CN115498357A - Functional composite diaphragm based on tantalum-based MXene derivative and preparation method and application thereof - Google Patents
Functional composite diaphragm based on tantalum-based MXene derivative and preparation method and application thereof Download PDFInfo
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
- H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a functional composite diaphragm based on tantalum-based MXene derivatives, and a preparation method and application thereof 4 AlC 3 Etching the powder with acid liquor to obtain MXene nano-sheets, oxidizing the etched MXene nano-sheets by using hydrogen peroxide as a matrix through an oxidation method, and calcining at high temperature to realize the decoration of oxide Ta with the size of quantum dots on the surfaces of the MXene nano-sheets 2 O 5 Thereby forming a heterojunction Ta with rich active sites on the surface 4 C 3 ‑Ta 2 O 5 A composite material; mixing Ta 4 C 3 ‑Ta 2 O 5 Mixing the composite material with carbon source powder to prepare slightly flowing slurry, and finally, uniformly coating the slurry on a polypropylene film to prepare Ta 4 C 3 ‑Ta 2 O 5 a/C composite modified diaphragm; the composite modified diaphragm realizes effective protection on a metal lithium cathode, and successfully prevents dissolution and diffusion of polysulfide, so that excellent electrochemical performance is endowed to a lithium-sulfur battery.
Description
Technical Field
The invention belongs to the technical field of functional materials, relates to a battery composite diaphragm, and particularly relates to a functional composite diaphragm based on a tantalum-based MXene derivative, and a preparation method and application thereof.
Background
With the increasingly prominent global energy crisis and environmental pollution problems, the development of energy-saving and environment-friendly related industries is highly emphasized, and the development of new energy storage systems has become common knowledge on the global scale. The lithium-sulfur battery has become one of the best choices of the next generation of novel energy storage devices due to the advantages of high theoretical specific capacity, high energy density, safety, environmental protection and the like. Unfortunately, the development of lithium sulfur batteries faces embarrassing problems such as low coulombic efficiency and irreversible loss of solution by polysulfide shuttling effect, S 8 And Li 2 Poor conductivity of S causes problems such as slow kinetics of oxidation. In particular, the shuttling effect of polysulfides and the growth of lithium dendrites during charge and discharge of the lithium sulfur battery become key factors limiting the development of commercial lithium sulfur batteries.
To overcome the above challenges, researchers have made great efforts in sulfur host construction, separator modification, and lithium metal negative electrode protection. Among them, the modification of the separator is an effective means for preventing the "shuttle effect" caused by the dissolution and diffusion of polysulfide and inhibiting the growth of lithium dendrite. Recently, transition metal carbides typified by MXene have been widely used as energy storage materials due to their unique accordion structure, excellent mechanical properties, and chemical stability. However, a single MXene material has the problems of relatively poor conductivity, poor adsorption capacity to LiPSs and the like. The structural advantages of each component can be fully exerted by introducing heterojunction engineering, so that the electrochemical performance of the lithium-sulfur battery is improved.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the functional composite diaphragm based on the tantalum-based MXene derivative, the preparation method and the application thereof, the functional composite diaphragm is used as a lithium-sulfur battery diaphragm, the effective protection on a metal lithium cathode is realized, the dissolution and diffusion of polysulfide are successfully prevented, and the preparation process is simple and environment-friendly.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a functional composite diaphragm based on a tantalum-based MXene derivative comprises the following steps:
The invention also has the following technical characteristics:
preferably, the acid solution in the step 1 comprises HF acid with the mass fraction of less than or equal to 40% or the concentration of 12 mol.L -1 The HCl solution of (1);
LiF is added into the HCl solution, and the mass-to-volume ratio of LiF to the HCl solution is 1.
Preferably, the drying conditions described in step 1 and step 3 include vacuum drying at 60 ℃ for 12h or freeze drying.
Preferably, the sufficient stirring in the step 2 is stirring for 4 to 6 hours at a rotating speed of 600r/min by using a magnetic stirrer.
Preferably, the intensive stirring in step 3 is a mixed stirring of magnetic stirring and an ultrasonic cell disruptor.
Preferably, the volume ratio of argon gas to hydrogen gas in the argon-hydrogen mixed gas in the step 4 is 8.
Preferably, the carbon source in step 5 is BP2000, graphene, acetylene black or carbon nanotubes.
