KR20130088426A - A positive electrode for lithium-sulfur battery and lithium-sulfur battery comprising the same - Google Patents

Abstract

PURPOSE: An anode for a lithium-sulfur battery is provided to suppress the flow out of a polysulfide which is a charging/discharging intermediate product of the anode active material into an electrolyte according to introduction of an anion immobilization materials in the lithium-sulfur anode thereby the capacity retention rate of the lithium-sulfur battery is improved. CONSTITUTION: An anode for a lithium-sulfur battery comprises the followings: elemental sulfur (S8); anode active material which comprises sulfur series compound and a mixture thereof; a conductive material; a binder, and an anion immobilization material. A content of the anion immobilization material is 0.5-50 weight%; an average size of a particle of the anion immobilization material is 0.01-10 micron. The conductive material is selected from a group which comprises a graphite material, a carbon-based material and conductivity polymer. In addition, the lithium-sulfur battery comprises an anode, a cathode, a separator which is interposed between anode and cathode, and electrolyte. [Reference numerals] (AA) Volume (mAh/g electrode); (BB) Number of cycle; (CC) Implementation example 3; (DD) Implementation example 2; (EE) Implementation example 1; (FF) Comparison example 1

Description

A positive electrode for lithium-sulfur battery comprising an anion immobilization material and a lithium-sulfur battery comprising the same {A positive electrode for lithium-sulfur battery and lithium-sulfur battery comprising the same}

The present invention relates to a lithium-sulfur battery positive electrode including an anion-immobilized material and a lithium-sulfur battery including the same, and more particularly, the charge-discharge intermediate product of the positive electrode active material as the anion-immobilized material is introduced into the lithium-sulfur positive electrode The present invention relates to a positive electrode for a lithium-sulfur battery including an anion-immobilized material in which the capacity retention rate of the lithium-sulfur battery is greatly improved by suppressing the outflow of phosphorus polysulfide into the electrolyte, and a lithium-sulfur battery including the same.

The interest in electrochemical devices, a key component, is rapidly increasing due to expectations for the continuous expansion of the portable electronic device market and the explosive growth of the electric vehicle and energy storage devices markets. The most widely used device among electrochemical devices is a secondary battery, and lithium secondary batteries are leading the market in terms of operating voltage, energy, and power density. Lithium secondary batteries have better performance than conventional secondary batteries such as lead acid batteries using Ni-Cd and Ni-MH (Nickel-Metal Hydrate), but safety problems such as ignition and explosion due to the use of non-aqueous electrolyte And the manufacturing process is difficult disadvantages. In addition, there are a number of problems to be solved such as high energy density, high temperature reliability, low temperature characteristics, and unit cost for the use of electric vehicles and energy storage devices.

In particular, in order to realize high energy density, development of an electrode active material having a large theoretical capacity is required. However, the theoretical capacity of the transition metal oxide, which is a conventional cathode active material for lithium secondary batteries, is about 250 mAh / g or less, and it is not easy to implement a high energy density battery. In order to overcome this problem, development of a lithium-sulfur battery using a sulfur-based compound as a cathode active material is being actively conducted.

Lithium-sulfur batteries use a sulfur-based compound having a sulfur-sulfur bond as a positive electrode active material, and a carbon-based material in which metal ions such as lithium metal, lithium alloy, or lithium ion are inserted / deinserted. It is a secondary battery used as a negative electrode active material. In the reduction reaction (discharged), the SS bond is broken and the oxidation number of S decreases, and in the oxidation reaction (charged), the oxidation-reduction reaction of the SS bond is formed by increasing the oxidation number of S and the electrical energy is stored and stored. Create

The lithium-sulfur battery has an energy density of 3860 mAh / g using lithium metal used as a negative electrode active material, and an energy density of 1675 mAh / g using sulfur (S ₈ ) used as a positive electrode active material. Among the most promising cells in terms of energy density. In addition, the sulfur-based compound used as a positive electrode active material has the advantage that it is a cheap and environmentally friendly material.

However, there is no example in which lithium-sulfur battery system has been successfully commercialized yet. Lithium-sulfur batteries have a problem of using sulfur as an active material, and having a low utilization rate of sulfur participating in the electrochemical redox reaction in the battery with respect to the amount of sulfur introduced, and in fact, shows a very low battery capacity unlike the theoretical capacity.

