CN107579235B - Preparation method of Mxene/S oxide compound applied to lithium-sulfur battery anode - Google Patents
Preparation method of Mxene/S oxide compound applied to lithium-sulfur battery anode Download PDFInfo
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Abstract
A preparation method of an oxidized Mxene/S compound applied to a lithium-sulfur battery anode relates to a preparation method of an S compound applied to a lithium-sulfur battery anode. The invention aims to solve the technical problem that the existing preparation method of the Mxene/S compound is complex in process. The invention comprises the following steps: firstly, preparing Mxene powder; secondly, oxidizing; and thirdly, a water bath method. The invention adopts high-conductivity Mxene oxide as S carrier, has simple and safe preparation process and low production cost, is expected to be produced in large scale, and has very high specific capacity and cycling stability when used as the anode material of the lithium-sulfur battery. The preparation method is applied to preparation of the lithium-sulfur battery cathode material.
Description
Technical Field
The invention relates to a preparation method of an S compound applied to a lithium-sulfur battery anode.
Background
The lithium-sulfur battery, as one of the new systems that have the most promising future development prospects to replace the traditional lithium-ion secondary battery, has the advantages of high specific capacity, large energy density, sufficient raw material sources and the like, but has many crucial problems to be solved urgently. Due to the low conductivity of the positive electrode active material S, the prospect of application to lithium sulfur batteries is too low. Therefore, although it is proposed, it has not been paid due attention. In 2009, the nazzer group first compounded S with mesoporous carbon by a method of impregnation to prepare a positive electrode material, and pulled back the sight of people to the lithium sulfur battery. The mesoporous carbon not only enables sulfur to participate in electrochemical reaction in a smaller particle size, but also improves the conductivity of the material by the carbon skeleton, so that the activity of the battery anode is enhanced. According to the idea, the positive performance of the sulfur anode can be improved from the following two aspects of 1, reducing the size of the sulfur; 2. the conductivity of the material is improved. In addition, the problem of dissolution of lithium polysulfide, which is an intermediate product generated in stages during the discharge reaction between S and lithium, is a direction in which researchers pay more attention, and the poor cycle stability is the most important reason for hindering the development of lithium-sulfur batteries because the lithium polysulfide solution dissolves into the electrolyte during the cyclic charge and discharge process and generates a shuttle effect.
In summary, the selection of a support material with high conductivity, high dispersion confinement for S, and adsorption for lithium polysulfide is key to improving the performance of lithium sulfur cells. The current studies on modification of S are roughly divided into the following categories: 1. conductive polymer/S; 2. carbon material/S; 3. metal or metal oxide/S. The limitations for S also spread from simple physical confinement to the chemisorption step. Especially, the metal oxide/S composite material is one of the hot spots of the present research for the equilibrium state of the wetting and adsorption of polysulfide. However, most metal oxides have poor conductivity and need to be compounded with carbon materials to obtain higher conductivity, so that rate capability is poor and reaction efficiency is low. And is not easy to prepare.
The Mxene is used as a conductive material, the material has extremely high conductivity and large surface area, and rich groups on the surface can effectively adsorb polysulfide.
Taking Ti, Al, Si graphite powder and the like as raw materials, adopting a ball milling and mixing process, preparing MAX powder through pressureless sintering, then chemically etching the synthesized MAX powder at room temperature by using a chemical liquid phase etching method to obtain an accordion-shaped graphene two-dimensional Mxene material, ultrasonically stripping the accordion-shaped Mxene material in water, and filtering supernatant of the water solution to obtain the single-piece Mxene. For example, Ti3AlC2 is formed by alternately arranging Ti-C layers and Al atomic layers, when reaction occurs, the Al atomic layers are corroded off from the layers, the adjacent Ti-C layers are separated from each other, the stripped Ti-C layers have exposed Ti which can meet the appropriate ligand, and the reaction is carried out in an aqueous solution of HF acid, so-OH and-F are combined with the Ti-C layers, and the surface of the generated Mxene has functional groups such as hydroxyl, F and the like.
Disclosure of Invention
The invention provides a preparation method of an oxidized Mxene/S compound applied to a lithium-sulfur battery anode, aiming at solving the technical problem that the existing preparation method of the Mxene/S compound is complex in process.
