CN107579235A - A kind of preparation method of oxidation Mxene/S compounds applied to lithium-sulphur cell positive electrode - Google Patents
A kind of preparation method of oxidation Mxene/S compounds applied to lithium-sulphur cell positive electrode Download PDFInfo
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Abstract
A kind of preparation method of oxidation Mxene/S compounds applied to lithium-sulphur cell positive electrode, is related to a kind of preparation method of the S compounds applied to lithium-sulphur cell positive electrode.The present invention is to solve the technical problem of the preparation method complex process of current Mxene/S compounds.The present invention：First, Mxene powder is prepared；2nd, aoxidize；3rd, immersion method.The present invention is used as S carriers using the oxidation Mxene of high conductivity, and preparation process is simply, safety, production cost is low, is expected to large-scale production, has very high specific capacity and cyclical stability as lithium sulfur battery anode material.The present invention is applied to prepare lithium sulfur battery anode material.
Description
Technical field
The present invention relates to a kind of preparation method of the S compounds applied to lithium-sulphur cell positive electrode.
Background technology
Lithium-sulfur cell has as one of following most promising new system of replacement conventional lithium ion secondary cell
The advantages that specific capacity is high, energy density is big, sufficient raw, but there is also many vital problems demands to solve.
Due to positive electrode active materials S low electric conductivity, people are caused it is expected lithium-sulfur cell application prospect too low.Thus while put forward
But never receive due attention.Nazzer seminars in 2009 are first by S by incorporating the method and mesoporous carbon that impregnate
It is compound, positive electrode is prepared, the sight of people is withdrawn on lithium-sulfur cell from newly.Because mesoporous carbon not only makes sulphur with smaller
Particle size participates in electrochemical reaction, and carbon skeleton also improves materials conductive performance, and then strengthens battery positive electrode active.Press
According to this thinking, sulphur cathode performance can be improved in terms of following two:1st, by the size reduction of sulphur；2nd, the conduction of material is improved
Property.In addition, S and the problems of dissolution of the more lithium sulfides of intermediate product generated step by step during lithium generation exoelectrical reaction, are researchers
The direction more paid close attention to, because during cycle charge-discharge, more lithium sulfide solution are dissolved into electrolyte and produce shuttle
Effect, so cyclical stability extreme difference, this is the most important reason for hindering lithium-sulfur cell development.
To sum up, selection with high conductivity, to the confinement of S high degree of dispersion formulas, to carrier material of more lithium sulfides with adsorptivity
Material is the key for improving lithium-sulfur cell performance.The study on the modification for S is roughly divided into following a few classes at present：1st, conducting polymer/
S；2nd, carbon material/S；3rd, metal or metal oxide/S.Limitation for S is also from simple physics confinement to the step of chemisorbed
Rapid expansion.Especially metal oxide/S composites, wetting and absorption for polysulfide reach poised state, are current
One of focus of research.But the bad needs of the most of electric conductivity of metal oxide with carbon material is compound obtains higher conduction
Property, therefore high rate performance is bad, reaction efficiency is also very low.And it is not easy to prepare.
Using Mxene as conductive material, not only electric conductivity is high for this material, surface area is big, and the base that surface is abundant
Polysulfide can effectively be adsorbed in group, can be equal on surface with minimum particle by S using the group on surface in preparation process
Even forming core, while reach the purpose of high dispersive, high efficiency, chemisorbed.
With Ti, Al, Si graphite powder etc. for raw material, using ball mill mixing technique, pressureless sintering can prepare MAX powders, so
The graphene two of accordion like must be arrived by carrying out chemical etching to the MAX powders of synthesis at room temperature with chemical liquid phase etching method afterwards
Mxene materials are tieed up, ultrasound is peeled off in water by the Mxene of accordion like, and aqueous solution supernatant liquid filtering has just obtained single sheet
Mxene.Such as Ti3AlC2 is that Ti-C layers are alternately arranged with Al atomic layers and formed, when react occur when, Al atomic layers will be from layer
Between be corroded, adjacent Ti-C layers will be separated from each other, and the Ti-C layers being lifted off of all have exposed Ti, can meet close
Suitable part, and reacting is carried out in the aqueous solution of HF acid, thus-OH and-F just combined with Ti-C layers it is upper so that give birth to
Into Mxene surfaces carry the functional group such as hydroxyl and F.
