CN106450205B - Two-dimensional transition group metal carbon/nitride and nano sulfur particle composite material and preparation and application thereof - Google Patents

Two-dimensional transition group metal carbon/nitride and nano sulfur particle composite material and preparation and application thereof Download PDF

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CN106450205B
CN106450205B CN201610951729.6A CN201610951729A CN106450205B CN 106450205 B CN106450205 B CN 106450205B CN 201610951729 A CN201610951729 A CN 201610951729A CN 106450205 B CN106450205 B CN 106450205B
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nitride
dimensional transition
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杨建�
唐欢
杜飞
潘丽梅
冯永宝
丘泰
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Nanjing Tech University
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Abstract

The invention relates to a two-dimensional transition metal carbon/nitride and nano sulfur particle composite material, and preparation and application thereof. The composite material is composed of a two-dimensional transition metal carbon/nitride MXene nanosheet and nano sulfur particles, wherein the nano sulfur particles grow in situ on the surface of the two-dimensional transition metal carbon/nitride MXene nanosheet and are expressed as S @ MXene. Mixing stable suspension of single-layer or few-layer two-dimensional transition metal carbon/nitride MXene nanosheets with sodium thiosulfate or sodium polysulfide solution, adopting formic acid as a reducing agent to enable nano sulfur generated by reaction to uniformly grow on the surface of the two-dimensional MXene nanosheets, and neutralizing, washing and centrifuging to obtain the two-dimensional transition metal carbon/nitride and nano sulfur particle composite material which is used as a lithium-sulfur battery anode. The high-conductivity two-dimensional transition metal carbon/nitride MXene nanosheet carrier is uniformly compounded with the nano sulfur particles, a binder and a conductive agent are not required to be introduced, the high-conductivity two-dimensional transition metal carbon/nitride MXene nanosheet carrier serving as the positive electrode of the lithium-sulfur battery has excellent electrochemical performance, the process is simple, and the requirement of mass production can be met.

Description

Two-dimensional transition group metal carbon/nitride and nano sulfur particle composite material and preparation and application thereof
Technical Field
The invention belongs to the technical field of nano composite materials, and particularly relates to a two-dimensional transition group metal carbon/nitride and nano sulfur particle composite material, and preparation and application thereof.
Background
The lithium-sulfur (Li-S) battery is a novel high-capacity energy storage system with great development prospect, has the outstanding advantages of high theoretical energy density, low cost, environmental protection and the like, and has the theoretical specific capacity of 1675mAh g-1The theoretical specific energy density of the constructed lithium secondary battery system can reach 2600Wh kg-1The lithium ion battery is 7 times of the current commercial lithium ion battery, and has wide application prospect in the emerging technical fields of power batteries for new energy automobiles and the like. However, the problems that the sulfur conductivity of the positive active material is poor, the volume change is large in the charging and discharging process, and the lithium polysulfide formed in the process is easy to be separated and dissolved in the electrolyte to cause the shuttle effect are needed to be solved.
In view of the above problems, scientists and engineers have conducted a great deal of research and study on lithium-sulfur battery positive electrode materials, and carbon, conductive polymers, metal oxides, and the like are used as sulfur positive electrode carriers to form composite positive electrodes. MXene is a new two-dimensional transition metal carbon/nitride with a chemical formula of Mn+1XnTx(M is an early transition metal element, X is carbon or/and nitrogen, n is 1, 2 or 3, T represents a surface functional group such as-F, -O or-OH, etc.)n+1XnThe nano-sheet is formed by alternately stacking n layers of X atoms and n +1 layers of M atoms, wherein the M atom layer is positioned on the outermost layer). It is prepared from ternary laminated compound MAX phase (chemical formula is M)n+1AXnWherein M, X, n has the meaning of Mn+1XnTxThe same as in the above, A is a main group element III and IV) to selectively corrode atoms of the A layer. MXene prepared at present has Ti3C2Tx、Ti2CTx、(Ti0.5,Nb0.5)2CTx、(V0.5,Cr0.5)3C2Tx、Ti3CNTx、Ta4C3Tx、V2CTx、Nb2CTx、Nb4C3Tx、(Nb0.8,Ti0.2)4C3Tx、(Nb0.8,Zr0.2)4C3Tx、Mo2TiC2Tx、Mo2Ti2C3Tx、Mo2CTx、Cr2TiC2Tx、Zr3C2Tx、Ti4N3Tx[Anasori B,Xie Y,BeidaghiM,et al.Two-Dimensional,Ordered,Double Transition Metals Carbides(MXenes),ACSNano,2015,9(10):9507-9516.Zhou J,Zha X-H,Chen F-Y,et al.A Two-DimensionalZirconium Carbide by Selective Etching of Al3C3from Nanolaminated Zr3Al3C5,Angew Chem Int Edit,2016,55(16):5008-5013.]