CN110085805B - Composite anode and application thereof in solid polymer lithium ion battery - Google Patents

Composite anode and application thereof in solid polymer lithium ion battery Download PDF

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CN110085805B
CN110085805B CN201910362411.8A CN201910362411A CN110085805B CN 110085805 B CN110085805 B CN 110085805B CN 201910362411 A CN201910362411 A CN 201910362411A CN 110085805 B CN110085805 B CN 110085805B
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lithium ion
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CN110085805A (en
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孙学良
梁健能
孙乾
罗婧
赵阳
卢世刚
张立
赵尚骞
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University of Western Ontario
China Automotive Battery Research Institute Co Ltd
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China Automotive Battery Research Institute Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The invention relates to a composite anode and application thereof in a solid polymer electrolyte battery. The composite positive electrode includes: a high voltage anode and a protective layer coated on the high voltage anode; the protective layer material is selected from an atomic layer deposition material and/or a molecular layer deposition material. The invention adopts the atomic layer deposition/molecular layer deposition technology to coat the lithium ion battery anode material to form a protective layer, thereby preventing the decomposition of polymer-based electrolyte in the solid lithium ion battery containing the anode material and further improving the cycle performance of the solid lithium ion battery under high charging voltage.

Description

Composite anode and application thereof in solid polymer lithium ion battery
Technical Field
The invention relates to a composite anode and application thereof, belonging to the technical field of energy materials.
Background
Solid lithium ion batteryHas high safety and reliability, and has received more and more attention in recent years. The key technology of solid-state lithium ion batteries is solid-state electrolytes. The most common solid electrolytes today are of several types, such as polymer-based solid electrolytes, oxide-based solid electrolytes, sulfide-based solid electrolytes, Li3N and LiBH4And the like, among which polymer-based solid electrolytes are one of the earliest developed and most focused solid electrolytes.
Polymer-based solid electrolyte technology based on polyethers has been applied to commercial electric vehicles. It uses a lithium negative electrode and LiFePO4The anode material can provide 30 kilowatt-hour of electric power, and the driving mileage is 250 kilometers. However, since LiFePO4The specific capacity and the energy density are low, and the requirement of longer driving mileage cannot be met.
LiCoO2,LiNiO2And LiMnO2The base anode material has higher theoretical energy density and can provide enough energy to meet the requirement of driving mileage. However, when a polymer-based solid electrolyte is used for such a lithium ion positive electrode material, since such a positive electrode material requires a relatively high charging voltage, which is already higher than the electrochemical stability window of the polymer-based solid electrolyte, problems such as decomposition of the electrolyte and rapid decay of the battery capacity may occur during charge and discharge.
Disclosure of Invention
In order to solve the technical problems, the invention adopts the atomic layer deposition/molecular layer deposition technology to coat the lithium ion battery anode material to form a protective layer, thereby preventing the decomposition of polymer-based electrolyte in the solid lithium ion battery containing the anode material and further improving the cycle performance of the solid lithium ion battery under high charging voltage.
The technical scheme of the invention is as follows:
a composite positive electrode comprising: a high voltage anode and a protective layer coated on the high voltage anode; the protective layer material is selected from an atomic layer deposition material and/or a molecular layer deposition material;
the atomic layer deposition material is specifically selected from oxides and lithium-containing compounds; said oxideSpecifically, it may be selected from Al2O3,TiO2,ZrO2,Fe2O3,AlPO4,FePO4One or more of isooxides; the lithium-containing compound may be selected in particular from LiAlO2,LiTaO3,Li3PO4,Li2SiO3,LiNbO3And one or more of these lithium-containing compounds.
The molecular layer deposition material is selected from one or more of Alucon (aluminum-based organic-inorganic composite film), Zrucon (zirconium-based organic-inorganic composite film), polyurea (polyurea) and the like.