The content of the invention
The present invention is to solve the technical problem of the preparation method complex process of current Mxene/S compounds, and is provided
A kind of preparation method of oxidation Mxene/S compounds applied to lithium-sulphur cell positive electrode.
The preparation method of the oxidation Mxene/S compounds applied to lithium-sulphur cell positive electrode of the present invention is to enter according to the following steps
Capable：
First, Mxene powder is prepared：MAX phases are mixed with HF solution, 6h~40h is stirred, natural stratification, then will
Pelleting centrifugation, it is neutral to repeat filtering and washing to filtrate with deionized water and alcohol, and accordion like Mxene powder is obtained after drying
End；The quality of described MAX phases and the volume ratio of HF solution are 1g:(50mL~200mL)；The mass concentration of described HF solution
For 10%~40%；
2nd, aoxidize：By accordion like Mxene powder in Ar and O2Mixed atmosphere and temperature be 100 DEG C~900 DEG C of bar
2h~20h is heat-treated under part, in Ar and O2Mixed atmosphere under be cooled to room temperature, obtain the Mxene powder of surface oxidation；It is described
Ar and O2Mixed atmosphere in oxygen volume fraction be 1%~10%；
3rd, immersion method：The Mxene powder of surface oxidation is added in the aqueous solution in the source containing S, stirred, salt is added dropwise
Acid solution, successively by centrifuging, washing and dry, that is, obtain aoxidizing Mxene/S compounds；The Mxene of described surface oxidation
Mass ratio with S sources in the aqueous solution in the source containing S is 1:(1~10)；The concentration of the aqueous solution in the described source containing S is 0.05mol/L
~2mol/L；Described concentration of hydrochloric acid solution is 0.1mol/L~3mol/L；Described S sources and the material of HCl in hydrochloric acid solution
Amount ratio be 1:(2.5~12).
Another preparation method of the oxidation Mxene/S compounds applied to lithium-sulphur cell positive electrode of the present invention is by following
What step was carried out：
First, Mxene powder is prepared：MAX phases are mixed with HF solution, 6h~40h is stirred, natural stratification, then will
Pelleting centrifugation, it is neutral to repeat filtering and washing to filtrate with deionized water and alcohol, and accordion like Mxene powder is obtained after drying
End, accordion like Mxene powder is dispersed in water, ultrasonic 0.5h~10h, stands, take upper suspension to be centrifuged, dried
It is dry, obtain sheet Mxene powder；The quality of described MAX phases and the volume ratio of HF solution are 1g:(50mL~200mL)；It is described
HF solution mass concentration be 10%~40%；
2nd, aoxidize：By sheet Mxene powder in Ar and O2Mixed atmosphere and temperature be 100 DEG C~900 DEG C under conditions of
2h~20h is heat-treated, in Ar and O2Mixed atmosphere under be cooled to room temperature, obtain the Mxene powder of surface oxidation；Described Ar
And O2Mixed atmosphere in oxygen volume fraction be 1%~10%；
3rd, immersion method：The Mxene powder of surface oxidation is added in the aqueous solution in the source containing S, stirred, salt is added dropwise
Acid solution, successively by centrifuging, washing and dry, that is, obtain aoxidizing Mxene/S compounds；The Mxene of described surface oxidation
Mass ratio with S sources in the aqueous solution in the source containing S is 1:(1~10)；The concentration of the aqueous solution in the described source containing S is 0.05mol/L
~2mol/L；Described concentration of hydrochloric acid solution is 0.1mol/L~3mol/L；Described S sources and the material of HCl in hydrochloric acid solution
Amount ratio be 1:(2.5~12).