Thus, in Korean Patent Application No. 10-2001-0042633, a method of improving sulfur utilization in an electrochemical redox reaction in a battery has been proposed as a method of attaching an anionic polymer to a separator to suppress the migration of polysulfide to the cathode. There is a problem that there is a limit in suppressing the escape of the polysulfide in the anode.

Accordingly, the present inventors have made diligent efforts to solve the above problems, and as a result, the capacity of the lithium-sulfur battery is suppressed by introducing an anion-immobilized material into the lithium-sulfur battery, thereby preventing polysulfide, which is a charge / discharge intermediate product of the positive electrode active material, from leaking into the electrolyte. It was confirmed that the retention rate was greatly improved, and the present invention was completed.

SUMMARY OF THE INVENTION An object of the present invention is to provide a lithium-sulfur battery positive electrode including an anion-immobilized material in a lithium-sulfur positive electrode in order to suppress the leakage of polysulfide, which is a charge / discharge intermediate product of the positive electrode active material, into an electrolyte, and a lithium-sulfur battery including the same. It is.

In order to achieve the above object, the present invention is a sulfur element (S ₈ ); A cathode active material consisting of a sulfur-based compound and mixtures thereof; Conductive material; bookbinder; And it provides a positive electrode for a lithium-sulfur battery comprising an anion immobilization material.

The present invention also provides a lithium-sulfur battery including a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode, an electrolyte solution.

In the lithium-sulfur battery including the anion-immobilized material according to the present invention, as the anion-immobilized material is introduced, polysulfide, which is a charge / discharge intermediate product of the positive electrode active material, is prevented from leaking into the electrolyte, thereby greatly improving the capacity retention rate of the lithium-sulfur battery. Can be.

1 is a graph showing the capacity retention rate of a lithium-sulfur battery including a positive electrode for a lithium-sulfur battery according to the present invention.

In order to fully understand the present invention, operational advantages of the present invention, and objects achieved by the practice of the present invention, reference should be made to the accompanying drawings and the accompanying drawings which illustrate preferred embodiments of the present invention. Hereinafter, the present invention will be described in detail with reference to the preferred embodiments of the present invention with reference to the accompanying drawings. However, the present invention can be implemented in various different forms, and is not limited to the embodiments described. In order to clearly describe the present invention, parts that are not related to the description are omitted, and the same reference numerals in the drawings denote the same members.

In the present specification, when a part "includes" a certain component, this means that it may further include other components, without excluding the other components unless otherwise stated.

Hereinafter, the present invention will be described in detail, but the scope of the present invention is not limited thereto.

The present invention, in one aspect, elemental sulfur (S ₈ ); A cathode active material consisting of a sulfur-based compound and mixtures thereof; Conductive material; bookbinder; And it relates to a positive electrode for a lithium-sulfur battery comprising an anion immobilization material.

According to the present invention, the anion-immobilizing material may be used as an inorganic material containing a group IIIA element as long as the anion and Lewis acid-Lewis base interaction in the non-aqueous electrolyte are possible. Specific anion fixing materials include boron oxide (B ₂ O ₃ ), aluminum oxide (Al ₂ O ₃ ), aluminum fluoride (AlF ₃ ), aluminum chloride (AlCl ₃ ), and the like as the anion fixing material is introduced. By suppressing the outflow of the polysulfide which is the charge / discharge intermediate product of the active material into the electrolyte, the capacity retention rate of the lithium-sulfur battery can be greatly improved.

According to the present invention, the particle size of the anion stabilizer is not limited, but in order to form a uniform electrode and anion fixing effect, the particle size is preferably in the range of 0.01 to 10 μm. If it is less than 0.01㎛ dispersibility is not easy to control the dispersibility of the positive electrode slurry, if it exceeds 10㎛ there is a problem in that the anion fixation effect is lower than the introduction content.