The preparation method of the Mxene/S oxide compound applied to the positive electrode of the lithium-sulfur battery is carried out according to the following steps:
firstly, preparing Mxene powder, namely mixing MAX phase and HF solution, stirring for 6-40 h, naturally standing for layering, centrifuging the precipitate, repeatedly performing suction filtration and washing by using deionized water and alcohol until the filtrate is neutral, and drying to obtain accordion-shaped Mxene powder, wherein the volume ratio of the MAX phase to the HF solution is 1g (50m L-200 m L), and the mass concentration of the HF solution is 10-40%;
secondly, oxidation: mixing accordion-like Mxene powder in Ar and O2Is heat treated for 2 to 20 hours under the condition that the temperature is between 100 and 900 ℃, and then the mixture is treated with Ar and O2Cooling to room temperature under the mixed atmosphere of (1) to obtain surface-oxidized Mxene powder; ar and O2The volume fraction of oxygen in the mixed atmosphere is 1-10%;
and thirdly, a water bath method, namely adding the surface-oxidized Mxene powder into an aqueous solution containing an S source, uniformly stirring, dropwise adding a hydrochloric acid solution, and sequentially centrifuging, washing and drying to obtain the oxidized Mxene/S compound, wherein the mass ratio of the surface-oxidized Mxene to the S source in the aqueous solution containing the S source is 1 (1-10), the concentration of the aqueous solution containing the S source is 0.05 mol/L-2 mol/L, the concentration of the hydrochloric acid solution is 0.1 mol/L-3 mol/L, and the ratio of the S source to the amount of HCl substances in the hydrochloric acid solution is 1 (2.5-12).
The other preparation method of the Mxene/S oxide compound applied to the positive electrode of the lithium-sulfur battery is carried out according to the following steps:
firstly, preparing Mxene powder, namely mixing MAX phase and HF solution, stirring for 6-40 h, naturally standing for layering, centrifuging a precipitate, repeatedly performing suction filtration and washing by deionized water and alcohol until a filtrate is neutral, drying to obtain accordion-shaped Mxene powder, dispersing the accordion-shaped Mxene powder in water, performing ultrasonic treatment for 0.5-10 h, standing, taking an upper suspension for centrifuging, and drying to obtain sheet Mxene powder, wherein the volume ratio of the MAX phase to the HF solution is 1g (50m L-200 m L), and the mass concentration of the HF solution is 10-40%;
secondly, oxidation: mixing the flaky Mxene powder in Ar and O2Is heat treated for 2 to 20 hours under the condition that the temperature is between 100 and 900 ℃, and then the mixture is treated with Ar and O2Cooling to room temperature under the mixed atmosphere of (1) to obtain surface-oxidized Mxene powder; ar and O2The volume fraction of oxygen in the mixed atmosphere is 1-10%;
and thirdly, a water bath method, namely adding the surface-oxidized Mxene powder into an aqueous solution containing an S source, uniformly stirring, dropwise adding a hydrochloric acid solution, and sequentially centrifuging, washing and drying to obtain the oxidized Mxene/S compound, wherein the mass ratio of the surface-oxidized Mxene to the S source in the aqueous solution containing the S source is 1 (1-10), the concentration of the aqueous solution containing the S source is 0.05 mol/L-2 mol/L, the concentration of the hydrochloric acid solution is 0.1 mol/L-3 mol/L, and the ratio of the S source to the amount of HCl substances in the hydrochloric acid solution is 1 (2.5-12).
The method has the advantages that the method for preparing the Mxene/S oxide compound is simple, safe and low in cost, the prepared material can effectively adsorb the agglomerated lithium sulfide, the electrode conductivity is improved, and the lithium-sulfur battery serving as the positive electrode has high specific capacity, high cycling stability and long service life.
The oxidized Mxene/S compound is a cathode material of a lithium-sulfur battery prepared by taking oxidized Mxene as a carrier and through an innovative method of chemically loading S through in-situ water bath. The compound comprises Mxene oxide and elemental sulfur, wherein the Mxene oxide is in an accordion shape or a single sheet shape, and the surface of the Mxene oxide contains a large amount of-OH and F-Ions; the Mxene oxide and sulfur are compounded by an in-situ water bath methodThe sulfur is uniformly dispersed on the surface of the oxidized Mxene in a nano-scale manner, and the mass content of S in the compound is 10-80%.
