Electrode material, preparation method thereof and capacitor

Abstract

The invention provides an electrode material, a preparation method thereof and a capacitor. The electrode material comprises a cyclodextrin inclusion compound of an alkylaniline compound, a pyrrole polymer and a chitosan polymer, and the cyclodextrin inclusion compound of the alkylaniline compound, the pyrrole polymer and the chitosan polymer are interwoven to form a network structure. In the application, the cyclodextrin inclusion compound of the alkylaniline compound, the pyrrole polymer and the chitosan polymer can be interwoven with one another to form a three-dimensional network structure with a stable structure, so that the anti-swelling performance and the mechanical performance of the electrode material are improved.

Description

Technical Field

[0001] The present application relates to the technical field of capacitors, and in particular to an electrode material and a preparation method thereof, and a capacitor. Background Art

[0002] As an energy storage device, capacitors have become an important direction of energy storage due to their high power density, long cycle life and fast charging and discharging characteristics. With the increasing demand for high-performance capacitors, flexible electrode materials have broad application prospects in flexible electronics, wearable devices and other fields. Compared with traditional hard electrode materials, flexible electrode materials not only need to have good conductivity and electrochemical properties, but also need to meet certain mechanical flexibility and stability to adapt to working environments such as bendable and foldable.

[0003] In the related art, flexible electrode materials generally include conductive hydrogels, which include high molecular polymers. The network structure formed by the high molecular polymers in the conductive hydrogels plays the main mechanical role. However, the degree of cross-linking of the network structure of the conductive hydrogels is not high enough, resulting in poor mechanical properties and anti-swelling properties of the flexible electrode materials, which affects the overall performance of the capacitor. Summary of the invention

[0004] The embodiments of the present application provide an electrode material and a preparation method thereof and a capacitor, which can improve the technical problem that the mechanical properties and anti-swelling properties of the flexible electrode material are poor, which affects the comprehensive performance of the capacitor.

[0005] In a first aspect, an embodiment of the present application provides an electrode material, which includes a cyclodextrin inclusion complex of an alkylaniline compound, a pyrrole polymer and a chitosan polymer, wherein the cyclodextrin inclusion complex of an alkylaniline compound, the pyrrole polymer and the chitosan polymer are intertwined to form a network structure.

[0006] In one embodiment, the mass percentage of the cyclodextrin inclusion complex of the alkylaniline compound in the electrode material is 15%-20%; and / or

[0007] The mass percentage of the pyrrole polymer in the electrode material is 25%-35%; and / or

[0008] The mass percentage of the chitosan polymer in the electrode material is 50%-60%; and / or

[0009] The alkylaniline compound has an alkyl chain, the number of carbon atoms in the alkyl chain is n, n is an integer, 10≤n≤20; and / or

[0010] The cyclodextrin includes at least one of α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin.

[0011] In one embodiment, the alkylaniline compound includes at least one of 4-dodecylaniline, 4-hexadecylaniline, and 4-octadecylaniline.

[0012] In a second aspect, an embodiment of the present application provides a method for preparing an electrode material, the method for preparing an electrode material comprising the following steps:

[0013] Providing a first mixed solution, wherein the first mixed solution comprises an alkylaniline compound and cyclodextrin, wherein at least a portion of the alkylaniline compound is located in the cavity of the cyclodextrin to form a cyclodextrin inclusion complex of the alkylaniline compound;

[0014] Adding a pyrrole monomer and a first initiator to the first mixed solution, performing a polymerization reaction, washing and purifying, and obtaining a mixture, wherein the mixture includes a pyrrole polymer, and the pyrrole polymer is formed by a polymerization reaction of the pyrrole monomer;

[0015] Chitosan and a second initiator are added to the mixture to make the chitosan undergo a cross-linking reaction to generate a chitosan polymer, thereby obtaining an electrode material. The electrode material includes the cyclodextrin inclusion complex of the alkylaniline compound, the pyrrole polymer and the chitosan polymer intertwined with each other.

[0016] In one embodiment, the first mixed solution further includes lithocholic acid nanotubes;

[0017] In the step of adding the pyrrole monomer and the first initiator into the first mixed solution to perform a polymerization reaction, the pyrrole monomer can undergo a polymerization reaction on the surface of the lithocholic acid nanotube to form the pyrrole polymer.

[0018] In one embodiment, the method for preparing the first mixed solution comprises the following steps:

[0019] Adding an alkylaniline compound to an aqueous solution of cyclodextrin to obtain a first solution, wherein the first solution includes a cyclodextrin inclusion complex of the alkylaniline compound;

[0020] adding lithocholic acid into an aqueous sodium hydroxide solution to obtain a second solution containing the lithocholic acid nanotubes;

[0021] The first solution is added to the second solution to obtain the first mixed solution.

[0022] In one embodiment, in the step of adding the alkylaniline compound to the aqueous solution of cyclodextrin to obtain the first solution, the temperature of mixing the alkylaniline compound and the aqueous solution of cyclodextrin is 15°C-25°C, and / or the mixing is stirring mixing, the stirring speed is 450rpm / min-550rpm / min, and / or the mixing time is 10h-14h; and / or

[0023] The molar ratio of the alkylaniline compound to the cyclodextrin is (1-2): (1-2); and / or

[0024] The cyclodextrin includes at least one of α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin; and / or

[0025] The alkylaniline compound has an alkyl chain, the number of carbon atoms in the alkyl chain is n, and n is an integer, 10≤n≤20.

