A polyarylate separator for a battery with a lithium alloy negative electrode and its application

Abstract

This application relates to the technical field of lithium batteries, and specifically discloses a polyarylate separator for batteries with a lithium alloy negative electrode and its application. In the separator of this application, through the hydrogen bonds formed by the synergistic association between the components inside the coating and the strengthening effects generated by each component respectively, the overall tensile ability of the separator is significantly improved, fully overcoming the defect of insufficient tensile strength of the existing separator. The separator of this application is not prone to breakage during the production, installation, and operation of lithium batteries, can remain stable for a long time, and is conducive to fully realizing the improvement of the stability of lithium batteries.

Description

Technical Field

[0001] This application relates to the technical field of lithium batteries. More specifically, it relates to a polyarylate separator for batteries with a lithium alloy negative electrode and its application. Background Art

[0002] Lithium batteries are rechargeable batteries. The related concept was first proposed in the United States in the 1950s and entered the practical stage in the 1970s. Lithium batteries mainly work by the movement of lithium ions between the positive and negative electrodes and play an important role in emerging high-end fields such as electric vehicles, 3C electronic products, and energy storage power stations. With the booming development of these fields in recent years, new products have put forward higher requirements for the stability of lithium batteries.

[0003] Traditional lithium batteries use lithium metal as the negative electrode material. During the charging process, lithium ions gain electrons at the cathode and are reduced to lithium metal. The lithium metal produced in this case is prone to form dendrites with a relatively large specific surface area, which not only easily leads to battery short circuits but also affects the chemical activity of the electrolyte solvent, bringing huge safety hazards to lithium batteries and reducing the stability of lithium batteries. Since the 1960s, scholars at home and abroad have been studying methods to inhibit dendrite growth, and lithium alloy negative electrode materials are one of the important research results. Lithium alloy negative electrode materials refer to alloys formed by lithium and elements such as aluminum, boron, silicon, tin, carbon, and bismuth, which can well inhibit the growth of dendrites and improve the stability of lithium batteries. And according to relevant research, in PEO polymer gel electrolytes, lithium alloys have higher cycle stability than metallic lithium at different current densities. The full-cell performance test with an LFP positive electrode shows that lithium alloys have better electrochemical performance than pure lithium metal and can solve a series of problems existing in pure lithium metal negative electrodes. In addition, in PEO gel polymer electrolytes added with LLZTO, lithium alloy electrodes also show excellent electrochemical performance.

[0004] Regarding the above related technologies, the inventor believes that although using lithium alloys as the negative electrode material can improve the stability of lithium batteries to a certain extent, the current lithium battery separators generally have low tensile strength and are prone to breakage during the production, installation, and operation of lithium batteries, resulting in the failure of lithium batteries and making it difficult to fully improve the stability of lithium batteries. Summary of the Invention

[0005] In the related technology, the tensile strength of lithium battery separators is generally low and they are easily damaged, making it difficult to fully improve the stability of lithium batteries. To improve this defect, this application provides a polyarylate separator for batteries with a lithium alloy negative electrode and its application.

[0006] In the first aspect, this application provides a polyarylate separator for batteries with a lithium alloy negative electrode, adopting the following technical solution:

[0007] A polyarylate separator for a battery with a lithium alloy negative electrode, the separator comprising a base film and a coating, the coating being coated on the surface of the base film, the coating being formed after curing a polyarylate coating solution, the polyarylate coating solution comprising the following components by weight percentage: aromatic polyester 15-20%, nanocellulose 1.2-1.6%, adhesive 3-5%, reinforcing agent 3.2-3.6%, filler 4.3-4.5%, and the balance being made up to 100% with a solvent; the reinforcing agent comprises polyimide, the filler comprises a filled powder and a modified whisker, the modified whisker being an inorganic whisker grafted with a copolymer chain segment on the surface, and the copolymer chain segment having an amino group.

