CN115101718A - Mxene-polyaniline composite negative electrode material and preparation method and application thereof - Google Patents
Mxene-polyaniline composite negative electrode material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 claims abstract description 153
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- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 32
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
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- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
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- 125000003277 amino group Chemical group 0.000 description 5
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/137—Electrodes based on electro-active polymers
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H01M4/1399—Processes of manufacture of electrodes based on electro-active polymers
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- H01M4/00—Electrodes
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention provides an Mxene-polyaniline composite negative electrode material and a preparation method and application thereof. The negative electrode material comprises a Mxene base material and a modified polyaniline material loaded in the Mxene base material; the modified polyaniline material is a polyaniline material doped with phytic acid. The invention utilizes a coprecipitation method which is simple to operate, takes phytic acid as a dispersing agent to dope polyaniline and takes an Mxene material as a substrate to prepare the composite cathode material, and the composite material is used in a lithium ion battery, thereby not only improving the reversible specific capacity of a single material, but also improving the cycling stability of the material.
Description
Technical Field
The invention belongs to the technical field of negative electrode materials, and particularly relates to an Mxene-polyaniline composite negative electrode material as well as a preparation method and application thereof.
Background
Lithium ion batteries have received a great deal of attention because of their advantages of high voltage, high energy density, long life, high safety, and the like. MXene, a common negative electrode material of lithium batteries, has been developed and applied to some extent in the field of energy storage.
In the prior art, a chemical liquid phase method is often adopted to etch an MXene material, so that the MXene material with a stacked multi-layer structure can be obtained, then a dimethyl sulfoxide solvent is used as an intercalating agent to further perform ultrasonic treatment on the MXene material, and a few-layer or single-layer lamellar structure is obtained by stripping, however, the intercalation capability of a single intercalating agent is limited, so that the stripping method is low in yield, the obtained monolithic layer structure is easy to stack again, namely, the stability is poor, the embedding rate of electrolyte ions between the MXene material layers is reduced, and the specific capacitance of the material is low.
CN109671949A discloses an MXene-based flexible composite negative electrode material, which specifically comprises the steps of loading a transition metal sulfide on a two-dimensional layered structure of an MXene material by a hydrothermal method, so that agglomeration effect and layer structure collapse of the MXene material are avoided, the volume expansion phenomenon of a transition metal polysulfide material in a charging process is relieved, and the cycling stability of the material is improved.
Therefore, there is a need in the art to develop an MXene-based anode material having not only good structural stability and high specific capacity but also good cycle stability.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an Mxene-polyaniline composite negative electrode material, and a preparation method and application thereof. According to the invention, the composite negative electrode material is prepared by using a coprecipitation method which is simple to operate, the phytic acid is used as a dispersing agent to dope the polyaniline, and the Mxene material is used as a substrate, and the composite material is used in the lithium ion battery, so that the reversible specific capacity of a single material is improved, and the cycling stability of the material is also improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides an Mxene-polyaniline composite negative electrode material, which comprises an Mxene substrate material and a modified polyaniline material loaded in the Mxene substrate material;
the modified polyaniline material is a polyaniline material doped with phytic acid.
According to the invention, the polyaniline material synthesized by doping phytic acid is loaded between or on the surface of the MXene material layer by a chemical oxidation method, so that the MXene material is prevented from stacking and the molecular chain of polyaniline is prevented from being agglomerated. The phytic acid contains 6 phosphate radicals, can interact with a plurality of amino groups in a polyaniline chain to form a three-dimensional network structure, and can be connected with functional groups on the surface of the MXene material through hydrogen bonds, so that the insertion of the polyaniline into the layers of the MXene material is promoted, the specific surface area and the space structure of the material are improved, and the reversible specific capacity of a single material is improved.
Preferably, the mass ratio of the Mxene substrate material to the modified polyaniline material in the Mxene-polyaniline composite negative electrode material is (2-5): 1, and for example, the mass ratio may be 2:1, 2.2:1, 2.5:1, 2.8:1, 3:1, 3.2:1, 3.5:1, 3.8:1, 4:1, 4.2:1, 4.5:1, 4.8:1, and 5: 1.
