CN112695461B - Preparation method of MXene material diaphragm applied to lithium ion battery - Google Patents
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Abstract
The invention discloses a preparation method of an MXene material diaphragm applied to a lithium ion battery, which comprises the step of synthesizing Ti3AlC2Powder; mixing Ti3AlC2Adding the powder into a hydrochloric acid solution, uniformly stirring, slowly adding LiF in the stirring process, raising the temperature to a certain temperature, stirring and reacting for 20-30 h, respectively washing precipitates for 3 times by using deionized water and absolute ethyl alcohol, centrifuging, filtering, drying for 7-10 h under the vacuum condition of 75-85 ℃ to obtain multilayer Ti3C2Powder; a plurality of layers of Ti3C2Adding the powder into deionized water, performing ultrasonic treatment at 50-60 ℃ for 3-5 h in a nitrogen atmosphere, adding urea, performing ultrasonic treatment at the temperature, centrifuging, taking the upper solution, and freeze-drying to obtain layered Ti3C2Powder; will separate into layers Ti3C2Adding the powder into a mixed solvent, adding graphene oxide, ultrasonically stirring for 2-3 hours, adding polyvinylidene fluoride, continuously stirring for 3-5 hours, transferring the mixture into an electrostatic spinning injection pump, carrying out electrostatic spinning to obtain a fiber membrane, and then carrying out electrostatic spinning on the fiber membrane on a roller press under the pressure of 30-34MAnd rolling Pa, and drying at 50-60 ℃ to obtain the diaphragm.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery diaphragms, and particularly relates to a preparation method of an MXene material diaphragm applied to a lithium ion battery.
Background
The clean energy can reduce the dependence on fossil energy reserves, but the clean energy is often all restricted by natural conditions in practical application, and the energy storage device can improve the efficiency of various energy utilizations, makes up for the defect that the clean energy is restricted by natural conditions, and the battery is a commonly used energy storage device. The lithium ion battery has the advantages of high energy density, high working voltage, long cycle life, environmental friendliness and the like, and is a battery with excellent performance and wide application range.
The two-dimensional nanomaterial has a special structure, can provide a more convenient and faster channel for the insertion and the separation of lithium, has good stability, and has important significance on the development of the two-dimensional nanomaterial with high specific capacity and long cycle life for the lithium ion battery. MXene is a novel two-dimensional layered transition metal carbide/nitride, has high specific surface area, excellent conductivity and abundant surface functional groups, and is a hotspot of current research in the field of electrochemical energy storage. However, as with other two-dimensional materials, the MXene material has a two-dimensional layered structure which enables spontaneous stacking during the assembly process, so that the lithium ion battery separator prepared from the MXene material has a compact structure formed by stacking, which affects the permeation of electrolyte and the transmission of ions, and finally affects the effective utilization of MXene surface active sites, and limits the expression of electrochemical properties, resulting in the defects of high separator bulk resistance, low porosity, poor conductivity and the like.
Disclosure of Invention
Aiming at the defects of high diaphragm body resistance, low porosity, poor conductivity and the like existing in the application of the MXene material diaphragm to the lithium ion battery, the invention aims to provide a preparation method of the MXene material diaphragm applied to the lithium ion battery, which comprises the step-by-step etching of Ti3AlC2Method for obtaining multilayer Ti by powder3C2Powder, then successively adding a plurality of layers of Ti3C2Powder ultrasonic modification to obtain layered Ti3C2And compounding the powder with graphene oxide and polyvinylidene fluoride, performing high-pressure electrospinning, and rolling to obtain the MXene material diaphragm.
The preparation method comprises the following steps:
s1: synthesis of Ti3AlC2And (3) powder.
S2: mixing Ti3AlC2Adding the powder into a hydrochloric acid solution, uniformly stirring, slowly adding LiF in the stirring process, heating to 50-60 ℃, stirring and reacting for 20-30 h at the temperature, respectively washing precipitates for 3 times by using deionized water and absolute ethyl alcohol, centrifuging, filtering, drying for 7-10 h at 75-85 ℃ under a vacuum condition to obtain multilayer Ti3C2And (3) powder.
