Preparation method of CuAg / HEO electrode material with coating structure

Abstract

The invention belongs to the field of supercapacitor electrode materials, and particularly relates to a preparation method of a CuAg / HEO electrode material with a coating structure. Aiming at the problem of low energy density caused by low intrinsic conductivity of the high-entropy oxide, the invention provides a corresponding solution which is characterized in that an alloy phase generated in situ in a high-entropy oxide system is uniformly distributed in the high-entropy oxide system to form a coating structure. According to the invention, an in-situ generated CuAg alloy phase / HEO coating structure is proposed for the first time, the alloy phase has high intrinsic conductivity, so that the conductivity of the high-entropy oxide can be locally improved, long-distance transmission of electrons can be realized, a reaction region can be widened, the electrochemical energy storage capability can be improved, and high energy density can be realized while high power density is considered.

Description

Technical Field

[0001] The present invention belongs to the field of supercapacitor electrode materials, and particularly relates to a preparation method of a CuAg / HEO electrode material with a coating structure. Background Art

[0002] A supercapacitor (SC) is an energy storage device that can be charged and discharged quickly. Due to its high power density, excellent cycle stability, environmental friendliness and no pollution, it has received extensive attention from research scholars. However, due to its low energy density, it cannot meet the requirements of actual production, which hinders large-scale production applications. Therefore, designing and developing a supercapacitor with both energy density and power density is an urgent problem to be solved in the field of supercapacitors.

[0003] The electrode material is an important part of the supercapacitor device, which directly affects the electrochemical energy storage performance of the supercapacitor to a great extent. Among many electrode materials, transition metal oxides have attracted much attention due to their large theoretical capacitance, easy activation of structure, and low pollution. However, due to the low specific surface area of transition metal oxides, lack of active sites and poor stability, they cannot exhibit the best electrochemical energy storage performance.

[0004] In order to improve the above defects of transition metal oxides, in recent years, research scholars have begun to try to transform transition metal oxides by "entropy engineering". While stabilizing their phase structure and improving their service life, the original or additional active sites are retained, so as to achieve the improvement of cycle stability and energy density. On the one hand, the high-entropy oxide (HEO) synthesized under the guidance of "entropy engineering" stabilizes the crystal structure due to high entropy, inhibiting the fragmentation and collapse of the crystal structure during the charge and discharge process; on the other hand, high entropy promotes the increase of reactive active sites, improving the reversible capacity of the energy storage device. However, at the same time, in high-entropy oxides, the complex arrangement of various cations and the high degree of internal grain disorder cause serious lattice distortion, resulting in the aggregation of electrons at grain boundaries, causing a decrease in the long-distance electron transport rate.

[0005] Therefore, designing a reasonable high-entropy oxide composition, under the condition of meeting the high-entropy effect, and improving its conductivity by auxiliary means, realizing the long-distance transport of reaction electrons, expanding the reaction area, improving the utilization rate of active sites, and enhancing the energy storage performance. This can not only expand the material system of high-entropy oxides, but also deeply understand its electrochemical energy storage mechanism, providing important support for the development of electrochemical energy storage devices, and having important research significance and application value.

[0006] At present, most of the related research focuses on the composition design and morphology regulation of HEO. For example, Li et al. prepared a series of (FeCoCrMn) with different pore sizes 3 O 4The best electrochemical performance of the HEO sample is: E m = 53 Wh Kg -1 , P m = 400.8 W Kg -1 . The (FeCoCrMnNi) 3 O 4 HEO prepared by Yin et al. through low-temperature calcination has E m = 103.8 Wh Kg -1 , P m = 225 W Kg -1 . Certain progress has been made in the research on the preparation of high-entropy oxides and their electrochemical energy storage performance. These studies provide important references and guidance for the application and development of high-entropy oxides and have broad application prospects in the field of electrochemical energy storage. However, limited by the low intrinsic conductivity of oxides, oxides cannot fully exert their electrochemical activity. In recent years, research scholars have improved the conductivity of oxides through the optimization of composite material systems. For example, Che et al. prepared a Co 3 O 4 @MnO 2 heterostructure. At 1 A g -1 , C m = 671 F g -1 . The assembled Co 3 O 4 @MnO 2 / / AC ASC device has an energy density of 34.1 Wh Kg -1 and a power density of 750 W Kg -1 . Kumbhar prepared ZnCo 2 O 4 -MnO 2 nanosheets through two steps of electrodeposition and hydrothermal treatment. At 1 A g -1 , C m = 2057 F g -1 . The assembled ZnCo 2 O 4 -MnO 2 / / AC ASC has a maximum energy density of 69 Wh Kg -1 at a current density of 0.75 A g -1 and a maximum power density of 4.9 KW Kg -1 at a current density of 6.25 A g -1 . The above improvement methods mainly involve the target oxide and the active oxide MnO 2Interact to form a heterostructure, thereby improving its electrical conductivity. However, the alloy phase has excellent intrinsic electrical conductivity, and there has been no reported example of combining the alloy phase with the oxide system to synergistically enhance the electrochemical energy storage capacity. The present invention proposes a completely new strategy for enhancing the electrochemical energy storage capacity of high-entropy oxides: in-situ generating an alloy phase in the high-entropy oxide system to form a coating structure. The alloy phase serves as a "post station" for electron transport and can achieve longer-distance electron transport.