The invention also discloses a functional composite diaphragm based on the tantalum-based MXene derivative prepared by the method and application of the functional composite diaphragm in a lithium-sulfur battery.
Compared with the prior art, the invention has the following technical effects:
MXene is obtained through a chemical etching method, the process is simple to operate, green, pollution-free and good in etching effect, and the molecular formula is represented as Ta 4 C 3 T x (wherein T is x Representing functional groups containing-F, -O, -Cl and-OH), oxidizing the etched MXene nanosheet serving as a substrate by an oxidation method, oxidizing the substrate by using hydrogen peroxide, and calcining the substrate at high temperature to obtain the oxide Ta with the size of quantum dots decorated on the surface of the MXene nanosheet 2 O 5 Thereby forming a heterojunction Ta with rich active sites on the surface 4 C 3 -Ta 2 O 5 A composite material; the heterostructure material gives full play to the structure of each component, ta 4 C 3 The ultra-high conductivity and excellent mechanical property can accelerate charge transfer and form a protective film on the surface of the lithium metal to prevent the growth of lithium dendrite, ta 2 O 5 The surface of the lithium-sulfur battery has strong adsorption capacity to polysulfide under synergistic action, so that the lithium-sulfur battery can effectively protect the lithium metal cathode and successfully prevent the polysulfide from being dissolved and diffused, and therefore, the lithium-sulfur battery has excellent electrochemical performance;
the functional composite diaphragm based on the tantalum-based MXene derivative is simple in preparation process and environment-friendly, and the 'rock-bird' strategy provides a new visual field for a high-energy-density lithium-sulfur energy storage system and lithium metal protection.
Drawings
FIGS. 1-2 are hetero-structured Ta prepared in example 1 4 C 3 -Ta 2 O 5 SEM images of the composite;
FIGS. 3-5 are the heterostructure Ta prepared in example 1 4 C 3 -Ta 2 O 5 TEM images of the composite;
FIG. 6 is the heterostructure Ta prepared in example 1 4 C 3 -Ta 2 O 5 An XRD pattern of the composite material;
FIG. 7 is the heterostructure Ta prepared in example 1 4 C 3 -Ta 2 O 5 A steady state curve chart of the/C-PP symmetrical battery, wherein an internal chart is an impedance spectrum before and after polarization;
FIG. 8 shows the heterostructure Ta prepared in example 1 4 C 3 -Ta 2 O 5 The scanning speed of the/C-PP battery is 0.1-0.5 mV.s -1 Is circulatedA ring voltammogram;
FIG. 9 shows heterostructure Ta prepared in example 1 4 C 3 -Ta 2 O 5 An isostatic pressure charging and discharging voltage curve diagram of the/C-PP battery;
FIG. 10 shows heterostructure Ta prepared in example 1 4 C 3 -Ta 2 O 5 Short cycle performance diagram of/C-PP battery;
FIG. 11 shows heterostructure Ta prepared in example 1 4 C 3 -Ta 2 O 5 A rate performance diagram of the/C-PP battery;
FIG. 12 shows heterostructure Ta prepared in example 1 4 C 3 -Ta 2 O 5 the/C-PP symmetrical battery is 10mA cm -2 ,10mAh·cm -2 Electrostatic cycling performance map of (a).
Detailed Description
The present invention will be explained in further detail with reference to examples.
Example 1:
the embodiment provides a preparation method of a functional composite diaphragm based on a tantalum-based MXene derivative, which specifically comprises the following steps:
step 1: 2g of MAX phase Ta 4 AlC 3 Gradually and slowly adding the powder into a reaction kettle containing 50mLHF (less than or equal to 40 percent), and magnetically stirring for 96 hours at the temperature of 45 ℃; then, the obtained suspension is centrifuged at 8000,5min and washed repeatedly with deionized water and absolute ethyl alcohol until the pH value is 7; finally, the obtained lower precipitate is dried in vacuum for 12h at 60 ℃ to obtain Ta 4 C 3 T x Nanosheet powder;
and 2, step: 0.5g of Ta was weighed 4 C 3 T x Adding into deionized water, stirring for 6 hr at 600r/min with magnetic stirrer to obtain 3.0 mg/mL solution -1 Ta 4 C 3 T x A suspension;
and step 3: 200 mL3.0wt.% of H 2 O 2 Dropwise adding into 40mL of the suspension, vigorously stirring with a magnetic stirrer and an ultrasonic cell disruptor until the solution is uniformly mixed, and then performing vacuum filtrationFiltering with air, collecting precipitate, vacuum drying the obtained filter cake at 60 deg.C for 12 hr, and collecting powder;
and 4, step 4: the powder obtained is mixed with Ar/H 2 Under a (90/10, vol/vol) gas flow, at a temperature rising rate of 5 ℃ C. Min -1 Annealing at 900 deg.C for 2h, cooling to room temperature to obtain Ta 4 C 3 -Ta 2 O 5 A heterostructure composite powder material;
and 5: weighing 0.1g of the powder and 0.1g of BP2000 powder, then weighing 0.0222g of polyvinylidene fluoride (PVDF) adhesive, mixing, adding N-methylpyrrolidone (NMP) to prepare paste which is slightly diluted, and finally, uniformly coating the paste on one side of a polypropylene film (PP) to obtain the Ta film with the coating thickness of 25 mu m 4 C 3 -Ta 2 O 5 a/C composite modified diaphragm.