。Ti3C2TxIs currently the most studied MXene. MXene has unique Two-dimensional morphology, larger comparative area and good electric conduction and mechanical properties, so the MXene has wide application prospect in the fields of energy storage, catalysis, composite Materials, environmental management and the like [ Naguib M, Mochalin V N, Barsum MW, et al.25th analytical apparatus: MXenes: A New Family of Two-dimensional Materials, Advanced Materials,2014,26(7): 992-class 1005).]In particular, excellent performance has been shown as electrode materials for electrochemical energy storage devices such as supercapacitors and lithium Ion Batteries [ Naguib M, Halim J, Lu J, et al, New Two-Dimensional Niobium and variable carbon materials advances materials for Li-Ion Batteries, Journal of the American Chemical Society,2013,135(43): 15966-15969. Lukatsiya M R, Mashtalir O, Ren C E, et al, Caposition and High volume catalysis of Two-Dimensional titanium carbide, Science 1505, 2013,341(6153): 1502-.]. In addition, the outer surface of the MXene nanosheet is a transition metal atomic layer, and the surface of the MXene nanosheet has a surface chemical environment similar to that of graphene oxide, so that the MXene nanosheet is a novel positive electrode sulfur active substance carrier material of a Li-S battery. At present, hydrofluoric acid is widely adopted to selectively corrode an A atomic layer, and then a series of procedures such as intercalation, stripping and the like are carried outMXene suspensions were prepared [ Naguib, M.et al. two-dimensional nanocrystalline by epitaxy of Ti3AlC2.Adv.Mater,2011,23:4248–4253.]。
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a two-dimensional transition group metal carbon/nitride and nano sulfur particle composite material; the invention also aims to provide a preparation method of the material, which has simple process and can meet the requirement of mass production; it is also an object of the present invention to provide the use of the above materials.
The technical scheme of the invention is as follows: a two-dimensional transition group metal carbon/nitride and nano sulfur particle composite material is characterized in that: the composite material is composed of novel two-dimensional transition metal carbon/nitride MXene nanosheets and nano sulfur particles, wherein the nano sulfur particles generated by reduction grow on the surfaces of the two-dimensional transition metal carbon/nitride MXene nanosheets in situ and are uniformly dispersed, and the nano sulfur particles are expressed as S @ MXene.
Preferably, the nano sulfur particle size is 20-500 nm, and the mass content of sulfur in S @ MXene is 10-80 wt%.
The two-dimensional transition metal carbon/nitride MXene is preferably: ti3C2Tx、Ti2CTx、Ti3CNTx、(Ti0.5,Nb0.5)2CTx、(V0.5,Cr0.5)3C2Tx、Ta4C3Tx、V2CTx、Nb2CTx、Nb4C3Tx、(Nb0.8,Ti0.2)4C3Tx、(Nb0.8,Zr0.2)4C3Tx、Mo2TiC2Tx、Mo2Ti2C3Tx、Mo2CTx、Cr2TiC2Tx、Zr3C2TxOr Ti4N3Tx。
The invention also provides a preparation method of the two-dimensional transition group metal carbon/nitride and nano sulfur particle composite material, which comprises the following specific steps:
1) mixing a sodium polysulfide or sodium thiosulfate solution with a two-dimensional transition metal carbon/nitride MXene nanosheet suspension to obtain a mixed suspension;
2) slowly dripping a formic acid solution into the mixed suspension prepared in the step 1) while stirring by magnetic force;
3) after complete reaction, neutralizing by using ammonia water until the pH value of the suspension is 6.5-7.3, and centrifuging;
4) washing the precipitate obtained by centrifugation with deionized water, and centrifuging to obtain the two-dimensional transition metal carbon/nitride and nano sulfur particle composite material.
Preferably, the two-dimensional transition metal carbon/nitride MXene nanosheet suspension is prepared by the following method, and the specific steps are as follows: dissolving LiF in hydrochloric acid, slowly adding a ternary layered compound MAX powder into the solution, stirring and reacting at 30-40 ℃, washing and centrifuging a reaction product by using ethanol until the pH value of supernatant is 6.2-6.5, adding a dried solid sample into deionized water, ultrasonically stripping under the protection of flowing argon, and centrifuging to obtain a few-layer or single-layer two-dimensional transition group metal carbon/nitride MXene nanosheet suspension; the concentration of the suspension is 0.2-1.5 mg/ml.
