CN115466417A - MXene/polyphosphazene-based flexible electrode material and preparation method and application thereof - Google Patents
MXene/polyphosphazene-based flexible electrode material and preparation method and application thereof Download PDFInfo
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- 229920002627 poly(phosphazenes) Polymers 0.000 title claims abstract description 51
- 239000007772 electrode material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000003828 vacuum filtration Methods 0.000 claims abstract description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 36
- 239000002135 nanosheet Substances 0.000 claims description 30
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- UBIJTWDKTYCPMQ-UHFFFAOYSA-N hexachlorophosphazene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 UBIJTWDKTYCPMQ-UHFFFAOYSA-N 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 8
- 238000004108 freeze drying Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910010041 TiAlC Inorganic materials 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 4
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 3
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000138 intercalating agent Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000003457 sulfones Chemical class 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
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- 150000002500 ions Chemical class 0.000 abstract description 16
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- 239000002131 composite material Substances 0.000 abstract description 12
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- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 239000002356 single layer Substances 0.000 abstract description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract 1
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
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- 239000011737 fluorine Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
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- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- NYYLKNDBZDKKAV-UHFFFAOYSA-N ClP1N=PN=P[N]1 Chemical compound ClP1N=PN=P[N]1 NYYLKNDBZDKKAV-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
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- 238000002484 cyclic voltammetry Methods 0.000 description 1
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- 230000002349 favourable effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
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- 230000006872 improvement Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
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- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
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- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
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- NZJMPGDMLIPDBR-UHFFFAOYSA-M tetramethylazanium;hydroxide;hydrate Chemical compound O.[OH-].C[N+](C)(C)C NZJMPGDMLIPDBR-UHFFFAOYSA-M 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
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Abstract
The invention discloses a preparation method and application of a high-oxidation-resistance MXene/polyphosphazene flexible electrode material. The method obtains a large amount of single-layer or few-layer two-dimensional MXene by etching and stripping the fluorine-containing solution, prepares the MXene/polyphosphazene compound by adopting a one-step in-situ polymerization method, and then prepares the MXene/polyphosphazene conductive film electrode with the sandwich structure by a vacuum filtration method. After the surface modification, the space between the MXene composite material layers is increased, which is beneficial to the rapid transmission of electrolyte ions and the exposure of active sites; the composite material has higher affinity for electrolyte ions, and further improves the interlayer ion transmission speed and the ion storage capacity; and the polyphosphazene with the modified surface hinders the reaction of MXene and oxygen, and the oxidation resistance of MXene is effectively improved. The preparation method has the advantages of controllable operation flow and simple process, and the prepared flexible thin film electrode material has the characteristics of good oxidation resistance, high capacity, excellent flexibility and the like, does not need a conductive agent or an adhesive, greatly reduces the cost, and has great application potential in the field of energy storage.
Description
Technical Field
The invention belongs to the technical field of electrode materials, and particularly relates to a preparation method and application of a polyphosphazene surface modified MXene flexible electrode material.
Background
With the rapid development of science and technology, wearable electronic equipment brings convenience to our lives. The wearable system has great application prospects in the aspects of health aging, patient monitoring, emergency management, family energy management, self health management and the like. In order to realize the commercialization of wearable electronic devices, the power supply components thereof also need to be flexible and have high performance, and therefore, the high-performance flexible energy storage device will increasingly show its potential market value. The electrode material is a key factor influencing the performance of energy storage devices (batteries, super capacitors and the like), and the development of the electrode material with high flexibility and high capacity is a great problem.
MXene is a novel two-dimensional transition metal carbon/nitride, loosely stacked nanosheets are obtained by etching and stripping, and the nanosheets have abundant surface functional groups (-OH, = O, -Cl or-F) and few point defects. The conductive inner transition metal carbon/nitride layer can rapidly provide electrons for the electrochemical active sites; the sub-nanometer interlayer slits between the 2D sheets can ensure rapid ion transmission; the excellent mechanical properties of two-dimensional materials allow the formation of self-supporting flexible electrodes without binders, which makes MXene considered an ideal flexible energy storage device electrode material.
Studies have shown that MXene materials store charge in an intercalated manner and that interlayer spacing is one of the prerequisites for limiting electrolyte ion diffusion. However, strong binding energy (graphite and MoS) between MXene nanosheets 2 2-6 times higher) and a high young's modulus perpendicular to the lamellae, indicating that monolayer MXene flakes tend to form stacked structures, severely limiting electrolyte ion penetration and rapid transport. Therefore, it is very important to design a fast ion migration channel.