The invention is applied to a water bath method, and can successfully prepare the Mxene oxide/S compound by adopting a mode that an S source solution and HCl are instantly nucleated in situ at an F (fluorine) terminal of the Mxene oxide, wherein the Mxene oxide has extremely high conductivity and large surface area (500 parts)2/g～1600m2G), and the abundant groups on the surface can effectively adsorb polysulfide, and the groups on the surface in the preparation process can uniformly nucleate S on the surface by extremely small particles, and simultaneously, the purposes of high dispersion, high efficiency and chemical adsorption are achieved.
The method adopts ion exchange to compound a sulfur-containing group on the surface of the oxidized Mxene, and then links sulfur on the surface of the oxidized Mxene in situ through an oxidation reaction.
After the Mxene material is subjected to oxidation treatment, the material structure is more stable, the conductivity is further improved, and the electrochemical activity of the material is more favorably improved.
The oxidized Mxene is an accordion-shaped or single-sheet two-dimensional layered compound, wherein M represents a transition metal element, and X represents carbon or nitrogen.
Compared with the prior art, the invention has the following advantages:
1. the high-conductivity Mxene oxide is used as an S carrier, the preparation process is simple and safe, the production cost is low, and large-scale production is expected;
2. the surface of the oxidized Mxene material is provided with hydroxyl groups, has good wettability with liquid S, is convenient to dip S, and has F on the surface-Ion exchange or adsorption is generated by introducing S source, and S and an oxidized Mxene carrier can be chemically linked, so that the discharge intermediate product lithium polysulfide can be effectively adsorbed, and the shuttle effect is reduced;
3. the oxidized Mxene/S compound prepared by the invention has extremely high conductivity and large surface area, can uniformly nucleate S on the surface by extremely small particles, and simultaneously achieves the purposes of high dispersion, high efficiency and chemical adsorption;
4. the Mxene/S oxide compound prepared by the invention has great effect as the anode material of the lithium-sulfur batteryHigh specific capacity and cycling stability, especially can meet the high capacity operation of the battery under the condition of large current charging and discharging, and discharge at 2C and 5C, the maximum discharge capacity reaches 1600mAhg-1About, after 1000 cycles, the capacity can still be maintained at 800mAhg-1Left and right.
A in the MAX phase represents a main group element Si or Al.
The lithium-sulfur battery is a lithium-sulfur battery taking one or more of lithium hexafluorophosphate, lithium perchlorate, lithium hexafluoroarsenate, lithium trifluoromethanesulfonate and lithium bis (trifluoromethyl) imide sulfonate as lithium salts.
Drawings
FIG. 1 is an SEM image of the accordion-like Mxene powder obtained in test four-step one;
FIG. 2 is a surface oxidized Mxene powder obtained from run one step two;
FIG. 3 is an oxidized Mxene/S complex obtained from test step three;
FIG. 4 is a transmission electron micrograph of surface oxidized Mxene powder (accordion-like) from run two step two;
FIG. 5 is a transmission electron microscope image of the oxidized Mxene/S complex (sheet) obtained in the third step of the experiment;
FIG. 6 is a cyclical stability curve;
fig. 7 is a charge-discharge capacity curve diagram of the button cell prepared in the seventh test under different multiplying factors.