Inventive process have the advantage that provide a kind of simple, safe, inexpensive preparation oxidation Mxene/S compounds
Method, and prepared material can effectively adsorb poly- lithium sulfide, improve electrode conductivuty, and have as the lithium-sulfur cell of positive pole
There is the life-span of height ratio capacity, high circulation stability and length.
The oxidation Mxene/S compounds of the present invention are a kind of to aoxidize Mxene as carrier, pass through the water-bath in situ of innovation
The method for learning load S, prepares lithium sulfur battery anode material.The compound includes oxidation Mxene and elemental sulfur, wherein aoxidizing
Mxene is accordion like or single sheet, and substantial amounts of-OH and F is contained on its surface-Ion；It is to pass through that it is compound with sulphur, which to aoxidize Mxene,
Water bath Method synthesis in situ, sulphur is dispersed in Nano grade aoxidizes Mxene surfaces, and S mass content is in compound
10%~80%.
The present invention is used in immersion method, using S sources solution and HCl oxidation Mxene F (fluorine) terminal forming core in situ immediately
Mode can successfully prepare oxidation Mxene/S compounds, not only electric conductivity is high by oxidation Mxene, surface area is big by (5002/g
~1600m2/ g), and the group that surface is enriched can effectively adsorb polysulfide, utilize the base on surface in preparation process
Group, can by S with minimum particle in surface homogeneous nucleation, while reach the purpose of high dispersive, high efficiency, chemisorbed.
The present invention is aoxidizing Mxene surface recombination sulfur-containing groups using ion exchange, then by oxidation reaction that sulphur is former
Position is linked at oxidation Mxene surfaces.
The Mxene materials of the present invention are after oxidation processes, and material structure is more stable, and electric conductivity also further increases,
It is more beneficial for improving the electro-chemical activity of material.
The oxidation Mxene of the present invention is the two-dimensional layer compound of accordion like or single sheet, and M represents transition metal member
Element, X represent carbon or nitrogen.
The present invention has the following advantages that compared with prior art：
1st, using the oxidation Mxene of high conductivity as S carriers, preparation process is simple, safety, production cost is low, is expected to
Large-scale production；
2nd, oxidation Mxene material surfaces carry oh group, have good wetability with liquid S, are easy to impregnate S, and table
The F in face-Introduced with S sources and ion exchange or absorption occurs, S and oxidation Mxene carriers can be subjected to chemical bonds, can
The effectively absorption electric discharge poly- lithium sulfide of intermediate product, reduces shuttle effect；
3rd, not only electric conductivity is high, surface area is big for oxidation Mxene/S compounds prepared by the present invention, can be by S with minimum
Particle in surface homogeneous nucleation, while reach the purpose of high dispersive, high efficiency, chemisorbed；
4th, the oxidation Mxene/S compounds that prepare of the present invention as lithium sulfur battery anode material with very high specific capacity and
Cyclical stability, it especially still can meet that the high power capacity of battery operates in the situation of high current charge-discharge, be discharged in 2C, 5C,
Discharge capacity is up to 1600mAhg-1Left and right, capacity remains to be maintained at 800mAhg after the circulation of 1000 circles-1Left and right.
A in MAX phases represents major element Si or Al.
The lithium-sulfur cell of the present invention is with lithium hexafluoro phosphate, lithium perchlorate, hexafluoroarsenate lithium, trifluoromethyl sulfonic acid lithium, two
One or two or more kinds in one trifluoromethane sulfonic acid imide li are the lithium-sulfur cell of lithium salts.
Brief description of the drawings
Fig. 1 is the SEM figures for testing the accordion like Mxene powder obtained in four steps one；
Fig. 2 is the Mxene powder for testing the surface oxidation that a step 2 obtains；
Fig. 3 is to test the oxidation Mxene/S compounds that a step 3 obtains；
Fig. 4 is the transmission electron microscope picture for the Mxene powder (accordion like) for testing the surface oxidation that two step 2 obtain；
Fig. 5 is the transmission electron microscope picture for testing the oxidation Mxene/S compounds (sheet) that three step 2 obtain；
Fig. 6 is stable circulation linearity curve；
Fig. 7 is the charge/discharge capacity curve map for testing seven button cells prepared under different multiplying.