[0008] By adopting the above technical solution, the present application prepares a coating on the surface of the base film using a polyarylate coating solution, and adds nanocellulose, a reinforcing agent and a filler to the polyarylate coating solution, and preferably uses polyimide as a component of the reinforcing agent. Nanocellulose is a green and renewable nanomaterial obtained by hydrolyzing natural cellulose and has a large number of hydroxyl groups on the surface; on the one hand, the polyimide in the reinforcing agent can achieve reinforcement through the rigidity of the aromatic ring and imide ring itself, and on the other hand, it can also participate in the formation of hydrogen bonds through the nitrogen and oxygen atoms in the imide ring; the modified whisker in the filler inherits the good mechanical properties of the inorganic whisker and can form hydrogen bonds with components such as nanocellulose, polyimide and aromatic polyester through the copolymer chain segment grafted on the surface. Through the hydrogen bonds formed by the synergistic association between the components inside the coating and the reinforcement effects generated by each component, the overall tensile ability of the separator is significantly improved, thus effectively overcoming the defect of insufficient tensile strength of the existing separator. Therefore, the separator of the present application is not easily damaged during the production, installation and operation of lithium batteries, can remain stable for a long time, and is conducive to fully improving the stability of lithium batteries.

[0009] Preferably, the modified whisker is prepared according to the following method:

[0010] (1) Dry the inorganic whisker, then mix the inorganic whisker and a silane coupling agent and add them to an ethanol aqueous solution, first perform ultrasonic dispersion, and then perform oil bath heating to obtain a silanized whisker; in this step, the silane coupling agent includes γ-methacryloxypropyltrimethoxysilane.

[0011] (2) Add the silanized whisker and SDS to water and perform ultrasonic dispersion to obtain a whisker dispersion liquid. Add an aqueous solution of potassium persulfate and a monomer to the whisker dispersion liquid, and perform a heating reaction under nitrogen protection. After the reaction is completed, perform demulsification, filtration and drying to obtain a modified whisker; in this step, the monomer includes acrylamide.

[0012] By adopting the above technical solution, the present application first treats the inorganic whiskers with a silane coupling agent to introduce carbon-carbon double bonds on the surface of the inorganic whiskers, and then makes them copolymerize with monomers under the initiation of potassium persulfate, thereby grafting copolymer segments containing amino groups on the surface of the inorganic whiskers to obtain modified whiskers.

[0013] Preferably, in step (1) of preparing the modified whiskers, the inorganic whiskers used are one of potassium titanate whiskers and mesoporous titanium dioxide whiskers.

[0014] By adopting the above technical solution, the present application optimizes the type of inorganic whiskers, and the above two types of whiskers can be used as matrix materials to prepare modified whiskers.

[0015] Preferably, in step (2) of preparing the modified whiskers, the monomers used also include fatty acids.

[0016] By adopting the above technical solution, fatty acids can introduce carboxyl groups into the copolymer segments, and the long-chain hydrocarbon group structure of fatty acids itself provides a large activity range for the carboxyl groups, which is conducive to the full formation of hydrogen bonds, enabling the tensile strength of the coating to be improved and helping to fully overcome the defect of insufficient tensile strength of the existing separator.

[0017] Preferably, the fatty acid is selected from oleic acid or linolenic acid.

[0018] By adopting the above technical solution, compared with oleic acid, there are three carbon-carbon double bonds in linolenic acid that can participate in polymerization, so it can increase the number of branches of the copolymer segments, which is conducive to the full formation of hydrogen bonds, enabling the tensile strength of the coating to be improved and helping to fully overcome the defect of insufficient tensile strength of the existing separator.

[0019] Preferably, in step (2) of preparing the modified whiskers, the monomers used also include styrene.

[0020] By adopting the above technical solution, the benzene ring introduced by styrene can make the copolymer segments on the surface of the modified whiskers have good compatibility with aromatic polyesters and polyimides, which is conducive to the uniform dispersion of the modified whiskers, promotes the uniform distribution of hydrogen bonds, thereby improving the tensile strength of the coating and enhancing the overall tensile strength of the separator.

[0021] Preferably, in step (2) of preparing the modified whiskers, the monomers used also include polyethylene glycol acrylate.

[0022] By adopting the above technical solution, after polyethylene glycol acrylate participates in copolymerization, it can introduce polyethylene glycol branches into the copolymer chain segments. The polyethylene glycol branches contain a large number of ether bonds, have good deformability, are easy to entangle with other chain segments, and the ether bonds can also participate in the formation of hydrogen bonds. When cooperating with components such as nanocellulose, polyimide, and aromatic polyester, it can further increase the distribution density of hydrogen bonds, which helps to improve the overall tensile strength of the separator.