Example 2:
the embodiment provides a preparation method of a functional composite diaphragm based on a tantalum-based MXene derivative, which specifically comprises the following steps:
step 1: 1g of MAX phase Ta 4 AlC 3 The powder was gradually and slowly added to a container containing 30mL of 12 mol. L -1 HCl in a reaction kettle containing 1.5g of a lithium fluoride (LiF) mixed solution, magnetically stirring at 45 ℃ for 48h, then centrifuging the obtained suspension at 8000rpm for 5min and repeatedly washing with deionized water and absolute ethanol to a pH value of 7; finally, the obtained precipitate is dried in vacuum for 12h at 60 ℃ to obtain Ta 4 C 3 T x Nanosheet powder;
step 2: 0.5g of Ta are weighed out 4 C 3 T x Adding into deionized water, stirring with magnetic stirrer at 600r/min for 4 hr to obtain a solution with a concentration of 1.0 mg/mL -1 Ta 4 C 3 T x A suspension;
and 3, step 3: 10m L3.0wt.% of H 2 O 2 Dropwise adding the mixture into 40mL of the suspension, violently stirring the mixture by adopting magnetic stirring and an ultrasonic cell disruptor until the solution is uniformly mixed, then collecting precipitates by adopting vacuum filtration, and carrying out vacuum drying on the obtained filter cake at 60 ℃ for 12 hours to collect powder;
and 4, step 4: the obtained powder was put under Ar/H 2 Under (80/20, vol/vol) gas flow, at a temperature rise rate of 8 ℃ min -1 Annealing and heat preservation at 800 ℃ for 3h, and cooling after sintering to obtain Ta 4 C 3 -Ta 2 O 5 A heterostructure composite powder material;
and 5: weighing 0.1g of the powder and 0.1g of graphene powder, and then weighing 0.0222g of polyvinylidene fluoride (PVDF) adhesive; then adding N-methylpyrrolidone (NMP) to prepare slurry which is pasty and slightly diluted, and finally uniformly coating the slurry on one side of a polypropylene film (PP) to the thickness of 25 mu m to prepare the Ta 4 C 3 -Ta 2 O 5 a/C composite modified diaphragm.
Example 3:
the embodiment provides a preparation method of a functional composite diaphragm based on a tantalum-based MXene derivative, which specifically comprises the following steps:
step 1: 2g of MAX phase Ta 4 AlC 3 Gradually and slowly adding the powder into a reaction kettle containing 50mLHF (less than or equal to 40 percent), magnetically stirring for 72 hours at the temperature of 45 ℃, centrifuging the obtained suspension at 8000,5 minutes, repeatedly washing with deionized water and absolute ethyl alcohol until the pH value is 7, and finally, freeze-drying the obtained lower precipitate to obtain Ta 4 C 3 T x Nanosheet powder;
step 2: 0.5g of Ta was weighed 4 C 3 T x Adding into deionized water, stirring with magnetic stirrer at 600r/min for 6 hr to obtain solution with concentration of 4.0 mg/mL -1 Ta 4 C 3 T x A suspension;
and step 3: 200 mL5.0wt.% of H 2 O 2 Dropwise adding the mixture into 30mL of the suspension, mixing the mixture by adopting a magnetic stirring and ultrasonic cell disruption instrument, violently stirring the mixture until the solution is uniformly mixed, then collecting precipitates by adopting vacuum filtration, and collecting powder after freeze-drying the obtained filter cake;
and 4, step 4: the powder obtained is mixed with Ar/H 2 Under a (90/10, vol/vol) gas flow, at a temperature rising rate of 10 ℃ min -1 Annealing at 900 DEG CKeeping the temperature for 4 hours by fire, and cooling to room temperature after sintering to obtain Ta 4 C 3 -Ta 2 O 5 A heterostructure-composite powder material;
and 5: weighing 0.08g of the powder and 0.02g of acetylene black powder, then weighing 0.0222g of polyvinylidene fluoride (PVDF) adhesive, and adding N-methylpyrrolidone (NMP) to prepare slurry which is pasty and slightly diluted; finally, evenly coating the slurry on one side of a polypropylene film (PP) with the coating thickness of 25 mu m to prepare the Ta 4 C 3 -Ta 2 O 5 a/C composite modified diaphragm.