Preferably, the stirring speed of the stirring reaction at 30-40 ℃ is 200-500rpm, and the stirring time is 6-24 h; the ultrasonic frequency of the ultrasonic stripping is 40-100kHz, and the ultrasonic stripping time is 0.5-1.5 h; the rotating speed of centrifugation after ultrasonic stripping is 2500-4000 rpm, and the centrifugation time is 0.5-1.5 h.
Preferably, the concentration of the sodium thiosulfate or sodium polysulfide solution is 0.2-1 mol/L; the concentration of formic acid is 1-3 mol/L, the dripping speed of formic acid is 0.1-0.3 ml/s, the solution is continuously dripped until the pH value is 6-6.8 after the solution is completely changed into milk white, and then ammonia water is used for neutralization; the concentration of the ammonia water is 0.2-1 mol/L.
The invention also provides application of the two-dimensional transition group metal carbon/nitride and nano sulfur particle composite material in a lithium sulfur battery anode.
The two-dimensional transition group metal carbon/nitride and nano sulfur particle composite material is used for the Li-S battery anode, a conductive agent, a binder and paste can be added into a dried two-dimensional transition group metal carbon/nitride and nano sulfur particle composite material according to the traditional process, and then the dried two-dimensional transition group metal carbon/nitride and nano sulfur particle composite material is coated on an aluminum foil, or the slurry-shaped two-dimensional transition group metal carbon/nitride and nano sulfur particle composite material can be directly coated on the aluminum foil or the suspension of the slurry-shaped two-dimensional transition group metal carbon/nitride and nano sulfur particle composite material is filtered on a PP battery diaphragm to prepare the anode. As one of the preferable embodiments, the slurry-like two-dimensional transition group metal carbon/nitride and nano sulfur particle composite obtained by centrifugation is directly coated on an aluminum foil current collector (the coating thickness is 10-40 μm), or the washed two-dimensional transition group metal carbon/nitride and nano sulfur particle composite suspension is suction-filtered on a PP battery diaphragm to obtain a composite positive electrode/diaphragm integrated structure (the positive electrode thickness is 20-50 μm), and the button 2032 lithium sulfur battery can be assembled after vacuum drying for 12-24 hours.
Has the advantages that:
1. the method comprises the steps of uniformly mixing a sodium polysulfide or sodium thiosulfate solution with a two-dimensional transition metal carbon/nitride MXene nanosheet suspension, then dropwise adding a formic acid reducing agent, and growing the nano sulfur particles generated by reduction in situ on the surface of the two-dimensional transition metal carbon/nitride MXene. In the prepared two-dimensional transition group metal carbon/nitride/nano sulfur particle composite material, the nano sulfur particles and the two-dimensional transition group metal carbon/nitride MXene nanosheets are compounded and uniformly dispersed, the combination is firm, the contact area is large, the whole preparation process is simple, and the sulfur fixing effect of the two-dimensional transition group metal carbon/nitride MXene nanosheets can be fully exerted.
2. The two-dimensional transition metal carbon/nitride and nano sulfur particle composite material is used as the Li-S battery anode, and the two-dimensional transition metal carbon/nitride MXene with excellent conductivity, larger comparative area and unique surface chemical environment is used as a carrier of a sulfur active substance, so that the conductivity of the sulfur anode can be improved, a unique sulfur fixing effect can be achieved, the problem of shuttle effect of lithium polysulfide can be effectively inhibited, and the cycle performance of the battery and the utilization rate of the sulfur active substance can be improved.
3. According to the invention, the slurry-like two-dimensional transition group metal carbon/nitride and nano sulfur particle composite material is directly coated on the aluminum foil current collector, or the suspension of the composite material is subjected to suction filtration on the PP battery diaphragm to prepare the anode, so that the introduction of a binder and a conductive agent can be avoided, the internal resistance of the battery is further reduced, and meanwhile, the process is simple and is easily compatible with the existing lithium sulfur battery production process and equipment.
Drawings
FIG. 1 is a two-dimensional transition metal carbide Ti prepared in example 13C2And a two-dimensional transition metal carbide Ti with a sulfur content of 70 wt%3C2XRD patterns of the composite with nano-sulfur particles;
FIG. 2 is a two-dimensional transition metal carbide Ti with a sulfur content of 70 wt.% prepared in example 13C2Scanning electron microscope images of the composite material with the nano sulfur particles;
FIG. 3 is a two-dimensional transition metal carbide Ti with a sulfur content of 70 wt.% prepared in example 23C2Scanning electron microscope images of the composite material with the nano sulfur particles;
FIG. 4 is a two-dimensional transition metal carbide Ti with a sulfur content of 70 wt.% prepared in example 53Scanning electron microscope images of the CN and nano sulfur particle composite material;
FIG. 5 is a two-dimensional transition metal carbide Ti of 70 wt.% sulfur content prepared in example 13C2The nano sulfur particle composite material is used as a first charge-discharge curve of the lithium sulfur battery anode under the multiplying power of 0.5C;
FIG. 6 shows two-dimensional transition metal carbide Ti in examples 1 and 2 of the present invention3C2And the composite material with the nano sulfur particles is used as the positive electrode of the lithium sulfur battery for 100 times of cycle stability tests at 0.5C rate.