[0007] The in-situ generated CuAg / HEO coating structure has the following advantages: (1) The CuAg alloy phase can improve the electrical conductivity of HEO and broaden the reaction region; (2) The in-situ generated CuAg alloy phase is uniformly distributed in the HEO system and will not cause local agglomeration; (3) The CuAg alloy phase can also contribute a part of the double-layer capacitance to the electrode material and enhance the energy storage performance of the composite material. Summary of the Invention

[0008] In view of the problem that the low intrinsic electrical conductivity of high-entropy oxides leads to low energy density, the present invention proposes a corresponding solution. The feature lies in that an alloy phase generated in-situ in the high-entropy oxide system is uniformly distributed in the high-entropy oxide system to form a coating structure. This patent first proposes an in-situ generated CuAg alloy phase / HEO coating structure. Since the alloy phase has high intrinsic electrical conductivity, it can improve the electrical conductivity of high-entropy oxides, enable long-distance electron transport, broaden the reaction region, and improve the electrochemical energy storage capacity. While taking into account the high power density, high energy density is achieved.

[0009] A preparation method of an electrode material with an in-situ generated CuAg / HEO coating structure is characterized by including the following steps:

[0010] (1) Dissolve cobalt nitrate, nickel nitrate, chromium nitrate, manganese nitrate, copper nitrate and iron nitrate in deionized water, stir well, and then add citric acid and ethylene glycol to the solution and continue to stir until evenly mixed;

[0011] (2) Heat the mixed solution obtained in step (1) in a water bath until a colloid is obtained;

[0012] (3) Place the colloid obtained in step (2) in an oven to evaporate the water and obtain a precursor;

[0013] (4) Grind the precursor obtained in step (3) into powder, put it into a tubular furnace, control the temperature at 600 °C, and calcine for 6 h; after cooling with the furnace, take out the sample and grind it into powder to obtain high-entropy oxide powder;

[0014] (5) Weigh the high-entropy oxide powder obtained in step (4), dissolve it in deionized water, immediately add silver nitrate and ethylene glycol, stir evenly under light-shielded conditions, pour the solution into a reaction kettle and seal it;

[0015] (6) Place the reaction kettle into an incubator, heat it to 180 °C, keep it warm for 6 h, cool it to room temperature after the reaction ends, and filter the reaction solution to obtain the initially formed product.

[0016] (7) Collect the initially formed product obtained in step (6), wash it alternately with deionized water and absolute ethanol, and then place it in a vacuum drying oven to dry in a vacuum environment to obtain the CuAg / HEO electrode material with an in-situ formed coating structure.

[0017] In step (1), the molar ratio of cobalt nitrate, nickel nitrate, chromium nitrate, manganese nitrate, copper nitrate and iron nitrate is 1:1:1:1:1:10, the molar ratio of citric acid to the sum of metal ions is 1.5 - 3.5:1, and the volume ratio of ethylene glycol to the solution is 3 - 5:40 - 50.

[0018] In step (2), control the water bath temperature at 80 °C.

[0019] In step (3), control the oven temperature at 65 °C and the drying time at 12 h.