Example 4:
the embodiment provides a preparation method of a functional composite diaphragm based on a tantalum-based MXene derivative, which specifically comprises the following steps:
step 1: 2g of MAX phase Ta 4 AlC 3 Gradually and slowly adding the powder into a reaction kettle containing 50mLHF (less than or equal to 40%), magnetically stirring for 96h at 45 ℃, centrifuging the obtained suspension for 8000,5min, repeatedly washing with deionized water and absolute ethyl alcohol until the pH value is 7, and finally, drying the obtained lower precipitate for 12h at 60 ℃ in vacuum to obtain Ta 4 C 3 T x Nanosheet powder;
step 2: 0.5g of Ta was weighed 4 C 3 T x Adding into deionized water, stirring for 5 hr at 600r/min with magnetic stirrer to obtain 5.0 mg/mL solution -1 Ta 4 C 3 T x A suspension;
and 3, step 3: 30mL4.0wt.% of H 2 O 2 Dropwise adding the mixture into 50mL of the suspension, stirring the mixture vigorously to obtain a solution, mixing the solution uniformly, collecting precipitates by vacuum filtration, and drying the obtained filter cake at 60 ℃ in vacuum for 12 hours to collect powder;
and 4, step 4: the powder obtained is mixed with Ar/H 2 Under (90/10, vol/vol) gas flow, at a temperature rise rate of 5 ℃ min -1 Annealing at 1000 deg.C for 3h, cooling to room temperature to obtain Ta 4 C 3 -Ta 2 O 5 A heterostructure composite powder material;
and 5: balanceTaking 0.1g of the powder and 0.1g of carbon nano tubes, then weighing 0.0222g of polyvinylidene fluoride (PVDF) adhesive, adding N-methylpyrrolidone (NMP) to prepare paste which is slightly diluted; finally, uniformly coating the slurry on one side of a polypropylene film (PP) with the coating thickness of 25 mu m to prepare the Ta 4 C 3 -Ta 2 O 5 a/C composite modified diaphragm.
FIGS. 1 to 12 are the heterostructure Ta prepared in example 1 4 C 3 -Ta 2 O 5 The morphology and phase composition of the composite material, and the dynamic behavior and electrochemical performance analysis of the assembled battery are specifically analyzed as follows:
1. topography analysis
As shown in FIG. 1, the MAX phase showed a larger etch spacing after HF etching, indicating that MXene-Ta was obtained by successful etching 4 C 3 T x (ii) a As shown in fig. 2, diluted hydrogen peroxide (H) 2 O 2 ) After the solution, a large amount of Ta atoms are exposed on MXene nano-sheets, and the obtained product is calcined at high temperature to form oxide Ta with the size of quantum dots 2 O 5 。
As shown in FIG. 3, MXene-Ta after HF etching 4 C 3 T x Thin and numerous nanoplates are present. FIG. 5 shows that quantum dot-sized spherical particles Ta appear in MXene nanosheets 2 O 5 And Ta 4 C 3 D spacing of
(002) crystal face of (Ta) and (Ta) 2 O 5 D spacing of
The (002) crystal face of (b) coexists in the common nanosheet; at the same time, ta 4 C 3 (002) And Ta 2 O 5 (002) A well-defined interface is also shown between them (shown in fig. 4), which facilitates charge transfer and accelerates the catalytic conversion of the LiPSs.