Due to the exposure of a high proportion of metal atoms on the surface, the unsaturated defects of MXene are easily oxidized to a high-valence metal oxide semiconductor even under ambient conditions and accompany the collapse of a two-dimensional structure. This changes the surface chemistry and morphology of MXene, which ultimately reduces the performance of MXene in applications such as power storage. This not only limits the use of MXene itself, but also presents a significant challenge to the preparation of MXene-based composite materials.
Polyphosphazenes are representative organic-inorganic hybrid materials, in which nitrogen and phosphorus atoms in the main chain are alternately arranged by single bonds and double bonds. Due to the wide variety of pendant groups, such polymers have many excellent physical and chemical properties, as well as related application properties. Most fundamentally, the unique backbone structure ensures its natural flame retardant synergy and thermal stability.
Disclosure of Invention
In order to simultaneously solve the problems of MXene self-stacking and easy oxidation, the invention provides an MXene/poly-nitrile-based flexible electrode material and a preparation method and application thereof. According to the invention, the polyphosphazene is modified on the surface of MXene by a one-step polymerization method, the interlayer spacing is increased, the quick transmission of electrolyte ions and the full contact between ions and active sites are ensured, the oxidation of MXene is inhibited, and the prepared product shows excellent performance when being applied to the fields of super capacitors and various ion batteries.
The MXene composite material provided by the invention is prepared by catalyzing polyphosphazene with triethylamine, reacting an R monomer with a surface end group, and grafting the R monomer on the surface of an MXene nanosheet in situ, and is expressed as MXene/polyphosphazene.
The technical scheme provided by the invention is as follows:
in a first aspect, the invention provides a preparation method of an MXene/polyphosphazene-based flexible electrode material, which comprises the following steps:
(1) Adding MAX phase powder into LiF/HCl or hydrofluoric acid solution, stirring and reacting for a certain time under a heating condition, washing, adding deionized water into a LiF/HCl system for stripping, adding an organic matter intercalator into a hydrofluoric acid system for stripping, and freeze-drying the upper suspension to obtain MXene nanosheets;
(2) Dispersing MXene nanosheets into an organic solvent containing hexachlorocyclotriphosphazene and an R monomer, and adding a catalyst for reaction under the protection of inert gas to obtain MXene/polyphosphazene;
(3) Dispersing MXene/polyphosphazene and MXene nanosheets in water, performing vacuum filtration, and naturally drying in the air to obtain the flexible film.
Further, in the step (1), the MAX phase powder includes but is not limited to Ti 3 AlC 2 ,Ti 2 AlC,Ti 3 AlCN,Ti 2 AlN,Ti 4 AlN 3 ,Ti 3 SiC 2 ,Ti 2 SnC,Ti 3 SnC 2 ,Ta 2 AlC,Ta 4 AlC3,Nb 2 AlC,Nb 4 AlC 3 ,V 2 AlC,V 4 AlC 3 ,V 2 GeC,V 2 GaC,V 2 ZnC,V 2 SnC,Mo 2 Ga 2 C,Mo 2 GeC,Cr 2 AlC,Mo 2 Ti 2 AlC 3 ,Mo 2 TiAlC 2 ,VCrAlC,TiVAlC,Ti 2 VAlC 2 ,Cr 2 TiAlC,TiNbAlC,VNbAlC,(W 2/3 Y 1/3 ) 2 AlC,(Mo 2/3 Y 1/3 ) 2 AlC,Mo 2/3 Sc 1/3 AlC。
Further, in the step (1), the concentration of the hydrochloric acid solution is 6-12M, and the mass ratio of LiF to MAX phase powder is 1-6; the concentration of the hydrofluoric acid solution is 10-40wt%; the reaction time is 24-168 hours under heating and stirring.
Further, in the step (1), the organic intercalant includes but is not limited to dimethyl sulfoxide, tetramethyl ammonium hydroxide and tetrabutyl ammonium hydroxide, and Li remained in the etching step after MXene is etched by using LiF/HCl system + The interlaminar acting force of the MXene nanosheets can be weakened, so that multiple layers of MXene can be stripped to obtain few layers of MXene nanosheets only by adding deionized water; after MXene is etched by using an HF system, an organic intercalator is additionally added to weaken the interlayer acting force of MXene nanosheets so as to achieve the effect of stripping multiple layers of MXene.