[0020] In step (5), for every 150 mg of high-entropy oxide powder weighed, add 40 mL of deionized water to dissolve it. The molar ratio of the sum of metal cations in the high-entropy oxide powder to Ag ions is 1:0.5 - 2, and the volume ratio of ethylene glycol to deionized water is 5 - 15:40.

[0021] Compared with the prior art, the present invention has the following obvious effects:

[0022] A preparation method of a CuAg / HEO electrode material with an in-situ formed coating structure disclosed by the present invention, by reasonably designing the composition of the high-entropy oxide, selecting Co element according to high chemical compatibility; selecting Fe and Ni elements according to high electrochemical activity; selecting Cr and Mn elements according to ionic multi-valence states; selecting Cu element according to charge compensation. The atomic size differences of the 6 kinds of metals are relatively small. While satisfying sufficient configurational entropy, it also preserves a relatively large polyhedral gap, facilitating ion transport. Considering that Cu has charge compensation and the CuAg alloy has high electrical conductivity, silver nitrate and a reducing agent are selected to partially displace Cu atoms from the lattice of the high-entropy oxide, and a CuAg / HEO electrode material with an in-situ formed coating structure is generated through a chemical reaction. In the application as an electrode material, the alloy phase can serve as a "post station" for long-distance electron transport, enabling the electrode material to more effectively exchange electrons with the electrolyte and improving the energy storage capacity of the supercapacitor.

[0023] The electrode material prepared by the method for preparing an electrode material with an in-situ generated CuAg / HEO coating structure disclosed in the present invention has a higher specific capacitance while maintaining fast charge and discharge compared with the HEO electrode material. In the voltage window of 0.2 - 0.55V, the maximum specific capacitance is 3834F g -1 . Description of the Drawings

[0024] Figure 1 It shows a schematic flow chart of a CuAg / HEO electrode material with an in-situ generated coating structure prepared by this method.

[0025] Figure 2 It shows the XRD pattern of a CuAg / HEO electrode material with an in-situ generated coating structure prepared in Examples 1 - 4.

[0026] Figure 3 It shows the SEM image of a CuAg / HEO electrode material with an in-situ generated coating structure prepared in Example 1.

[0027] Figure 4 It shows the SEM image of a CuAg / HEO electrode material with an in-situ generated coating structure prepared in Example 2.

[0028] Figure 5 It shows the SEM image of a CuAg / HEO electrode material with an in-situ generated coating structure prepared in Example 3.

[0029] Figure 6 It shows the SEM image of a CuAg / HEO electrode material with an in-situ generated coating structure prepared in Example 4.

[0030] Figure 7 It shows the performance test chart of a CuAg / HEO electrode material with an in-situ generated coating structure prepared in Example 1.

[0031] Figure 8 It shows the performance test chart of a CuAg / HEO electrode material with an in-situ generated coating structure prepared in Example 2.

[0032] Figure 9 It shows the performance test chart of a CuAg / HEO electrode material with an in-situ generated coating structure prepared in Example 3.

[0033] Figure 10 It shows the performance test chart of a CuAg / HEO electrode material with an in-situ generated coating structure prepared in Example 4.

[0034] Figure 11 It shows the mapping diagram of a CuAg / HEO electrode material with an in-situ generated coating structure prepared in Example 2. Detailed implementation manners

[0035] In order to enable those skilled in the art to better understand the solution of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts shall fall within the protection scope of the present invention.

[0036] The present invention will be further described below in conjunction with specific embodiments.

[0037] Embodiment 1:

[0038] (1) Dissolve 1.1 mmol of cobalt nitrate, 1.1 mmol of nickel nitrate, 1.1 mmol of chromium nitrate, 1.1 mmol of manganese nitrate, 1.1 mmol of copper nitrate and 11 mmol of iron nitrate in deionized water, stir well, and add 24.75 mmol of citric acid and 3 mL of ethylene glycol after mixing evenly, and continue to stir until evenly mixed;

[0039] (2) Heat the solution in step (1) in a water bath, control the water temperature at 80 °C until a colloid is obtained;

[0040] (3) Place the colloid in step (2) in an oven, control the temperature at 65 °C, and evaporate to dryness for 12 h to obtain a precursor;