2. Analysis of phase composition
As shown in FIG. 6, we succeeded in obtaining Ta 4 C 3 T x From Ta 4 AlC 3 Stripping in MAX phase; derived from the parent Ta 4 AlC 3 The peak intensity of (a) is greatly reduced after HF treatment; in particular, the (002) plane peak is obviously widened and shifted to 5.83 degrees towards a lower 2 theta angle, namely, the newly appeared low-angle (002) plane peak is a typical characteristic peak of most of reported high-frequency etched MXenes, which indicates that the whole sample is converted into MXenes, and Ta appears in an XRD pattern of oxidation treatment 4 C 3 And Ta 2 O 5 Two characteristic peaks, which indicate successful preparation of heterostructure Ta 4 C 3 -Ta 2 O 5 A composite material.
3. Analysis of kinetic behavior
As shown in fig. 7, li of the modified separator was tested + Mobility conditions; ta 4 C 3 -Ta 2 O 5 Li of/C-PP separator + The mobility coefficient is 4.31 (much higher than Ta) 4 C 3 C-PP separator), which indicates Ta 4 C 3 -Ta 2 O 5 the/C-PP diaphragm realizes Li + The channel also greatly hinders the migration of the anionic groups of the LiPSs.
As shown in FIG. 8, the modified cell was tested at scan rates of 0.1-0.5 mV. S -1 Cyclic voltammogram of (a); hetero-junction Ta 4 C 3 -Ta 2 O 5 Show Ta 4 C 3 Significant enhancement of the value of the internal slope in part, indicating Ta 4 C 3 And Ta 2 O 5 With synergistic enhancement effects, helping to achieve optimum kinetic performance, rather than from Ta 4 C 3 (or Ta) 2 O 5 ) Sum of independent influences of (a).
4. Analysis of electrochemical Properties
As shown in fig. 9, compared to Ta 4 C 3 C-PP cell, ta 4 C 3 -Ta 2 O 5 the/C-PP cell exhibited a smaller voltage difference (0.22V), indicating that the heterostructure is advantageous for accelerating the polysulfide redox kinetics.
As shown in FIG. 10, ta at a current density of 0.2C 4 C 3 -Ta 2 O 5 the/C-PP battery has higher reversible discharge capacity and better cycle stability, and the capacity retention rate reaches 57.9 percent after 100 cycles (compared with the 2 nd cycle). In contrast, ta 4 C 3 The capacity of the/C-PP battery can only be kept at 28.1%, and a gradual attenuation process is provided.
As shown in fig. 11, the rate performance of the cells at different current densities was tested; ta 4 C 3 -Ta 2 O 5 The average reversible capacity of the/C-PP battery is 1262.3mAh g when the current density is 0.2C, 0.4C, 0.6C, 0.8C and 1C -1 、928.3mAh·g -1 、809.2mAh·g -1 、773.9mAh·g -1 And 738.5mAh · g -1 (ii) a Ta when the current density returns to 0.2C 4 C 3 -Ta 2 O 5 The capacity of the/C-PP cell can be substantially restored to the initial capacity of 0.2C.
As shown in FIG. 12, symmetric cells were tested at 20 mA-cm -2 /20mAh·cm -2 Long cycle performance of; the results show that the symmetric cell has a stable overpotential, indicating the heterojunction Ta 4 C 3 -Ta 2 O 5 Can have good electrochemical performance under high current density and stripping/plating capacity.
Finally, it is to be noted that: the above examples are only for illustrating the technical solutions of the present invention, and are not limited thereto. While the present invention has been described in detail and with reference to the foregoing embodiments, it should be understood by those skilled in the art that: modifications and equivalents may be made to the embodiments of the invention without departing from the spirit and scope of the invention, which is intended to be covered by the claims.