Embodiment
Embodiment one：Present embodiment is a kind of oxidation Mxene/S compounds applied to lithium-sulphur cell positive electrode
Preparation method, specifically carry out according to the following steps：
First, Mxene powder is prepared：MAX phases are mixed with HF solution, 6h~40h is stirred, natural stratification, then will
Pelleting centrifugation, it is neutral to repeat filtering and washing to filtrate with deionized water and alcohol, and accordion like Mxene powder is obtained after drying
End；The quality of described MAX phases and the volume ratio of HF solution are 1g:(50mL~200mL)；The mass concentration of described HF solution
For 10%~40%；
2nd, aoxidize：By accordion like Mxene powder in Ar and O2Mixed atmosphere and temperature be 100 DEG C~900 DEG C of bar
2h~20h is heat-treated under part, in Ar and O2Mixed atmosphere under be cooled to room temperature, obtain the Mxene powder of surface oxidation；It is described
Ar and O2Mixed atmosphere in oxygen volume fraction be 1%~10%；
3rd, immersion method：The Mxene powder of surface oxidation is added in the aqueous solution in the source containing S, stirred, salt is added dropwise
Acid solution, successively by centrifuging, washing and dry, that is, obtain aoxidizing Mxene/S compounds；The Mxene of described surface oxidation
Mass ratio with S sources in the aqueous solution in the source containing S is 1:(1~10)；The concentration of the aqueous solution in the described source containing S is 0.05mol/L
~2mol/L；Described concentration of hydrochloric acid solution is 0.1mol/L~3mol/L；Described S sources and the material of HCl in hydrochloric acid solution
Amount ratio be 1:(2.5~12).
Embodiment two：Present embodiment is unlike embodiment one：Described MAX phases are
Ti2AlC、Ti3AlC2Or Ti3SiC2.Other are identical with embodiment one.
Embodiment three：Present embodiment is unlike embodiment one or two：Described S sources are thio
Sodium sulphate or vulcanized sodium.Other are identical with embodiment one or two.
Embodiment four：Present embodiment is a kind of oxidation Mxene/S compounds applied to lithium-sulphur cell positive electrode
Preparation method, specifically carry out according to the following steps：
First, Mxene powder is prepared：MAX phases are mixed with HF solution, 6h~40h is stirred, natural stratification, then will
Pelleting centrifugation, it is neutral to repeat filtering and washing to filtrate with deionized water and alcohol, and accordion like Mxene powder is obtained after drying
End, accordion like Mxene powder is dispersed in water, ultrasonic 0.5h~10h, stands, take upper suspension to be centrifuged, dried
It is dry, obtain sheet Mxene powder；The quality of described MAX phases and the volume ratio of HF solution are 1g:(50mL~200mL)；It is described
HF solution mass concentration be 10%~40%；
2nd, aoxidize：By sheet Mxene powder in Ar and O2Mixed atmosphere and temperature be 100 DEG C~900 DEG C under conditions of
2h~20h is heat-treated, in Ar and O2Mixed atmosphere under be cooled to room temperature, obtain the Mxene powder of surface oxidation；Described Ar
And O2Mixed atmosphere in oxygen volume fraction be 1%~10%；
3rd, immersion method：The Mxene powder of surface oxidation is added in the aqueous solution in the source containing S, stirred, salt is added dropwise
Acid solution, successively by centrifuging, washing and dry, that is, obtain aoxidizing Mxene/S compounds；The Mxene of described surface oxidation
Mass ratio with S sources in the aqueous solution in the source containing S is 1:(1~10)；The concentration of the aqueous solution in the described source containing S is 0.05mol/L
~2mol/L；Described concentration of hydrochloric acid solution is 0.1mol/L~3mol/L；Described S sources and the material of HCl in hydrochloric acid solution
Amount ratio be 1:(2.5~12).