S3: a plurality of layers of Ti3C2Adding the powder into deionized water, carrying out ultrasonic treatment at 50-60 ℃ for 3-5 h in a nitrogen atmosphere, adding urea, carrying out ultrasonic treatment at the temperature for 40-60 min, centrifuging, wherein the centrifugation speed is 4000-6000 rpm/min, taking the upper layer solution, and freeze-drying to obtain layered Ti3C2And (3) powder.
S4: will separate into layers Ti3C2Adding the powder into a mixed solvent, adding graphene oxide, ultrasonically stirring for 2-3 h, adding polyvinylidene fluoride, wherein layered Ti is3C2The mass ratio of the powder to the graphene oxide to the polyvinylidene fluoride is (1-2) to (1-1.8) to (3.2-6.9), the mixture is continuously stirred for 3-5 hours, then the mixture is moved into an electrostatic spinning injection pump for electrostatic spinning to obtain a fiber membrane, then the fiber membrane is rolled on a roller press under the pressure of 30-34 MPa, and the membrane is dried at the temperature of 50-60 ℃ to obtain the membrane.
Preferably, the above-mentioned Ti3AlC2The powder and the synthesis are carried out by the following steps:
uniformly mixing titanium carbide powder, aluminum powder and titanium powder according to the molar ratio of (1.76-1.88) to (0.96-1.12) to (1-1.08), then placing the mixture in a tube furnace, heating the mixture from room temperature to 1400-1500 ℃ at the heating rate of 2-2.6 ℃/min in the nitrogen atmosphere, then preserving the heat at the temperature for 1.5-3 h, cooling, crushing, and grinding the mixture through a 500-mesh screen.
Preferably, the molar concentration of the hydrochloric acid solution in the step S2 is 8.5 to 10 mol/L.
As a preferred embodiment, the followingTi in the step S23AlC2The mass-volume ratio of the powder to the LiF to the hydrochloric acid solution is (5.36-5.85) g, (5.4-6) g, (105-135) mL.
Preferably, the multilayer Ti described in step S3 is used3C2The mass-volume ratio of the powder to the urea to the deionized water is (0.69-0.92) g, (1.44-1.68) g, (100-150) mL.
Preferably, the mixed solvent in the step S4 is an organic solvent and distilled water in a volume ratio of (0.6-0.8): (0.4-0.54).
More preferably, the organic solvent is N, N-dimethylformamide or N, N-dimethylacetamide.
Preferably, the electrostatic spinning injection voltage is 12-15 kV, the injection distance is 10-12 cm, and the injection speed is 0.2-0.32 mL/min.
Compared with the prior art, the invention has the following beneficial effects:
in the invention, Ti is gradually etched by adding LiF into hydrochloric acid solution3AlC2Obtaining a multilayer Ti3C2Powder, then urea is used for modification, and layered Ti is obtained after ultrasonic freeze drying3C2The powder is characterized in that functional groups such as-H, -F, -OH and the like exist on the surface of an MXene material, the functional groups and urea have strong affinity, the urea can be adsorbed on the surface of the MXene material, and then the MXene material is compounded with graphene oxide with excellent conductivity and then is combined with-F atoms in polyvinylidene fluoride to obtain the diaphragm with high mechanical strength, high liquid absorption rate and high conductivity.
Drawings
Fig. 1 is an SEM image of the separator prepared in example 1 of the present invention.
Detailed Description
The following embodiments of the present invention are described in detail, and the embodiments are implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, it should be noted that, for those skilled in the art, a plurality of modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Example 1
A preparation method of an MXene material diaphragm applied to a lithium ion battery specifically comprises the following steps:
s1: synthesis of Ti3AlC2Powder: uniformly mixing titanium carbide powder, aluminum powder and titanium powder according to the molar ratio of 1.76:0.96:1, then placing the mixture in a tube furnace, heating the mixture from room temperature to 1400 ℃ at the heating rate of 2 ℃/min in the nitrogen atmosphere, then preserving the heat for 1.5h at the temperature, cooling and crushing the mixture, and grinding the mixture through a 500-mesh screen.
