CN107369801A - A kind of MXene modifications composite diaphragm and preparation method thereof and the application in lithium-sulfur cell - Google Patents
A kind of MXene modifications composite diaphragm and preparation method thereof and the application in lithium-sulfur cell Download PDFInfo
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- CN107369801A CN107369801A CN201710511182.2A CN201710511182A CN107369801A CN 107369801 A CN107369801 A CN 107369801A CN 201710511182 A CN201710511182 A CN 201710511182A CN 107369801 A CN107369801 A CN 107369801A
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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
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
- H01M50/431—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
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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
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- 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
Abstract
The invention discloses a kind of MXene modification composite diaphragms and preparation method thereof and the application in lithium-sulfur cell.In the MXene modification composite diaphragms of the present invention, basement membrane is polyalkene diaphragm, and decorative material is that MXene is attached on the side surface of polyalkene diaphragm one with polymer or the compound of inorganic particle, decorative material.The present invention peels off the A layers in MAX by liquid phase in situ, one-step synthesis two-dimensional material MXene, then by MXene materials and polymer or inorganic particle it is compound after, vacuum filtration is attached on polyalkene diaphragm, obtains the MXene modifications composite diaphragm.MXene modification composite diaphragms are placed directly within lithium-sulfur cell, enhance the ionic conductivity and electron conduction of battery, while adsorb more lithium sulfides by force, suppresses more lithium sulfide shuttle effects, greatly improves the performance and security of battery.
Description
Technical field
The present invention relates to two-dimensional material MXene synthesis and application field, and in particular to a kind of MXene modifies composite diaphragm
And preparation method thereof with the application in lithium-sulfur cell.
Background technology
Since 21 century, the energy and environment are the two big hot issues in the present age, fossil energy it is a large amount of use so that
Industrial waste gas, waste water, waste residue cause large effect to living environment, and increasing people starts to advocate making for green energy resource
With the development and utilization of the clean energy resource such as solar energy, wind energy, nuclear energy is gradually brought into schedule, is badly in need of a kind of efficient energy storage now
Equipment stores unnecessary energy, and battery also result in extensive research interest as a kind of efficiently convenient energy storage device.
Spread all over the lithium ion battery of life every aspect by now from lead accumulator before, scientific researcher, which achieves, larger to be entered
Step, field of lithium ion battery achieve the electronic equipment such as faster development, mobile phone, notebook computer and also upgraded comparatively fast.But work as
Preceding lithium ion battery technology can not meet, similar to powerful devices such as electric automobiles, to be badly in need of a kind of novel high-energy metric density
Battery fill up this vacancy.
The material source of lithium-sulfur cell is abundant and cheap, predominantly the sulphur of nature rich content, possesses higher theory
Energy density（1675 mAh/ g）, therefore it is widely regarded as the most possible secondary cell for substituting lithium ion battery of future generation.
But the development of lithium-sulfur cell is there is also many problems, wherein, because discharging product is soluble in electrolyte, worn so as to cause
Shuttle effect, positive electrode sulphur and the problems such as its discharging product lithium sulfide electric conductivity is poor, volumetric expansion is serious, result in battery appearance
Measure rapid attenuation and poor cyclical stability.Moreover, the shuttle effect that the more lithium sulfides generated in discharge process are triggered is more
Safety problem can be triggered.So far, researchers devise various schemes to solve the above-mentioned problem of lithium-sulfur cell, most commonly
Using the positive electrode such as porous carbon materials, metal oxide of Nano grade by sulphur confinement in conductive frame, this plan
The physics and chemisorption of porous carbon nanomaterial are slightly not only make use of, suppresses more lithium sulfides and shuttles to negative pole, enhance
Chemical property, the sulphur of insulation is also combined together to the electric conductivity for improving positive electrode with conductive material tight.
Recent years, substantial amounts of research, which is intended to limit more lithium sulfides, passes through barrier film, and specific method is included in barrier film and positive pole
Between introduce a layer function interlayer, or survey coating layer of material close to positive pole with the traditional polyalkene diaphragm of modification in barrier film.