[0023] Preferably, the filled powder includes carbonized diatomaceous earth, and the carbonized diatomaceous earth is prepared by the following method: Mix diatomaceous earth and glucose in water, filter after stirring, dry the filter residue to constant weight, and then perform carbonization treatment in a muffle furnace to obtain carbonized diatomaceous earth.

[0024] By adopting the above technical solution, in this application, glucose is used as the carbon source to carbonize and modify diatomaceous earth. After carbonization modification, the obtained carbonized diatomaceous earth has a large surface roughness and many silanol groups, and can form a hydrogen bond cross-linked structure with higher complexity with components such as nanocellulose, polyimide, and aromatic polyester, which helps to improve the overall tensile strength of the separator.

[0025] Preferably, the dosage of the carbonized diatomaceous earth accounts for 3-5% of the total weight of the filler.

[0026] By adopting the above technical solution, this application optimizes the dosage range of carbonized diatomaceous earth, which helps to improve the overall tensile strength of the separator.

[0027] In the second aspect, this application provides an application of a polyarylate separator for a battery with a lithium alloy negative electrode, adopting the following technical solution.

[0028] An application of a polyarylate separator for a battery with a lithium alloy negative electrode, installing the polyarylate separator for a battery with a lithium alloy negative electrode as described in any one of the above in a lithium battery with a lithium alloy negative electrode.

[0029] By adopting the above technical solution, the lithium alloy negative electrode can prevent the generation of lithium dendrites during the operation of the lithium battery, reducing the impact of lithium dendrites on the stability of the lithium battery. And the separator has high stability and is not easily damaged during the production, installation, and operation of the battery, and can maintain stability for a long time, thus fully realizing the improvement of the stability of the lithium battery.

[0030] In summary, this application has the following beneficial effects:

[0031] 1. The separator of this application is not easily damaged during the production, installation, and operation of the lithium battery, can maintain stability for a long time, is beneficial to fully realizing the improvement of the stability of the lithium battery, and promotes the development of lithium battery technology.

[0032] 2. In this application, polyethylene glycol acrylate is preferably used as the monomer in the preparation of modified whiskers, which can introduce polyethylene glycol branches into the copolymer chain segments. The polyethylene glycol branches contain a large number of ether bonds, which have good deformability, are easy to entangle with other chain segments, and the ether bonds can also participate in the formation of hydrogen bonds. When cooperating with components such as nanocellulose, polyimide, and aromatic polyester, it can further increase the distribution density of hydrogen bonds, helping to improve the overall tensile strength of the separator.

[0033] 3. In this application, diatomite is carbonized and modified to obtain carbonized diatomite. The surface of carbonized diatomite has a large roughness and has many silanol groups, which can form a hydrogen bond cross-linked structure with higher complexity with components such as nanocellulose, polyimide, and aromatic polyester, helping to improve the overall tensile strength of the separator. Detailed implementation manners

[0034] The following further elaborates on this application in combination with examples, preparation examples, and comparative examples. The raw materials involved in this application can all be obtained through commercial channels.

[0035] Preparation example of modified whiskers

[0036] The following takes Preparation Example 1 as an example for illustration.

[0037] Preparation Example 1

[0038] In this preparation example, the ethanol aqueous solution is prepared from anhydrous ethanol and deionized water according to a volume ratio of 7:3; the inorganic whiskers are potassium titanate whiskers (average diameter is 47 nm, average length is 0.85 μm), the silane coupling agent is γ-methacryloxypropyltrimethoxysilane, and the monomer is acrylamide.

[0039] In this preparation example, the modified whiskers are prepared according to the following method:

[0040] (1) Dry the inorganic whiskers at 110 °C. After 5 h, mix 100 g of inorganic whiskers and 10 g of silane coupling agent and add them to 2 L of ethanol aqueous solution. First, perform ultrasonic dispersion for 1 h, and then perform oil bath heating at 100 °C for 3 h to obtain silanized whiskers;

[0041] (2) Add 100 g of silanized whiskers and 1 g of SDS to 2 L of water and perform ultrasonic dispersion to obtain a whisker dispersion liquid. Add 10 mL of potassium persulfate aqueous solution containing 0.25 g of potassium persulfate and 25 g of monomer to the whisker dispersion liquid, and perform a heating reaction at 80 °C for 6 h under nitrogen protection. After the reaction, perform demulsification, filtration, and drying to obtain modified whiskers.