[0026] In one embodiment, the alkylaniline compound includes at least one of 4-dodecylaniline, 4-hexadecylaniline, and 4-octadecylaniline.

[0027] In one embodiment, in the step of adding lithocholic acid to an aqueous sodium hydroxide solution to obtain a second solution containing the lithocholic acid nanotubes, the temperature at which the lithocholic acid and the aqueous sodium hydroxide solution are mixed is 45° C.-55° C., and / or the mixing is stirring mixing, the stirring speed is 450 rpm / min-550 rpm / min, and / or the mixing time is 22h-26h; and / or

[0028] The mass ratio between the lithocholic acid and the cyclodextrin inclusion complex of the alkylaniline compound is (1-2): (1-2).

[0029] In one embodiment, in the step of adding the pyrrole monomer and the first initiator to the first mixed solution, performing a polymerization reaction, washing and purifying to obtain a mixture, the polymerization reaction temperature is -1°C-9°C, and / or the polymerization reaction time is 10h-14h; and / or

[0030] The mass ratio of the pyrrole monomer to the first mixed solution is (1-2): (0.1-2); and / or

[0031] The first initiator comprises at least one of peroxytoluic acid, ammonium persulfate, sodium persulfate and potassium persulfate; and / or

[0032] The washing and purifying detergent comprises at least one of ethanol, propanol, propylene glycol and isopropanol.

[0033] In one embodiment, in the step of adding chitosan and a second initiator to the mixture to perform a cross-linking reaction to obtain an electrode material, the temperature of the cross-linking reaction is 65° C.-75° C., and / or the time of the cross-linking reaction is 20 min-40 min, and / or the mass ratio of the chitosan to the mixture is 3:(1-3); and / or

[0034] The second initiator includes at least one of azobisisobutyronitrile, azobisisovaleronitrile, azobisisoheptylonitrile, diethyl azodicarboxylate, di-2-methoxyethyl azodicarboxylate, di-tert-butyl azodicarboxylate, diisopropyl azodicarboxylate, dibenzyl azodicarboxylate, and dimethyl azodiisobutyrate.

[0035] In a third aspect, an embodiment of the present application provides a capacitor, comprising the electrode material as described above or the electrode material prepared by the preparation method as described above.

[0036] Beneficial effects of the embodiments of the present application:

[0037] In the present application, the electrode material includes a cyclodextrin inclusion compound of an alkylaniline compound, a pyrrole polymer and a chitosan polymer, and the cyclodextrin inclusion compound of an alkylaniline compound, the pyrrole polymer and the chitosan polymer are intertwined to form a network structure. In the present application, the cyclodextrin inclusion compound of an alkylaniline compound, the pyrrole polymer and the chitosan polymer are intertwined to form a network structure, and the binding between the cyclodextrin inclusion compound, the pyrrole polymer and the chitosan polymer is more firm and stable, and is not easy to loosen, which can improve the mechanical properties and anti-swelling properties of the electrode material. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] In order to more clearly illustrate the solutions in the present application or the prior art, a brief introduction is given below to the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0039] Figure 1 This is a SEM image of the electrode material prepared in Example 1 of the present application. DETAILED DESCRIPTION

[0040] The following will be combined with the drawings in the embodiments of the present application to clearly and completely describe the technical solutions in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work are within the scope of protection of the present application. In addition, it should be understood that the specific implementation methods described herein are only used to illustrate and explain the present application, and are not used to limit the present application. In the present application, unless otherwise stated, the directional words such as "upper" and "lower" used generally refer to the upper and lower parts of the device in actual use or working state, specifically the drawing direction in the accompanying drawings; while "inside" and "outside" refer to the outline of the device.

[0041] In the related technology, the mechanical properties and anti-swelling properties of flexible electrode materials are poor, which affects the comprehensive performance of the capacitor and needs to be further improved.

[0042] To solve the above problems, refer to Figure 1 , the embodiment of the present application provides an electrode material, including a cyclodextrin inclusion compound of an alkylaniline compound, a pyrrole polymer and a chitosan polymer, wherein the cyclodextrin inclusion compound of an alkylaniline compound, the pyrrole polymer and the chitosan polymer are intertwined to form a network structure. In this embodiment, the cyclodextrin inclusion compound of an alkylaniline compound, the pyrrole polymer and the chitosan polymer are intertwined to form a network structure, and the binding between the cyclodextrin inclusion compound, the pyrrole polymer and the chitosan polymer is more firm and stable, and is not easy to loosen, which can improve the mechanical properties and anti-swelling properties of the electrode material.