Such as have researcher design commercialization barrier film and collector between add one layer of porous carbon interlayer, using carbon-coating electric conductivity and
Physics hinders the effect of more lithium sulfides, greatly improves the utilization ratio of positive pole sulphur and the cyclicity of battery；There is researcher passing
Mesoporous carbon of the meso-porous carbon material of coated metal oxide modification or miscellaneous element doping etc. on system barrier film, using to more lithium sulfides
Chemisorption enhances the cyclical stability and high rate performance of lithium-sulfur cell.
Graphene or graphene oxide are equally served due to the unique structure of two-dimensional material and performance in barrier film modification
Very big effect, researcher demonstrates can play physics, chemistry in barrier film side one layer of very thin graphene oxide layer of introducing
The effect of the dual more lithium sulfides of obstruction.And the MXene materials of one of class grapheme material are two-dimentional early stage transition metal carbon or nitrogen
The general designation of compound, it is as obtained from by the A layer-selectives etching in MAX material.M in MAX represents early stage transition metal,
A represents the 3rd or the 4th major element, and the ene that X is represented in C or N, MXene represents some groups, including-OH ,-F or=
O.2011 first report separate MXene materials after, due to its unique structure and performance, the material in many fields all
It is widely used.And higher electron conduction is even more to impart MXene materials in the unique advantage of electrochemical field.
Have been reported that within 2015 and confirm Ti2CTx- MXene（T represents surface group）In titanium atom to the more sulphur of lithium-sulfur cell intermediate product
Changing lithium has strong suction-operated, therefore MXene materials are incorporated into lithium-sulfur cell field first.And the polymer after lithiumation
Nafion has been found to be that selectivity passes through lithium ion, there is preferable performance in lithium-sulfur cell.
The content of the invention
In order to solve the problems, such as lithium-sulfur cell because the cyclical stability of the shuttle effect initiation of more lithium sulfides is poor, efficiency is low,
The invention provides a kind of MXene to modify composite diaphragm.In MXene modification composite diaphragms, substrate is polyalkene diaphragm, modification
Material is ultra-high conductivity and can adsorb the MXene materials of more lithium sulfides and polymer or the compound of inorganic particle, modification by force
Material is attached on the side surface of polyalkene diaphragm one.
Present invention also offers a kind of preparation method of described MXene modification composite diaphragms.This method passes through liquid in situ
Mutually peel off the A layers in MAX, one-step synthesis two-dimensional material MXene, then by MXene materials and polymer or inorganic particle it is compound after,
It is attached on polyalkene diaphragm by vacuum filtration, polyalkene diaphragm is modified by simply filtering, is obtained described
MXene modifies composite diaphragm.
MXene materials are directly coated on commercialization barrier film, or with polymer compound action on commercialization barrier film,
Play a part of the more lithium sulfides of suppression to shuttle to negative pole；The present invention using different polymer or the exclusive advantage of inorganic particle with
MXene excellent specific property is compound, to the performance of the further modification of barrier film, preferably lifting lithium-sulfur cell.
Present invention also offers a kind of application of described MXene modification composite diaphragms in lithium-sulfur cell.
The present invention is achieved through the following technical solutions.
A kind of preparation method of MXene modifications composite diaphragm, comprises the following steps：
（1）Villiaumite is dissolved in acid solution, adds MAX powder, stirring and dissolving；
（2）By step（1）Obtained solution centrifugal is washed to after supernatant pH value reaches more than 6, continues to centrifuge and collect supernatant
Liquid, the supernatant of collection is dried, obtains MXene materials；
Centrifuge in water-washing process, supernatant is blackish green first for centrifugation, as centrifugation number increases, supernatant fluid color deepen until
Ater, finally collect pH and reach the supernatant after more than 6；
（3）Obtained MXene materials are mixed with polymer or inorganic particle, ultrasonic dissolution is adsorbed in solvent by filtering
In polyolefin（pp）On membrane surface, dry, obtain the MXene modifications composite diaphragm.
Polyalkene diaphragm is porous micro-pore septum, is advantageous to the attached of MXene and the compound of polymer or inorganic particle
.
Further, step（1）In, the villiaumite includes lithium fluoride or sodium fluoride.
Further, step（1）In, the acid solution includes 6 ~ 12M hydrochloric acid or 6 ~ 9M sulfuric acid.
Further, step（1）In, the mass ratio of the villiaumite and MAX powder is 1：1.
