistance was high because the volume ratio of the ionic liquid in the solvent component was as high as 30% by volume.
In the lithium secondary battery B8, since the concentration of the additive MA was as high as 5.0% by weight, the initial resistance was high. However, compared to the case where MA is added to an electrolytic solution having a conventional general composition (that is, containing a mixed solvent of EC, DMC, and EMC as a solvent and LiPF ₆ as a supporting salt) at a concentration of 5.0% by weight. The initial resistance is expected to be small.
In the lithium secondary battery B9, since the anion species of the ionic liquid is TFSI, the initial resistance is high.
In the lithium secondary battery B10, since MTFP was used as the fluorinated solvent for the electrolytic solution, the initial resistance was increased.
In the lithium secondary battery B11, since the cation species of the ionic liquid is EMIm which is an imidazolium ion, the initial resistance is increased.
In the lithium secondary battery B12, since the supporting salt is LiPF ₆ , the initial resistance is high, and the high-temperature cycle characteristics are deteriorated.
Note that, from the result of the lithium secondary battery B13, it is found that when the MA concentration is lowered to 0.03 mol / L, the high-temperature cycle characteristics are lowered.

From the above, it contains a difluoroacetic acid ester, a solvent component containing an ionic liquid, and a lithium imide salt as a supporting salt, and the ionic liquid contains a quaternary ammonium organic cation and an N (SO ₂ F) ₂ anion. The amount of the ionic liquid in the solvent component is in the range of 5% by volume or more and 20% by volume or less, and the concentration of the lithium imide salt is in the range of 1.5 mol / L or more and 2.5 mol / L or less. It can be seen that the non-aqueous electrolyte contained therein can improve the input / output characteristics and, in addition, improve the high-temperature cycle characteristics.

  As mentioned above, although the specific example of this invention was demonstrated in detail, these are only illustrations and do not limit a claim. The technology described in the claims includes various modifications and changes of the specific examples illustrated above.

20 wound electrode body 30 battery case 36 safety valve 42 positive electrode terminal 42a positive electrode current collector plate 44 negative electrode terminal 44a negative electrode current collector plate 50 positive electrode sheet (positive electrode)
52 Positive Electrode Current Collector 52a Positive Electrode Active Material Layer Non-Forming Portion 54 Positive Electrode Active Material Layer 60 Negative Electrode Sheet (Negative Electrode)
62 Negative electrode current collector 62a Negative electrode active material layer non-formed portion 64 Negative electrode active material layer 70 Separator sheet (separator)
80 Electrolytic solution 100 Lithium secondary battery

Claims (1)

A solvent component containing difluoroacetic acid ester and an ionic liquid;
A non-aqueous electrolyte containing a lithium imide salt as a supporting salt,
The ionic liquid is composed of a quaternary ammonium organic cation and an N (SO ₂ F) ₂ anion,
The amount of the ionic liquid in the solvent component is 5% by volume or more and 20% by volume or less,
The concentration of the lithium imide salt in the non-aqueous electrolyte is 1.5 mol / L or more and 2.5 mol / L or less.

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