[0043] In one embodiment, the mass percentage of the cyclodextrin inclusion complex of the alkylaniline compound in the electrode material is 15%-20%; optionally, the mass percentage of the cyclodextrin inclusion complex of the alkylaniline compound in the electrode material can be any one of 15%, 16%, 17%, 18%, 19%, 20%, etc. or a range between any two. In this embodiment, if the mass percentage of the cyclodextrin inclusion complex of the alkylaniline compound in the electrode material is too large, it is easy to increase the impedance of the electrode material and reduce the conductivity of the electrode material; if the mass percentage of the cyclodextrin inclusion complex of the alkylaniline compound in the electrode material is too small, it is easy to cause the cyclodextrin inclusion complex of the alkylaniline compound to improve the anti-swelling performance and mechanical properties of the electrode material. The effect is not ideal.

[0044] In one embodiment, the mass percentage of the pyrrole polymer in the electrode material is 25%-35%; optionally, the mass percentage of the pyrrole polymer in the electrode material can be any one of 25%, 27%, 29%, 31%, 33%, 35%, etc. or a range between any two. In this embodiment, the mass percentage of the pyrrole polymer in the electrode material is controlled in the range of 25%-35%, which can further ensure the conductive properties and mechanical properties of the electrode material.

[0045] In one embodiment, the mass percentage of the chitosan polymer in the electrode material is 50%-60%; optionally, the mass percentage of the chitosan polymer in the electrode material can be any one of 50%, 52%, 54%, 56%, 58%, 60%, etc. or a range between any two. In this embodiment, if the mass percentage of the chitosan polymer in the electrode material is too large, it is easy to increase the impedance of the electrode material and reduce the conductivity of the electrode material; if the mass percentage of the chitosan polymer in the electrode material is too small, it is easy to cause the chitosan polymer to improve the anti-swelling performance and mechanical properties of the electrode material. The effect is not ideal.

[0046] In one embodiment, the cyclodextrin inclusion complex of the alkylaniline compound is an inclusion complex formed by an alkylaniline compound molecule entering a hydrophobic cavity of a cyclodextrin molecule to undergo an inclusion reaction, and the alkylaniline compound has an alkyl chain, and the number of carbon atoms in the alkyl chain is n, where n is an integer, and 10≤n≤20. Optionally, n can be any one of 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20.

[0047] In this embodiment, the hydrophobic end of the alkylaniline compound enters the cavity of cyclodextrin and stably combines with cyclodextrin through van der Waals force to form a cyclodextrin inclusion complex of the alkylaniline compound. The alkylaniline compound has a long-chain structure and can be entangled with the pyrrole polymer molecular chain and the chitosan polymer molecular chain, further improving the anti-swelling performance of the electrode material.

[0048] In one embodiment, the cyclodextrin includes at least one of α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin.

[0049] In one embodiment, the alkylaniline compound includes at least one of 4-dodecylaniline, 4-hexadecylaniline, and 4-octadecylaniline.

[0050] The present application also provides a method for preparing the electrode material as described above, comprising the following steps:

[0051] S11, providing a first mixed solution, wherein the first mixed solution comprises an alkylaniline compound and cyclodextrin, wherein at least a portion of the alkylaniline compound is located in the cavity of the cyclodextrin to form a cyclodextrin inclusion complex of the alkylaniline compound;

[0052] S12, adding the pyrrole monomer and the first initiator to the first mixed solution, performing a polymerization reaction, washing and purifying, and obtaining a mixture, wherein the mixture includes a pyrrole polymer, and the pyrrole polymer is formed by a polymerization reaction of the pyrrole monomer;

[0053] S13, adding chitosan and a second initiator to the mixture to make the chitosan undergo a cross-linking reaction to generate a chitosan polymer, thereby obtaining an electrode material, wherein the electrode material comprises the cyclodextrin inclusion complex of the alkylaniline compound, the pyrrole polymer and the chitosan polymer intertwined with each other.

[0054] In this embodiment, when the pyrrole monomer undergoes polymerization reaction, a pyrrole polymer network structure with the pyrrole polymer as the matrix can be formed, and the pyrrole polymer molecular chain can be entangled with the cyclodextrin molecular chain and the alkylaniline compound molecular chain in the cyclodextrin inclusion complex, thereby fixing the cyclodextrin inclusion complex of the alkylaniline compound in the three-dimensional network structure constructed by the pyrrole polymer; chitosan and a second initiator are added to the mixture, and the chitosan molecules can undergo a cross-linking reaction under the action of the second initiator to generate a chitosan polymer network structure with the chitosan polymer as the matrix, and the chitosan polymer network structure and the pyrrole polymer network structure are intertwined, which can further improve the mechanical properties and anti-swelling properties of the electrode material.

[0055] In one embodiment, the first mixed solution further includes lithocholic acid nanotubes; in step S12, pyrrole monomers can undergo polymerization reaction on the surface of lithocholic acid nanotubes to form pyrrole polymers.