Further, in the step (1), MXene nanosheets include, but are not limited to, ti 3 C 2 ,Ti 2 C,Ti 3 CN,V 4 C 3 ,V 2 C,Nb 4 C 3 ,Nb 2 C,Mo 2 C,Mo 1.33 C,Mo 2 Ti 2 C 3 ,Mo 2 TiC,W 1.33 C。
Further, in the step (2), the R monomer includes, but is not limited to, 4' diaminodiphenyl sulfone, 4' dihydroxydiphenyl sulfone, 4' diaminodiphenyl ether, 4' dihydroxydiphenyl ether, 4' dimercaptodiphenyl ether.
Further, in the step (2), the organic solvent is anhydrous acetonitrile.
Further, in the step (2), the catalyst is triethylamine.
Further, in the step (2), the mass ratio of hexachlorocyclotriphosphazene to MXene nanosheet is 1-100, the reaction temperature is 60-90 ℃, and the heating time is 6-18 hours.
Further, in the step (3), the mass ratio of the MXene/polyphosphazene to the MXene nanosheet is 0.5-4.
The method adopted by the invention can obtain the MXene nanosheets with large surfaces and rich terminal functional groups (-OH, = O, -F, -Cl), the chlorocyclotriphosphazene and the R monomer generate nucleophilic substitution polycondensation reaction under the catalysis of triethylamine to generate polyphosphazene, and the P-Cl group of the hexachlorocyclotriphosphazene can react with-OH on the MXene nanosheets to anchor the polyphosphazene on the MXene surfaces.
In a second aspect, the invention provides an MXene/polyphosphazene based flexible electrode material prepared by the method of the first aspect.
In a third aspect, the invention provides an application of the MXene/polyphosphazene-based flexible electrode material in the second aspect as an electrode material of a super capacitor or a battery.
The invention has the following beneficial effects:
the method effectively prevents MXene layers from self-stacking by modifying the surfaces of MXene by polyphosphazenes and R monomers, increases the interlayer spacing, widens an MXene interlayer channel, and is favorable for quick transmission of electrolyte ions. Increased interlayer spacing enables a high ion accessible surface, exposing more electrochemically active sites; the composite material has higher affinity for electrolyte ions, and the interlayer ion transmission speed and the ion storage capacity are further improved. These characteristics allow the composite materials to achieve higher capacity and rate capability when used as electrode materials. In addition, the polyphosphazene with the modified surface hinders the reaction of MXene and oxygen, and the oxidation resistance of MXene is effectively improved.
Drawings
FIG. 1 is a schematic diagram of a polyphosphazene modified MXene technical route (using Ti 3 C 2 For example).
FIG. 2 shows MXene (as Ti) 3 C 2 Example) and MXene/polyphosphazene (XRD pattern).
FIG. 3 shows MXene (as Ti) after six months storage at room temperature 3 C 2 Examples) and XRD patterns of MXene/polyphosphazene.
FIG. 4 shows MXene (as Ti) 3 C 2 Examples) and MXene/polyphosphazene cyclic voltammograms.
FIG. 5 shows MXene (as Ti) 3 C 2 For example) and MXene/polyphosphazene multiplier performance plots.
Detailed Description
The present invention will be described in detail with reference to the following examples, but the scope of the present invention is not limited to the following examples.
Example 1
The MXene/polyphosphazene based flexible electrode material is prepared by the following steps:
(1) 1g LiF was added to 25ml 9M HCl solution, and dissolved for 5 minutes with stirring. Thereafter, 1g of Ti 3 AlC 2 The powder was added to the above solution and reacted at 40 ℃ for 24 hours. The powder obtained from the reaction was then washed with deionized water and centrifuged until the pH of the wash supernatant was close to 6. Multilayer Ti obtained by washing 3 C 2 Adding 100ml of deionized water, performing ultrasonic treatment for 1 hour under the protection of nitrogen, and performing centrifugal separation to obtain dark green supernatant, namely few-layer Ti 3 C 2 And (5) nanosheets, and freeze-drying for later use.