S2: mixing Ti3AlC2Adding the powder into a hydrochloric acid solution with the molar concentration of 8.5mol/L, then uniformly stirring, and slowly adding LiF, wherein Ti is added in the solution3AlC2The mass-volume ratio of the powder, LiF and hydrochloric acid solution is 5.36g:5.4g:105mL, the temperature is raised to 50 ℃, then the mixture is stirred and reacted for 20 hours under the temperature condition, precipitates are respectively washed for 3 times by deionized water and absolute ethyl alcohol, centrifugation and filtration are carried out, and the precipitates are dried for 7 hours under the vacuum condition of 75 ℃ to obtain multilayer Ti3C2And (3) powder.
S3: a plurality of layers of Ti3C2Adding the powder into deionized water, performing ultrasound at 50 deg.C for 3 hr under nitrogen atmosphere, adding urea, and performing ultrasound at the temperature for 40min, wherein multiple layers of Ti are present3C2The mass volume ratio of the powder, the urea and the deionized water is 0.69g:1.44g:100mL, the mixture is centrifuged, wherein the centrifugation speed is 4000rpm/min, and the layered Ti is obtained after the upper layer solution is taken and freeze-dried3C2And (3) powder.
S4: will separate into layers Ti3C2Adding the powder into a mixed solvent of N, N-dimethylformamide and distilled water with the volume ratio of 0.6:0.4, then adding graphene oxide, ultrasonically stirring for 2h, then adding polyvinylidene fluoride, wherein Ti is layered3C2Continuously stirring the powder, the graphene oxide and the polyvinylidene fluoride for 3 hours at a mass ratio of 1:1:3.2, transferring the mixture into an electrostatic spinning injection pump, performing electrostatic spinning to obtain a fiber membrane, and then rolling the fiber membrane on a roller, wherein the injection voltage is 12kV, the injection distance is 10cm, and the injection speed is 0.2mL/minRolling the film on a press at a pressure of 30MPa, and drying the film at 50 ℃ to obtain the diaphragm.
Example 2
A preparation method of an MXene material diaphragm applied to a lithium ion battery specifically comprises the following steps:
s1: synthesis of Ti3AlC2Powder: uniformly mixing titanium carbide powder, aluminum powder and titanium powder according to the molar ratio of 1.88:1.12:1.08, then placing the mixture in a tube furnace, heating the mixture from room temperature to 1500 ℃ at the heating rate of 2.6 ℃/min under the nitrogen atmosphere, then preserving the heat for 3 hours at the temperature, cooling and crushing the mixture, and grinding the mixture through a 500-mesh screen.
S2: mixing Ti3AlC2Adding the powder into a hydrochloric acid solution with the molar concentration of 8.5-10 mol/L, uniformly stirring, and slowly adding LiF (lithium iron phosphate) in the stirring process, wherein Ti is3AlC2The mass-volume ratio of the powder, LiF and hydrochloric acid solution is 5.85g:6g:135mL, the temperature is raised to 60 ℃, then the mixture is stirred and reacted for 30 hours under the temperature condition, precipitates are respectively washed for 3 times by deionized water and absolute ethyl alcohol, centrifugation and filtration are carried out, and the precipitates are dried for 10 hours under the vacuum condition of 85 ℃ to obtain multilayer Ti3C2And (3) powder.
S3: a plurality of layers of Ti3C2Adding the powder into deionized water, performing ultrasonic treatment at 60 deg.C for 5 hr under nitrogen atmosphere, adding urea, and performing ultrasonic treatment at the temperature for 60min, wherein multiple layers of Ti are formed3C2The mass volume ratio of the powder to the urea to the deionized water is 0.92g:1.68g:150mL, the mixture is centrifuged, wherein the centrifugation speed is 6000rpm/min, and the layered Ti is obtained after the upper layer solution is taken and freeze-dried3C2And (3) powder.