[0056] In this embodiment, the molecular chains of traditional pyrrole polymers are disorderly distributed, and frequent collisions and obstruction of electron transmission paths are prone to occur during the transmission of electrons in the pyrrole polymer, resulting in poor conductivity of the electrode material; the first mixed liquid includes lithocholic acid nanotubes, and the lithocholic acid nanotubes provide a template for the pyrrole monomer. After the pyrrole monomer is added to the first mixture, it can be electrostatically adsorbed on the surface of the lithocholic acid nanotubes and arranged in order according to the morphology of the lithocholic acid nanotubes. The pyrrole monomer directly undergoes polymerization reaction on the surface of the lithocholic acid nanotubes, and the generated pyrrole polymer molecular chains grow along the surface of the lithocholic acid nanotube template under the guidance of the lithocholic acid nanotube template to gradually form a tubular structure of the pyrrole polymer. The molecular chains of the tubular structure of the pyrrole polymer are more orderly arranged, which can improve the electron transmission efficiency and thereby improve the conductivity of the electrode material.

[0057] In one embodiment, in step S12, a washing and purification operation is performed after the polymerization reaction to remove the lithocholic acid nanotube template and other impurities that do not participate in the reaction, thereby further improving the purity of the electrode material and reducing the impact of impurities on the electrode material; at the same time, after removing the lithocholic acid nanotube template, tubular vacancies can be formed in the pyrrole polymer, which is convenient for the subsequent addition of chitosan and the second initiator to the mixture for a cross-linking reaction. Part of the chitosan can enter the tubular vacancies of the pyrrole polymer and generate chitosan polymers in the tubular vacancies, which can further improve the connection strength between the chitosan polymer and the pyrrole polymer, thereby improving the mechanical properties and anti-swelling properties of the electrode material.

[0058] In one embodiment, the detergent includes at least one of ethanol, propanol, propylene glycol, and isopropanol.

[0059] In one embodiment, the method for preparing the first mixed solution comprises the following steps:

[0060] S111, adding an alkylaniline compound to an aqueous solution of cyclodextrin, and mixing them uniformly to obtain a first solution, wherein the first solution includes a cyclodextrin inclusion complex of the alkylaniline compound;

[0061] S112, adding lithocholic acid to an aqueous sodium hydroxide solution and mixing them evenly to obtain a second solution containing lithocholic acid nanotubes;

[0062] S113, adding the first solution into the second solution, mixing evenly, to obtain a first mixed solution.

[0063] In one embodiment, in step S111, the mixing temperature is 15°C-25°C, the mixing is stirring mixing, the stirring speed is 450rpm / min-550rpm / min, and the mixing time is 10h-14h. Optionally, the mixing temperature can be any one of 15°C, 17°C, 20°C, 22°C, 25°C, etc., or a range between any two of them; the stirring speed can be any one of 450rpm / min, 470rpm / min, 500rpm / min, 520rpm / min, 550rpm / min, etc., or a range between any two of them; the mixing time can be any one of 10h, 11h, 12h, 13h, 14h, etc., or a range between any two of them.

[0064] In one embodiment, the cyclodextrin includes at least one of α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin.

[0065] In one embodiment, the alkylaniline compound has an alkyl chain, and the number of carbon atoms in the alkyl chain is n, where n is an integer, and 10≤n≤20. Optionally, n can be any one of 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20. In this embodiment, the hydrophobic end of the alkylaniline compound enters the cavity of cyclodextrin and stably combines with cyclodextrin through van der Waals force to form a cyclodextrin inclusion complex of the alkylaniline compound, and the alkylaniline compound has a long chain structure and can be entangled with the pyrrole polymer molecular chain and the chitosan polymer molecular chain, further improving the anti-swelling performance of the electrode material.

[0066] In one embodiment, the alkylaniline compound includes at least one of 4-dodecylaniline, 4-hexadecylaniline, and 4-octadecylaniline. In this embodiment, the alkylaniline compound can be directly purchased commercially, and the raw materials are easily available, which can save the synthesis steps of the alkylaniline compound and simplify the production process of the electrode material.

[0067] In one embodiment, in step S111, the molar ratio of the alkylaniline compound to the cyclodextrin is (1-2): (1-2); optionally, the molar ratio of the alkylaniline compound to the cyclodextrin can be any one of 1:2, 1:1, 1.5:1, 1.8:1, 2:1, etc., or a range between any two of them. In this embodiment, if the molar ratio of the alkylaniline compound to the cyclodextrin is too large, it is easy to cause an excessive content of the alkylaniline compound, increase the impedance of the electrode material, and reduce the conductivity of the electrode material; if the molar ratio of the alkylaniline compound to the cyclodextrin is too small, it is easy to cause an excessive content of the alkylaniline compound, and the effect of the alkylaniline compound on improving the anti-swelling performance of the electrode material is not ideal.

[0068] In one embodiment, in step S112, lithocholic acid, as an amphiphilic molecule, contains a hydrophilic end and a hydrophobic end. Lithocholic acid can self-assemble in an aqueous sodium hydroxide solution. Lithocholic acid molecules can interact through hydrogen bonds and van der Waals forces to aggregate into lithocholic acid nanotubes with a nanotubular structure.

[0069] In one embodiment, in step S112, the mixing temperature is 45°C-55°C, the mixing is stirring mixing, the stirring speed is 450rpm / min-550rpm / min, and the mixing time is 22h-26h. Optionally, the mixing temperature can be any one of 45°C, 47°C, 49°C, 52°C, 55°C, etc., or a range between any two of them; the stirring speed can be any one of 450rpm / min, 470rpm / min, 500rpm / min, 520rpm / min, 550rpm / min, etc., or a range between any two of them; the mixing time can be any one of 22h, 23h, 24h, 25h, 26h, etc., or a range between any two of them.