Detailed Description
The first embodiment is as follows: the embodiment is a preparation method of an oxidized Mxene/S compound applied to a lithium-sulfur battery anode, which is specifically carried out according to the following steps:
firstly, preparing Mxene powder, namely mixing MAX phase and HF solution, stirring for 6-40 h, naturally standing for layering, centrifuging the precipitate, repeatedly performing suction filtration and washing by using deionized water and alcohol until the filtrate is neutral, and drying to obtain accordion-shaped Mxene powder, wherein the volume ratio of the MAX phase to the HF solution is 1g (50m L-200 m L), and the mass concentration of the HF solution is 10-40%;
secondly, oxidation: will handConcertina-like Mxene powders in Ar and O2Is heat treated for 2 to 20 hours under the condition that the temperature is between 100 and 900 ℃, and then the mixture is treated with Ar and O2Cooling to room temperature under the mixed atmosphere of (1) to obtain surface-oxidized Mxene powder; ar and O2The volume fraction of oxygen in the mixed atmosphere is 1-10%;
and thirdly, a water bath method, namely adding the surface-oxidized Mxene powder into an aqueous solution containing an S source, uniformly stirring, dropwise adding a hydrochloric acid solution, and sequentially centrifuging, washing and drying to obtain the oxidized Mxene/S compound, wherein the mass ratio of the surface-oxidized Mxene to the S source in the aqueous solution containing the S source is 1 (1-10), the concentration of the aqueous solution containing the S source is 0.05 mol/L-2 mol/L, the concentration of the hydrochloric acid solution is 0.1 mol/L-3 mol/L, and the ratio of the S source to the amount of HCl substances in the hydrochloric acid solution is 1 (2.5-12).
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the MAX phase is Ti2AlC、Ti3AlC2Or Ti3SiC2. The rest is the same as the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: the S source is sodium thiosulfate or sodium sulfide. The others are the same as in the first or second embodiment.
The fourth concrete implementation mode: the embodiment is a preparation method of an oxidized Mxene/S compound applied to a lithium-sulfur battery anode, which is specifically carried out according to the following steps:
firstly, preparing Mxene powder, namely mixing MAX phase and HF solution, stirring for 6-40 h, naturally standing for layering, centrifuging a precipitate, repeatedly performing suction filtration and washing by deionized water and alcohol until a filtrate is neutral, drying to obtain accordion-shaped Mxene powder, dispersing the accordion-shaped Mxene powder in water, performing ultrasonic treatment for 0.5-10 h, standing, taking an upper suspension for centrifuging, and drying to obtain sheet Mxene powder, wherein the volume ratio of the MAX phase to the HF solution is 1g (50m L-200 m L), and the mass concentration of the HF solution is 10-40%;
secondly, oxidation: mixing the flaky Mxene powder in Ar and O2Is heat treated for 2 to 20 hours under the condition that the temperature is between 100 and 900 ℃, and then the mixture is treated with Ar and O2Cooling to room temperature under the mixed atmosphere of (1) to obtain surface-oxidized Mxene powder; ar and O2The volume fraction of oxygen in the mixed atmosphere is 1-10%;
and thirdly, a water bath method, namely adding the surface-oxidized Mxene powder into an aqueous solution containing an S source, uniformly stirring, dropwise adding a hydrochloric acid solution, and sequentially centrifuging, washing and drying to obtain the oxidized Mxene/S compound, wherein the mass ratio of the surface-oxidized Mxene to the S source in the aqueous solution containing the S source is 1 (1-10), the concentration of the aqueous solution containing the S source is 0.05 mol/L-2 mol/L, the concentration of the hydrochloric acid solution is 0.1 mol/L-3 mol/L, and the ratio of the S source to the amount of HCl substances in the hydrochloric acid solution is 1 (2.5-12).
The fifth concrete implementation mode: the fourth difference between this embodiment and the specific embodiment is that: the MAX phase is Ti2AlC、Ti3AlC2Or Ti3SiC2. The rest is the same as the fourth embodiment.
The sixth specific implementation mode: the fifth embodiment is different from the fifth embodiment in that: the S source is sodium thiosulfate or sodium sulfide. The rest is the same as the fifth embodiment.