[0042] Preparation Example 2

[0043] This preparation example is different from Preparation Example 1 in that the inorganic whiskers used in step (1) are mesoporous titanium dioxide whiskers (average diameter 120 nm, average length 1.2 μm, specific surface area 65 m 2 / g).

[0044] Preparation Example 3

[0045] This preparation example is different from Preparation Example 2 in that the monomer used in step (2) further includes fatty acid, and the molar ratio of fatty acid to acrylamide is 1:35. The fatty acid selected is oleic acid.

[0046] Preparation Example 4

[0047] This preparation example is different from Preparation Example 3 in that the fatty acid selected is linolenic acid.

[0048] Preparation Example 5

[0049] This preparation example is different from Preparation Example 4 in that the monomer used in step (2) further includes styrene, and the molar ratio of styrene to acrylamide is 1:10.

[0050] Preparation Example 6

[0051] This preparation example is different from Preparation Example 5 in that the monomer used in step (2) further includes polyethylene glycol acrylate (average molecular weight 2800).

[0052] Preparation Example of Carbonized Diatomite

[0053] Taking Preparation Example 7 as an example, it is described as follows.

[0054] Preparation Example 7

[0055] In this preparation example, the carbonized diatomite is prepared according to the following method:

[0056] 50 g of diatomite with an average particle size of 20 nm and 50 g of glucose are added to 0.5 L of water and mixed. After stirring at a rate of 400 rpm for 6 h, filtration is carried out. The filter residue is dried to constant weight at 70 °C, and then carbonization treatment is carried out at a temperature of 300 °C for 2 h in a muffle furnace to obtain carbonized diatomite.

[0057] Examples

[0058] Examples 1-5

[0059] Taking Example 1 as an example, it is described as follows.

[0060] Example 1

[0061] In this embodiment, the aromatic polyester is the aromatic polyester (LCPT820) provided by Mitsubishi Engineering-Plastics Corporation of Japan, the reinforcing agent is polyimide (model P84@NT2), the average length of the nanocellulose is 280 nm, and the average diameter is 5 nm; the filler is composed of a filled powder and modified whiskers. The amount of the filled powder accounts for 2.5% of the total weight of the filler. The filled powder is diatomaceous earth with an average particle size of 20 nm. The modified whiskers are prepared according to the method of Preparation Example 1. The adhesive is a vinylidene fluoride-trifluoroethylene copolymer, and the solvent is DMF.

[0062] This embodiment provides a polyarylate separator for a battery with a lithium alloy negative electrode, including a base film and a coating. The base film is a PET non-woven fabric with a thickness of 25 μm and a porosity of 59%. The coating is coated on the surface of the base film. The coating is formed after curing a polyarylate coating solution. The polyarylate coating solution includes the following components by weight percentage: 15% of aromatic polyester, 1.2 - 1.6% of nanocellulose, 3 - 5% of adhesive, 3.2 - 3.6% of reinforcing agent, 4.3 - 4.5% of filler, and the balance is made up to 100% with solvent.

[0063] The polyarylate separator for a battery with a lithium alloy negative electrode in this embodiment is prepared according to the following method:

[0064] (1) Mix the aromatic polyester, nanocellulose, adhesive, reinforcing agent, filler and solvent to obtain a polyarylate coating solution for standby;

[0065] (2) Adopt the gravure coating method and coat the polyarylate coating solution on both sides of the base film at a coating rate of 5 m / min to obtain a coating layer;

[0066] (3) Perform steam preheating on the coating layer for 15 s in an environment with 95% humidity, and then perform hot air drying to cure the coating layer into a coating with a thickness of 7.5 μm, so as to obtain a polyarylate separator for a battery with a lithium alloy negative electrode.

[0067] This embodiment provides an application of a polyarylate separator for a battery with a lithium alloy negative electrode. The polyarylate separator of this embodiment is installed in a lithium battery with a lithium alloy negative electrode.

[0068] As shown in Table 1, the main difference between Examples 1 - 5 lies in the different raw material ratios of the polyarylate coating solution.

[0069] Table 1 Raw material ratios of the polyarylate coating solution

[0070]

[0071] Examples 5 - 10

[0072] As shown in Table 2, the difference between Examples 5 - 10 lies in the different preparation examples of the modified whiskers.