[0070] In one embodiment, in step S112, the mass ratio of lithocholic acid to the cyclodextrin inclusion complex of the alkylaniline compound is (1-2): (1-2). Optionally, the mass ratio of lithocholic acid to the alkylaniline compound can be any one of 1:2, 1:1, 1.5:1, 1.8:1, 2:1, etc., or a range between any two of them.

[0071] In one embodiment, in step S12, the polymerization reaction temperature is -1°C-9°C, and the polymerization reaction time is 10h-14h. Optionally, the polymerization reaction temperature can be any one of -1°C, 0°C, 2°C, 4°C, 6°C, 8°C, 9°C, etc., or a range between any two of them; the polymerization reaction time can be any one of 10h, 11h, 12h, 13h, 14h, etc., or a range between any two of them. In this embodiment, if the polymerization reaction temperature is too high, it is easy to cause the polymerization reaction rate to be too fast, resulting in an implosion phenomenon; if the polymerization reaction temperature is too low, it is easy to cause the polymerization reaction rate to be too slow and the conversion rate to be reduced, and the mechanical strength of the obtained pyrrole polymer is low.

[0072] In one embodiment, in step S12, the mass ratio between the pyrrole monomer and the first mixed solution is (1-2): (0.1-2). Optionally, the mass ratio between the pyrrole monomer and the first mixed solution can be any one of 1:2, 1:1, 1.5:1, 2:1, 2:0.5, 2:0.1, etc., or a range between any two. In this embodiment, if the amount of pyrrole monomer added is too much, it is easy to cause the molecular weight and rigidity of the generated pyrrole polymer to be too large, and the pyrrole polymer is prone to breakage; if the amount of pyrrole monomer added is too little, it is easy to cause the content of the generated conductive pyrrole polymer to be reduced, thereby reducing the conductive properties and mechanical properties of the electrode material.

[0073] In one embodiment, the first initiator includes at least one of peroxytoluic acid, ammonium persulfate, sodium persulfate, and potassium persulfate.

[0074] In one embodiment, in step S13, the temperature of the cross-linking reaction is 65°C-75°C, and the time of the cross-linking reaction is 20min-40min. Optionally, the temperature of the cross-linking reaction can be any one of 65°C, 68°C, 70°C, 72°C, 74°C, 75°C, etc., or a range between any two of them; the time of the cross-linking reaction can be any one of 20min, 24min, 28min, 30min, 35min, 40min, etc., or a range between any two of them. In this embodiment, if the temperature of the cross-linking reaction is too high, it is easy to cause the cross-linking reaction rate to be too fast, resulting in an explosion phenomenon; if the temperature of the cross-linking reaction is too low, it is easy to cause the cross-linking reaction rate to be too slow and the conversion rate to be reduced, and the mechanical strength of the obtained chitosan polymer is low.

[0075] In one embodiment, in step S13, the mass ratio of chitosan to the mixture is 3:(1-3). Optionally, the mass ratio of chitosan to the mixture can be any one of 3:1, 3:1.5, 3:2, 3:3, etc. or a range between any two of them. In this embodiment, if the amount of chitosan added is too little, it is easy to cause a reduction in the amount of chitosan polymer generated, thereby reducing the anti-swelling performance and mechanical properties of the electrode material; if the amount of chitosan added is too much, it is easy to increase the impedance of the electrode material, thereby reducing the conductive performance of the electrode material.

[0076] In one embodiment, the second initiator includes at least one of azobisisobutyronitrile, azobisisovaleronitrile, azobisisoheptanenitrile, diethyl azodicarboxylate, di-2-methoxyethyl azodicarboxylate, di-tert-butyl azodicarboxylate, diisopropyl azodicarboxylate, dibenzyl azodicarboxylate, and dimethyl azodiisobutyrate.

[0077] The present application also provides a capacitor, comprising the electrode material as described above.

[0078] The above scheme is further described below in conjunction with specific implementation examples. The preferred embodiments of the present application are described in detail as follows:

[0079] Example 1

[0080] This embodiment provides a method for preparing an electrode material, comprising the following steps:

[0081] 1. At 20°C, 4-dodecylaniline was gradually added dropwise to 20 mL of an aqueous solution containing γ-cyclodextrin, and the mixture was continuously stirred at 500 rpm / min for 12 hours to obtain a first solution of a cyclodextrin inclusion complex containing 4-dodecylaniline; wherein the molar ratio of 4-dodecylaniline to γ-cyclodextrin was 1:1.

[0082] 2. At 50°C, add lithocholic acid to a sodium hydroxide solution and dissolve evenly to obtain a second solution. Add 10 mL of the first solution to the second solution, and stir at 500 rpm / min for 24 hours to obtain a first mixed solution, in which the mass ratio of lithocholic acid to the cyclodextrin inclusion complex of 4-dodecylaniline is 2:1.