Embodiment five：Present embodiment is unlike embodiment four：Described MAX phases are
Ti2AlC、Ti3AlC2Or Ti3SiC2.Other are identical with embodiment four.
Embodiment six：Present embodiment is unlike embodiment five：Described S sources are thiosulfuric acid
Sodium or vulcanized sodium.Other are identical with embodiment five.
The present invention is verified with tests below：
Experiment one：This experiment is a kind of preparation method of oxidation Mxene/S compounds applied to lithium-sulphur cell positive electrode, is had
Body is carried out according to the following steps：
First, Mxene powder is prepared：MAX phases are mixed with HF solution, stir 20h, natural stratification then will precipitation
Centrifugation, it is neutral to repeat filtering and washing to filtrate with deionized water and alcohol, and accordion like Mxene powder is obtained after drying；Institute
The quality for the MAX phases stated and the volume ratio of HF solution are 1g:100mL；The mass concentration of described HF solution is 20%；
2nd, aoxidize：By accordion like Mxene powder in Ar and O2Mixed atmosphere and temperature be 100 DEG C under conditions of heat
20h is handled, in Ar and O2Mixed atmosphere under be cooled to room temperature, obtain the Mxene powder of surface oxidation；Described Ar and O2's
The volume fraction of oxygen is 1% in mixed atmosphere；
3rd, immersion method：The Mxene powder of surface oxidation is added in the aqueous solution in the source containing S, stirred, salt is added dropwise
Acid solution, successively by centrifuging, washing and dry, that is, obtain aoxidizing Mxene/S compounds；The Mxene of described surface oxidation
Mass ratio with S sources in the aqueous solution in the source containing S is 1:5；The concentration of the aqueous solution in the described source containing S is 0.5mol/L；Described
Concentration of hydrochloric acid solution is 1mol/L；The ratio of described S sources and the amount of HCl material in hydrochloric acid solution is 1:5.
Described MAX phases are Ti3SiC2, oxidation Mxene/S compounds are oxidation Ti3C2Ene/S compounds；Described S sources
For sodium thiosulfate.
Experiment two：This experiment is a kind of preparation method of oxidation Mxene/S compounds applied to lithium-sulphur cell positive electrode, is had
Body is carried out according to the following steps：
First, Mxene powder is prepared：MAX phases are mixed with HF solution, stir 40h, natural stratification then will precipitation
Centrifugation, it is neutral to repeat filtering and washing to filtrate with deionized water and alcohol, and accordion like Mxene powder is obtained after drying；Institute
The quality for the MAX phases stated and the volume ratio of HF solution are 1g:100mL；The mass concentration of described HF solution is 40%；
2nd, aoxidize：By accordion like Mxene powder in Ar and O2Mixed atmosphere and temperature be 300 DEG C under conditions of heat
1h is handled, in Ar and O2Mixed atmosphere under be cooled to room temperature, obtain the Mxene powder of surface oxidation；Described Ar and O2It is mixed
The volume fraction for closing oxygen in atmosphere is 10%；
3rd, immersion method：The Mxene powder of surface oxidation is added in the aqueous solution in the source containing S, stirred, salt is added dropwise
Acid solution, successively by centrifuging, washing and dry, that is, obtain aoxidizing Mxene/S compounds；The Mxene of described surface oxidation
Mass ratio with S sources in the aqueous solution in the source containing S is 1:10；The concentration of the aqueous solution in the described source containing S is 1mol/L；Described salt
Acid solutions are 1mol/L；The ratio of described S sources and the amount of HCl material in hydrochloric acid solution is 1:5.
Described MAX phases are Ti3AlC2, oxidation Mxene/S compounds are oxidation Ti3C2Ene/S compounds；Described S sources
For vulcanized sodium.