S4: will separate into layers Ti3C2Adding the powder into a mixed solvent of N, N-dimethylacetamide and distilled water with a volume ratio of 0.8:0.54, then adding graphene oxide, ultrasonically stirring for 3 hours, then adding polyvinylidene fluoride, wherein Ti is layered3C2Continuously stirring the powder, the graphene oxide and the polyvinylidene fluoride for 5 hours at a mass ratio of 2:1.8:6.9, transferring the powder, the graphene oxide and the polyvinylidene fluoride into an electrostatic spinning injection pump, wherein the injection voltage is 15kV, the injection distance is 12cm, the injection speed is 0.32mL/min, and performing electrostatic spinningAnd obtaining a fiber film, then rolling the fiber film on a rolling machine at the pressure of 34MPa, and drying the fiber film at the temperature of 60 ℃ to obtain the diaphragm.
Example 3
A preparation method of an MXene material diaphragm applied to a lithium ion battery specifically comprises the following steps:
s1: synthesis of Ti3AlC2Powder: uniformly mixing titanium carbide powder, aluminum powder and titanium powder according to a molar ratio of 1.82:1.06:1.02, then placing the mixture in a tube furnace, heating the mixture from room temperature to 1450 ℃ at a heating rate of 2-2.6 ℃/min in a nitrogen atmosphere, then preserving heat for 2 hours at the temperature, cooling and crushing the mixture, and grinding the mixture through a 500-mesh screen.
S2: mixing Ti3AlC2Adding the powder into a hydrochloric acid solution with the molar concentration of 9mol/L, uniformly stirring, and slowly adding LiF, wherein Ti is added in the LiF solution3AlC2The mass-volume ratio of the powder, LiF and hydrochloric acid solution is 5.44g:5.6g:115mL, the temperature is raised to 55 ℃, then the mixture is stirred and reacted for 25 hours under the temperature condition, precipitates are respectively washed for 3 times by deionized water and absolute ethyl alcohol, centrifugation and filtration are carried out, and the precipitates are dried for 8 hours under the vacuum condition of 80 ℃ to obtain multilayer Ti3C2And (3) powder.
S3: a plurality of layers of Ti3C2Adding the powder into deionized water, performing ultrasonic treatment at 55 deg.C for 4 hr under nitrogen atmosphere, adding urea, and performing ultrasonic treatment at the temperature for 50min, wherein multiple layers of Ti are present3C2The mass volume ratio of the powder, the urea and the deionized water is 0.72g:1.48g:120mL, the mixture is centrifuged, wherein the centrifugation speed is 5000rpm/min, and the layered Ti is obtained after the upper layer solution is taken and freeze-dried3C2And (3) powder.
S4: will separate into layers Ti3C2Adding the powder into a mixed solvent of N, N-dimethylformamide and distilled water with the volume ratio of 0.68:0.44, then adding graphene oxide, ultrasonically stirring for 2.5h, then adding polyvinylidene fluoride, wherein Ti is layered3C2The mass ratio of the powder to the graphene oxide to the polyvinylidene fluoride is 1.3:1.4:4.4, the mixture is continuously stirred for 4 hours and then is transferred into an electrostatic spinning injection pump, wherein the injection voltage is 13kV, the injection distance is 11cm, and the injection speed is highThe rate is 0.24mL/min, electrostatic spinning is carried out to obtain a fiber membrane, then rolling is carried out on a rolling machine under the pressure of 32MPa, and drying is carried out at the temperature of 55 ℃ to obtain the diaphragm.
Example 4
A preparation method of an MXene material diaphragm applied to a lithium ion battery specifically comprises the following steps:
s1: synthesis of Ti3AlC2Powder: uniformly mixing titanium carbide powder, aluminum powder and titanium powder according to the molar ratio of 1.86:1.09:1.06, then placing the mixture in a tube furnace, heating the mixture from room temperature to 1450 ℃ at the heating rate of 2.4 ℃/min in the nitrogen atmosphere, then preserving the heat for 2.5h at the temperature, cooling and crushing the mixture, and grinding the mixture through a 500-mesh screen.
S2: mixing Ti3AlC2Adding the powder into a hydrochloric acid solution with the molar concentration of 9.5mol/L, then uniformly stirring, and slowly adding LiF, wherein Ti is added in the solution3AlC2The mass-volume ratio of the powder, LiF and hydrochloric acid solution is 5.82g:5.9g:130mL, the temperature is raised to 60 ℃, then the mixture is stirred and reacted for 30 hours under the temperature condition, precipitates are respectively washed for 3 times by deionized water and absolute ethyl alcohol, centrifugation and filtration are carried out, and the precipitates are dried for 9 hours under the vacuum condition of 80 ℃ to obtain multilayer Ti3C2And (3) powder.