[0083] 3. Add pyrrole monomer to the first mixed solution and disperse it evenly. After shaking in a shaker for 30 minutes, add sodium persulfate solution, then pour into a mold, and let stand in a 4°C refrigerator for 12 hours to obtain a second mixed solution, wherein the mass ratio between the pyrrole monomer and the first mixed solution is 2:1.

[0084] 4. Wash the second mixed solution with an ethanol solution and filter to remove unreacted substances and lithocholic acid nanotubes to obtain a mixture.

[0085] 5. Add chitosan aqueous solution and 2,2'-azobisisobutyronitrile to the mixture, heat in an oven at 70°C for 30 minutes to obtain an electrode material, wherein the mass ratio between chitosan and the mixture is 3:1.

[0086] Example 2

[0087] The difference between Example 2 and Example 1 is that:

[0088] In step 1, the mass ratio of 4-dodecylaniline to γ-cyclodextrin is 1:2; the rest is the same as in Example 1.

[0089] Example 3

[0090] The difference between Example 3 and Example 1 is that:

[0091] In step 1, the mass ratio of 4-dodecylaniline to γ-cyclodextrin is 2:1; the rest is the same as in Example 1.

[0092] Example 4

[0093] The difference between Example 4 and Example 1 is that:

[0094] In step 2, the mass ratio of lithocholic acid to the cyclodextrin inclusion complex of 4-dodecylaniline is 1:1, and the rest is the same as in Example 1.

[0095] Example 5

[0096] The difference between Example 5 and Example 1 is that:

[0097] In step 2, the mass ratio of lithocholic acid to the cyclodextrin inclusion complex of 4-dodecylaniline is 1:2, and the rest is the same as in Example 1.

[0098] Example 6

[0099] The difference between Example 6 and Example 1 is that:

[0100] In step 3, the mass ratio of the pyrrole monomer to the first mixed solution is 2:0.1; the rest is the same as in embodiment 1.

[0101] Example 7

[0102] The difference between Example 7 and Example 1 is that:

[0103] In step 3, the mass ratio of the pyrrole monomer to the first mixed solution is 1:2; the rest is the same as in Example 1.

[0104] Example 8

[0105] The difference between Example 8 and Example 1 is that:

[0106] In step 5, the mass ratio of chitosan to the mixture is 3:3; the rest is the same as in Example 1.

[0107] Example 9

[0108] The difference between Example 9 and Example 1 is that:

[0109] The operation of step 4 was not performed; the rest was the same as in Example 1.

[0110] Example 10

[0111] The difference between Example 10 and Example 1 is that:

[0112] In step 1, the mass ratio of 4-dodecylaniline to γ-cyclodextrin is 0.2:2; the rest is the same as in Example 1.

[0113] Embodiment 11

[0114] The difference between Example 11 and Example 1 is that:

[0115] In step 2, the mass ratio of lithocholic acid to the cyclodextrin inclusion complex of 4-dodecylaniline is 0.5:2, and the rest is the same as in Example 1.

[0116] Example 12

[0117] The difference between Example 12 and Example 1 is that:

[0118] In step 3, the mass ratio of the pyrrole monomer to the first mixed solution is 0.5:2; the rest is the same as in Example 1.

[0119] Embodiment 13

[0120] The difference between Example 13 and Example 1 is that:

[0121] In step 5, the mass ratio of chitosan to the mixture is 3:5; the rest is the same as in embodiment 1.

[0122] Embodiment 14

[0123] The difference between Example 14 and Example 1 is that:

[0124] Step 2 is: providing a sodium hydroxide solution, adding 10 mL of the first solution to the sodium hydroxide solution, and stirring at 500 rpm / min for 24 hours to obtain a first mixture; the rest is the same as Example 1.

[0125] Embodiment 15

[0126] The difference between Example 15 and Example 1 is that:

[0127] In step 1, 4-dodecylaniline is replaced by 4-hexadecylaniline; the rest is the same as in Example 1.

[0128] Comparative Example 1

[0129] The difference between Comparative Example 1 and Example 1 is:

[0130] Step 1 is: providing a first solution, wherein the first solution is composed of a γ-cyclodextrin aqueous solution; the rest is the same as in Example 1.

[0131] Comparative Example 2

[0132] The difference between Comparative Example 2 and Example 1 is:

[0133] Step 5 is not performed;

[0134] The corresponding change of step 4 is: washing the second mixed solution with an ethanol solution, filtering to remove unreacted substances and lithocholic acid nanotubes, and obtaining an electrode material; the rest is the same as in Example 1.

[0135] Test Method

[0136] The electrode materials obtained in Examples 1 to 15 and Comparative Examples 1 and 2 were subjected to tensile performance tests, electrochemical performance tests, and anti-swelling performance tests. The specific test methods are as follows:

[0137] (I) Tensile performance test:

[0138] According to ASTM D638 standard, the tensile properties of the electrode materials of the embodiments and comparative examples were tested using an electronic universal testing machine.