In the invention, the capacitance and the cycling stability of the composite material can be improved by adjusting the mass ratio of the Mxene substrate material to the modified polyaniline material. The mass ratio is too low, so that a large amount of modified polyaniline is agglomerated on the surface of MXene, and the circulation stability of the composite material is not high due to the volume expansion effect of polyaniline as a pseudocapacitance material; on the contrary, the effect of the modified polyaniline with too high mass ratio is smaller, and the capacity of the composite negative electrode material is not obviously improved.
As a preferable technical scheme of the invention, the mass ratio of the Mxene substrate material to the modified polyaniline material in the Mxene-polyaniline composite negative electrode material is 3: 1.
Preferably, the Mxene substrate material comprises Ti 2 CT x 、Ti 3 C 2 T x Or Ti 4 C 3 T x Any one or a combination of at least two of them, wherein T x Selected from hydroxyl, fluorine atom or carbonyl.
In a second aspect, the present invention provides a method for preparing the Mxene-polyaniline composite negative electrode material according to the first aspect, the method comprising the steps of:
(1) mixing aniline and phytic acid solution to form dispersion A, adding phytic acid solution of ammonium persulfate to perform secondary mixing, and filtering after reaction to obtain a modified polyaniline material;
(2) mixing an Mxene material with a solvent A to form an Mxene material solution, then adding a solvent B to carry out secondary mixing, and centrifuging to obtain the Mxene substrate material;
(3) and (3) mixing the Mxene substrate material obtained in the step (2) with a phytic acid solution to form a dispersion liquid of the Mxene substrate material, adding the modified polyaniline material obtained in the step (1), mixing at a low temperature to obtain a mixed solution, and filtering to obtain the Mxene-polyaniline composite negative electrode material.
Preferably, the concentration of the phytic acid solution in the step (1) is 0.05 to 0.09mol/L, preferably 0.07mol/L, for example, 0.05mol/L, 0.06mol/L, 0.07mol/L, 0.08mol/L, 0.09mol/L, and the values in the above range are not listed for brevity.
According to the invention, the concentration of the phytic acid solution is adjusted, so that the interaction between phosphate radicals carried by phytic acid and amino groups on a plurality of polyaniline chains is facilitated to form a three-dimensional network structure, and the phosphate radicals and the amino groups on MXene surfaces can be connected with functional groups on the MXene surfaces through hydrogen bonds to promote the insertion of polyaniline into MXene layers, so that the specific surface area and the space structure of the material are improved, and the reversible specific capacity of a single material is improved. If the concentration of the phytic acid is too low, the effect of phosphate radical cannot be exerted, and the conductivity of the synthesized polyaniline is low; on the contrary, the concentration of the phytic acid is too high, the fluidity of the mixed glue solution is low, the prepared polyaniline is easy to agglomerate, and the mixing of MXene and polyaniline is not facilitated, so that the polyaniline cannot be loaded between MXene layers or on the surface of the MXene layers.
Preferably, the mixing temperature in step (1) is-2 to 2 ℃, for example, -2 ℃, -1 ℃, 0 ℃, 1 ℃, 2 ℃.
Preferably, the mixing in step (1) is performed under stirring.
Preferably, the mass concentration of the dispersion A in the step (1) is 11 to 17mg/mL, and may be, for example, 11mg/mL, 12mg/mL, 13mg/mL, 14mg/mL, 15mg/mL, 16mg/mL, or 17 mg/mL.
Preferably, the mass ratio of ammonium persulfate to aniline in step (1) is (2.8-3.1): 1, preferably 2.94:1, and may be, for example, 2.8:1, 2.82:1, 2.85:1, 2.88:1, 2.9:1, 2.92:1, 2.94:1, 2.95:1, 2.98:1, 3:1, 3.1:1, and the values in the above ranges are not listed for brevity.
In the invention, the mass ratio of ammonium persulfate to aniline is adjusted, which is beneficial to improving the yield of polyaniline and has high conductivity of the synthesized polyaniline. If the mass ratio of the ammonium persulfate to the aniline is too low, the ammonium persulfate serving as an oxidant is quickly consumed, the reaction is incomplete, and the yield of the polyaniline is low; on the contrary, the mass ratio of the two is too high, the possibility of generating small molecular products is also increased, and the conductivity and the yield of the synthesized polyaniline are lower.