(2) Weighing 200mg of less Ti 3 C 2 The nanosheets were dispersed in 100ml of anhydrous acetonitrile containing 10mg of hexachlorocyclotriphosphazene and 24mg of 4,4' -diamino-diphenylsulfone, followed by addition of a small amount of triethylamine, and reacted at 85 ℃ for 12 hours under nitrogen protection. After cooling to room temperature, washing the product with anhydrous acetonitrile, and vacuum drying to obtain the MXene/polyphosphazene composite material.
(3) And (3) weighing 10mg of MXene/polyphosphazene and 5mg of MXene, dispersing in 30ml of deionized water, and carrying out vacuum filtration to obtain the flexible self-supporting thin film electrode.
The prepared material is subjected to X-ray powder diffraction characterization (see figure 2), and the interlayer spacing of the MXene composite material modified by the polyphosphazene surface is increased from 1.26nm of few-layer MXene to 1.47nm.
After six months of storage at room temperature of MXene/polyphosphazene and MXene, no significant oxidation of MXene/polyphosphazene was observed, whereas TiO was observed with MXene 2 The surface modified polyphosphazene effectively improves the oxidation resistance of MXene (see FIG. 3).
The prepared film electrode is directly used as a working electrode and is in 3 MH 2 SO 4 In electrolyte solution, 2mV s -1 Was performed at a scanning rate of (2) and the specific capacitance was found to be determined from 286 fg when unmodified -1 Increased to 380 Fg -1 (see fig. 4), the magnification characteristic is increased from 6% to 60% (see fig. 5).
Example 2
Preparing MXene/polyphosphazene based flexible electrode material, comprising the following steps:
(1) 0.5g of Nb 4 AlC 3 Dispersed in 40mL of 50% HF solution and reacted at room temperature for 100 hours. The powder obtained from the reaction was then washed with deionized water and centrifuged until the pH of the wash supernatant was close to 6. Washing the resulting multilayered Nb 4 C 3 Adding into 10ml 2.5wt% tetramethylammonium hydroxide water solution, shaking by hand for 15 min, and centrifuging to obtain supernatant as few-layer Nb 4 C 3 And (5) nanosheets, and freeze-drying for later use.
(2) Weighing 200mg of few-layer Nb 4 C 3 The nano-sheets are dispersed in 100ml of anhydrous acetonitrile solution containing 10mg of hexachlorocyclotriphosphazene and 24mg4,4' dihydroxy diphenyl sulfone, and then a small amount of triethylamine is added to react for 12 hours at 85 ℃ under the protection of nitrogen. After cooling to room temperature, washing the product with anhydrous acetonitrile, and vacuum drying to obtain the MXene/polyphosphazene composite material.
(3) And (3) weighing 10mg of MXene/polyphosphazene and 5mg of MXene, dispersing in 30ml of deionized water, and carrying out vacuum filtration to obtain the flexible self-supporting film electrode.
Example 3
Preparing MXene/polyphosphazene based flexible electrode material, comprising the following steps:
(1) 2g LiF is added into 25ml 12M HCl solution, stirred for 5 minutes and dissolved for standby. Then 1g of Mo 2 Ga 2 C powder was added to the above solution and reacted at 40 ℃ for 168 hours. The powder obtained from the reaction was then washed with deionized water, centrifuged, washed three times with 1M HCl and 1M LiCl solutions in sequence, and then washed with deionized water until the pH of the supernatant was close to 6. Multilayer Mo obtained in washing 2 C, adding 100ml of deionized water, performing ultrasonic treatment for 1 hour under the protection of nitrogen, and performing centrifugal separation to obtain supernatant, namely the few-layer Mo 2 And C nanosheet, and freeze drying for later use.
(2) Weighing 200mg of less-layer Mo 2 Dispersing the C nanosheets into 100ml of anhydrous acetonitrile solution containing 10mg of hexachlorocyclotriphosphazene and 24mg of 4,4' -diaminodiphenyl ether, adding a small amount of triethylamine, and reacting at 85 ℃ for 12 hours under the protection of nitrogen. After cooling to room temperature, washing the product with anhydrous acetonitrile, and vacuum drying to obtain the MXene/polyphosphazene composite material.
(3) And (3) weighing 10mg of MXene/polyphosphazene and 5mg of MXene, dispersing in 30ml of deionized water, and carrying out vacuum filtration to obtain the flexible self-supporting thin film electrode.