Detailed Description
The technical scheme of the invention is clearly and completely described by combining the specific embodiment. It should be noted that the following description is only a preferred example of the present invention and is not intended to limit the present invention, and those skilled in the art can make various modifications and changes. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Example 1
(1) Two-dimensional transition metal carbide Ti3C2Preparation of nanosheet suspension: 10mL of dilute HCl with the concentration of 6M and 0.666g of LiF are added into a plastic bottle, and 1g of ternary layered carbide Ti which is sieved by a 400-mesh sieve is slowly added under magnetic stirring3AlC2Powder, and magnetic stirring is carried out for 22 hours at the rotating speed of 250r.p.m at the temperature of 35 ℃, products are washed and centrifuged by ethanol after the reaction is finished until the pH value of supernatant is 6.2, 0.1g of the dried precipitate is added into 50mL of deionized water at room temperature, ultrasonic stripping is carried out for 1 hour at the ultrasonic frequency of 40kHz under the protection of flowing argon, and then the mixture is centrifuged for 1 hour at the rotating speed of 3500r.p.m to obtain few-layer or single-layer two-dimensional transition group metal carbide Ti3C2A stable suspension of nanoplatelets at a concentration of 0.6 mg/ml.
(2) Two-dimensional transition metal carbide Ti3C2Preparing a composite material with the nano sulfur particles: 11mL of 0.2mol L-1Sodium polysulfide solution and 100mL Ti3C2TxMixing the nano-sheet suspension, and stirring for 10min at the speed of 250r/min on a magnetic stirrer; 2mol of L-1Dripping formic acid solution into the mixed solution at the speed of 0.1ml/s until the solution is completely milky, continuing dripping formic acid until the pH value is 6.5, and growing nano sulfur particles generated by the reaction on Ti3C2TxAnd (3) the surface of the nanosheet. With 0.5mol L-1Neutralizing with ammonia water to pH 7, centrifuging, washing the precipitate with deionized water, and centrifuging to obtain clay-like two-dimensional transition metal carbide Ti with sulfur content of 70 wt%3C2With the nano-sulfur particle composite (fig. 1, fig. 2), the sulfur particle size is in the range of 20 to 150 nm, and the XRD pattern of the composite of the following examples is substantially identical to that of example 1.
(3) And (3) electrochemical performance testing: a clay-like two-dimensional transition metal carbide Ti3C2The nano sulfur particle composite material is uniformly coated on an aluminum foil current collector by a coating machine (the coating thickness is 1)7 μm), vacuum drying for 24h, then compacting, and cutting into pieces to be used as a positive electrode; a lithium plate is taken as a negative electrode, a Celgard diaphragm is adopted, and the electrolyte is selected to have the concentration of 1mol L-1LiTFSI/DOL-DME (volume ratio 1:1) and 0.1mol L of-1LiNO of3And assembling the button lithium-sulfur battery. Constant current charging and discharging are carried out under the multiplying power of 0.5C, and the first discharge capacity is 1035mAh g-1(FIG. 4), the discharge capacity after 100 cycles was 907mAh g-1。
Example 2
(1) Two-dimensional transition metal carbide Ti3C2Preparation of nanosheet suspension: 10mL of dilute HCl with the concentration of 6M and 0.666g of LiF are added into a plastic bottle, and 1g of ternary layered carbide Ti which is sieved by a 400-mesh sieve is slowly added under magnetic stirring3AlC2Powder is stirred for 15 hours under the magnetic force at the rotating speed of 250r.p.m at the temperature of 30 ℃, after the reaction is finished, the product is washed by ethanol and centrifuged until the pH value of supernatant is 6.3, 0.2g of the dried precipitate at room temperature is added into 150mL of deionized water, ultrasonic stripping is carried out for 1 hour under the ultrasonic frequency of 40kHz under the protection of flowing argon, and then the mixture is centrifuged for 1 hour at the rotating speed of 3500r.p.m to obtain few-layer or single-layer two-dimensional transition group metal carbide Ti3C2A stable suspension of nanoplatelets at a concentration of 0.2 mg/ml.