Experiment three：This experiment is a kind of preparation method of oxidation Mxene/S compounds applied to lithium-sulphur cell positive electrode, is had
Body is carried out according to the following steps：
First, Mxene powder is prepared：MAX phases are mixed with HF solution, stir 6h, natural stratification, then will precipitate from
The heart, it is neutral to repeat filtering and washing to filtrate with deionized water and alcohol, accordion like Mxene powder is obtained after drying, by hand
Organ shape Mxene powder is dispersed in water, ultrasonic 2h, is stood, is taken upper suspension to be centrifuged, and is dried, is obtained sheet Mxene
Powder；The quality of described MAX phases and the volume ratio of HF solution are 1g:100mL；The mass concentration of described HF solution is
10%；
2nd, aoxidize：By sheet Mxene powder in Ar and O2Mixed atmosphere and temperature be 900 DEG C under conditions of be heat-treated
10h, in Ar and O2Mixed atmosphere under be cooled to room temperature, obtain the Mxene powder of surface oxidation；Described Ar and O2Mixing
The volume fraction of oxygen is 10% in atmosphere；
3rd, immersion method：The Mxene powder of surface oxidation is added in the aqueous solution in the source containing S, stirred, salt is added dropwise
Acid solution, successively by centrifuging, washing and dry, that is, obtain aoxidizing Mxene/S compounds；The Mxene of described surface oxidation
Mass ratio with S sources in the aqueous solution in the source containing S is 1:1.5；The concentration of the aqueous solution in the described source containing S is 0.1mol/L；It is described
Concentration of hydrochloric acid solution be 0.5mol/L；The ratio of described S sources and the amount of HCl material in hydrochloric acid solution is 1:5.
Described MAX phases are Ti3AlC2, oxidation Mxene/S compounds are oxidation Ti3C2Ene/S compounds；Described S
Source is sodium thiosulfate.
Experiment four：This experiment is a kind of preparation method of oxidation Mxene/S compounds applied to lithium-sulphur cell positive electrode, is had
Body is carried out according to the following steps：
First, Mxene powder is prepared：MAX phases are mixed with HF solution, stir 10h, natural stratification then will precipitation
Centrifugation, it is neutral to repeat filtering and washing to filtrate with deionized water and alcohol, and accordion like Mxene powder is obtained after drying, will
Accordion like Mxene powder is dispersed in water, ultrasonic 2h, is stood, is taken upper suspension to be centrifuged, and is dried, is obtained sheet
Mxene powder；The quality of described MAX phases and the volume ratio of HF solution are 1g:100mL；The mass concentration of described HF solution
For 20%；
2nd, aoxidize：By sheet Mxene powder in Ar and O2Mixed atmosphere and temperature be 300 DEG C under conditions of be heat-treated
6h, in Ar and O2Mixed atmosphere under be cooled to room temperature, obtain the Mxene powder of surface oxidation；Described Ar and O2Gaseous mixture
The volume fraction of oxygen is 5% in atmosphere；
3rd, immersion method：The Mxene powder of surface oxidation is added in the aqueous solution in the source containing S, stirred, salt is added dropwise
Acid solution, successively by centrifuging, washing and dry, that is, obtain aoxidizing Mxene/S compounds；The Mxene of described surface oxidation
Mass ratio with S sources in the aqueous solution in the source containing S is 1:3；The concentration of the aqueous solution in the described source containing S is 0.2mol/L；Described
Concentration of hydrochloric acid solution is 1mol/L；The ratio of described S sources and the amount of HCl material in hydrochloric acid solution is 1:5.
Described MAX phases are Ti2AlC, oxidation Mxene/S compounds are oxidation Ti2Cene/S compounds；Described S sources are
Sodium thiosulfate.
Fig. 1 is the SEM figures for testing the accordion like Mxene powder obtained in four steps one, can be clearly from picture
See after HF solution etches, the Ti of accordion pattern is presented2Cene。
Fig. 2 is the Mxene powder for testing the surface oxidation that a step 2 obtains, and Fig. 3 is to test the oxygen that a step 3 obtains
Change Mxene/S compounds, from picture it can be seen that after peroxidating, Ti3C2Ene sheet surfaces uniformly distributed one layer and receive
The particle of meter level, this demonstrate TiO2Particle is successfully attached to Ti3C2Ene top layers, with oxidation Tis of the S after compound3C2Ene/S pieces
Filled between layer by S, but still retain certain space, accommodate caused volumetric expansion in discharge process.