S3: a plurality of layers of Ti3C2Adding the powder into deionized water, carrying out ultrasonic treatment for 3-5 h at 60 ℃ in a nitrogen atmosphere, adding urea, and carrying out ultrasonic treatment for 60min at the temperature, wherein the Ti layers are formed3C2The mass volume ratio of the powder, the urea and the deionized water is 0.91g:1.66g:140mL, the mixture is centrifuged, wherein the centrifugation speed is 6000rpm/min, and the layered Ti is obtained after the upper layer solution is taken and freeze-dried3C2And (3) powder.
S4: will separate into layers Ti3C2Adding the powder into a mixed solvent of N, N-dimethylformamide and distilled water with the volume ratio of 0.74:0.52, then adding graphene oxide, ultrasonically stirring for 3h, then adding polyvinylidene fluoride, wherein Ti is layered3C2The mass ratio of the powder to the graphene oxide to the polyvinylidene fluoride is 1.8:1.7:6.6, the mixture is continuously stirred for 4 hours and then is transferred into an electrostatic spinning injection pump, wherein the injection voltage is14kV, the injection distance of 11cm and the injection speed of 0.31mL/min, carrying out electrostatic spinning to obtain a fiber membrane, then rolling on a roller press at the pressure of 33MPa, and drying at the temperature of 60 ℃ to obtain the diaphragm.
Experimental example: the membranes prepared in examples 1 to 4 were subjected to the following performance tests: (1) the mechanical property is tested by adopting a tensile testing machine, and the tensile is carried out at the strain rate of 1 mm/min;
(2) the imbibition rate test was performed by placing a diaphragm in the electrolyte (1M LiPF)6Dissolving in EC/DMC/EMC 1:1:1), weighing the diaphragm mass after absorption saturation, and calculating the liquid absorption rate by the following formula:
wherein EU is the liquid absorption rate, W0And W is the weight of the separator before and after soaking in the electrolyte;
(3) the conductivity was measured using an electrochemical workstation, with a frequency range of 100mHz to 100kHz, calculated by the following formula:
where σ is the ionic conductivity, d is the thickness of the separator, R is the bulk resistance, and A is the electrode area;
(4) the porosity was measured using a surface area tester, the porosity was measured by soaking in n-butanol, calculated using the following formula:
where ρ is the n-butanol density, W2Is the mass of the diaphragm after absorbing n-butanol, W1Is the dry diaphragm mass; wherein the test results are shown in table 1,
table 1. results of performance testing:
as can be seen from Table 1, the separators prepared in the embodiments 1 to 4 of the present invention have mechanical strength of more than 29MPa, liquid absorption rate of more than 328%, bulk resistance of less than 0.48 Ω, conductivity of more than 1.31mS/cm, and porosity of more than 80.8%, which indicates that the separators prepared in the embodiments of the present invention have good electrochemical properties.