(2) Two-dimensional transition metal carbide Ti3C2Preparing a composite material with the nano sulfur particles: 3.6mL of 0.8mol L-1Sodium thiosulfate solution and 200mL Ti3C2TxMixing the nano-sheet suspension, and stirring for 10min at the speed of 250r/min on a magnetic stirrer; 2mol of L-1Dripping formic acid solution into the mixed solution at the speed of 0.2ml/s until the solution is completely milky, continuing dripping formic acid until the pH value is 6.5, and growing nano sulfur particles generated by the reaction on Ti3C2TxAnd (3) the surface of the nanosheet. With 0.2mol of L-1Neutralizing with ammonia water to pH 7.1, centrifuging, washing the precipitate with deionized water to obtain Ti as the two-dimensional transition metal carbide with sulfur content of 70 wt%3C2And the size of the suspension of the nano sulfur particle composite material is 50-500 nm.
(3) And (3) electrochemical performance testing: two-dimensional transition metal carbide Ti3C2Performing suction filtration on the suspension and the nano sulfur particle composite material on a PP (polypropylene) battery diaphragm to obtain a composite anode/diaphragm integrated structure (shown in figure 3), wherein the thickness of the composite anode is 45 mu m, a cut piece is taken as an anode after vacuum drying for 24h, a lithium piece is taken as a cathode, a Celgard diaphragm is adopted, and the concentration of electrolyte is 1mol L- 1LiTFSI/DOL-DME (volume ratio 1:1) and 0.1mol L of-1LiNO of3And assembling the button lithium-sulfur battery. Constant current charge and discharge are carried out at a multiplying power of 0.5C, and the first discharge capacity is 1005mAh g-1Discharge capacity after 100 cycles was 621mAh g-1。
Example 3
(1) Two-dimensional transition metal carbide Ti3C2Preparation of nanosheet suspension: 10mL of dilute HCl with the concentration of 6M and 0.666g of LiF are added into a plastic bottle, and 1g of ternary layered carbide Ti which is sieved by a 400-mesh sieve is slowly added under magnetic stirring3AlC2Powder is stirred for 24 hours under the magnetic force at the rotating speed of 300r.p.m at the temperature of 35 ℃, after the reaction is finished, the product is washed by ethanol and centrifuged until the pH value of supernatant is 6.2, 0.3g of the dried precipitate is added into 50mL of deionized water at room temperature, ultrasonic stripping is carried out for 1 hour under the ultrasonic frequency of 80kHz under the protection of flowing argon, and then the mixture is centrifuged for 1 hour at the rotating speed of 3000r.p.m to obtain few-layer or single-layer two-dimensional transition group metal carbide Ti3C2A stable suspension of nanoplatelets at a concentration of 1.1 mg/ml.
(2) Two-dimensional transition metal carbide Ti3C2Preparing a composite material with the nano sulfur particles: 8.6mL of 0.4mol L-1Sodium thiosulfate solution with 100mL Ti3C2TxMixing the nano-sheet suspension, and stirring for 10min at the speed of 250r/min on a magnetic stirrer; 2mol of L-1Dripping formic acid solution into the mixed solution at the speed of 0.1ml/s until the solution is completely milky, continuing dripping formic acid until the pH value is 6.5, and growing nano sulfur particles generated by the reaction on Ti3C2TxAnd (3) the surface of the nanosheet. With 0.7mol of L-1Neutralizing with ammonia water until pH of suspension is 6.8, centrifuging, and precipitatingThe starch is washed by deionized water again and centrifuged to obtain clay-like two-dimensional transition metal carbide Ti with the sulfur content of 50 wt%3C2With the nano sulfur particle composite material, the size of the sulfur particle is 20 to 200 nanometers.
(3) And (3) electrochemical performance testing: a clay-like two-dimensional transition metal carbide Ti3C2Uniformly coating the nano sulfur particle composite material on an aluminum foil current collector by adopting a coating machine (the coating thickness is 20 mu m), carrying out vacuum drying for 24h, then compacting, and cutting pieces to be used as a positive electrode; a lithium plate is taken as a negative electrode, a Celgard diaphragm is adopted, and the electrolyte is selected to have the concentration of 1mol L-1LiTFSI/DOL-DME (volume ratio 1:1) and 0.1mol L of-1LiNO of3And assembling the button lithium-sulfur battery. Constant current charging and discharging are carried out under the multiplying power of 0.5C, and the first discharge capacity is 1060mAh g-1And the discharge capacity after 100 cycles is 859mAh g-1。
Example 4
(1) Two-dimensional transition metal carbide Ti3C2Preparation of nanosheet suspension: 10mL of dilute HCl with the concentration of 6M and 0.666g of LiF are added into a plastic bottle, and 1g of ternary layered carbide Ti which is sieved by a 400-mesh sieve is slowly added under magnetic stirring3AlC2Powder, and magnetic stirring is carried out for 20 hours at the rotating speed of 400r.p.m at the temperature of 40 ℃, after the reaction is finished, the product is washed by ethanol and centrifuged until the pH value of supernatant is 6.2, 0.1g of the dried precipitate is added into 50mL of deionized water at room temperature, ultrasonic stripping is carried out for 1 hour at the ultrasonic frequency of 50kHz under the protection of flowing argon, and then the mixture is centrifuged for 1 hour at the rotating speed of 3000r.p.m to obtain few-layer or single-layer two-dimensional transition group metal carbide Ti3C2A stable suspension of nanoplatelets at a concentration of 0.7 mg/ml.