Claims (9)
1. A preparation method of a functional composite diaphragm based on a tantalum-based MXene derivative is characterized by comprising the following steps:
step 1, mixing MAX phase Ta 4 AlC 3 Gradually and slowly adding the powder into a reaction kettle containing excessive acid liquor, and magnetically stirring for 48-96 hours at 45 ℃; then theCentrifuging the obtained suspension and repeatedly washing with deionized water and absolute ethyl alcohol until the pH value is 7; finally, the lower precipitate obtained is dried to obtain Ta 4 C 3 T x Nanosheet powder;
step 2, weighing Ta prepared in step 1 4 C 3 T x Adding into deionized water, fully stirring to obtain the product with the concentration of 1.0-5.0 mg/mL -1 Ta of 4 C 3 T x A suspension;
step 3, adding 10-30mL3.0-5.0 wt.% d of H 2 O 2 Dropwise adding the mixture into 30-50 mL of the suspension prepared in the step 2, violently stirring the mixture until the solution is uniformly mixed, then collecting precipitates by vacuum filtration, drying the obtained filter cake and collecting powder;
step 4, putting the powder prepared in the step 3 under argon-hydrogen mixed gas flow, and heating at the rate of 5-10 ℃ for min -1 Annealing at 800-1000 ℃ for 2-4 h, cooling to room temperature after sintering to obtain Ta 4 C 3 -Ta 2 O 5 A heterostructure composite powder material;
step 5, respectively weighing the powder prepared in the step 4 and carbon source powder according to the weight ratio of 1 or 8 to prepare mixed powder, then weighing a polyvinylidene fluoride adhesive according to the mass percentage of 10%, adding the polyvinylidene fluoride adhesive into the mixed powder, uniformly mixing, dropwise adding N-methyl pyrrolidone to prepare slightly flowing slurry, and finally uniformly coating the slurry on one side of a polypropylene film to obtain Ta with the coating thickness of 25 microns 4 C 3 -Ta 2 O 5 a/C composite modified diaphragm.
2. The method for preparing the functional composite separator based on the tantalum-based MXene derivative as claimed in claim 1, wherein the acid solution of step 1 comprises HF acid with mass fraction of less than or equal to 40% or HF acid with concentration of 12 mol.L -1 The HCl solution of (1);
LiF is added into the HCl solution, and the mass-to-volume ratio of LiF to the HCl solution is 1.
3. The method for preparing the functional composite separator based on the tantalum-based MXene derivative as claimed in claim 1, wherein the drying conditions in step 1 and step 3 comprise vacuum drying at 60 ℃ for 12h or freeze drying.
4. The method for preparing the functional composite diaphragm based on the tantalum-based MXene derivative of claim 1, wherein the sufficient stirring in the step 2 is stirring for 4-6 h at 600r/min by using a magnetic stirrer.
5. The method for preparing the functional composite diaphragm based on the tantalum-based MXene derivative of claim 1, wherein the intensive stirring of step 3 is a mixed stirring of magnetic stirring and ultrasonic cell disruption machine.
6. The method for preparing the functional composite diaphragm based on the tantalum-based MXene derivative as claimed in claim 1, wherein the volume ratio of argon gas to hydrogen gas in the argon-hydrogen mixed gas in step 4 is 8.
7. The method for preparing the functional composite diaphragm based on the tantalum-based MXene derivative of claim 1, wherein the carbon source in the step 5 is BP2000, graphene, acetylene black or carbon nanotube.
8. A functional composite separator based on tantalum-based MXene derivatives prepared by the method of any one of claims 1 to 8.
9. Use of the tantalum-based MXene derivative-based functional composite separator of claim 8 in a lithium-sulfur battery.
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Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104496461A (en) * | 2014-12-23 | 2015-04-08 | 陕西科技大学 | Method for preparing cubic titanium dioxide/two-dimensional nano-titanium carbide composite material |
| CN106430195A (en) * | 2016-10-14 | 2017-02-22 | 北京大学 | MXene material and preparation method and application thereof |
| WO2018184238A1 (en) * | 2017-04-08 | 2018-10-11 | 深圳市佩成科技有限责任公司 | Ti3c2tx/pvdf/celgard composite separator |