Preferably, the reaction temperature in step (1) is-2 to 2 ℃, for example, -2 ℃, -1 ℃, 0 ℃, 1 ℃, 2 ℃.
Preferably, the reaction time in the step (1) is 4-7 h, for example, 4h, 5h, 6h, 7 h.
Preferably, the step (1) further comprises a vacuum drying process after the filtration.
Preferably, the time of the vacuum drying process is 6-9h, for example, 6h, 7h, 8h, 9 h.
Preferably, the solvent a in step (2) comprises dimethyl sulfoxide.
Preferably, the temperature of the mixing in the step (2) is 35 to 45 ℃, for example, 35 ℃, 38 ℃, 40 ℃, 42 ℃ and 45 ℃.
Preferably, the mixing time in step (2) is 20-30h, for example, 20h, 22h, 25h, 28h, 30 h.
Preferably, the mass concentration of the Mxene material solution in the step (2) is 0.07-0.12 g/mL, such as 0.07g/mL, 0.08g/mL, 0.09g/mL, 0.1g/mL, 0.11g/mL, 0.12g/mL, and the values in the above ranges are not listed for brevity.
Preferably, the solvent B in the step (2) is deionized water.
Preferably, the secondary mixing in step (2) is treated under ultrasound.
Preferably, the centrifugation in step (2) is further followed by a washing treatment.
Preferably, the concentration of the phytic acid solution in the step (3) is 0.05 to 0.09mol/L, preferably 0.07mol/L, for example, 0.05mol/L, 0.06mol/L, 0.07mol/L, 0.08mol/L, 0.09mol/L, and the values in the above ranges are not listed in order to simplify the disclosure.
Preferably, the mixing in step (3) is carried out under ultrasound.
Preferably, the temperature of the low-temperature mixing in the step (3) is-2 to 2 ℃, for example, -2 ℃, -1 ℃, 0 ℃, 1 ℃, 2 ℃.
Preferably, the time for low-temperature mixing in step (3) is 8-11h, for example, 8h, 9h, 10h, 11 h.
Preferably, the mass concentration of the mixed solution in the step (3) is 11-17mg/mL, and may be, for example, 11mg/mL, 12mg/mL, 13mg/mL, 14mg/mL, 15mg/mL, 16mg/mL, 17 mg/mL.
Preferably, the mass ratio of the modified polyaniline material obtained in the step (1) to the Mxene base material obtained in the step (2) in the step (3) is 1 (2-5), preferably 1:3, and may be, for example, 1:2, 1:2.2, 1:2.5, 1:2.8, 1:3, 1:3.2, 1:3.5, 1:3.8, 1:4, 1:4.2, 1:4.5, 1:4.8, or 1: 5.
Preferably, the filtering in step (3) further comprises a vacuum drying process.
Preferably, the temperature of the vacuum drying process is 40-60 ℃, for example, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃.
Preferably, the time of the vacuum drying process is 6-9h, for example, 6h, 7h, 8h, 9 h.
In a third aspect, the present invention provides a negative electrode sheet comprising a negative electrode active material, a binder, and a conductive agent, the negative electrode active material comprising the Mxene-polyaniline composite negative electrode material according to the first aspect.
In a fourth aspect, the invention provides a lithium ion battery, which comprises a positive plate, a negative plate, an electrolyte and a diaphragm, wherein the negative plate is the negative plate according to the third aspect.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the polyaniline material synthesized by doping phytic acid is loaded between or on the surface of the MXene material layer by a chemical oxidation method, so that the MXene material is prevented from stacking and the molecular chain of polyaniline is prevented from being agglomerated. The phytic acid contains 6 phosphate radicals, can interact with a plurality of amino groups in a polyaniline chain to form a three-dimensional network structure, and can be connected with functional groups on the surface of the MXene material through hydrogen bonds, so that the insertion of the polyaniline into the MXene material layers is promoted, the specific surface area and the space structure of the material are improved, and the reversible specific capacity of a single material is improved.
Drawings
Fig. 1 is an SEM image of the Mxene-polyaniline composite negative electrode material provided in example 1.