(2) Two-dimensional transition metal carbide Ti3C2Preparing a composite material with the nano sulfur particles: 2.7mL of 0.2mol L-1Sodium thiosulfate solution with 100mL Ti3C2TxMixing the nano-sheet suspension, and stirring for 10min at the speed of 250r/min on a magnetic stirrer; 2mol of L-1The formic acid solution was added dropwise to the above mixed solution at a rate of 0.3ml/s until the solution was completely milky white, followed byFormic acid is continuously dripped until the pH value is 6.4, and the nano sulfur particles generated by the reaction grow on Ti3C2TxAnd (3) the surface of the nanosheet. With 1mol L-1Neutralizing with ammonia water to pH 6.9, centrifuging, washing the precipitate with deionized water, and centrifuging to obtain clay-like two-dimensional transition metal carbide Ti with sulfur content of 20 wt%3C2With the nano sulfur particle composite material, the size of the sulfur particle is 20 to 200 nanometers.
(3) And (3) electrochemical performance testing: a clay-like two-dimensional transition metal carbide Ti3C2Uniformly coating the nano sulfur particle composite material on an aluminum foil current collector by adopting a coating machine (the thickness of the coating is 19 mu m), carrying out vacuum drying for 24h, and then compacting and cutting into pieces to be used as a positive electrode; a lithium plate is taken as a negative electrode, a Celgard diaphragm is adopted, and the electrolyte is selected to have the concentration of 1mol L-1LiTFSI/DOL-DME (volume ratio 1:1) and 0.1mol L of-1LiNO of3And assembling the button lithium-sulfur battery. Constant current charging and discharging are carried out under the multiplying power of 0.5C, and the first discharge capacity is 1275mAh g-1And the discharge capacity after 100 cycles is 1012mAh g-1。
Example 5
(1) Two-dimensional transition metal carbide Ti3Preparation of CN nanosheet suspension: 10mL of diluted HCl with the concentration of 6M and a certain amount of LiF are added into a plastic bottle, and 1g of ternary layered carbide Ti which is sieved by a 400-mesh sieve is slowly added under magnetic stirring3AlCN powder is stirred for 6 hours at the rotating speed of 400r.p.m at the temperature of 30 ℃, after the reaction is finished, the product is washed by ethanol and centrifuged until the pH value of supernatant is 6.5, the precipitate is dried at room temperature, 0.1g of the dried precipitate is added into 50mL of deionized water, under the protection of flowing argon, ultrasonic stripping is carried out for 1.3 hours at the ultrasonic frequency of 60kHz, and then the precipitate is centrifuged for 0.5 hour at the rotating speed of 3000r.p.m to obtain few-layer or single-layer two-dimensional transition metal carbide Ti3A stable suspension of CN nanoplatelets at a concentration of 1.2 mg/ml.
(2) Two-dimensional transition metal carbide Ti3Preparing a CN and nano sulfur particle composite material: 14.6mL0.6molL-1Sodium thiosulfate solution with 100mL Ti3CNTxMixing the nano-sheet suspension, and stirring at 250r/min on a magnetic stirrer10 min; 2mol of L-1Dripping formic acid solution into the mixed solution at the speed of 0.2ml/s until the solution is completely milky, continuing dripping formic acid until the pH value is 6.6, and growing nano sulfur particles generated by the reaction on Ti3C2TxAnd (3) the surface of the nanosheet. With 0.5mol L-1Neutralizing with ammonia water to pH 7.2, centrifuging, washing the precipitate with deionized water, and centrifuging to obtain clay-like two-dimensional transition metal carbide Ti with sulfur content of 70 wt%3CN is compounded with nanometer sulfur particle, and the size of the sulfur particle is 20-300 nm.