The protective layer can be coated on the surface of the positive active material particles or directly coated on the surface of the high-voltage positive electrode; further, the protective layer can be a single atomic layer deposition coating layer and a molecular layer deposition coating layer, and can also be a composite coating layer formed by combining two or more atomic layer deposition/molecular layer deposition.
The composite positive electrode further comprises a conductive agent, a binder composed of a polymer solid electrolyte or other polymers, and the like.
The voltage range of the high-voltage anode is between 2.7 and 4.3V.
The high-voltage anode is made of a material selected from LiMO2、LiNPO4、LiY2O4One or more of the lithium ion anode materials are mixed; wherein M is selected from one or a combination of Co, Ni and Mn; n is selected from one or a combination of more of Fe, Co and Mn; y is selected from one or a combination of Co, Ni and Mn.
The composite anode is prepared by coating a protective layer on the surface of a high-voltage anode by an atomic layer deposition method or a molecular layer deposition method. The thickness of the protective layer film is controlled by controlling different deposition turns.
The invention also provides a solid-state lithium ion battery which comprises the composite anode.
The electrolyte of the solid lithium ion battery is a solid polymer-based electrolyte; the solid polymer-based electrolyte is formed by compounding a polymer and a lithium salt; further, the solid polymer-based electrolyte includes: (a) polymer + lithium salt; (b) polymer + lithium salt + inorganic filler; (c) the composite electrolyte is a sandwich structure formed by polymer electrolyte/inorganic solid electrolyte/polymer electrolyte.
Wherein, the polymer can be one or a mixed polymer of two or more of polyethylene oxide (PEO) or other polymers containing EO branches, Polyacrylonitrile (PAN) or derivatives thereof, polymethyl methacrylate (PMMA) or derivatives thereof and PVDF-HFP.
Wherein the lithium salt has a chemical formula of LiX. Wherein X is an anion having a delocalized charge, preferably ClO4、PF6、BF6、AsF6、CF3SO3、(CF3SO2)2N (TFSI) or (C)2F5SO2)2N (BETI).
Inorganic material fillers, such as solid inorganic lithium ion conductor fillers, can also be added to the solid polymer electrolyte to improve the ion conductivity and mechanical strength of the polymer solid electrolyte.
The invention has the following beneficial effects:
according to the invention, the surface of the lithium ion anode is coated with the protective layer prepared by Atomic Layer Deposition (ALD) or Molecular Layer Deposition (MLD), so that the stability of the interface between the anode and the solid polymer electrolyte in the lithium ion battery is improved, and the polymer high-voltage solid lithium ion battery with high performance is obtained.
Drawings
FIG. 1 is a schematic representation of the uniform, very thin atomic layer deposition coated LiCoO obtained in example 12High magnification transmission electron microscopy.
Fig. 2 is a structural type of the solid polymer-based electrolyte battery.
FIG. 3 is a comparison of example 1 solid LiCoO with and without ALD coating2The charge and discharge performance of the battery; wherein the charging and discharging voltage is 2.7-4.2V, and the temperature is 60 ℃.
Figure 4 is a graph comparing the charge and discharge performance of solid state NMC811 batteries of example 3 with and without an atomic layer deposition coating; wherein the charging and discharging voltage is 2.7-4.3V, and the temperature is 60 ℃.
Fig. 5 is a graph comparing the charge and discharge performance of solid-state NMC622 cells with and without ald cladding in example 4; wherein the charging and discharging voltage is 2.7-4.3V, and the temperature is 60 ℃.