Claims (6)
1. The preparation method of the MXene material diaphragm applied to the lithium ion battery is characterized by comprising the step of gradually etching Ti3AlC2Method for obtaining multilayer Ti by powder3C2Powder, and then continuing to form multiple Ti layers3C2Powder ultrasonic modification to obtain layered Ti3C2Compounding the powder with graphene oxide and polyvinylidene fluoride, performing high-pressure electrospinning, and rolling to obtain an MXene material diaphragm, wherein the injection voltage of the high-pressure electrospinning is 12-15 kV, the injection distance is 10-12 cm, and the injection speed is 0.2-0.32 mL/min;
the preparation method comprises the following steps:
s1: synthesis of Ti3AlC2Powder;
s2: mixing Ti3AlC2Adding the powder into a hydrochloric acid solution, uniformly stirring, slowly adding LiF in the stirring process, heating to 50-60 ℃, stirring and reacting for 20-30 h at the temperature, respectively washing precipitates for 3 times by using deionized water and absolute ethyl alcohol, centrifuging, filtering, drying for 7-10 h at 75-85 ℃ under a vacuum condition to obtain multilayer Ti3C2Powder;
s3: a plurality of layers of Ti3C2Adding the powder into deionized water, performing ultrasonic treatment at 50-60 ℃ for 3-5 h in a nitrogen atmosphere, adding urea, performing ultrasonic treatment at the temperature for 40-60 min, and centrifuging at the centrifugation speed of 4000-6000 rpmmin, taking the upper layer solution, and freeze-drying to obtain layered Ti3C2Powder;
s4: will separate into layers Ti3C2Adding the powder into a mixed solvent, adding graphene oxide, ultrasonically stirring for 2-3 h, adding polyvinylidene fluoride, wherein layered Ti is3C2The mass ratio of the powder to the graphene oxide to the polyvinylidene fluoride is (1-2) to (1-1.8) to (3.2-6.9), the mixture is continuously stirred for 3-5 hours, then the mixture is moved into an electrostatic spinning injection pump for electrostatic spinning to obtain a fiber film, then the fiber film is rolled on a roller press under the pressure of 30-34 MPa, and the fiber film is dried at the temperature of 50-60 ℃ to obtain a diaphragm;
the Ti3AlC2The synthesis of the powder comprises the following steps: uniformly mixing titanium carbide powder, aluminum powder and titanium powder according to the molar ratio of (1.76-1.88) to (0.96-1.12) to (1-1.08), then placing the mixture in a tube furnace, heating the mixture from room temperature to 1400-1500 ℃ at the heating rate of 2-2.6 ℃/min in the nitrogen atmosphere, then preserving the heat at the temperature for 1.5-3 h, cooling, crushing, and grinding the mixture through a 500-mesh screen.
2. The method for preparing the MXene material separator for the lithium ion battery according to claim 1, wherein the hydrochloric acid solution in step S2 has a molar concentration of 8.5-10 mol/L.
3. The method for preparing the MXene material separator for the lithium ion battery as claimed in claim 1, wherein the Ti content in step S23AlC2The mass-volume ratio of the powder to the LiF to the hydrochloric acid solution is (5.36-5.85) g, (5.4-6) g, (105-135) mL.
4. The method for preparing the MXene material separator for the lithium ion battery as claimed in claim 1, wherein the multilayer Ti of step S33C2The mass-volume ratio of the powder to the urea to the deionized water is (0.69-0.92) g, (1.44-1.68) g, (100-150) mL.
5. The method as claimed in claim 1, wherein the mixed solvent in step S4 comprises distilled water and an organic solvent at a volume ratio of (0.6-0.8): (0.4-0.54).
6. The method according to claim 5, wherein the organic solvent is N, N-dimethylformamide or N, N-dimethylacetamide.
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| CN202011467364.2A CN112695461B (en) | 2020-12-14 | 2020-12-14 | Preparation method of MXene material diaphragm applied to lithium ion battery |
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| CN202011467364.2A CN112695461B (en) | 2020-12-14 | 2020-12-14 | Preparation method of MXene material diaphragm applied to lithium ion battery |
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| CN113692211B (en) * | 2021-08-09 | 2024-02-20 | 中国人民解放军陆军工程大学 | Preparation method of composite film electromagnetic protection material based on MXene-rGO |
| CN113991244B (en) * | 2021-10-25 | 2024-01-09 | 深圳欣视界科技有限公司 | Preparation method of polyvinylidene fluoride membrane material with uniform pore diameter |
| CN113882154B (en) * | 2021-10-26 | 2023-05-26 | 陕西科技大学 | Flexible PPy/MXene-PDA photo-thermal fabric for solar evaporator and preparation method thereof |
| CN114094279A (en) * | 2021-11-02 | 2022-02-25 | 惠州锂威新能源科技有限公司 | Composite diaphragm and preparation method thereof |
| CN114865226B (en) * | 2022-05-25 | 2023-01-13 | 齐齐哈尔大学 | Preparation method and application of MXene-based inorganic particle/PVDF-based polymer composite diaphragm |
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