According to the present invention, the composition ratio of the anion-immobilized material of the positive electrode for a lithium-sulfur battery is preferably in the range of 0.5% by weight to 50% by weight, more preferably 1% by weight to 25% by weight. If the content of the anion immobilization material is too low, it is not possible to give an anion immobilization effect. If the content of the anion immobilization material is too high, there is a problem that the capacity of the electrode is too low because the content of the positive electrode active material is relatively reduced instead of increasing the anion immobilization effect.

According to the present invention, the positive electrode active material may use elemental sulfur (S ₈ ), a sulfur-based compound, or a mixture thereof. The sulfur-based compound is selected from the group consisting of Li ₂ S _n (n ≧ 1), an organic sulfur compound, and carbon-sulfur polymer ((C ₂ S _x ) n: x = 2.5 to 50, n ≥ 2) Can be used. In addition, the conductive material for allowing electrons to move smoothly in the positive electrode active material together with the positive electrode active material is not particularly limited, and a conductive material or a conductive polymer such as a graphite material or a carbon material may be preferably used. The graphite material is KS 6 (manufactured by Timcal) and the carbon material is super P (MMM company), ketjen black, denka black, acetylene black, carbon black, and the like. . Examples of the conductive polymer include polyaniline, polythiophene, polyacetylene, polypyrrole, and the like. These conductive conductive materials may be used alone or in combination of two or more thereof.

According to the present invention, a general binder which serves to attach the positive electrode active material to the current collector is polyvinylidene fluoride, a copolymer of polyvinylidene fluoride and hexafluoropropylene, poly (vinylacetate), poly (vinyl Butyral-co-vinyl alcohol-co-vinyl acetate), poly (methylmethacrylate-co-ethyl acrylate), polyacrylonitrile, polyvinyl chloride-co-vinyl acetate, polyvinylalcohol, poly (1- Vinylpyrrolidone-co-vinyl acetate), cellulose acetate, polyvinylpyrrolidone, polyacrylate, polymethacrylate, polyolefin, polyurethane, polyvinyl ether, acrylonitrile-butadiene rubber, styrene-butadiene rubber, Acrylonitrile-butadiene styrene, sulfonated styrene / ethyl-butylene / styrene triblock copolymer, polyethylene oxide, oils thereof Body can be selected from the group consisting of blends, copolymers, and the like, preferably using a polyvinylidene fluoride.

The current collector is not particularly limited, but conductive materials such as stainless steel, aluminum, copper, titanium, and the like are preferably used, and more preferably, a carbon-coated aluminum current collector is used. The use of an Al substrate coated with carbon has an advantage in that the adhesion to the active material is excellent, the contact resistance is low, and the corrosion by polysulfide of aluminum can be prevented, compared with the non-carbon coated Al substrate.

In addition, the anode of the present invention may include a coating layer made of a polymer, an inorganic material, an organic material or a mixture thereof.

The polymers include polyvinylidene fluoride, copolymers of polyvinylidene fluoride and hexafluoropropylene, poly (vinylacetate), poly (vinyl butyral-co-vinyl alcohol-co-vinyl acetate), poly (methylmetha) Acrylate-co-ethyl acrylate), polyacrylonitrile, polyvinyl chloride-co-vinyl acetate, polyvinylalcohol, poly (1-vinylpyrrolidone-co-vinyl acetate), cellulose acetate, polyvinylpyrroly Don, polyacrylate, polymethacrylate, polyolefin, polyurethane, polyvinyl ether, acrylonitrile-butadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene styrene, sulfonated styrene / ethylene-butylene / styrene Triblock copolymer, polyethylene oxide and mixtures thereof, preferably polyvinylidene fluoride It can be used.

The inorganic materials include colloidal silica, amorphous silica, surface treated silica, colloidal alumina, amorphous alumina, tin oxide, titanium oxide, titanium sulfide (TiS ₂ ), vanadium oxide, zirconium oxide (ZrO ₂ ), iron oxide (Iron). Oxide), iron sulfide (Iron Sulfide, FeS), iron titanate (Iron titanate, FeTiO ₃ ), barium titanate (Vanadium titanate, BaTiO ₃ ), and mixtures thereof, preferably colloidal silica or colloidal alumina Can be used.

According to another aspect of the present invention, in a lithium-sulfur battery including a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode, an electrolyte solution, the positive electrode is a lithium- which is the positive electrode of any one of claims 1 to 7. Relates to a sulfur battery.