Further, step（1）In, in the MAX, M is early stage transition metal, and A is III A races or IV A races element,
X is C or N.
Preferably, step（1）In, the MAX is Ti3AlC2。
Further, step（1）In, the stirring and dissolving is to stir 12 ~ 36h at 30 ~ 45 DEG C, in situ by stirring and dissolving
MAX is peeled off, synthesizes MXene.
Further, step（2）In, in the MXene, M is early stage transition metal, X be C or N, ene include-
OH ,-F or=O.
Preferably, step（2）In, the MXene is Ti3C2。
Further, step（2）In, the rotating speed of the centrifugation is 3000rpm.
Further, step（2）In, the time for continuing centrifugation is 0.5 ~ 1h.
Further, step（3）In, the solid-liquid ratio of the MXene materials and solvent is 0.09 ~ 0.1mg/mL.
Further, step（3）In, the polymer includes perfluorinated sulfonic acid（Nafion）With cetyl trimethyl bromination
Ammonium（CTAB）One or more of.
Further, step（3）In, the inorganic particle includes one or more of silica and titanium dioxide.
Cation selective permeability material Nafion introducing, while being beneficial to physics obstruction more lithium sulfides, selection
Property passes through lithium ion；And the introducing of CTAB or inorganic particle, be advantageous to regulate and control interlamellar spacing, be advantageous to the transmission of lithium ion, simultaneously
The electron conduction with conductive material MXene composite strengthenings.
Further, step（3）In, the polymer phase is 10 ~ 25% for MXene weight/mass percentage composition.
Further, step（3）In, the inorganic particle is 10 ~ 30% relative to MXene weight/mass percentage composition.
Further, step（3）In, the ultrasonic dissolution is ultrasonic dissolution under argon gas atmosphere in the process of solvent, ultrasonic
Time is more than 0.5h.
Further, step（3）In, the solvent includes one or more of water and ethanol.
Further, step（3）In, it is described to filter as vacuum filtration.
Further, step（2）、（3）In, the drying is to be dried in vacuo at normal temperatures.
A kind of MXene modification composite diaphragm as made from the preparation method described in any of the above-described, substrate be polyolefin every
Film, decorative material are ultra-high conductivity and can adsorb the compound of the MXene materials of more lithium sulfides and polymer or inorganic particle by force
Thing, decorative material are attached on the side surface of polyalkene diaphragm one.
A kind of application of the described MXene modification composite diaphragms in lithium-sulfur cell, composite diaphragm is modified by the MXene
It is placed directly within lithium-sulfur cell, and MXene modification composite diaphragms are unattached answering for MXene materials and polymer or inorganic particle
Negative pole of the compound side close to battery.
MXene materials have the advantage that：（1）Electron conduction is good（It can reach 5000S/cm）, can be matched in excellence or beauty with graphene；（2）
Preferable hydrophily, early stage transition metal atoms surface can carry more hydrophilic radical in building-up process, mainly include-OH ,-
F or=O, making material, solubility is preferable in water and in common organic solvents；（3）Unique two-dimensional slice structure can make lithium,
Sodium, potassium, ammonium ion and DMSO, CTAB, N2H4Inserted Deng organic matter embedded to interlayer to regulate and control interlamellar spacing；（4）In lithium-sulfur cell
In, the early stage transition metal atoms in MXene have preferable adsorption effect to the more lithium sulfides of intermediate product, can effectively suppress to wear
Shuttle effect, greatly improve lithium-sulfur cell and follow bad stability；（5）Possess preferable mechanical performance.
Due to the excellent specific property that MXene materials have, therefore formd between conventional polyolefins barrier film and positive electrode
One layer of zero defect, high electron conduction and the thin layer that can effectively obstruct more lithium sulfides so that equipped with the MXene modification it is compound every
The lithium-sulfur cell of film is achieved on cyclical stability and specific capacity and is obviously improved.
Compared with prior art, the present invention has advantages below and technique effect：
（1）MXene powder produced by the present invention is that monolithic layer, micron order, defect are few, and synthetic method is simply efficient, does not use
HF but use villiaumite, security outclass traditional hf etching method.