Fig. 6 is a graph comparing the charge and discharge performance of solid-state NMC811 cells coated with and without a layer of molecular deposition of example 2, with charge and discharge voltages of 2.8-4.3V at a temperature of 60 ℃.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1
The embodiment provides a preparation method of a polymer high-voltage solid-state lithium ion battery, which comprises the following steps:
(1) preparation of solid polymer electrolyte membrane: firstly PEO, LiClO4And LLZO (garnet type solid electrolyte) was dried, then 0.121 g of LLZO was dissolved in 25 ml of Acetonitrile (AN) and sonicated for 5 hours, 0.6g of PEO and 0.094g of LiClO4 were added to the AN and stirred for 24 hours, and a solution containing PEO-LiClO was added4-the homogeneous mixture of LLZO-AN is coated on a teflon evaporating dish; first dried at room temperature overnight, the solvent was slowly evaporated, and then it was placed in an oven at 60 ℃ for vacuum drying for 48h to obtain a PEO-LiClO4-LLZO solid polymer electrolyte membrane, which was immediately transferred to a glove box filled with argon and stored for more than 3 days.
(2) Preparing a positive electrode material matrix: LiCoO with a certain mass ratio2Coating the slurry of conductive carbon black, PVdF and NMP on an aluminum foil, and drying in a vacuum oven at 120 ℃ to obtain a LiCoO2 positive electrode material matrix;
(3) preparing a composite positive electrode: and (3) placing the anode material substrate obtained in the step (2) into an atomic layer deposition reaction bin. Al (Al)2O3The films were prepared in a Gemstar-8(Arradiance, USA) atomic layer deposition system. In this process, Trimethylaluminum (TMA) and water (H)2O) as a precursor reactant for deposition, both precursors being used at room temperature. The electrode material was placed in an ALD reaction chamber, the reaction chamber vacuum was maintained at 400 mTorr. Deposition temperature of alumina film is 1At 20 ℃. The alumina deposition process comprises the following steps: 0.01s/40s/0.01s/70s (TMA pulse/purge/H2O pulse/purge). The thickness of the alumina film is controlled by controlling different ALD deposition turns. In this example, 10 rounds of alumina film were deposited on the electrode material.
(4) Preparing a battery: and (3) assembling a layer of lithium metal cathode, a layer of the solid polymer electrolyte membrane obtained in the step (1) and the composite anode obtained in the step (3) to obtain the button battery with the model 2032.
The obtained button cell is placed in an environment at 60 ℃ for testing.
Example 2
The embodiment provides a preparation method of a polymer high-voltage solid-state lithium ion battery, which comprises the following steps:
(1) firstly PEO, LiClO4And LLZO (garnet type solid electrolyte) was dried, then 0.121 g of LLZO was dissolved in 25 ml of Acetonitrile (AN) and sonicated for 5 hours, 0.6g of PEO and 0.094g of LiClO4Adding into the AN and stirring for 24 hr, adding PEO-LiClO4The homogeneous mixture of-LLZO-AN was coated on a Teflon evaporating dish and first dried overnight at room temperature, the solvent was slowly evaporated, and then it was placed in AN oven at 60 ℃ and dried under vacuum for 48h to obtain PEO-LiClO4-LLZO solid polymer electrolyte membrane, immediately transferred into a glove box filled with argon and stored for more than 3 days.
(2) The NMC811 electrode material was placed in a molecular layer deposition reaction chamber and the Alucone film was prepared in a Gemstar-8 (aradiate, USA) atomic layer/molecular layer deposition system. In this process, Trimethylaluminum (TMA) and Ethylene Glycol (EG) serve as the precursor reactants for deposition. EG was heated to 85 degrees celsius to give precursor vapor and TMA was kept at room temperature. The electrode material was placed in the MLD reaction chamber, and the reaction chamber vacuum was maintained at 400 mTorr. The deposition temperature of the alumina film was 120 ℃. The alumina deposition process comprises the following steps: 0.01s/40s/0.01s/70s (TMA pulse/purge/EG pulse/purge). The thickness of the alucone film is controlled by controlling the deposition number of different MLDs. In this example, 20 turns of alucone film are deposited on the electrode material.
(3) And (3) assembling a layer of lithium metal negative electrode, a layer of polymer solid electrolyte obtained in the step (1) and a layer of positive electrode material obtained in the step (2) to obtain the button battery with the model 2032.
The obtained button cell is placed in an environment at 60 ℃ for testing.