The invention was verified with the following tests:
test one: the test is a preparation method of an oxidized Mxene/S compound applied to a lithium-sulfur battery anode, and is specifically carried out according to the following steps:
firstly, preparing Mxene powder, namely mixing MAX phase and HF solution, stirring for 20h, naturally standing for layering, centrifuging the precipitate, repeatedly performing suction filtration and washing by deionized water and alcohol until the filtrate is neutral, and drying to obtain accordion-shaped Mxene powder, wherein the volume ratio of the MAX phase to the HF solution is 1g:100m L, and the mass concentration of the HF solution is 20%;
secondly, oxidation: mixing accordion-like Mxene powder in Ar and O2Is carried out for 20 hours under the condition of 100 ℃ in the mixed atmosphere and in Ar and O2Cooling to room temperature under mixed atmosphere to obtain surface oxidized Mxene powder; ar and O2The volume fraction of oxygen in the mixed atmosphere of (2) is 1%;
and thirdly, a water bath method, namely adding the surface-oxidized Mxene powder into an aqueous solution containing an S source, uniformly stirring, dropwise adding a hydrochloric acid solution, and sequentially centrifuging, washing and drying to obtain the oxidized Mxene/S compound, wherein the mass ratio of the surface-oxidized Mxene to the S source in the aqueous solution containing the S source is 1:5, the concentration of the aqueous solution containing the S source is 0.5 mol/L, the concentration of the hydrochloric acid solution is 1 mol/L, and the mass ratio of the S source to the HCl in the hydrochloric acid solution is 1: 5.
The MAX phase is Ti3SiC2The oxidized Mxene/S compound is oxidized Ti3C2ene/S complex; the S source is sodium thiosulfate.
And (2) test II: the test is a preparation method of an oxidized Mxene/S compound applied to a lithium-sulfur battery anode, and is specifically carried out according to the following steps:
firstly, preparing Mxene powder, namely mixing MAX phase and HF solution, stirring for 40h, naturally standing for layering, centrifuging the precipitate, repeatedly performing suction filtration and washing by deionized water and alcohol until the filtrate is neutral, and drying to obtain accordion-shaped Mxene powder, wherein the volume ratio of the MAX phase to the HF solution is 1g:100m L, and the mass concentration of the HF solution is 40%;
secondly, oxidation: mixing accordion-like Mxene powder in Ar and O2Is heat treated for 1h under the condition of the temperature of 300 ℃, and Ar and O2Cooling to room temperature under the mixed atmosphere of (1) to obtain surface-oxidized Mxene powder; ar and O2The volume fraction of oxygen in the mixed atmosphere of (2) is 10%;
and thirdly, a water bath method, namely adding the surface-oxidized Mxene powder into an aqueous solution containing an S source, uniformly stirring, dropwise adding a hydrochloric acid solution, and sequentially centrifuging, washing and drying to obtain the oxidized Mxene/S compound, wherein the mass ratio of the surface-oxidized Mxene to the S source in the aqueous solution containing the S source is 1:10, the concentration of the aqueous solution containing the S source is 1 mol/L, the concentration of the hydrochloric acid solution is 1 mol/L, and the mass ratio of the S source to the HCl in the hydrochloric acid solution is 1: 5.
The MAX phase is Ti3AlC2The oxidized Mxene/S compound is oxidized Ti3C2ene/S complex; the S source is sodium sulfide.
And (3) test III: the test is a preparation method of an oxidized Mxene/S compound applied to a lithium-sulfur battery anode, and is specifically carried out according to the following steps:
firstly, preparing Mxene powder, namely mixing MAX phase and HF solution, stirring for 6h, naturally standing for layering, centrifuging a precipitate, repeatedly performing suction filtration and washing by deionized water and alcohol until a filtrate is neutral, drying to obtain accordion-shaped Mxene powder, dispersing the accordion-shaped Mxene powder in water, performing ultrasonic treatment for 2h, standing, centrifuging an upper suspension, and drying to obtain sheet Mxene powder, wherein the volume ratio of the MAX phase to the HF solution is 1g:100m L, and the mass concentration of the HF solution is 10%;
secondly, oxidation: mixing the flaky Mxene powder in Ar and O2Is carried out for 10 hours under the conditions of mixed atmosphere and temperature of 900 ℃, and Ar and O2Cooling to room temperature under the mixed atmosphere of (1) to obtain surface-oxidized Mxene powder; ar and O2The volume fraction of oxygen in the mixed atmosphere of (2) is 10%;
and thirdly, a water bath method, namely adding the surface-oxidized Mxene powder into an aqueous solution containing an S source, uniformly stirring, dropwise adding a hydrochloric acid solution, and sequentially centrifuging, washing and drying to obtain the oxidized Mxene/S compound, wherein the mass ratio of the surface-oxidized Mxene to the S source in the aqueous solution containing the S source is 1:1.5, the concentration of the aqueous solution containing the S source is 0.1 mol/L, the concentration of the hydrochloric acid solution is 0.5 mol/L, and the mass ratio of the S source to the HCl in the hydrochloric acid solution is 1: 5.