（2）MXene materials are introduced to lithium-sulfur cell barrier film field by the present invention, are on the one hand led using the height of MXene materials
The electron conduction of lithium-sulfur cell is electrically significantly enhanced, on the other hand because early stage transition metal atoms are to more lithium sulfides
Suction-operated and MXene unique two-dimensional structure, Nafion cation permselective, the tune of CTAB or inorganic particle
Control interlamellar spacing characteristic so that composite diaphragm preferably improves lithium-sulfur cell under the cooperative effect of physics and chemical dual barrier
Cycle performance.
（3）Preparation method of the present invention is simple to operate, take less, energy consumption is low, cost is low, is advantageous to large-scale industry metaplasia
Production.
（4）The present invention possesses the common of pp and MXene and polymer by the composite diaphragm for being simply filtered by vacuum to obtain
Characteristic, existing abundant hole have unilateral excellent electric conductivity again, enhance the ionic conductivity and electron conduction of battery, together
When adsorb more lithium sulfides by force, prevent more lithium sulfides shuttle from triggering Li dendrite to negative pole, greatly improve the performance and peace of battery
Quan Xing.
Brief description of the drawings
Fig. 1 is raw materials used Ti in the embodiment of the present invention3AlC2The SEM figures of powder.
Fig. 2 is Ti made from embodiment 13C2The SEM figures of material.
Fig. 3 is Ti made from embodiment 13C2The XRD of material.
Fig. 4 is Ti made from embodiment 13C2The TEM figures of material.
Fig. 5 is that the SEM of Nafion@pp composite diaphragms made from embodiment 4 schemes.
Fig. 6 is Ti made from embodiment 63C2The SEM figures of@Nafion modification composite diaphragms.
Fig. 7 is Ti in embodiment 73C2@SiO2Modify the cycle performance figure that composite diaphragm is applied to lithium-sulfur cell.
Fig. 8 is conventional polyolefins barrier film, Nafion@pp composite diaphragms and Ti3C2@Nafion modification composite diaphragm difference
Applied to the cycle performance figure in lithium-sulfur cell.
Fig. 9 is Ti3C2@CTAB modification composite diaphragms are applied to the cycle performance figure of lithium-sulfur cell.
Embodiment
The present invention is described in further detail below in conjunction with specific embodiment and accompanying drawing, but the invention is not restricted to
This.
In the specific embodiment of the invention, Ti is peeled off by liquid phase in situ3AlC2In Al layers, one-step synthesis two-dimensional material
Ti3C2, then by Ti3C2After material and polymer or inorganic particle are compound, it is attached on polyalkene diaphragm, is led to by vacuum filtration
Cross simple filter to be modified polyalkene diaphragm, obtain Ti3C2Modify composite diaphragm.
Raw materials used Ti in the specific embodiment of the invention3AlC2The SEM figures of powder are as shown in figure 1, as shown in Figure 1, raw material
Ti3AlC2For three-dimensional block structure.
Embodiment 1
Lithium fluoride, watery hydrochloric acid liquid phase peel off monolithic layer Ti3C2
（1）2 grams of LiF are taken to be dissolved in 20 milliliters of 6M hydrochloric acid, stirring and dissolving；
（2）Take 2 grams of Ti3AlC2Powder, it is slowly added in 10 minutes to step（1）Solution in, at 45 DEG C stir 12h dissolving；
（3）By step（2）Obtained solution centrifugal is washed 10 times（3000rpm, each 5min）So that supernatant pH reaches 6.2,
It is further continued for centrifugation 1 hour（3000rpm）, and supernatant is collected, the supernatant of collection is preserved under ar gas environment, obtains Ti3C2
The aqueous solution（0.1mg/ml）.
Ti will be obtained3C2The aqueous solution（0.1mg/ml）It is dried in vacuo at normal temperatures, obtains Ti3C2Material.
Obtained Ti3C2The SEM figures of material, as shown in Fig. 2 as shown in Figure 2, the Ti of preparation3C2Material is monolithic layer material
Material.
Obtained Ti3C2The XRD of material, as shown in figure 3, from the figure 3, it may be seen that the characteristic peak of the aluminium in material has disappeared,
Illustrate Ti3AlC2In aluminium etched completely.
Obtained Ti3C2The TEM figures of material, as shown in figure 4, as shown in Figure 4, obtained nanometer sheet size is 0.5 ~ 1 μm.