(3) And (3) electrochemical performance testing: two-dimensional transition metal carbide Ti3Uniformly coating CN and nano sulfur particle composite material on an aluminum foil current collector by using a coating machine (the coating thickness is 14 mu m), drying for 24h in vacuum, then cutting pieces as a positive electrode, taking a lithium piece as a negative electrode, adopting a Celgard diaphragm, and selecting electrolyte with the concentration of 1mol L-1LiTFSI/DOL-DME (volume ratio 1:1) and 0.1mol L of-1LiNO of3And assembling the button lithium-sulfur battery. Constant current charging and discharging are carried out at the multiplying power of 0.5C, and the first discharge capacity is 930mAh g-1The discharge capacity after 100 cycles was 812mAh g-1。
Example 6
(1) Two-dimensional transition metal carbide Ti3Preparation of CN nanosheet suspension: 10mL of dilute HCl with the concentration of 6M and 0.662g of LiF are added into a plastic bottle, and 1g of ternary layered carbide Ti which is sieved by a 400-mesh sieve is slowly added under magnetic stirring3AlCN powder, stirring for 8 hours under the magnetic force at the rotating speed of 250r.p.m at the temperature of 30 ℃, washing and centrifuging a product by using ethanol after the reaction is finished until the pH value of supernatant is 6.6, drying a precipitate at room temperature, adding 0.2g of the dried precipitate into 150mL of deionized water, ultrasonically stripping for 1 hour under the ultrasonic frequency of 80kHz under the protection of flowing argon, and then centrifuging for 1 hour at the rotating speed of 3000r.p.m to obtain few-layer or single-layer two-dimensional transition group metal carbide Ti3A stable suspension of CN nanoplatelets at a concentration of 1.8 mg/ml.
(2) Two-dimensional transition metal carbide Ti3Preparing a CN and nano sulfur particle composite material: 16.4mL0.8molL-1Sodium thiosulfate solution and 100mL Ti3Mixing the CN nano-sheet suspension, and stirring for 10min at the speed of 250r/min on a magnetic stirrer; 3mol of L-1Dripping formic acid solution into the mixed solution at the speed of 0.2ml/s until the solution is completely milky, continuing dripping formic acid until the pH value is 6.5, and growing nano sulfur particles generated by the reaction on Ti3CN nanosheet surface. With 0.2mol of L-1Neutralizing with ammonia water to pH 7.1, centrifuging, washing the precipitate with deionized water to obtain Ti as the two-dimensional transition metal carbide with sulfur content of 70 wt%3CN and nano sulfur particle composite material, and the sulfur particle size is 20-400 nm.
(3) And (3) electrochemical performance testing: two-dimensional transition metal carbide Ti3Performing suction filtration on the CN and nano sulfur particle composite material suspension on a PP battery diaphragm to obtain a composite anode/diaphragm integrated structure, wherein the thickness of the composite anode is 21 mu m, a cut piece is taken as an anode after vacuum drying for 24h, a lithium piece is taken as a cathode, a Celgard diaphragm is adopted, and the concentration of electrolyte is 1mol L-1LiTFSI/DOL-DME (volume ratio 1:1) and 0.1mol L of-1LiNO of3And assembling the button lithium-sulfur battery. Constant current charging and discharging are carried out under the multiplying power of 0.5C, and the first discharge capacity is 1057mAh g-1And the discharge capacity after 100 cycles is 846mAh g-1。
Example 7
(1) Two-dimensional transition metal carbide Ti2Preparation of a C nanosheet suspension: 10mL of diluted HCl with the concentration of 6M and a certain amount of LiF are added into a plastic bottle, and 1g of ternary layered carbide Ti which is sieved by a 400-mesh sieve is slowly added under magnetic stirring2AlC powder is stirred for 15 hours at the temperature of 40 ℃ at 220r.p.m, after the reaction is finished, the product is washed by ethanol and centrifuged until the pH value of supernatant is 6.3, 0.2g of the dried precipitate at room temperature is added into 50mL of deionized water, under the protection of flowing argon, ultrasonic stripping is carried out for 1.25 hours at the ultrasonic frequency of 80kHz, and then the precipitate is centrifuged for 1 hour at the rotating speed of 3000r.p.m to obtain few-layer or single-layer two-dimensional transition group metal carbide Ti2And C nano-sheet stable suspension, wherein the concentration of the suspension is 0.9 mg/ml.
(2) Two-dimensional transition metal carbide Ti2C and nano sulfur particle composite materialThe preparation of (1): 21.1mL of 0.2mol L-1Sodium thiosulfate solution with 100mL Ti2CTxMixing the nano-sheet suspension, and stirring for 10min at the speed of 250r/min on a magnetic stirrer; 1mol of L-1Dripping formic acid solution into the mixed solution at the speed of 0.1ml/s until the solution is completely milky, continuing dripping formic acid until the pH value is 6.3, and growing nano sulfur particles generated by the reaction on Ti2CTxAnd (3) the surface of the nanosheet. With 0.7mol of L-1Neutralizing with ammonia water to pH 7.1, centrifuging, washing the precipitate with deionized water, and centrifuging to obtain clay-like two-dimensional transition metal carbide Ti with sulfur content of 60 wt%2C and nano sulfur particle composite material, the size of the sulfur particle is 20 to 300 nanometers.