Fig. 4 is the transmission electron microscope picture for testing the Mxene powder (accordion like) of surface oxidation that two step 2 obtain, Fig. 5
It is the transmission electron microscope picture for testing the oxidation Mxene/S compounds (sheet) that three step 2 obtain, finds out that lamella is very thin in figure, table
Granular oxide be present and in the Ti of accordion like in face3C2In ene, each thick-layer is by many piece individual layers
Ti3C2Ene compositions.
Experiment five：The oxidation Mxene/S compounds prepared, carbon black and binding agent will be tested to mix, slurry is tuned into, applies
On aluminium foil, 50 DEG C of drying 24h, anode pole piece is obtained, is used as using lithium to electrode, button cell is assembled into glove box,
And carry out electro-chemical test；The solute of described binding agent is Kynoar, and solvent is 1-METHYLPYRROLIDONE, the matter of solute
It is 10% to measure fraction；The mass ratio for aoxidizing the solute of Mxene/S compounds, carbon black and binding agent is 8:1:1.
Experiment six：The four oxidation Mxene/S compounds prepared, carbon black and binding agent will be tested to mix, slurry is tuned into, applies
On aluminium foil, 50 DEG C of drying 24h, anode pole piece is obtained, is used as using lithium to electrode, button cell is assembled into glove box,
And carry out electro-chemical test；The solute of described binding agent is Kynoar, and solvent is 1-METHYLPYRROLIDONE, the matter of solute
It is 10% to measure fraction；The mass ratio for aoxidizing the solute of Mxene/S compounds, carbon black and binding agent is 8:1:1.
Experiment seven：The three oxidation Mxene/S compounds prepared, carbon black and binding agent will be tested to mix, slurry is tuned into, applies
On aluminium foil, 50 DEG C of drying 24h, anode pole piece is obtained, is used as using lithium to electrode, button cell is assembled into glove box,
And carry out electro-chemical test；The solute of described binding agent is Kynoar, and solvent is 1-METHYLPYRROLIDONE, the matter of solute
It is 10% to measure fraction；The mass ratio for aoxidizing the solute of Mxene/S compounds, carbon black and binding agent is 8:1:1.
Fig. 6 is stable circulation linearity curve, and curve 1 is to test six button cells prepared to charge under 5C multiplying powers, and curve 2 is
Button cell prepared by experiment six discharges under 5C multiplying powers, and curve 3 is to test five button cells prepared to discharge under 2C multiplying powers,
Curve 4 is to test five button cells prepared to charge under 5C multiplying powers, as seen from the figure, under larger current, two kinds of button electricity
Chi Jun shows good cyclical stability, and initial capacity is in 1500mAhg-1, it is remaining after the circulation of 1000 circles
800mAhg-1, remained in that higher capacity.
Fig. 7 is the charge/discharge capacity curve map for testing seven button cells prepared under different multiplying, and curve 1 is 0.5C,
Curve 2 is 1C, and curve 3 is 2C, and curve 4 is 5C, as seen from the figure the oxidation Ti of single sheet3C2Ene/S composites are as positive pole
Material ground high rate performance, exists, the capacity of material progressively diminishes, when electric current increases back again in electric current from small increase process
0.5C, the capacity of material respond immediately to initial level, illustrate that material has very high reaction power, and charging and discharging curve base
This coincidence, illustrate that the cycle efficieny of this material is good.