[0041] (4) Grind the precursor in step (3) into powder, put it into a tubular furnace, control the temperature at 600 °C, and calcine for 6 h; take out the sample after cooling with the furnace and grind it into powder to obtain high-entropy oxide powder;

[0042] (5) Weigh 116.5 mg of high-entropy oxide powder, dissolve it in deionized water, immediately add 42.5 mg of silver nitrate and 10 mL of ethylene glycol, stir evenly under light-shielded conditions, and pour the solution into a reaction kettle and seal it;

[0043] (6) Place the reaction kettle in an incubator, heat it to 180 °C, keep it warm for 6 h, cool it to room temperature after the reaction is completed, and filter the reaction solution to obtain the initially formed product;

[0044] (7) Collect the initially formed product in step (6), wash it alternately with deionized water and absolute ethanol, and then place it in a vacuum drying oven to dry in a vacuum environment to obtain an in-situ generated CuAg / HEO coated structure electrode material. Figure 2The column where x = 0.5 shows the XRD result diagram in this embodiment. It shows that on the basis of retaining the original HEO spinel structure, diffraction peaks of Ag also appear in the obtained electrode material, indicating that the CuAg alloy is a single solid solution with Cu as solute atoms and Ag as solvent atoms, preliminarily proving the preliminary synthesis of the target material. Figure 3 This is the SEM diagram in this embodiment. The results show that the CuAg alloy adheres to large HEO particles without obvious agglomeration, proving the successful synthesis of the coated structure of the target material. Figure 7 This is the CV curve and GCD curve of this embodiment. The CV curve has a pair of obvious redox peaks, indicating that this electrode material can store electrical energy through reversible redox reactions. By Figure 7 calculating the GCD curve, its specific capacitance is 2743 F g -1 .

[0045] Example 2:

[0046] (1) Dissolve 1.1 mmol of cobalt nitrate, 1.1 mmol of nickel nitrate, 1.1 mmol of chromium nitrate, 1.1 mmol of manganese nitrate, 1.1 mmol of copper nitrate and 11 mmol of iron nitrate in deionized water, stir well, and after mixing evenly, add 24.75 mmol of citric acid and 3 mL of ethylene glycol, and continue to stir until evenly mixed;

[0047] (2) Heat the solution in step (1) in a water bath, control the water temperature at 80 °C until a colloid is obtained;

[0048] (3) Place the colloid in step (2) in an oven, control the temperature at 65 °C, and evaporate to dryness for 12 h to obtain a precursor;

[0049] (4) Grind the precursor in step (3) into powder, put it into a tube furnace, control the temperature at 600 °C, and calcine for 6 h; after cooling with the furnace, take out the sample and grind it into powder to obtain high-entropy oxide powder;

[0050] (5) Weigh 86.21 mg of the high-entropy oxide powder, dissolve it in deionized water, then add 62.9 mg of silver nitrate and 10 mL of ethylene glycol, stir evenly under light-shielded conditions, and pour the solution into a reaction kettle and seal it;

[0051] (6) Place the reaction kettle in a constant temperature oven, heat it to 180 °C, keep it warm for 6 h, after the reaction is completed, cool it to room temperature, and filter the reaction solution to obtain the initial product formed;

[0052] (7) Collect the initial product in step (6), wash it alternately with deionized water and absolute ethanol, and then place it in a vacuum drying oven to dry in a vacuum environment to obtain an in-situ generated CuAg / HEO coated structure electrode material. Figure 2The column where x = 1.0 shows the XRD result diagram in this example. It shows that on the basis of retaining the original HEO spinel structure, diffraction peaks of Ag also appear, indicating that the CuAg alloy is a single solid solution with Cu as the solute atom and Ag as the solvent atom, initially proving the preliminary synthesis of the target material. Figure 4 This is the SEM diagram in this example. The results show that the CuAg alloy adheres to large HEO particles without obvious agglomeration, proving the successful synthesis of the coated structure of the target material. Figure 8 This is the CV curve and GCD curve of this example. The CV curve has a pair of obvious redox peaks, indicating that the electrode material can store electrical energy through reversible redox reactions. By Figure 8 calculating the GCD curve, its specific capacitance is 3834 F g -1 . Figure 11 This is the HAADF-STEM image and the elemental distribution mapping diagram of this example. The more intuitive results show that small CuAg alloys adhere to the periphery of large HEO particles, forming a coated structure. The distribution rules of Ag and Cu elements in the small particles are highly consistent, confirming from the perspective of elemental distribution that the small particles are CuAg alloys rather than other metal simple substances. In the large particles, each element is evenly distributed without obvious segregation, ensuring the basic structure of HEO.