The non-aqueous solvents include benzene, fluorobenzene, toluene, trifluorotoluene, xylene, cyclohexane, tetrahydrofuran, 2-methyl tetrahydrofuran, cyclohexanone, ethanol, isopropyl alcohol, dimethyl carbonate, Ethylmethyl carbonate, diethyl carbonate, methylpropyl carbonate, methylpropionate, ethylpropionate, methyl acetate, ethyl acetate, propyl acetate, dimethoxy ethane, 1,3-dioxolane, diglyme, tetraglyme, ethylene At least one solvent selected from the group consisting of carbonate, propylene carbonate, γ-butyrolactone and sulfolane is used.

The electrolytic salt lithium salt is lithium trifluoromethansulfonimide (lithium trifluoromethansulfonimide), lithium triflate (lithium triflate), lithium perchlorate (lithium perclorate), lithium hexafluoro azenate (LiAsF ₆ ), lithium trifluor Romethanesulfonate (CF ₃ SO ₃ Li), LiPF ₆ , LiBF ₄ or tetraalkylammonium, for example tetrabutylammonium tetrafluoroborate, or a liquid salt at room temperature, for example 1-ethyl-3-methyl One or more imidazolium salts such as imidazolium bis (perfluoroethyl sulfonyl) imide and the like can be used. The non-aqueous solvent includes lithium salt at a concentration of 0.5 to 2.0 M. At this time, when the concentration of the lithium salt is less than 0.5M, there is a problem that the ion conductivity is low due to the low concentration of lithium ions in the electrolyte, the ion conductivity is lowered again due to the high viscosity of the electrolyte when the concentration of the lithium salt is higher than 2.0M There is this.

It is preferable that the solvent used for mixing the positive electrode active material, the conductive material, the binder, and the anion-immobilized material has a low boiling point. This can be achieved by mixing uniformly, since the solvent can be easily removed. At this time, the solvent is acetone (acetone), tetrahydrofuran (tetrahydrofuran), methylene chloride (methylene chloride), chloroform (chloroform), dimethylformamide (dimethylformamide), N-methyl-2-pyrrolidone (N-methyl-2 -pyrrolidone, NMP), cyclohexane, water or a mixture thereof, preferably N-methyl-2-pyrrolidone (N-methyl-2-pyrrolidone, NMP) Can be.

Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these embodiments are only for illustrating the present invention and that the scope of the present invention is not construed as being limited by these embodiments.

Comparative example  1: B ₂ O ₃ Cathode for lithium-sulfur battery containing 0% by weight

N-methyl-2 pyrrolidone (NMP) as a solvent in 58 wt% sulfur powder as a positive electrode active material, 28 wt% carbon black as a conductive material, and 14 wt% polyvinylidene fluoride (PVdF) as a binder. ) Was added in an amount of 4 to 5 times the weight ratio of the active material, the conductive material and the binder, and the mixed slurry was applied to an Al foil having a thickness of 15 μm and dried in an oven at 65 ° C. for 2 to 3 hours to prepare an electrode. At this time, the elemental sulfur (S ₈ ) powder was used as a powder having a particle size of 254um or less, and after drying the electrode was subjected to a roll press (roll press) to adjust the thickness and density of the electrode.

Example  1: B ₂ O ₃  2.9% by weight of lithium-sulfur battery positive electrode

B ₂ O ₃ with an average particle diameter of about 500 nm is 2.9 wt% as an anion stabilizing material, 55.1 wt% sulfur powder as the positive electrode active material, 28 wt% carbon black as the conductive material, and polyvinylidene fluoride as the binder (PVdF) was prepared in the same manner as in Comparative Example 1 except for 14% by weight.

Example  2: B ₂ O ₃  Cathode for lithium-sulfur battery containing 5.8% by weight

B ₂ O ₃ with an average particle diameter of about 500 nm is 5.8 wt% as an anion stabilizing material, 52.2 wt% sulfur powder as the positive electrode active material, 28 wt% carbon black as the conductive material, and polyvinylidene fluoride as the binder (PVdF) was prepared in the same manner as in Comparative Example 1 except for 14% by weight.