Example 4
The MXene/polyphosphazene based flexible electrode material is prepared by the following steps:
(1) 1g of Mo 2/3 Sc 1/3 AlC was dispersed in 20mL HF solution and reacted at room temperature for 24 hours. The powder obtained from the reaction was then washed with deionized water and centrifuged until the pH of the wash supernatant was close to 6. Multilayer Mo obtained by washing 1.33 Adding the C into 50ml of 8wt% tetramethylammonium hydroxide aqueous solution, shaking by hand for 15 minutes, washing by deionized water, and performing centrifugal separation to obtain supernatant, namely few-layer Mo 1.33 And C nanosheet, and freeze drying for later use.
(2) Weighing 200mg of less-layer Mo 1.33 Dispersing the C nanosheets into 100ml of anhydrous acetonitrile solution containing 10mg of hexachlorocyclotriphosphazene and 24mg of 4,4' -dihydroxy diphenyl ether, adding a small amount of triethylamine, and reacting at 85 ℃ for 12 hours under the protection of nitrogen. After cooling to room temperature, washing the product with anhydrous acetonitrile, and vacuum drying to obtain the MXene/polyphosphazene composite material.
(3) And (3) weighing 10mg of MXene/polyphosphazene and 5mg of MXene, dispersing in 30ml of deionized water, and carrying out vacuum filtration to obtain the flexible self-supporting thin film electrode.
Example 5
Preparing MXene/polyphosphazene based flexible electrode material, comprising the following steps:
(1) 1g of V 2 AlC was dispersed in 20mL HF solution and reacted at 35 ℃ for 120 hours. The powder obtained from the reaction was then washed with deionized water and centrifuged until the pH of the wash supernatant was close to 6. Multilayer V obtained by washing 2 C is added into 30ml of 25wt% tetramethylammonium hydroxide aqueous solution, stirred for 12h, washed by deionized water, and subjected to ultrasound for 30min under the protection of nitrogen, and the supernatant obtained by centrifugal separation is the few-layer V 2 And C nanosheet, and freeze drying for later use.
(2) Weighing 200mg of few layers V 2 Dispersing the C nanosheets into 100ml of anhydrous acetonitrile solution containing 10mg of hexachlorocyclotriphosphazene and 24mg of 4,4' -dimercaptodiphenylether, then adding a small amount of triethylamine, and reacting for 12 hours at 85 ℃ under the protection of nitrogen. ColdAnd cooling to room temperature, washing the product with anhydrous acetonitrile, and performing vacuum drying to obtain the MXene/polyphosphazene composite material.
(3) And (3) weighing 10mg of MXene/polyphosphazene and 5mg of MXene, dispersing in 30ml of deionized water, and carrying out vacuum filtration to obtain the flexible self-supporting thin film electrode.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any modification, equivalent replacement, and improvement made by those skilled in the art within the technical scope of the present invention should be included in the scope of the present invention.
Claims (10)
1. A preparation method of MXene/polyphosphazene based flexible electrode material is characterized by comprising the following steps:
(1) Adding MAX phase powder into LiF/HCl or hydrofluoric acid solution, stirring and reacting for a certain time under a heating condition, washing, adding deionized water into a LiF/HCl system for stripping, adding an organic matter intercalator into a hydrofluoric acid system for stripping, and freeze-drying the upper suspension to obtain MXene nanosheets;
(2) Dispersing MXene nanosheets into an organic solvent containing hexachlorocyclotriphosphazene and an R monomer, and adding a catalyst to react under the protection of inert gas to obtain MXene/polyphosphazene;
(3) And dispersing the MXene/polyphosphazene and MXene nanosheets in water, performing vacuum filtration, and naturally drying in the air to obtain the flexible film.
2. The method of claim 1, wherein: in the step (1), the MAX phase powder contains Ti 3 AlC 2 ,Ti 2 AlC,Ti 3 AlCN,Ti 2 AlN,Ti 4 AlN 3 ,Ti 3 SiC 2 ,Ti 2 SnC,Ti 3 SnC 2 ,Ta 2 AlC,Ta 4 AlC3,Nb 2 AlC,Nb 4 AlC 3 ,V 2 AlC,V 4 AlC 3 ,V 2 GeC,V 2 GaC,V 2 ZnC,V 2 SnC,Mo 2 Ga 2 C,Mo 2 GeC,Cr 2 AlC,Mo 2 Ti 2 AlC 3 ,Mo 2 TiAlC 2 ,VCrAlC,TiVAlC,Ti 2 VAlC 2 ,Cr 2 TiAlC,TiNbAlC,VNbAlC,(W 2/3 Y 1/3 ) 2 AlC,(Mo 2/3 Y 1/3 ) 2 AlC,Mo 2/3 Sc 1/3 AlC。
3. The method of claim 1, wherein: in the step (1), the concentration of the hydrochloric acid solution is 6-12M, and the mass ratio of LiF to MAX phase powder is 1-6; the concentration of the hydrofluoric acid solution is 10-40wt%; the reaction time is 24-168 hours under heating and stirring.