| KR20200095643A (en) * | 2019-01-31 | 2020-08-11 | 재단법인차세대융합기술연구원 | Manufacturing Method of Mxene Quantum Dot |
| KR20210079442A (en) * | 2019-12-19 | 2021-06-30 | 우석대학교 산학협력단 | Anode material with graphene-mxene-silicon of secondary battery and the method thereof |
| CN113578297A (en) * | 2021-08-27 | 2021-11-02 | 陕西科技大学 | Oxygen-terminated monolayer titanium carbide composite titanium dioxide photocatalyst and preparation method thereof |
| CN114023963A (en) * | 2021-10-26 | 2022-02-08 | 陕西科技大学 | MXene @ TiS2-TiO2Flexible composite film and preparation method thereof |
| CN114039060A (en) * | 2021-11-09 | 2022-02-11 | 北京师范大学 | N-TiO2/Ti3C2TxHeterogeneous MXene structure material, preparation and application thereof |
| WO2022032744A1 (en) * | 2020-08-10 | 2022-02-17 | 五邑大学 | Nbs2/mxene composite material and preparation method therefor |
| CN114195151A (en) * | 2021-12-13 | 2022-03-18 | 河北科技大学 | Preparation method of single-layer MXene material |
| CN114204208A (en) * | 2020-08-26 | 2022-03-18 | 中南大学 | Preparation method of PVDF-CTFE-based lithium-sulfur battery composite diaphragm |
| CN114452826A (en) * | 2021-12-14 | 2022-05-10 | 长安大学 | Light-driven self-cleaning Ti3C2@TiO2-C3N4Preparation method of heterojunction separation membrane |
| CN114464954A (en) * | 2022-01-07 | 2022-05-10 | 大连理工大学 | MXene @ WS for lithium-sulfur battery2Heterostructure material and application thereof |
| CN114649635A (en) * | 2022-03-11 | 2022-06-21 | 江苏大学 | Preparation method and application of bimetal nitride multifunctional diaphragm |
-
2022
- 2022-07-07 CN CN202210791457.3A patent/CN115498357A/en active Pending
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104496461A (en) * | 2014-12-23 | 2015-04-08 | 陕西科技大学 | Method for preparing cubic titanium dioxide/two-dimensional nano-titanium carbide composite material |
| CN106430195A (en) * | 2016-10-14 | 2017-02-22 | 北京大学 | MXene material and preparation method and application thereof |
| WO2018184238A1 (en) * | 2017-04-08 | 2018-10-11 | 深圳市佩成科技有限责任公司 | Ti3c2tx/pvdf/celgard composite separator |
| KR20200095643A (en) * | 2019-01-31 | 2020-08-11 | 재단법인차세대융합기술연구원 | Manufacturing Method of Mxene Quantum Dot |
| KR20210079442A (en) * | 2019-12-19 | 2021-06-30 | 우석대학교 산학협력단 | Anode material with graphene-mxene-silicon of secondary battery and the method thereof |
| WO2022032744A1 (en) * | 2020-08-10 | 2022-02-17 | 五邑大学 | Nbs2/mxene composite material and preparation method therefor |
| CN114204208A (en) * | 2020-08-26 | 2022-03-18 | 中南大学 | Preparation method of PVDF-CTFE-based lithium-sulfur battery composite diaphragm |
| CN113578297A (en) * | 2021-08-27 | 2021-11-02 | 陕西科技大学 | Oxygen-terminated monolayer titanium carbide composite titanium dioxide photocatalyst and preparation method thereof |
| CN114023963A (en) * | 2021-10-26 | 2022-02-08 | 陕西科技大学 | MXene @ TiS2-TiO2Flexible composite film and preparation method thereof |
| CN114039060A (en) * | 2021-11-09 | 2022-02-11 | 北京师范大学 | N-TiO2/Ti3C2TxHeterogeneous MXene structure material, preparation and application thereof |
| CN114195151A (en) * | 2021-12-13 | 2022-03-18 | 河北科技大学 | Preparation method of single-layer MXene material |
| CN114452826A (en) * | 2021-12-14 | 2022-05-10 | 长安大学 | Light-driven self-cleaning Ti3C2@TiO2-C3N4Preparation method of heterojunction separation membrane |
| CN114464954A (en) * | 2022-01-07 | 2022-05-10 | 大连理工大学 | MXene @ WS for lithium-sulfur battery2Heterostructure material and application thereof |
| CN114649635A (en) * | 2022-03-11 | 2022-06-21 | 江苏大学 | Preparation method and application of bimetal nitride multifunctional diaphragm |
Non-Patent Citations (2)
| Title |
|---|
| ALIREZA RAFIEERAD、WEIANG YAN、KESHAV NARAYAN ALAGARSAMY.ETAL: "Fabrication of Smart Tantalum Carbide MXene Quantum Dots with Intrinsic Immunomodulatory Properties for Treatment of Allograft Vasculopathy", 《ADVANCED FUNCTIONAL MATERIALS》, vol. 31, pages 2106786 - 2106786 * |
| ZHAOXIA CAO、JIAN GUO、SHENGNAN CHEN.ETAL: "In situ synthesis of an ultrafine heterostructural Nb2O5–NbC polysulfide promotor for highperformance Li–S batteries", 《JOURNAL OF MATERIALS CHEMISTRY A》, vol. 9, pages 21867 - 21876 * |
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