Detailed Description
The technical solution of the present invention is further explained by combining the drawings and the detailed description. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides an Mxene-polyaniline composite cathode material which comprises Ti 3 C 2 T x Base material and supported on Ti 3 C 2 T x A modified polyaniline material in a base material; the modified polyaniline material is a polyaniline material doped with phytic acid. Wherein Ti in the Mxene-polyaniline composite cathode material 3 C 2 T x The mass ratio of the substrate material to the polyaniline is 3: 1.
The preparation method of the negative electrode material comprises the following steps:
(1) stirring aniline and a phytic acid solution with the concentration of 0.07mol/L under an ice bath condition to form a dispersion liquid A (the mass concentration is 15mg/mL), then adding an equal volume of phytic acid solution containing ammonium persulfate (the concentration is 0.07mol/L) for secondary mixing, wherein the mass ratio of ammonium sulfate to aniline is 2.94:1, carrying out polymerization reaction for 5 hours under the ice bath condition, then carrying out vacuum filtration to collect precipitates, and drying for 7 hours in a vacuum oven at 50 ℃ to obtain a modified polyaniline material;
(2) mixing Ti 3 C 2 T x Stirring with dimethyl sulfoxide at 40 deg.C for 24h to obtain Ti with concentration of 0.1g/mL 3 C 2 T x Adding deionized water into the material solution for ultrasonic treatment for 4 hours, centrifuging, washing and drying to obtain the Ti 3 C 2 T x A base material;
(3) ti obtained in the step (2) 3 C 2 T x Carrying out ultrasonic treatment on a substrate material and a phytic acid solution with the concentration of 0.07mol/L for 2 hours to form Ti 3 C 2 T x And (2) adding the modified polyaniline material obtained in the step (1) into the dispersion liquid of the substrate material, stirring at low temperature for 9 hours under an ice bath condition to obtain a mixed solution (the mass concentration is 15mg/mL), then carrying out vacuum filtration on the mixed solution to collect precipitates, and drying in a vacuum oven at 50 ℃ for 7 hours to obtain the Mxene-polyaniline composite negative electrode material.
Fig. 1 is an SEM image of the Mxene-polyaniline composite negative electrode material provided in example 1, where Mxene has an obvious layered structure, and rod-like polyaniline is successfully inserted between Mxene sheets to enlarge the specific surface area of the composite material, which is beneficial to improving the composite performance of the material.
Example 2
The embodiment provides an Mxene-polyaniline composite cathode material which comprises Ti 3 C 2 T x Base material and supported on Ti 3 C 2 T x A modified polyaniline material in a base material; the modified polyaniline material is a phytic acid-doped polyaniline material. Wherein Ti in the Mxene-polyaniline composite cathode material 3 C 2 T x The mass ratio of the substrate material to the polyaniline is 2.5: 1.
The preparation method of the negative electrode material comprises the following steps:
(1) stirring aniline and a phytic acid solution with the concentration of 0.06mol/L under an ice bath condition to form a dispersion A (the mass concentration is 13mg/mL), then adding an isovolumetric phytic acid solution (the concentration is 0.06mol/L) containing ammonium persulfate to perform secondary mixing, wherein the mass ratio of ammonium sulfate to aniline is 2.85:1, performing polymerization reaction for 6 hours under the ice bath condition, then performing vacuum filtration to collect precipitates, and drying for 7 hours in a vacuum oven at 50 ℃ to obtain a modified polyaniline material;
(2) mixing Ti 3 C 2 T x The material and dimethyl sulfoxide were stirred at 38 ℃ for 28h to form Ti at a concentration of 0.08g/mL 3 C 2 T x Adding deionized water into the material solution, performing ultrasonic treatment for 4 hours, centrifuging, washing and drying to obtain the Ti 3 C 2 T x A base material;
(3) ti obtained in the step (2) 3 C 2 T x Carrying out ultrasonic treatment on a substrate material and a phytic acid solution with the concentration of 0.06mol/L for 2 hours to form Ti 3 C 2 T x And (2) adding the modified polyaniline material obtained in the step (1) into the dispersion liquid of the substrate material, stirring at low temperature for 10 hours under an ice bath condition to obtain a mixed solution (the mass concentration is 13mg/mL), then carrying out vacuum filtration on the mixed solution to collect precipitates, and drying in a vacuum oven at 50 ℃ for 7 hours to obtain the Mxene-polyaniline composite negative electrode material.