Embodiment 2
Lithium fluoride, dilute sulfuric acid liquid phase peel off monolithic layer Ti3C2
（1）5 grams of LiF are taken to be dissolved in 50 milliliters of 9M sulfuric acid, stirring and dissolving under ice bath；
（2）Take 5 grams of Ti3AlC2Powder, step is slowly added in 10 minutes（1）Solution in, at 30 DEG C stir 24h dissolving；
（3）Obtained solution centrifugal is washed（3000rpm, each 5min）So that supernatant pH reaches 6.3, is further continued for centrifuging
0.5 hour（3000rpm）, and supernatant is collected, it is dried in vacuo under normal temperature, obtains Ti3C2Material.
Ti made from the present embodiment3C2SEM figures, XRD and the TEM figures of material respectively referring to Fig. 2, Fig. 3 and Fig. 4, preparation
Ti3C2Material is that the characteristic peak of the monolithic layer that nanometer sheet size is 0.5 ~ 1 μm or the aluminium in few sheet layer material and material has disappeared,
Illustrate after changing sour species and treatment conditions, the Ti of high quality can still be made3C2Nanometer sheet.
Embodiment 3
Lithium fluoride, concentrated hydrochloric acid liquid phase peel off monolithic layer Ti3C2
（1）5 grams of LiF are taken to be dissolved in 50 milliliters of 12M concentrated hydrochloric acid, stirring and dissolving under ice bath；
（2）Take 5 grams of Ti3AlC2Powder, step is slowly added in 10 minutes（1）Solution in, at 35 DEG C stir 36h dissolving；
（3）Obtained solution centrifugal is washed（3000rpm, each 5min）So that supernatant pH reaches 6.1, is further continued for centrifuging
0.5 hour（3000rpm）, and supernatant is collected, it is dried in vacuo under normal temperature, obtains Ti3C2Material.
Obtained Ti3C2SEM figures, XRD and the TEM of material are schemed respectively referring to Fig. 2, Fig. 3 and Fig. 4, the Ti of preparation3C2Material
Expect that the characteristic peak for the aluminium in monolithic layer material and material that nanometer sheet size is 0.5 ~ 1 μm has disappeared.
Embodiment 4
Synthesize Nafion@pp composite diaphragms
（1）Take commercialized Nafion solution to be dissolved in ethanol, be configured to 0.05mg/mL Nafion solution；
（2）The above-mentioned solution of 40mL is taken to be filtered by vacuum to pp（Polyalkene diaphragm）On, dry 12 hours, obtain in normal-temperature vacuum
Nafion@pp composite diaphragms.
The SEM of obtained Nafion@pp composite diaphragms is schemed as shown in figure 5, Nafion forms one layer of cause in pp substrates
Close flawless film.
Embodiment 5
Synthesize Ti3C2@CTAB modify composite diaphragm
（1）0.4mg CTAB powder is dissolved in ethanol, is configured to 0.1mg/mL CTAB solution；
（2）By Ti3C2With CTAB mass ratio 4:1, take the Ti of 16mL embodiments 13C2Solution and above-mentioned CTAB solution, argon gas gas
Ultrasound dissolves for 12 hours under atmosphere；
（3）By step（2）Obtained mixed solution is filtered by vacuum to commercialized polyalkene diaphragm, and normal-temperature vacuum is dried, and is obtained
To Ti3C2@CTAB modify composite diaphragm.
Embodiment 6
Synthesize Ti3C2@Nafion modify composite diaphragm
（1）The Ti for taking 20mL embodiments 1 to prepare3C2Solution, the Nafion solution that 4mL embodiments 3 configure, mixed under ar gas environment
Ultrasonic 1h is closed, obtains mixed solution；
（2）By step（1）Obtained mixed solution is filtered by vacuum to commercialized polyalkene diaphragm, and normal-temperature vacuum is dried, and is obtained
To Ti3C2@Nafion modify composite diaphragm；
Obtained Ti3C2The SEM of@Nafion modification composite diaphragms is schemed as shown in fig. 6, it will be appreciated from fig. 6 that Nafion and Ti3C2Very well
Ground mixes, and forms fine and close flawless film.