Example  3: B ₂ O ₃  Cathode for lithium-sulfur battery containing 11.6 wt%

B ₂ O ₃ with an average particle diameter of about 500 nm is 11.6 wt% as an anion stabilizing material, 46.4 wt% sulfur powder as a positive electrode active material, 28 wt% carbon black as a conductive material, and polyvinylidene fluoride as a binder (PVdF) was prepared in the same manner as in Comparative Example 1 except for 14% by weight.

Experimental Example  One : Charging and discharging  evaluation

The positive electrode prepared in Comparative Example 1, Example 1, Example 2, Example 3, lithium metal negative electrode, porous polyethylene separator having a porosity of 40% and a thickness of 20㎛, 1,3-Dioxolane and TEGDME in a volume ratio of 65 units A 2032 coin cell was prepared using an electrolyte containing 1M LiTFSI lithium salt in an organic solvent mixed with 35.

The coin cell was charged and discharged between 1.5V and 2.5V at a current rate of 0.1C to measure the capacity retention rate of the lithium-sulfur battery.

As a result, as shown in FIG. 1, in the case of the lithium-sulfur battery positive electrode manufactured in Comparative Example 1, since the polysulfide flowed out of the positive electrode into the electrolyte during charging and discharging, the capacity retention rate was 33.9% after 30 charge and discharge cycles. (661 mAh / g → 224 mAh / g), while the positive electrode for the lithium-sulfur battery prepared in Examples 1 to 3 had a lower initial capacity value in proportion to the anion fixation content, but a capacity maintenance rate was greatly improved. Indicated. However, when the content of the anion stabilizer is low as in Example 1, the capacity retention rate is not largely improved to 49.7% (608 mAh / g → 302 mAh / g). The initial capacity value is so low that high capacity characteristics of the lithium-sulfur battery are difficult to be properly implemented. Therefore, it is necessary to select an appropriate anion stabilizer content, such as the positive electrode for a lithium-sulfur battery prepared in Example 2, it can exhibit a high initial melt value and excellent cycle characteristics.

The specific parts of the present invention have been described in detail above, and it is apparent to those skilled in the art that such specific descriptions are merely preferred embodiments, and thus the scope of the present invention is not limited thereto. something to do. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.

Claims (18)