[0139] (II) Electrochemical performance test:

[0140] The electrochemical performance test of the electrode material was carried out under a three-electrode system. The electrode material itself was a long strip electrode material with a total length of 15 mm (effective length of 10 mm), a width of 5 mm, and a thickness of 1.5 mm. The counter electrode was 3 cm 2 The graphite sheet was used as the reference electrode, the Ag / AgCl electrode was used as the reference electrode, and 1M KCl solution was used as the liquid electrolyte. Before the electrochemical test, the electrode material was immersed in 1M KCl solution for 24 hours, and the electrolyte solution on the surface was gently blotted with filter paper after being taken out. The working voltage window of the GCD test was -0.2-0.6V, and the electrode material was tested after 50% deformation and cyclic stretching for 50 times at a current density of 1A / g.

[0141] The above electrode material was used as the working electrode, the platinum sheet as the counter electrode (1×1 cm2), the calomel electrode as the reference electrode, and 6 mol / L KOH as the electrolyte to measure the capacitance retention of the electrode material after 3000 cycles at 1 A / g.

[0142] (III) Anti-swelling performance test:

[0143] First, prepare cylindrical electrode materials of the same size (8 mm in height and 10 mm in diameter) and weigh their original mass (Ws). Then, place the electrode materials in a fixed volume of deionized water and keep them at 37°C for 24 hours. Take out the electrode materials at regular intervals, gently dry the surface water with filter paper and weigh their mass (W) until the mass of the electrode materials no longer changes. The mass at this time is recorded as (Wsw).

[0144] The swelling ratio is calculated using the following formula:

[0145] SR=(Wsw-Ws) / Ws×100%;

[0146] Each sample was tested 3 times, and the data was the average of the 3 times.

[0147] The test results are shown in Table 1 below:

[0148] Table 1

[0149]

[0150]

[0151] Based on the test results of Examples 1 to 15 and Comparative Examples 1 and 2, it can be seen that the electrode materials prepared in Examples 1 to 14 have good mechanical properties and anti-swelling properties, which shows that the electrode materials prepared in this application, alkylaniline compounds, pyrrole polymers and chitosan polymers can improve the anti-swelling properties and mechanical properties of the electrode materials.

[0152] From the comparison between Examples 1-13, Example 15 and Example 14, it can be seen that the introduction of lithocholic acid nanotube templates in the process of preparing electrode materials can improve the arrangement order of pyrrole polymer molecules, thereby improving the conductive properties of the electrode materials.

[0153] From the comparison between Example 1 and Example 9, it can be seen that when preparing the electrode material, washing the second mixture with a detergent can remove the lithocholic acid nanotube template and other impurities that do not participate in the reaction, which can further improve the purity of the electrode material, reduce the impact of impurities on the electrode material, and improve the conductivity of the electrode material; at the same time, after removing the lithocholic acid nanotube template, tubular vacancies can be formed in the pyrrole polymer, and part of the chitosan can enter the tubular vacancies of the pyrrole polymer and generate chitosan polymers in the tubular vacancies, which can further improve the connection firmness between the chitosan polymer and the pyrrole polymer, thereby improving the mechanical properties of the electrode material.

[0154] From the comparison among Example 1, Example 2 and Example 10, it can be seen that when preparing electrode materials, controlling the mass ratio between alkylaniline compounds and cyclodextrin within an appropriate range can further improve the structural stability of the electrode materials, reduce impedance, and ensure the anti-swelling properties, mechanical properties and conductive properties of the electrode materials.

[0155] From the comparison of Example 1, Example 4, Example 5 and Example 11, it can be seen that when preparing the electrode material, controlling the mass ratio between lithocholic acid and the cyclodextrin inclusion complex of alkylaniline compounds within an appropriate range can further ensure the adsorption effect of pyrrole monomer on lithocholic acid nanotubes, thereby improving the conductive properties of the electrode material.

[0156] From the comparison of Example 1, Example 6, Example 7 and Example 12, it can be seen that when preparing electrode materials, controlling the mass ratio between the pyrrole monomer and the first mixed solution within an appropriate range can reduce the formation of disordered pyrrole polymers, ensure the conductive properties of the pyrrole polymers, and thus improve the conductive properties of the electrode materials.

[0157] From the comparison among Example 1, Example 8 and Example 13, it can be seen that when preparing the electrode material, controlling the mass ratio between chitosan and the mixture within an appropriate range can further improve the structural stability of the electrode material, reduce the impedance, and ensure the anti-swelling property, mechanical property and conductive property of the electrode material.

[0158] The embodiments of the present application are introduced in detail above. Specific examples are used in this article to illustrate the principles and implementation methods of the present application. The description of the above embodiments is only used to help understand the method and core idea of ​​the present application. At the same time, for technical personnel in this field, according to the idea of ​​the present application, there will be changes in the specific implementation method and application scope. In summary, the content of this specification should not be understood as a limitation on the present application.

Claims

1. An electrode material, characterized in that: The electrode material comprises a cyclodextrin inclusion compound of an alkylaniline compound, a pyrrole polymer and a chitosan polymer. The cyclodextrin inclusion compound of an alkylaniline compound, the pyrrole polymer and the chitosan polymer are interwoven to form a network structure.