Embodiment 7
Synthesize Ti3C2@SiO2Modify composite diaphragm
（1）The Ti for taking 200mL embodiments 1 to prepare3C2Solution；Take 2mg Nano-meter SiO_2s2The ultrasonic dissolution in 20mL water, obtains concentration
For 0.1mg/mL SiO2Solution；
（2）By step（1）Ti3C2Solution and SiO2Solution mixes ultrasonic 0.5h under ar gas environment, obtains mixed solution；
（3）Obtained mixed solution is filtered by vacuum to commercialized polyalkene diaphragm, normal-temperature vacuum is dried, and obtains Ti3C2@
SiO2Modify composite diaphragm.
Ti3C2@SiO2Modify composite diaphragm and be applied to the performance map of lithium-sulfur cell as shown in fig. 7, as shown in Figure 7, introducing nothing
Machine particle SiO2Afterwards, MXene interlamellar spacing is increased, is advantageous to the transmission of lithium ion so that the specific capacity and cyclicity of battery
Further improvement can have been obtained, it is average often to enclose capacity attenuation 0.27%.
Embodiment 8
Conventional polyolefins diaphragm application is in lithium-sulfur cell
（1）Take 70mg sublimed sulfurs, 20mg conductions are black, grind 0.5h after under vacuum conditions 155 DEG C heating 10h；
（2）By step（1）After obtained powder mull 0.5h, 125 milligrams of 8wt% Kynoar is added（PVDF）Solution（It is molten
Agent is the pyrrolidones of N methyl two）As binding agent, it is coated on aluminium foil after grinding 0.5h, is dried at 60 DEG C；
（3）By step（2）Obtained thin slice punching is into the specifications of Φ 12, as cell positive material；Conventional polyolefins barrier film is rushed
Piece, as battery diaphragm, assembles button lithium-sulfur cell into the specifications of Φ 16.
Embodiment 9
Ti3C2@Nafion modification composite diaphragms are applied in lithium-sulfur cell
（1）Take 70mg sublimed sulfurs, 20mg conductions are black, grind 0.5h after under vacuum conditions 155 DEG C heating 10h；
（2）By step（1）After obtained powder mull 0.5h, 125 milligrams of 8wt% PVDF solution is added（Solvent is N methyl two
Pyrrolidones）, it is coated on aluminium foil after grinding 0.5h, is dried at 60 DEG C；
（3）By step（2）Obtained thin slice punching is into the specifications of Φ 12, as cell positive material；Embodiment 6 is synthesized
Ti3C2@Nafion modify composite diaphragm punching into the specifications of Φ 16 as battery diaphragm, and unattached have Ti3C2The one of@Nafion
Side assembles button lithium-sulfur cell close to negative pole.
Fig. 8 is conventional polyolefins barrier film, Nafion@pp composite diaphragms and Ti3C2@Nafion modification composite diaphragm difference
Applied to the cycle performance figure of the battery in lithium-sulfur cell, obtained, as shown in Figure 8, Ti3C2@Nafion modification composite diaphragms are effective
Limitation more lithium sulfides shuttle effect, preferably improve the cycle performance of lithium-sulfur cell；Perfluorinated sulfonic acid barrier film is due to thing
The effect that reason hinders equally limits the shuttle of more lithium sulfides, relatively conventional polyalkene diaphragm, preferably improves following for battery
Ring performance.
By using Ti3C2The synergy that strong absorption and Nafion to more lithium sulfides pass through to the selectivity of lithium ion,
Collective effect improves the performance of lithium-sulfur cell in lithium-sulfur cell.
Embodiment 10
Ti3C2@CTAB modification composite diaphragms are applied in lithium-sulfur cell
（1）70mg sublimed sulfurs, the mixing of 20mg Ketjen blacks are taken, is ground 0.5 hour, lower 155 DEG C of vacuum environment heats 10 hours；
（2）By step（1）After obtained powder mull 0.5h, 125 milligrams of 8wt% PVDF solution is added（Solvent is N methyl two
Pyrrolidones）, it is coated on aluminium foil after grinding 0.5 hour, is dried at 60 DEG C；
（3）By step（2）Obtained thin slice punching is into the specifications of Φ 12, as cell positive material；Embodiment 4 is synthesized
Ti3C2@CTAB modify composite diaphragm punching into being used as lithium-sulfur cell barrier film after Φ 16, and unattached have Ti3C2The one of@CTAB
Side assembles button lithium-sulfur cell close to negative pole.