[0073] Preparation Examples of Modified Whiskers

[0074]

[0075]

[0076] Example 11

[0077] The difference between this example and Example 10 is that the filled powder is diatomite carbide of Preparation Example 7.

[0078] Example 12

[0079] The difference between this example and Example 11 is that the dosage of the modified diatomite accounts for 3% of the total weight of the filler.

[0080] Example 13

[0081] The difference between this example and Example 11 is that the dosage of the modified diatomite accounts for 4% of the total weight of the filler.

[0082] Example 14

[0083] The difference between this example and Example 11 is that the dosage of the modified diatomite accounts for 5% of the total weight of the filler.

[0084] Comparative Example

[0085] Comparative Example 1

[0086] The difference between this comparative example and Example 1 is that the components of the polyarylate coating solution do not include modified whiskers.

[0087] Comparative Example 2

[0088] The difference between this comparative example and Example 1 is that the modified whiskers are replaced with unmodified potassium titanate whiskers.

[0089] Comparative Example 3

[0090] The difference between this comparative example and Example 1 is that the components of the polyarylate coating solution do not include nanocellulose.

[0091] Comparative Example 4

[0092] The difference between this comparative example and Example 1 is that the components of the polyarylate coating solution do not include reinforcing agents.

[0093] Performance Detection Test Method

[0094] The tensile strength of the diaphragms of each example and comparative example was detected using a universal tensile testing machine (Zwick Z100). When testing, the sample size selected was 20 mm × 80 mm, and the tensile speed was set at 10 mm / min. After the detection, based on the tensile strength of Comparative Example 1, the ratio between the tensile strength of each example and comparative example and the tensile strength of Comparative Example 1 was calculated, and this ratio was recorded as the relative tensile strength. The results are shown in Table 3.

[0095] Table 3 Relative Tensile Strength

[0096]

[0097]

[0098] Combining Examples 1-5 and Comparative Examples 1-4 and referring to Table 3, it can be seen that the diaphragms of Examples 1-5 had relatively high measured relative tensile strength. This is because the modified whiskers, polyimide in Examples 1-5 themselves have a certain reinforcing effect, and the modified whiskers can form hydrogen bonds with components such as nanocellulose, polyimide, and aromatic polyester through the copolymer segments grafted on the surface. Therefore, the coatings of Examples 1-5 had high tensile properties, fully improving the overall tensile strength of the diaphragms. In contrast, it was difficult for Comparative Examples 1-4 to fully achieve the synergistic effect among components such as modified whiskers, nanocellulose, polyimide, and aromatic polyester, so the overall tensile strength of the diaphragms was not effectively improved.

[0099] Combining Example 5 and Comparative Example 6 and referring to Table 3, it can be seen that the modified whiskers prepared using potassium titanate whiskers and mesoporous titanium dioxide whiskers could both achieve the preparation of modified whiskers, and both could improve the tensile strength of the diaphragm through synergistic cooperation with other components. Among them, the modified whiskers prepared using mesoporous titanium dioxide whiskers could contribute more to the tensile strength of the diaphragm.

[0100] Combining Example 6 and Examples 7-8 and referring to Table 3, it can be seen that both oleic acid and linolenic acid could have a certain improvement effect on the tensile strength of the diaphragm. Among them, since linolenic acid could provide more branched chains, the relative tensile strength measured in Example 8 was higher.

[0101] Combining Example 8 and Example 9 and referring to Table 3, it can be seen that the relative tensile strength measured in Example 9 was higher than that in Example 8. This is because the benzene ring introduced by styrene could make the copolymer segments on the surface of the modified whiskers have good compatibility with aromatic polyester and polyimide, which was conducive to the uniform dispersion of the modified whiskers, promoted the uniform distribution of hydrogen bonds, thus improving the tensile ability of the coating and increasing the overall tensile strength of the diaphragm.

[0102] Combined with Example 9 and Example 10 and in conjunction with Table 3, it can be seen that the relative tensile strength measured in Example 10 is higher than that in Example 9. This is because after polyethylene glycol acrylate participates in copolymerization, it can introduce polyethylene glycol branches into the copolymer chain segments. The polyethylene glycol branches contain a large number of ether bonds, which have good deformability, are easy to entangle with other chain segments, and the ether bonds can also participate in the formation of hydrogen bonds. When cooperating synergistically with components such as nanocellulose, polyimide, and aromatic polyester, it can further increase the distribution density of hydrogen bonds, contributing to improving the overall tensile strength of the separator.