4. The method of claim 1, wherein: in the step (1), the organic intercalation agent comprises dimethyl sulfoxide, tetramethyl ammonium hydroxide and tetrabutyl ammonium hydroxide.
5. The method of claim 1, wherein: in the step (2), the R monomer comprises 4,4' diaminodiphenyl sulfone, 4' dihydroxydiphenyl sulfone, 4' diaminodiphenyl ether, 4' dihydroxydiphenyl ether, 4' dimercaptodiphenyl ether.
6. The method of claim 1, wherein: in the step (2), the organic solvent is anhydrous acetonitrile, and the catalyst is triethylamine.
7. The method of claim 1, wherein: in the step (2), the mass ratio of hexachlorocyclotriphosphazene to MXene nanosheet is 1-100, the reaction temperature is 60-90 ℃, and the heating time is 6-18 hours.
8. The production method according to claim 1, characterized in that: in the step (3), the mass ratio of MXene/polyphosphazene to MXene nanosheets is 0.5-4.
9. An MXene/polyphosphazene based flexible electrode material is characterized in that: prepared by the process of any one of claims 1 to 8.
10. Use of the MXene/polyphosphazene based flexible electrode material of claim 9 as an electrode material for supercapacitors or batteries.
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CN114231036A (en) * | 2022-01-07 | 2022-03-25 | 广州市白云化工实业有限公司 | High-strength synergistic flame-retardant room-temperature vulcanized silicone rubber and preparation method thereof |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4110421A (en) * | 1976-10-12 | 1978-08-29 | Armstrong Cork Company | Catalytic process for the preparation of phosphazene polymers |
CN110474062A (en) * | 2019-08-02 | 2019-11-19 | 北京化工大学常州先进材料研究院 | A kind of preparation and application of efficient MXene titanium carbide cell catalyst |
CN112072126A (en) * | 2020-08-31 | 2020-12-11 | 华南理工大学 | Mxene flexible self-supporting lithium-air battery positive electrode material, Mxene flexible composite film and preparation method thereof |
CN113234103A (en) * | 2021-05-28 | 2021-08-10 | 青岛大学 | Phosphazene flame retardant and preparation method and application thereof |
CN114725380A (en) * | 2022-05-09 | 2022-07-08 | 江苏科技大学 | Self-supporting polyimide @ MXene flexible film and preparation method and application thereof |
-
2022
- 2022-07-28 CN CN202210898816.5A patent/CN115466417B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4110421A (en) * | 1976-10-12 | 1978-08-29 | Armstrong Cork Company | Catalytic process for the preparation of phosphazene polymers |
CN110474062A (en) * | 2019-08-02 | 2019-11-19 | 北京化工大学常州先进材料研究院 | A kind of preparation and application of efficient MXene titanium carbide cell catalyst |
CN112072126A (en) * | 2020-08-31 | 2020-12-11 | 华南理工大学 | Mxene flexible self-supporting lithium-air battery positive electrode material, Mxene flexible composite film and preparation method thereof |
CN113234103A (en) * | 2021-05-28 | 2021-08-10 | 青岛大学 | Phosphazene flame retardant and preparation method and application thereof |
CN114725380A (en) * | 2022-05-09 | 2022-07-08 | 江苏科技大学 | Self-supporting polyimide @ MXene flexible film and preparation method and application thereof |
Non-Patent Citations (1)
Title |
---|
ZHENTING YIN ET AL.: ""Inspired by placoid scale to fabricate MXene derivative biomimetic structure on the improvement of interfacial compatibility, mechanical property, and fire safety of epoxy nanocomposites"", 《CHEMICAL ENGINEERING JOURNAL》, vol. 431 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114231036A (en) * | 2022-01-07 | 2022-03-25 | 广州市白云化工实业有限公司 | High-strength synergistic flame-retardant room-temperature vulcanized silicone rubber and preparation method thereof |
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