Ti3C2@CTAB modification composite diaphragms apply to the cycle performance figure of lithium-sulfur cell as shown in figure 9, as shown in Figure 9,
Ti is embedded in by using CTAB3C2Interlayer regulates and controls Ti3C2Interlamellar spacing, with have the function that improve lithium ion conductive, simultaneously
Ti3C2Suppress the shuttle of more lithium sulfides, collective effect improves the specific capacity and cycle performance of battery in lithium-sulfur cell, average
Often enclose capacity attenuation 0.303%.
Claims (10)
1. a kind of preparation method of MXene modifications composite diaphragm, it is characterised in that comprise the following steps：
（1）Villiaumite is dissolved in acid solution, adds MAX powder, stirring and dissolving；
（2）By step（1）Obtained solution centrifugal is washed to after supernatant pH value reaches more than 6, continues to centrifuge and collect supernatant
Liquid, the supernatant of collection is dried, obtains MXene materials；
（3）Obtained MXene materials are mixed with polymer or inorganic particle, ultrasonic dissolution is adsorbed in solvent by filtering
On polyalkene diaphragm surface, dry, obtain the MXene modifications composite diaphragm.
A kind of 2. preparation method of MXene modifications composite diaphragm according to claim 1, it is characterised in that step（1）
In, the villiaumite includes lithium fluoride or sodium fluoride；The acid solution includes 6 ~ 12M hydrochloric acid or 6 ~ 9M sulfuric acid；The villiaumite with
The mass ratio of MAX powder is 1：1.
A kind of 3. preparation method of MXene modifications composite diaphragm according to claim 1, it is characterised in that step（1）
In, in the MAX, M is early stage transition metal, and A is III A races or IV A races element, and X is C or N.
A kind of 4. preparation method of MXene modifications composite diaphragm according to claim 1, it is characterised in that step（1）
In, the stirring and dissolving is to stir 12 ~ 36h at 30 ~ 45 DEG C.
A kind of 5. preparation method of MXene modifications composite diaphragm according to claim 1, it is characterised in that step（2）
In, in the MXene, M is early stage transition metal, and X is that C or N, ene include-OH ,-F or=O.
A kind of 6. preparation method of MXene modifications composite diaphragm according to claim 1, it is characterised in that step（2）
In, the rotating speed of the centrifugation is 3000rpm；The time for continuing centrifugation is 0.5 ~ 1h；The drying is to enter at normal temperatures
Row vacuum drying.
A kind of 7. preparation method of MXene modifications composite diaphragm according to claim 1, it is characterised in that step（3）
In, the solid-liquid ratio of the MXene materials and solvent is 0.09 ~ 0.1mg/mL；The polymer includes perfluorinated sulfonic acid and hexadecane
One or more of base trimethylammonium bromide；The inorganic particle includes one or more of silica and titanium dioxide；Institute
It is 10% ~ 25% for MXene weight/mass percentage composition to state polymer phase；The inorganic particle relative to MXene quality percentage
Content is 10% ~ 30%.
A kind of 8. preparation method of MXene modifications composite diaphragm according to claim 1, it is characterised in that step（3）
In, the ultrasonic dissolution is ultrasonic more than 0.5h under argon gas atmosphere in the process of solvent；The solvent is included in water and ethanol
More than one；It is described to filter as vacuum filtration；The drying is to be dried in vacuo at normal temperatures.
9. a kind of MXene modifications composite diaphragm, its feature exist as made from the preparation method described in any one of claim 1 ~ 8
In substrate is polyalkene diaphragm, and decorative material is that MXene is attached to polymer or the compound of inorganic particle, decorative material
On the side surface of polyalkene diaphragm one.
10. application of a kind of MXene modification composite diaphragms in lithium-sulfur cell described in right 9, it is characterised in that by described in
MXene modification composite diaphragms are placed directly within lithium-sulfur cell, and MXene modification composite diaphragms it is unattached have MXene materials with it is poly-
Negative pole of the compound side of compound or inorganic particle close to battery.
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