The MAX phase is Ti3AlC2Oxidizing the Mxene/S complex to Ti oxide3C2ene/S complex; the S source is sodium thiosulfate.
And (4) testing: the test is a preparation method of an oxidized Mxene/S compound applied to a lithium-sulfur battery anode, and is specifically carried out according to the following steps:
firstly, preparing Mxene powder, namely mixing MAX phase and HF solution, stirring for 10h, naturally standing for layering, centrifuging a precipitate, repeatedly performing suction filtration and washing by deionized water and alcohol until a filtrate is neutral, drying to obtain accordion-shaped Mxene powder, dispersing the accordion-shaped Mxene powder in water, performing ultrasonic treatment for 2h, standing, centrifuging an upper suspension, and drying to obtain sheet Mxene powder, wherein the volume ratio of the MAX phase to the HF solution is 1g:100m L, and the mass concentration of the HF solution is 20%;
secondly, oxidation: mixing the flaky Mxene powder in Ar and O2Is heat treated for 6 hours under the condition of the temperature of 300 ℃, and Ar and O2Cooling to room temperature under the mixed atmosphere of (1) to obtain surface-oxidized Mxene powder; ar and O2The volume fraction of oxygen in the mixed atmosphere of (2) is 5%;
and thirdly, a water bath method, namely adding the surface-oxidized Mxene powder into an aqueous solution containing an S source, uniformly stirring, dropwise adding a hydrochloric acid solution, and sequentially centrifuging, washing and drying to obtain the oxidized Mxene/S compound, wherein the mass ratio of the surface-oxidized Mxene to the S source in the aqueous solution containing the S source is 1:3, the concentration of the aqueous solution containing the S source is 0.2 mol/L, the concentration of the hydrochloric acid solution is 1 mol/L, and the mass ratio of the S source to the HCl in the hydrochloric acid solution is 1: 5.
The MAX phase is Ti2AlC, oxidizing Mxene/S compound to Ti oxide2A Cene/S complex; the S source is sodium thiosulfate.
FIG. 1 is an SEM image of the accordion-like Mxene powder obtained in the first step of the four tests, from which it can be clearly seen that Ti showing the accordion shape after etching by the HF solution2Cene。
FIG. 2 shows the surface-oxidized Mxene powder obtained in the second step of the test, and FIG. 3 shows the oxidized Mxene/S composite obtained in the third step of the test, in which Ti after oxidation is seen3C2The surface of the ene sheet layer is uniformly distributed with a layer of nano-scale particles, which indicates that TiO2The particles are successfully attached to Ti3C2ene surface layer, oxidized Ti after compounding with S3C2Between ene/S layersIs filled with S but still leaves a space to accommodate the volume expansion generated during discharge.
FIG. 4 is a transmission electron micrograph of the surface-oxidized Mxene powder (accordion-like) obtained in the second test, and FIG. 5 is a transmission electron micrograph of the oxidized Mxene/S composite (sheet-like) obtained in the second test, in which it is seen that the sheet is thin, the particulate oxide is present on the surface, and the Ti is accordion-like3C2In ene, each thick layer is composed of many single layers of Ti3C2ene.
And (5) testing: mixing the Mxene/S oxide compound prepared in the first test, carbon black and a binder, preparing slurry, coating the slurry on an aluminum foil, drying the aluminum foil for 24 hours at 50 ℃ to obtain a positive pole piece, assembling the positive pole piece into a button cell in a glove box by using lithium as a counter electrode, and performing electrochemical test; the solute of the binder is polyvinylidene fluoride, the solvent is N-methyl pyrrolidone, and the mass fraction of the solute is 10%; the mass ratio of the oxidized Mxene/S complex, carbon black and solute of the binder was 8:1: 1.
And (6) test six: mixing the Mxene/S oxide compound prepared in the fourth test, carbon black and a binder, preparing slurry, coating the slurry on an aluminum foil, drying the aluminum foil for 24 hours at 50 ℃ to obtain a positive pole piece, assembling the positive pole piece into a button cell in a glove box by using lithium as a counter electrode, and performing electrochemical test; the solute of the binder is polyvinylidene fluoride, the solvent is N-methyl pyrrolidone, and the mass fraction of the solute is 10%; the mass ratio of the oxidized Mxene/S complex, carbon black and solute of the binder was 8:1: 1.