Claims (6)
1. the preparation method of a kind of oxidation Mxene/S compounds applied to lithium-sulphur cell positive electrode, it is characterised in that applied to lithium
The preparation method of the oxidation Mxene/S compounds of sulphur cell positive electrode is carried out according to the following steps：
First, Mxene powder is prepared：MAX phases are mixed with HF solution, stir 6h~40h, natural stratification then will precipitation
Centrifugation, it is neutral to repeat filtering and washing to filtrate with deionized water and alcohol, and accordion like Mxene powder is obtained after drying；Institute
The quality for the MAX phases stated and the volume ratio of HF solution are 1g:(50mL~200mL)；The mass concentration of described HF solution is
10%~40%；
2nd, aoxidize：By accordion like Mxene powder in Ar and O2Mixed atmosphere and temperature be 100 DEG C~900 DEG C under conditions of
2h~20h is heat-treated, in Ar and O2Mixed atmosphere under be cooled to room temperature, obtain the Mxene powder of surface oxidation；Described Ar
And O2Mixed atmosphere in oxygen volume fraction be 1%~10%；
3rd, immersion method：The Mxene powder of surface oxidation is added in the aqueous solution in the source containing S, stirred, it is molten that hydrochloric acid is added dropwise
Liquid, successively by centrifuging, washing and dry, that is, obtain aoxidizing Mxene/S compounds；The Mxene of described surface oxidation is with containing S
The mass ratio in S sources is 1 in the aqueous solution in source:(1~10)；The concentration of the aqueous solution in the described source containing S be 0.05mol/L~
2mol/L；Described concentration of hydrochloric acid solution is 0.1mol/L~3mol/L；Described S sources and HCl material in hydrochloric acid solution
The ratio of amount is 1:(2.5~12).
2. a kind of preparation method of oxidation Mxene/S compounds applied to lithium-sulphur cell positive electrode according to claim 1,
It is characterized in that described MAX phases are Ti2AlC、Ti3AlC2Or Ti3SiC2。
3. a kind of preparation method of oxidation Mxene/S compounds applied to lithium-sulphur cell positive electrode according to claim 1,
It is characterized in that described S sources are sodium thiosulfate or vulcanized sodium.
4. the preparation method of a kind of oxidation Mxene/S compounds applied to lithium-sulphur cell positive electrode, it is characterised in that be by following
What step was carried out：
First, Mxene powder is prepared：MAX phases are mixed with HF solution, stir 6h~40h, natural stratification then will precipitation
Centrifugation, it is neutral to repeat filtering and washing to filtrate with deionized water and alcohol, and accordion like Mxene powder is obtained after drying, will
Accordion like Mxene powder is dispersed in water, ultrasonic 0.5h~10h, is stood, is taken upper suspension to be centrifuged, and is dried, is obtained
Sheet Mxene powder；The quality of described MAX phases and the volume ratio of HF solution are 1g:(50mL~200mL)；Described HF is molten
The mass concentration of liquid is 10%~40%；
2nd, aoxidize：By sheet Mxene powder in Ar and O2Mixed atmosphere and temperature be 100 DEG C~900 DEG C under conditions of heat at
2h~20h is managed, in Ar and O2Mixed atmosphere under be cooled to room temperature, obtain the Mxene powder of surface oxidation；Described Ar and O2
Mixed atmosphere in oxygen volume fraction be 1%~10%；
3rd, immersion method：The Mxene powder of surface oxidation is added in the aqueous solution in the source containing S, stirred, it is molten that hydrochloric acid is added dropwise
Liquid, successively by centrifuging, washing and dry, that is, obtain aoxidizing Mxene/S compounds；The Mxene powder of described surface oxidation
Mass ratio with S sources in the aqueous solution in the source containing S is 1:(1~10)；The concentration of the aqueous solution in the described source containing S is 0.05mol/L
~2mol/L；Described concentration of hydrochloric acid solution is 0.1mol/L~3mol/L；Described S sources and the material of HCl in hydrochloric acid solution
Amount ratio be 1:(2.5~12).
5. a kind of preparation method of oxidation Mxene/S compounds applied to lithium-sulphur cell positive electrode according to claim 1,
It is characterized in that described MAX phases are Ti2AlC、Ti3AlC2Or Ti3SiC2。
6. a kind of preparation method of oxidation Mxene/S compounds applied to lithium-sulphur cell positive electrode according to claim 1,
It is characterized in that described S sources are sodium thiosulfate or vulcanized sodium.
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