Example 3
The embodiment provides a preparation method of a polymer high-voltage solid-state lithium ion battery, which comprises the following steps:
(1) PEO, LiClO4 and LLZO (garnet type solid electrolyte) were dried first, then 0.121 g LLZO was dissolved in 25 ml Acetonitrile (AN) and sonicated for 5 hours, 0.6g PEO and 0.094g LiClO4 were added to the AN and stirred for 24 hours, the homogeneous mixture containing PEO-LiClO4-LLZO-AN was coated on a teflon evaporating dish and first dried overnight at room temperature, the solvent was slowly evaporated, and then it was vacuum-dried in AN oven at 60 ℃ for 48 hours to obtain a PEO-LiClO4-LLZO solid polymer electrolyte membrane, which was immediately transferred to a glove box filled with argon gas and stored for 3 days or more.
(2) Putting NMC811 electrode material into an atomic layer deposition reaction chamber, and putting lithium niobate (LiNbO)3) Films were prepared in a Savannah 100(Cambridge Nanotech Inc.) atomic layer deposition system. In this process, lithium tert-butoxide (LiOtBu), niobium ethoxide (nb (oet)5) and water are used as precursor reactants for the lithium tantalate thin film. Both LiOtBu and nb (oet)5 were heated to 170 degrees celsius to give precursor vapor, and water was kept at room temperature. The electrode material was placed in an ALD reaction chamber, which was maintained at 200mTorr vacuum. The deposition temperature of the lithium tantalate film was 235 ℃. The thickness of the lithium niobate thin film is controlled by controlling different ALD deposition turns. In this example, 20 turns of a thin film of lithium niobate are deposited on the electrode material.
(3) And (3) assembling a layer of lithium metal negative electrode, a layer of polymer solid electrolyte obtained in the step (1) and a layer of positive electrode material obtained in the step (2) to obtain the button battery with the model 2032.
The obtained button cell is placed in an environment at 60 ℃ for testing.
Example 4
(1) Firstly PEO, LiClO4Drying, 0.6g PEO and0.094g LiClO4add to the AN and stir for 24 hours. Then, the solution containing PEO-LiClO4The homogeneous mixture of-AN was coated on a Teflon evaporating dish and first dried overnight at room temperature, the solvent was slowly evaporated, then it was placed in AN oven at 60 ℃ and dried under vacuum for 48h to obtain PEO-LiClO4A solid polymer electrolyte membrane. The membrane was then immediately transferred to a glove box filled with argon and stored for more than 3 days.
(2) Coating slurry containing NMC622, conductive carbon black, PVdF and NMP in a certain mass ratio on an aluminum foil, and drying in a vacuum oven at 120 ℃ to obtain a LiCoO2 positive electrode material matrix;
(3) preparing a composite positive electrode: and (3) placing the anode material substrate obtained in the step (2) into an atomic layer deposition reaction bin. Al (Al)2O3The films were prepared in a Gemstar-8(Arradiance, USA) atomic layer deposition system. In this process, Trimethylaluminum (TMA) and water (H)2O) as a precursor reactant for deposition, both precursors being used at room temperature. The electrode material was placed in an ALD reaction chamber, the reaction chamber vacuum was maintained at 400 mTorr. The deposition temperature of the alumina film was 120 ℃. The alumina deposition process comprises the following steps: 0.01s/40s/0.01s/70s (TMA pulse/purge/H2O pulse/purge). The thickness of the alumina film is controlled by controlling different ALD deposition turns. In this example, 10 rounds of alumina film were deposited on the electrode material.
(4) Preparing a battery: and (3) assembling a layer of lithium metal cathode, a layer of the solid polymer electrolyte membrane obtained in the step (1) and the composite anode obtained in the step (3) to obtain the button battery with the model 2032.
The obtained button cell is placed in an environment at 60 ℃ for testing.
Example 5
This practice is essentially the same as "procedure of example 1" except that the solid polymer electrolyte membrane of step (1) is different, changing "PEO" to "PMMA".