Example 3
The embodiment provides an Mxene-polyaniline composite cathode material which comprises Ti 3 C 2 T x Base material and supported on Ti 3 C 2 T x A modified polyaniline material in a base material; the modified polyaniline material is a polyaniline material doped with phytic acid. Wherein Ti in the Mxene-polyaniline composite cathode material 3 C 2 T x The mass ratio of the substrate material to the polyaniline is 4: 1.
The preparation method of the negative electrode material comprises the following steps:
(1) stirring aniline and a phytic acid solution with the concentration of 0.08mol/L under an ice bath condition to form a dispersion liquid A (the mass concentration is 16mg/mL), then adding an isovolumetric phytic acid solution (the concentration is 0.08mol/L) containing ammonium persulfate to perform secondary mixing, wherein the mass ratio of ammonium sulfate to aniline is 3:1, performing polymerization reaction for 6 hours under the ice bath condition, performing vacuum filtration to collect precipitates, and drying for 7 hours in a vacuum oven at 50 ℃ to obtain a modified polyaniline material;
(2) mixing Ti 3 C 2 T x The material and dimethyl sulfoxide were stirred at 42 ℃ for 22h to form Ti at a concentration of 0.11g/mL 3 C 2 T x Adding deionized water into the material solution for ultrasonic treatment for 4 hours, centrifuging, washing and drying to obtain the Ti 3 C 2 T x A base material;
(3) ti obtained in the step (2) 3 C 2 T x Carrying out ultrasonic treatment on a substrate material and a phytic acid solution with the concentration of 0.08mol/L for 2 hours to form Ti 3 C 2 T x And (2) adding the modified polyaniline material obtained in the step (1) into the dispersion liquid of the substrate material, stirring at a low temperature for 10 hours under an ice bath condition to obtain a mixed solution (mass concentration is 16mg/mL), then carrying out vacuum filtration on the mixed solution to collect precipitates, and drying in a vacuum oven at 50 ℃ for 7 hours to obtain the Mxene-polyaniline composite negative electrode material.
Example 4
The embodiment provides an Mxene-polyaniline composite cathode material which comprises Ti 2 CT x Base material and supported on Ti 2 CT x A modified polyaniline material in a base material; the modified polyaniline material is a polyaniline material doped with phytic acid. Wherein Ti in the Mxene-polyaniline composite cathode material 2 CT x The mass ratio of the substrate material to the polyaniline is 2: 1.
The preparation method of the negative electrode material comprises the following steps:
(1) stirring aniline and a phytic acid solution with the concentration of 0.05mol/L under an ice bath condition to form a dispersion liquid A (the mass concentration is 11mg/mL), then adding an isovolumetric phytic acid solution (the concentration is 0.05mol/L) containing ammonium persulfate to perform secondary mixing, wherein the mass ratio of ammonium sulfate to aniline is 2.8:1, performing polymerization reaction for 4 hours under the ice bath condition, then performing vacuum filtration to collect precipitates, and drying in a vacuum oven at 50 ℃ for 6 hours to obtain a modified polyaniline material;
(2) mixing Ti 2 CT x The material and dimethyl sulfoxide were stirred at 35 ℃ for 30h to form Ti at a concentration of 0.07g/mL 2 CT x Adding deionized water into the material solution for ultrasonic treatment for 4 hours, centrifuging, washing and drying to obtain the Ti 2 CT x A base material;
(3) ti obtained in the step (2) 2 CT x Carrying out ultrasonic treatment on a substrate material and a phytic acid solution with the concentration of 0.05mol/L for 2 hours to form Ti 2 CT x And (2) adding the modified polyaniline material obtained in the step (1) into the dispersion liquid of the substrate material, stirring at low temperature for 8 hours under an ice bath condition to obtain a mixed solution (the mass concentration is 11mg/mL), then carrying out vacuum filtration on the mixed solution to collect precipitates, and drying in a vacuum oven at 40 ℃ for 9 hours to obtain the Mxene-polyaniline composite negative electrode material.