Test seven: mixing the Mxene/S oxide compound prepared in the third test, carbon black and a binder, preparing slurry, coating the slurry on an aluminum foil, drying the aluminum foil for 24 hours at 50 ℃ to obtain a positive pole piece, assembling the positive pole piece into a button cell in a glove box by using lithium as a counter electrode, and performing electrochemical test; the solute of the binder is polyvinylidene fluoride, the solvent is N-methyl pyrrolidone, and the mass fraction of the solute is 10%; the mass ratio of the oxidized Mxene/S complex, carbon black and solute of the binder was 8:1: 1.
FIG. 6 is a cycle stability curve, and curve 1 shows the 5C rate of the button cell prepared in the sixth testThe lower charge, curve 2 shows that the button cell prepared in the sixth test is discharged at the rate of 5C, curve 3 shows that the button cell prepared in the fifth test is discharged at the rate of 2C, and curve 4 shows that the button cell prepared in the fifth test is charged at the rate of 5C, and as seen from the figure, under larger current, the two button cells show good circulation stability, and the initial capacity is 1500mAhg-1After 1000 cycles, 800mAhg remained-1Higher capacity is still maintained.
FIG. 7 is a graph showing the charge and discharge capacity of the button cell prepared in test seven at different rates, wherein curve 1 is 0.5C, curve 2 is 1C, curve 3 is 2C, and curve 4 is 5C, and the single-sheet Ti oxide is shown in the graph3C2The multiplying power performance of the ene/S composite material as the cathode material is that the capacity of the material is gradually reduced in the process that the current is increased from small to small, and when the current is increased back to 0.5C, the capacity of the material is immediately restored to the initial level, which shows that the material has high reaction power, and the charging and discharging curves are basically overlapped, which shows that the cycle efficiency of the material is good.
Claims (2)
1. A preparation method of an oxidized Mxene/S compound applied to a lithium-sulfur battery anode is characterized in that the preparation method of the oxidized Mxene/S compound applied to the lithium-sulfur battery anode is carried out according to the following steps:
firstly, preparing Mxene powder, namely mixing MAX phase and HF solution, stirring for 6-40 h, naturally standing for layering, centrifuging the precipitate, repeatedly performing suction filtration and washing by using deionized water and alcohol until the filtrate is neutral, and drying to obtain accordion-shaped Mxene powder, wherein the volume ratio of the MAX phase to the HF solution is 1g (50m L-200 m L), the mass concentration of the HF solution is 10-40%, and the MAX phase is Ti2AlC、Ti3AlC2Or Ti3SiC2；
Secondly, oxidation: mixing accordion-like Mxene powder in Ar and O2Is heat treated for 2 to 20 hours under the condition that the temperature is between 100 and 900 ℃, and then the mixture is treated with Ar and O2Cooling to room temperature under the mixed atmosphere of (1) to obtain surface-oxidized Mxene powder; ar and O2Mixed atmosphere of (2)The volume fraction of the medium oxygen is 1-10%;
and thirdly, a water bath method, namely adding the surface-oxidized Mxene powder into an aqueous solution containing an S source, uniformly stirring, dropwise adding a hydrochloric acid solution, and sequentially centrifuging, washing and drying to obtain the oxidized Mxene/S compound, wherein the mass ratio of the surface-oxidized Mxene to the S source in the aqueous solution containing the S source is 1 (1-10), the concentration of the aqueous solution containing the S source is 0.05 mol/L-2 mol/L, the concentration of the hydrochloric acid solution is 0.1 mol/L-3 mol/L, and the ratio of the S source to the amount of HCl substances in the hydrochloric acid solution is 1 (2.5-12).
2. The method of claim 1, wherein the source of S is sodium thiosulfate or sodium sulfide.
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| CN108516528B (en) * | 2018-04-12 | 2019-11-08 | 大连理工大学 | A kind of three dimensional composite structure and its universal synthesis method based on three-dimensional MXene |
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