[0053] Example 3:

[0054] (1) Dissolve 1.1 mmol of cobalt nitrate, 1.1 mmol of nickel nitrate, 1.1 mmol of chromium nitrate, 1.1 mmol of manganese nitrate, 1.1 mmol of copper nitrate and 11 mmol of iron nitrate in deionized water, stir well, and after mixing evenly, add 24.75 mmol of citric acid and 3 mL of ethylene glycol, and continue to stir until evenly mixed;

[0055] (2) Heat the solution in step (1) in a water bath, control the water temperature at 80 °C until most of the water evaporates to obtain a colloid;

[0056] (3) Place the colloid in step (2) in an oven, control the temperature at 65 °C, and evaporate it for 12 h to obtain a precursor;

[0057] (4) Grind the precursor in step (3) into powder, put it into a tube furnace, control the temperature at 600 °C, and calcine for 6 h; after cooling with the furnace, take out the sample and grind it into powder to obtain high-entropy oxide powder;

[0058] (5) Weigh 69.9 mg of high-entropy oxide powder, dissolve it in deionized water, immediately add 51.0 mg of silver nitrate and 10 mL of ethylene glycol, stir evenly under light-shielded conditions, and pour the solution into a reaction kettle and seal it;

[0059] (6) Place the reaction kettle into an incubator, heat it to 180 °C, keep it warm for 6 h, cool it to room temperature after the reaction ends, and filter the reaction solution to obtain the initially formed product.

[0060] (7) Collect the initially formed product in step (6), wash it alternately with deionized water and absolute ethanol, and then place it in a vacuum drying oven to dry in a vacuum environment to obtain the in-situ generated CuAg / HEO-coated electrode material. Figure 2 The column with x = 1.5 in this example is the XRD result diagram, showing that the obtained electrode material has diffraction peaks of Ag in addition to retaining the original HEO spinel structure, indicating that the CuAg alloy is a single solid solution with Cu as solute atoms and Ag as solvent atoms, preliminarily proving the preliminary synthesis of the target material. Figure 5 This is the SEM diagram of this example. The results show that the CuAg alloy adheres to large HEO particles without obvious agglomeration, proving the successful synthesis of the coated structure of the target material. Figure 9 This is the CV curve and GCD curve of this example. The CV curve has a pair of obvious oxidation-reduction peaks, indicating that the electrode material can store electrical energy through reversible oxidation-reduction reactions. By Figure 9 calculating the GCD curve, its specific capacitance is 3341 F g -1 .

[0061] Example 4:

[0062] (1) Dissolve 1.1 mmol of cobalt nitrate, 1.1 mmol of nickel nitrate, 1.1 mmol of chromium nitrate, 1.1 mmol of manganese nitrate, 1.1 mmol of copper nitrate and 11 mmol of iron nitrate in deionized water, stir well, and add 24.75 mmol of citric acid and 3 mL of ethylene glycol after mixing evenly, and continue to stir until evenly mixed;

[0063] (2) Heat the solution in step (1) in a water bath, control the water temperature at 80 °C until a colloid is obtained;

[0064] (3) Place the colloid in step (2) in an oven, control the temperature at 65 °C, and evaporate it for 12 h to obtain a precursor;

[0065] (4) Grind the precursor in step (3) into powder, place it in a tube furnace, control the temperature at 600 °C, and calcine for 6 h; take out the sample and grind it into powder after cooling with the furnace to obtain high-entropy oxide powder;

[0066] (5) Weigh 61.0 mg of high-entropy oxide powder, dissolve it in deionized water, immediately add 44.5 mg of silver nitrate and 10 mL of ethylene glycol, stir evenly under light-shielded conditions, pour the solution into a reaction kettle and seal it;

[0067] (6) Place the reaction kettle into an incubator, heat it to 180 °C, keep it warm for 6 h, cool it to room temperature after the reaction ends, and filter the reaction solution to obtain the initially produced product;