Example 6
The present implementation is substantially the same as "step of example 1", except that the preparation of the positive electrode material matrix in step (2) is different, specifically, "PVdF" in step (2) is changed to "polymer electrolyte in step (1)".
Example 7
The present implementation is substantially the same as "step of example 1", except that "lithium metal" of step (4) is changed to "carbon negative electrode".
Example 8
This practice is essentially the same as "step of example 1" except that the protective layer is different, specifically Al of step (3)2O3The coating is changed into LiTaO3And (4) coating.
Example 9
The implementation is basically the same as the step of example 2, except that the protective layer is different, specifically: changing the Alucon coating in the step (3) into a polyurea coating.
Other embodiments are not exhaustive.
Effect testing
The structural and electrical properties of the solid-state lithium ion battery obtained in the above example were characterized and tested, and are summarized as follows:
as shown in the high-power transmission microscope of fig. 1, atomic layer deposition has the characteristics of uniform deposition and controllable thickness at a nanometer level. Similar to the atomic layer deposition technology, the molecular layer deposition technology has the same advantages, and the material deposited by the molecular layer deposition technology is an organic-inorganic composite material, has certain flexibility and better mechanical property. These advantages make the atomic layer deposition and the molecular layer deposition especially suitable for the interface modification of the anode material and the polymer electrolyte.
As shown in fig. 2, the present invention applies atomic layer deposition and molecular layer deposition techniques to improve the interfacial stability between the positive electrode material and the polymer electrolyte, and the studied solid polymer-based electrolyte includes (a) polymer + lithium salt, (b) polymer + lithium salt + inorganic filler; (c) a polymer electrolyte/inorganic solid electrolyte/polymer electrolyte sandwich structure composite electrolyte.
As shown in FIG. 3, atomic layer deposition coated LiCoO2The performance of the cathode material in a solid polymer-based electrolyte battery is greatly improved.
As shown in fig. 4, the performance of the atomic layer deposition coated NMC811 cathode material in a solid polymer-based electrolyte cell was greatly improved.
As shown in fig. 5, the performance of the atomic layer deposition coated NMC622 positive electrode material in a solid polymer-based electrolyte cell was greatly improved.
As shown in fig. 6, the performance of the molecular layer deposition coated NMC811 cathode material in a solid polymer-based electrolyte cell was greatly improved.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (4)

1. A solid state lithium ion battery based on a polymer-based electrolyte, comprising: compounding a positive electrode, a negative electrode and a polymer-based electrolyte;
the composite anode is a high-voltage anode and a protective layer coated on the high-voltage anode; or the composite positive electrode comprises a high-voltage positive electrode active material and a protective layer coated on the surface of the high-voltage positive electrode active material particles;
the voltage range of the high-voltage anode is between 2.7 and 4.3V;
the active material of the composite positive electrode is selected from LiMO2、LiNPO4Or LiY2O4One of (1); wherein M is selected from one or a combination of Co, Ni and Mn; n is selected from one or a combination of more of Fe, Co or Mn; y is selected from one or a combination of more of Co, Ni or Mn;
the protective layer is coated on the surface of the high-voltage anode or the particle surface of the high-voltage anode active material through molecular layer deposition;
the protective layer is made of an aluminum-based organic-inorganic composite film Alucone;
the polymer-based electrolyte is formed by compounding a polymer and a lithium salt; the polymer-based electrolyte is (a) a polymer + a lithium salt; or (b) polymer + lithium salt + inorganic filler; wherein the polymer is polyethylene oxide (PEO) or other polymer containing EO branches.
2. The solid state lithium ion battery of claim 1, wherein the protective layer is 10-20 layers.
3. The solid state lithium ion battery of claim 1, wherein the composite positive electrode comprises a conductive agent, a binder PVdF.
4. The solid state lithium ion battery of claim 1, wherein the polymer-based electrolyte further comprises a solid inorganic lithium ion conductor filler.
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