2. The electrode material according to claim 1, characterized in that The mass percentage of the cyclodextrin inclusion compound of the alkylaniline compound in the electrode material is 15%-20%; and / or The mass percentage of the pyrrole polymer in the electrode material is 25%-35%; and / or The mass percentage of the chitosan polymer in the electrode material is 50%-60%; and / or The alkylaniline compound has an alkyl chain, the number of carbon atoms in the alkyl chain is n, n is an integer, 10≤n≤20; and / or The cyclodextrin includes at least one of α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin.

3. The electrode material according to claim 2, characterized in that The alkylaniline compound includes at least one of 4-dodecylaniline, 4-hexadecylaniline and 4-octadecylaniline.

4. A method for preparing an electrode material according to any one of claims 1 to 3, characterized in that: The following steps are involved: Providing a first mixed solution, wherein the first mixed solution comprises an alkylaniline compound and cyclodextrin, wherein at least a portion of the alkylaniline compound is located in the cavity of the cyclodextrin to form a cyclodextrin inclusion complex of the alkylaniline compound; Adding a pyrrole monomer and a first initiator to the first mixed solution, performing a polymerization reaction, washing and purifying, and obtaining a mixture, wherein the mixture includes a pyrrole polymer, and the pyrrole polymer is formed by a polymerization reaction of the pyrrole monomer; Chitosan and a second initiator are added to the mixture to make the chitosan undergo a cross-linking reaction to generate a chitosan polymer, thereby obtaining an electrode material. The electrode material includes the cyclodextrin inclusion complex of the alkylaniline compound, the pyrrole polymer and the chitosan polymer intertwined with each other.

5. The preparation method according to claim 4, characterized in that: The first mixed solution also includes lithocholic acid nanotubes; In the step of adding the pyrrole monomer and the first initiator into the first mixed solution to perform a polymerization reaction, the pyrrole monomer can undergo a polymerization reaction on the surface of the lithocholic acid nanotube to form the pyrrole polymer.

6. The preparation method according to claim 5, characterized in that: The preparation method of the first mixed solution comprises the following steps: Adding an alkylaniline compound to an aqueous solution of cyclodextrin to obtain a first solution, wherein the first solution includes a cyclodextrin inclusion complex of the alkylaniline compound; adding lithocholic acid into an aqueous sodium hydroxide solution to obtain a second solution containing the lithocholic acid nanotubes; The first solution is added to the second solution to obtain the first mixed solution.

7. The preparation method according to claim 6, characterized in that: In the step of adding the alkylaniline compound to the aqueous solution of cyclodextrin to obtain the first solution, the temperature of mixing the alkylaniline compound and the aqueous solution of cyclodextrin is 15°C-25°C, and / or the mixing is stirring, the stirring speed is 450rpm / min-550rpm / min, and / or the mixing time is 10h-14h; and / or The molar ratio of the alkylaniline compound to the cyclodextrin is (1-2): (1-2); and / or The cyclodextrin includes at least one of α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin; and / or The alkylaniline compound has an alkyl chain, the number of carbon atoms in the alkyl chain is n, and n is an integer, 10≤n≤20.

8. The preparation method according to claim 7, characterized in that: The alkylaniline compound includes at least one of 4-dodecylaniline, 4-hexadecylaniline and 4-octadecylaniline.

9. The preparation method according to claim 6, characterized in that: In the step of adding lithocholic acid to the sodium hydroxide aqueous solution to obtain the second solution containing the lithocholic acid nanotubes, the temperature of mixing the lithocholic acid and the sodium hydroxide aqueous solution is 45°C-55°C, and / or the mixing is stirring mixing, the stirring speed is 450rpm / min-550rpm / min, and / or the mixing time is 22h-26h; and / or The mass ratio between the lithocholic acid and the cyclodextrin inclusion complex of the alkylaniline compound is (1-2): (1-2).

10. The preparation method according to claim 4, characterized in that: In the step of adding the pyrrole monomer and the first initiator to the first mixed solution, performing a polymerization reaction, washing and purifying to obtain a mixture, the polymerization reaction temperature is -1°C-9°C, and / or the polymerization reaction time is 10h-14h; and / or The mass ratio of the pyrrole monomer to the first mixed solution is (1-2): (0.1-2); and / or The first initiator comprises at least one of peroxytoluic acid, ammonium persulfate, sodium persulfate and potassium persulfate; and / or The washing and purifying detergent comprises at least one of ethanol, propanol, propylene glycol and isopropanol.

11. The preparation method according to claim 4, characterized in that: In the step of adding chitosan and a second initiator to the mixture to carry out a cross-linking reaction to obtain an electrode material, the temperature of the cross-linking reaction is 65° C.-75° C., and / or the time of the cross-linking reaction is 20 min-40 min, and / or the mass ratio of the chitosan to the mixture is 3:(1-3); and / or The second initiator includes at least one of azobisisobutyronitrile, azobisisovaleronitrile, azobisisoheptylonitrile, diethyl azodicarboxylate, di-2-methoxyethyl azodicarboxylate, di-tert-butyl azodicarboxylate, diisopropyl azodicarboxylate, dibenzyl azodicarboxylate, and dimethyl azodiisobutyrate.

12. A capacitor, characterized in that: The invention comprises the electrode material as claimed in any one of claims 1 to 3 or the electrode material prepared by the preparation method as claimed in any one of claims 4 to 11.

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