[0068] (7) Collect the initially produced product in step (6), wash it alternately with deionized water and absolute ethanol, and then place it in a vacuum drying oven to dry in a vacuum environment to obtain the in-situ generated CuAg / HEO coated-structured electrode material. Figure 2 In the column where x = 2.0 is the XRD result diagram of this example, showing that on the basis of retaining the original HEO spinel structure of the obtained electrode material, the diffraction peak of Ag also appears, indicating that the CuAg alloy is a single solid solution with Cu as the solute atom and Ag as the solvent atom, initially proving the preliminary synthesis of the target material. Figure 6 This is the SEM diagram of this example. The results show that the CuAg alloy adheres to large HEO particles and no obvious agglomeration occurs, proving the successful synthesis of the coated structure of the target material. Figure 10 This is the CV curve and GCD curve of this example. The CV curve has a pair of obvious redox peaks, indicating that the electrode material can achieve the storage of electrical energy through reversible redox reactions. By Figure 10 calculating the GCD curve, its specific capacitance is 2743 F g -1 .

Claims

1. A method for preparing a CuAg / HEO electrode material with a coating structure, characterized in that: The alloy phase generated in situ in the high entropy oxide system is evenly distributed in the high entropy oxide system to form a coating structure. The specific steps are as follows: (1) dissolving cobalt nitrate, nickel nitrate, chromium nitrate, manganese nitrate, copper nitrate and iron nitrate in deionized water and stirring thoroughly, adding citric acid and ethylene glycol to the solution after mixing evenly, and continuing to stir until the mixture is evenly mixed; (2) heating the mixed solution obtained in step (1) in a water bath until a colloid is obtained; (3) placing the colloid obtained in step (2) in an oven to evaporate the water to obtain a precursor; (4) grinding the precursor obtained in step (3) into powder, placing it in a tube furnace for calcination; after cooling in the furnace, taking out the sample and grinding it into powder to obtain a high entropy oxide powder; (5) Weighing high entropy oxide powder, dissolving it in deionized water, then adding silver nitrate and ethylene glycol, stirring evenly in a light-proof condition, and pouring the solution into a reaction kettle and sealing it; (6) placing the reactor in a thermostatic box, heating and maintaining the reaction, cooling to room temperature after the reaction is completed, and filtering the reaction liquid to obtain the generated primary product; (7) Collecting the preliminary finished product obtained in step (6), washing it alternately with deionized water and anhydrous ethanol, and then placing it in a vacuum drying oven and drying it under a vacuum environment to obtain a CuAg / HEO electrode material with an in-situ generated coating structure.

2. The method for preparing an electrode material with an in-situ generated CuAg / HEO coating structure according to claim 1, characterized in that: In step (1), the molar ratio of cobalt nitrate, nickel nitrate, chromium nitrate, manganese nitrate, copper nitrate and ferric nitrate is 1:1:1:1:1:10, the molar ratio of citric acid and the sum of metal ions is 1.5-3.5:1, and the volume ratio of ethylene glycol to the solution is 3-5:40-50.

3. The method for preparing an electrode material with an in-situ generated CuAg / HEO coating structure according to claim 1, characterized in that: In step (2), the water bath temperature is controlled at 80°C.

4. The method for preparing an electrode material with an in-situ generated CuAg / HEO coating structure according to claim 1, characterized in that: In step (3), the oven temperature is controlled at 65° C. and the drying time is 12 h.

5. The method for preparing an electrode material with an in-situ generated CuAg / HEO coating structure according to claim 1, characterized in that: In step (4), the calcination temperature is 600° C. and the calcination time is 6 hours.

6. The method for preparing an electrode material with an in-situ generated CuAg / HEO coating structure according to claim 1, characterized in that: In step (5), 150 mg of high entropy oxide powder is weighed and 40 mL of deionized water is added to dissolve the powder. The molar ratio of the sum of metal cations in the high entropy oxide powder to Ag ions is 1:0.5-2, and the volume ratio of ethylene glycol to deionized water is 5-15:

40.

7. The method for preparing an electrode material with an in-situ generated CuAg / HEO coating structure according to claim 1, characterized in that: In step (6), the heating temperature is increased to 180° C. and the heat preservation time is 6 h.

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