Example 5
The embodiment provides an Mxene-polyaniline composite cathode material which comprises Ti 2 CT x Base material and supported on Ti 2 CT x A modified polyaniline material in a base material; the modified polyaniline material is a polyaniline material doped with phytic acid. Wherein Ti in the Mxene-polyaniline composite cathode material 2 CT x The mass ratio of the substrate material to the polyaniline is 5: 1.
The preparation method of the negative electrode material comprises the following steps:
(1) stirring aniline and a phytic acid solution with the concentration of 0.09mol/L under an ice bath condition to form a dispersion A (the mass concentration is 17mg/mL), then adding an equal volume of phytic acid solution containing ammonium persulfate (the concentration is 0.09mol/L) for secondary mixing, wherein the mass ratio of ammonium sulfate to aniline is 3.1:1, carrying out polymerization reaction for 7 hours under the ice bath condition, then carrying out vacuum filtration to collect precipitates, and drying for 9 hours in a vacuum oven at 50 ℃ to obtain a modified polyaniline material;
(2) mixing Ti 2 CT x The material and dimethyl sulfoxide were stirred at 45 ℃ for 20h to form Ti at a concentration of 0.12g/mL 2 CT x Adding deionized water into the material solution for ultrasonic treatment for 4 hours, centrifuging, washing and drying to obtain the Ti 2 CT x A base material;
(3) ti obtained in the step (2) 2 CT x Carrying out ultrasonic treatment on a substrate material and a phytic acid solution with the concentration of 0.09mol/L for 2 hours to form Ti 2 CT x And (2) adding the modified polyaniline material obtained in the step (1) into the dispersion liquid of the substrate material, stirring at a low temperature for 11 hours under an ice bath condition to obtain a mixed solution (the mass concentration is 17mg/mL), then carrying out vacuum filtration on the mixed solution to collect precipitates, and drying in a vacuum oven at 60 ℃ for 6 hours to obtain the Mxene-polyaniline composite negative electrode material.
Example 6
The difference between the present example and example 1 is that the mass ratio of the Mxene substrate material to the polyaniline in the Mxene-polyaniline composite negative electrode material is 1:1, and the rest is the same as example 1.
Example 7
The difference between the present example and example 1 is that the mass ratio of the Mxene substrate material to the polyaniline in the Mxene-polyaniline composite negative electrode material is 8:1, and the rest is the same as example 1.
Example 8
This example is different from example 1 in that the mass ratio of ammonium persulfate to aniline in step (1) is 1:1, and the rest is the same as example 1.
Example 9
This example is different from example 1 in that the mass ratio of ammonium persulfate to aniline in step (1) is 6:1, and the rest is the same as example 1.
Example 10
This example is different from example 1 in that the concentration of the phytic acid solution in step (1) is 0.02mol/L, and the rest is the same as example 1.
Example 11
This example is different from example 1 in that the concentration of the phytic acid solution in step (1) was 0.2mol/L, and the rest was the same as example 1.
Example 12
This example is different from example 1 in that the mixed solution in step (3) has a mass concentration of 5mg/mL, and the rest is the same as example 1.
Example 13
This example is different from example 1 in that the mixed solution in step (3) has a mass concentration of 25mg/mL, and the other steps are the same as example 1.
Comparative example 1
This comparative example is different from example 1 in that only the operation of step (1) is carried out, and the others are the same as example 1.
Comparative example 2
This comparative example is different from example 1 in that only the operation of step (2) is carried out, and the others are the same as example 1.
Comparative example 3
This comparative example differs from example 1 in that the Mxene base material was replaced with a graphite material, and the rest was the same as example 1.
Comparative example 4
The comparative example provides an Mxene-polyaniline composite negative electrode material, but phytic acid is not added, and phytic acid is replaced by common hydrochloric acid with equal concentration, and the rest is the same as that in the example 1.
Application examples 1 to 13 and comparative application examples 1 to 4
The Mxene-polyaniline composite negative electrode materials provided in examples 1 to 13 and comparative examples 1 to 4 were prepared to obtain lithium metal half cells by the following methods:
mixing the obtained Mxene-polyaniline composite negative electrode material, a conductive agent Super P and a binder PVDF according to the mass ratio of 8:1:1, mixing with a proper amount of NMP solvent to prepare electrode slurry, uniformly coating the electrode slurry on copper foil, drying in a vacuum drying oven at 100 ℃ for 12 hours, preparing a negative electrode sheet with the diameter of 12mm by using a slicing machine, and assembling the negative electrode sheet, lithium metal and an electrolyte in a vacuum glove box filled with argon.