(3) And (3) electrochemical performance testing: two-dimensional transition metal carbide Ti2Uniformly coating the C and nano sulfur particle composite material on an aluminum foil current collector by using a coating machine (the coating thickness is 11 mu m), drying for 14h in vacuum, then cutting pieces as a positive electrode, using a lithium piece as a negative electrode, adopting a Celgard diaphragm, and selecting electrolyte with the concentration of 1mol L-1LiTFSI/DOL-DME (volume ratio 1:1) and 0.1mol L of-1LiNO of3And assembling the button lithium-sulfur battery. Constant current charging and discharging are carried out at the multiplying power of 0.5C, and the first discharge capacity is 1080mAh g-1And the discharge capacity after 100 cycles is 875mAh g-1。

Claims (7)

1. A two-dimensional transition group metal carbon/nitride and nano sulfur particle composite material is characterized in that: the composite material consists of a two-dimensional transition group metal carbon/nitride MXene nanosheet and nano sulfur particles, wherein the nano sulfur particles generated by reduction grow in situ on the surface of the two-dimensional transition group metal carbon/nitride MXene nanosheet and are expressed as S @ MXene; wherein the size of the nano sulfur particles is 20-500 nm, and the mass content of sulfur in S @ MXene is 10-80 wt%.
2. The two-dimensional transition group metal carbo/nitride and nano sulfur particle composite material of claim 1, wherein: the two-dimensional transition metal carbon/nitride MXene is as follows: ti3C2Tx、Ti2CTx、Ti3CNTx、(Ti0.5,Nb0.5)2CTx、(V0.5,Cr0.5)3C2Tx、Ta4C3Tx、V2CTx、Nb2CTx、Nb4C3Tx、(Nb0.8,Ti0.2)4C3Tx、(Nb0.8,Zr0.2)4C3Tx、Mo2TiC2Tx、Mo2Ti2C3Tx、Mo2CTx、Cr2TiC2Tx、Zr3C2TxOr Ti4N3Tx。
3. A method for preparing the two-dimensional transition group metal carbon/nitride and nano sulfur particle composite material of claim 1, comprising the following specific steps:
1) mixing a sodium polysulfide or sodium thiosulfate solution with a two-dimensional transition metal carbon/nitride MXene nanosheet suspension to obtain a mixed suspension;
2) dropwise adding a formic acid solution into the mixed suspension prepared in the step 1) while magnetically stirring;
3) after the reaction, ammonia water is adopted for neutralization until the pH value of the suspension is 6.5-7.3, and then centrifugation is carried out;
4) washing the precipitate obtained by centrifugation with deionized water, and centrifuging to obtain the two-dimensional transition metal carbon/nitride and nano sulfur particle composite material.
4. The method according to claim 3, wherein the two-dimensional transition metal carbon/nitride MXene nanosheet suspension is prepared by the following steps: dissolving LiF in hydrochloric acid, adding a ternary layered compound MAX powder into the solution, stirring and reacting at 30-40 ℃, washing and centrifuging a reaction product by using ethanol until the pH value of supernatant is 6.2-6.5, adding a dried solid sample into deionized water, ultrasonically stripping under the protection of flowing argon, and centrifuging to obtain a few-layer or single-layer two-dimensional transition group metal carbon/nitride MXene nanosheet suspension; the concentration of the suspension is 0.2-1.5 mg/ml.
5. The method according to claim 4, wherein the stirring rate of the stirring reaction at 30-40 ℃ is 200-500rpm, and the stirring time is 6-24 h; the ultrasonic frequency of the ultrasonic stripping is 40-100kHz, and the ultrasonic stripping time is 0.5-1.5 h; the rotating speed of centrifugation after ultrasonic stripping is 2500-4000 rpm, and the centrifugation time is 0.5-1.5 h.
6. The method of claim 3, wherein: the concentration of the sodium thiosulfate or sodium polysulfide solution is 0.2-1 mol/L; the concentration of formic acid is 1-3 mol/L, the dripping speed of formic acid is 0.1-0.3 ml/s, the solution is continuously dripped until the pH value is 6-6.8 after the solution is completely changed into milk white, and then ammonia water is used for neutralization; the concentration of the ammonia water is 0.2-1 mol/L.
7. Use of the two-dimensional transition group metal carbo/nitride and nano sulfur particle composite material of claim 1 in a positive electrode of a lithium sulfur battery.
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