[0103] Combined with Example 10, Example 11 - 14 and in conjunction with Table 3, it can be seen that the relative tensile strength measured in Example 11 - 14 is higher than that in Example 10. This is because after carbonization modification, the obtained carbonized diatomite surface has a large roughness and has more silanol groups, which can form a hydrogen bond cross-linked structure with higher complexity with components such as nanocellulose, polyimide, and aromatic polyester, contributing to improving the overall tensile strength of the separator. When the dosage of carbonized diatomite accounts for 3 - 5% of the total weight of the filler, the overall tensile performance of the separator is relatively good.

[0104] The above embodiments are merely explanations of the present application and do not limit the present application. Those skilled in the art can make modifications to the embodiments of the present application without creative contributions according to needs after reading this specification, but as long as they are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. A polyarylate separator for a battery with a lithium alloy negative electrode, characterized in that, The separator includes a base film and a coating. The coating is coated on the surface of the base film and is formed after curing a polyarylate coating solution. The polyarylate coating solution comprises the following components by weight percentage: aromatic polyester 15 - 20%, nanocellulose 1.2 - 1.6%, adhesive 3 - 5%, reinforcing agent 3.2 - 3.6%, filler 4.3 - 4.5%, and the balance is made up to 100% with a solvent; the reinforcing agent includes polyimide, the filler includes a filled powder and a modified whisker, the modified whisker is an inorganic whisker grafted with a copolymer segment on the surface, and the copolymer segment has an amino group; the filled powder includes carbonized diatomaceous earth, and the carbonized diatomaceous earth is prepared by the following method: Mix diatomaceous earth and glucose in water, filter after stirring, dry the filter residue to constant weight, and then perform carbonization treatment in a muffle furnace to obtain carbonized diatomaceous earth.

2. The polyarylate separator for batteries with a lithium alloy negative electrode according to claim 1, characterized in that, The modified whisker is prepared by the following method: (1) Dry the inorganic whisker, then mix the inorganic whisker and a silane coupling agent and add them to an ethanol aqueous solution. First, perform ultrasonic dispersion, and then perform oil bath heating to obtain a silanized whisker; in this step, the silane coupling agent includes γ-methacryloxypropyltrimethoxysilane; (2) Add the silanized whisker and SDS to water and perform ultrasonic dispersion to obtain a whisker dispersion liquid. Add an aqueous potassium persulfate solution and a monomer to the whisker dispersion liquid, and perform a heating reaction under nitrogen protection. After the reaction is completed, perform demulsification, suction filtration, and drying to obtain a modified whisker; in this step, the monomer includes acrylamide.

3. The polyarylate separator for a battery having a lithium alloy negative electrode according to claim 2, wherein, In step (1) of preparing the modified whisker, the inorganic whisker used is one of potassium titanate whisker and mesoporous titanium dioxide whisker.

4. The polyarylate separator for a battery having a lithium alloy negative electrode according to claim 2, wherein, In step (2) of preparing the modified whisker, the monomer used also includes a fatty acid.

5. The polyarylate separator for a battery with a lithium alloy negative electrode according to claim 4, characterized in that, The fatty acid is selected from oleic acid or linolenic acid.

6. The polyarylate separator for a battery having a lithium alloy negative electrode according to claim 2, wherein, In step (2) of preparing the modified whisker, the monomer used also includes styrene.

7. The polyarylate separator for a battery having a lithium alloy negative electrode according to claim 6, wherein, In step (2) of preparing the modified whisker, the monomer used also includes polyethylene glycol acrylate.

8. The polyarylate separator for a battery having a lithium alloy negative electrode according to claim 1, wherein, The dosage of the carbonized diatomaceous earth accounts for 3 - 5% of the total weight of the filler.

9. Application of a polyarylate separator for a battery with a lithium alloy negative electrode, characterized in that, Install the polyarylate separator for a battery with a lithium alloy negative electrode according to any one of claims 1 - 8 in a lithium battery with a lithium alloy negative electrode.

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