Test conditions
The lithium metal half-cells provided in application examples 1 to 13 and comparative application examples 1 to 4 were subjected to performance tests, the test methods were as follows: and placing the prepared lithium half-cell in an electrochemical workstation, carrying out 0.1C multiplying power charge-discharge cycle test, recording the initial specific capacity of the cell and the specific capacity after 120 cycles, and dividing the initial specific capacity by the specific capacity after 120 cycles to obtain the capacity retention rate. The test results are shown in table 1:
TABLE 1
As can be seen from table 1, in summary of examples 1 to 7 and comparative examples 1 to 2, the MXene/polyaniline composite material with a layered structure is prepared by compounding MXene and polyaniline, and the polyaniline is loaded on the surface and between layers of the MXene, so that the space structure of the material is increased and the reversible specific capacity and the cycling stability of the material are improved under the synergistic effect of the MXene and the polyaniline. The high content of polyaniline can cause a large amount of polyaniline to be agglomerated on the surface of MXene, and the volume expansion effect of the polyaniline serving as a pseudo-capacitor material causes the low cycling stability of the composite material; the content of polyaniline is too low, the action of polyaniline is small, and the capacity of the composite material is not obviously improved. Among them, the application of lithium ion batteries emphasizes the cycle stability; the MXene material has high cycling stability but low specific capacity due to the layered structure, namely the capacity retention rate is high; polyaniline has high capacity but low cycling stability when used as a pseudocapacitance material; examples 4 and 6 resulted in higher mass fraction of polyaniline than example 1, and thus higher initial capacity of examples 4 and 6.
As can be seen from the comparison between the example 1 and the examples 8 to 9, if the mass ratio of ammonium persulfate to aniline is too low, ammonium persulfate as an oxidant is quickly consumed, the reaction is incomplete, and the specific capacity of the composite material is reduced due to the reduction of the conductivity of polyaniline; on the contrary, the mass ratio of the two is too high, the possibility of generating small molecular products is also increased, and the conductivity and the yield of the synthesized polyaniline are lower.
As can be seen from the comparison between example 1 and examples 10-11, the concentration of phytic acid is too high or too low to facilitate the synthesis of polyaniline, resulting in low capacity and cycle stability of the synthesized composite material.
It is understood from the comparison between example 1 and examples 12-13 that too high or too low concentration of the mixed solution is not favorable for polyaniline to be inserted between the MXene layers, and the mixed solution and the MXene layers cannot be combined, so that the prepared synthetic material mainly comprises polyaniline, and the MXene can not play the electrochemical role only as a conductive agent. In the mixed solutions provided in examples 12 to 13 in the preparation process, Mxene and polyaniline cannot be effectively combined, Mxene only serves as a conductive agent (the effect is equivalent to Super P), and polyaniline plays a main role, so that the capacities of the negative electrode materials provided in examples 12 to 13 are higher.
As can be seen from the comparison between example 1 and comparative example 3, the wettability of the prepared graphite/polyaniline composite material in the electrolyte is weaker than that of the MXene/polyaniline composite material due to the hydrophilic functional groups (-OH, -F, ═ O) contained on the surface of MXene, and the specific capacity and the cycling stability are inferior to those of the present invention.
The comparison between the example 1 and the comparative example 4 shows that phosphate radical carried by phytic acid interacts with amino groups on a plurality of polyaniline chains to form a three-dimensional network structure, and can be connected with functional groups on the surface of MXene through hydrogen bonds to promote insertion of polyaniline into the MXene layers, so that the specific capacity and the cycling stability of the composite material prepared by hydrochloric acid are inferior to those of the composite material prepared by the invention.
The applicant states that the process of the present invention is illustrated by the above examples, but the present invention is not limited to the above process steps, i.e. it is not meant to imply that the present invention must rely on the above process steps to be carried out. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (10)
1. The Mxene-polyaniline composite cathode material is characterized by comprising an Mxene base material and a modified polyaniline material loaded in the Mxene base material;
the modified polyaniline material is a polyaniline material doped with phytic acid.