Elemental sulfur (S ₈ ); A cathode active material consisting of a sulfur-based compound and mixtures thereof;
Conductive material; bookbinder; And an anion immobilization material.
The cathode for a lithium-sulfur battery according to claim 1, wherein the anion-immobilizing material is an inorganic material containing a group IIIA element and is a material capable of interacting with polysulfide, which is an intermediate product of charge and discharge of a positive electrode active material, and a Lewis acid-Lewis base.
The method of claim 2, wherein the anion immobilization material is selected from the group consisting of boron oxide (B ₂ O ₃ ), aluminum oxide (Al ₂ O ₃ ), aluminum fluoride (AlF ₃ ) and aluminum chloride (AlCl ₃ ) A positive electrode for a lithium-sulfur battery, characterized in that.
The positive electrode for a lithium-sulfur battery according to claim 1, wherein the content of the anion-immobilizing material is 0.5% by weight to 50% by weight.
The positive electrode for a lithium-sulfur battery according to claim 1, wherein the average particle size of the anion-immobilized material is 0.01 to 10 µm.
The method of claim 1, wherein the sulfur-based compound is Li ₂ S _n (n ≧ 1), organo-sulfur compound and carbon-sulfur polymer [(C ₂ S _x ) _n , x = 2.5 to 50, n ≥ 2] A positive electrode for a lithium-sulfur battery, characterized in that selected from the group consisting of.
The cathode of claim 1, wherein the conductive material is selected from the group consisting of a graphite material, a carbon material, and a conductive polymer.
The method of claim 1, wherein the binder is polyvinylidene fluoride, copolymer of polyvinylidene fluoride and hexafluoropropylene, poly (vinylacetate), poly (vinyl butyral-co-vinyl alcohol-co-vinyl acetate ), Poly (methylmethacrylate-co-ethyl acrylate), polyacrylonitrile, polyvinyl chloride-co-vinyl acetate, polyvinyl alcohol, poly (1-vinylpyrrolidone-co-vinyl acetate), cellulose Acetate, polyvinylpyrrolidone, polyacrylate, polymethacrylate, polyolefin, polyurethane, polyvinyl ether, acrylonitrile-butadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene styrene, sulfonated styrene / Lithium, characterized in that selected from the group consisting of ethyl-butylene / styrene triblock copolymer, polyethylene oxide and mixtures thereof -Anode for sulfur battery.
The positive electrode for a lithium-sulfur battery according to claim 1, wherein the positive electrode comprises a coating layer made of a polymer, an inorganic material, an organic material, and a mixture thereof.
10. The polymer according to claim 9, wherein the polymer is polyvinylidene fluoride, a copolymer of polyvinylidene fluoride and hexafluoropropylene, poly (vinylacetate), poly (vinyl butyral-co-vinyl alcohol-co-vinyl acetate) , Poly (methylmethacrylate-co-ethyl acrylate), polyacrylonitrile, polyvinyl chloride-co-vinyl acetate, polyvinyl alcohol, poly (1-vinylpyrrolidone-co-vinyl acetate), cellulose acetate , Polyvinylpyrrolidone, polyacrylate, polymethacrylate, polyolefin, polyurethane, polyvinyl ether, acrylonitrile-butadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene styrene, sulfonated styrene / ethylene Lithium-sulfur, characterized in that it is selected from the group consisting of butylene / styrene triblock copolymers, polyethylene oxides and mixtures thereof Battery positive electrode.
The method of claim 9, wherein the inorganic material is colloidal silica, amorphous silica, surface-treated silica, colloidal alumina, amorphous alumina, tin oxide, titanium oxide, titanium sulfide (TiS ₂ ), vanadium oxide, zirconium oxide (ZrO ₂ ) Lithium-sulfur, characterized in that selected from the group consisting of iron oxide (Iron Oxide), iron sulfide (Iron Sulfide, FeS), iron titanate (FeTiO ₃ ), barium titanate (Vanadium titanate, BaTiO 3) and mixtures thereof Battery positive electrode.
A lithium-sulfur battery comprising a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode, and an electrolyte solution, wherein the positive electrode is the positive electrode of any one of claims 1 to 12.
The lithium-sulfur battery of claim 12, wherein the negative electrode comprises a negative electrode active material selected from the group consisting of lithium metal, lithium alloys, and materials capable of reversibly containing lithium ions.
The lithium-sulfur battery of claim 12, wherein the separator is selected from the group consisting of a polyolefin-based porous membrane and a nonwoven fabric formed of one or more polymers.
The lithium-sulfur battery of claim 12, wherein the electrolyte solution includes at least one lithium salt and at least one non-aqueous solvent.
The method of claim 15, wherein the electrolytic salt is lithium trifluoromethansulfonimide, lithium triflate, lithium perclorate, lithium hexafluoroazate (LiAsF ₆ ), lithium Trifluoromethanesulfonate (CF ₃ SO ₃ Li), LiPF ₆ , LiBF ₄ or tetraalkylammonium, tetrabutylammonium tetrafluoroborate, 1-ethyl-3-methylimidazolium bis (perfluoroethyl sulfonyl Lithium-sulfur battery, characterized in that at least one selected from the group consisting of imide and imidazolium salt.
The non-aqueous solvent according to claim 15, wherein the non-aqueous solvent is benzene, fluorobenzene, toluene, trifluorotoluene, xylene, cyclohexane, tetrahydrofuran, 2-methyl tetrahydrofuran, cyclohexanone, ethanol, isopropyl alcohol , Dimethyl carbonate, ethylmethyl carbonate, diethyl carbonate, methylpropyl carbonate, methyl propionate, ethyl propionate, methyl acetate, ethyl acetate, propyl acetate, dimethoxy ethane, 1,3-dioxolane, diglyme, tetra Lithium-sulfur battery, characterized in that at least one selected from the group consisting of glyme, ethylene carbonate, propylene carbonate, γ-butyrolactone and sulfolane.
16. The lithium-sulfur battery of claim 15, wherein the non-aqueous solvent comprises lithium salt at a concentration of 0.5 to 2.0 M.

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