2. The Mxene-polyaniline composite negative electrode material as claimed in claim 1, wherein the mass ratio of the Mxene base material to the modified polyaniline material in the Mxene-polyaniline composite negative electrode material is (2-5): 1.
3. The Mxene-polyaniline composite negative electrode material according to claim 2, wherein the mass ratio of the Mxene base material to the modified polyaniline material in the Mxene-polyaniline composite negative electrode material is 3: 1.
4. The Mxene-polyaniline composite anode material according to claim 1, wherein the Mxene base material comprises Ti 2 CT x 、Ti 3 C 2 T x Or Ti 4 C 3 T x Any one or a combination of at least two of them, wherein T x Selected from hydroxyl, fluorine atom or carbonyl.
5. A method of preparing the Mxene-polyaniline composite anode material according to any one of claims 1 to 4, characterized in that the method comprises the steps of:
(1) mixing aniline and phytic acid solution to form dispersion A, adding phytic acid solution of ammonium persulfate to perform secondary mixing, and filtering after reaction to obtain a modified polyaniline material;
(2) mixing an Mxene material with a solvent A to form an Mxene material solution, then adding a solvent B to carry out secondary mixing, and centrifuging to obtain the Mxene substrate material;
(3) and (3) mixing the Mxene substrate material obtained in the step (2) with a phytic acid solution to form a dispersion liquid of the Mxene substrate material, adding the modified polyaniline material obtained in the step (1), mixing at a low temperature to obtain a mixed solution, and filtering to obtain the Mxene-polyaniline composite negative electrode material.
6. The method according to claim 5, wherein the concentration of the phytic acid solution in the step (1) is 0.05-0.09 mol/L, preferably 0.07 mol/L;
preferably, the temperature of the mixing in the step (1) is-2 to 2 ℃;
preferably, the mixing in step (1) is carried out under stirring;
preferably, the mass concentration of the dispersion liquid A in the step (1) is 11-17 mg/mL;
preferably, the mass ratio of the ammonium persulfate to the aniline in the step (1) is (2.8-3.1): 1, preferably 2.94: 1;
preferably, the reaction temperature in the step (1) is-2 to 2 ℃;
preferably, the reaction time in the step (1) is 4-7 h;
preferably, the step (1) further comprises a vacuum drying process after the filtration;
preferably, the time of the vacuum drying process is 6-9 h.
7. The method according to claim 5 or 6, wherein the solvent A in step (2) comprises dimethyl sulfoxide;
preferably, the temperature of the mixing in the step (2) is 35-45 ℃;
preferably, the mixing time in the step (2) is 20-30 h;
preferably, the mass concentration of the Mxene material solution in the step (2) is 0.07-0.12 g/mL;
preferably, the solvent B in the step (2) is deionized water;
preferably, the secondary mixing in step (2) is treated under ultrasound;
preferably, the centrifugation in step (2) is further followed by a washing treatment.
8. The method according to any one of claims 5 to 7, wherein the concentration of the phytic acid solution in the step (3) is 0.05 to 0.09mol/L, preferably 0.07 mol/L;
preferably, the mixing in step (3) is performed under ultrasound;
preferably, the temperature of the low-temperature mixing in the step (3) is-2 to 2 ℃;
preferably, the time of the low-temperature mixing in the step (3) is 8-11 h;
preferably, the mass concentration of the mixed solution in the step (3) is 11-17 mg/mL;
preferably, the mass ratio of the modified polyaniline material obtained in the step (1) to the Mxene substrate material obtained in the step (2) in the step (3) is 1 (2-5), preferably 1: 3;
preferably, the filtering in step (3) further comprises a vacuum drying process;
preferably, the temperature of the vacuum drying process is 40-60 ℃;
preferably, the time of the vacuum drying process is 6-9 h.
9. A negative electrode sheet, characterized in that the negative electrode sheet comprises a negative electrode active material, a binder, and a conductive agent, the negative electrode active material comprising the Mxene-polyaniline composite negative electrode material according to any one of claims 1 to 4.
10. A lithium ion battery, characterized in that the lithium ion battery comprises a positive plate, a negative plate, an electrolyte and a diaphragm, wherein the negative plate is the negative plate according to claim 9.
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