CN114583130B - MXene coated sulfur composite material, preparation method of lithium sulfur battery positive electrode material and battery - Google Patents

MXene coated sulfur composite material, preparation method of lithium sulfur battery positive electrode material and battery Download PDF

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CN114583130B
CN114583130B CN202210219556.4A CN202210219556A CN114583130B CN 114583130 B CN114583130 B CN 114583130B CN 202210219556 A CN202210219556 A CN 202210219556A CN 114583130 B CN114583130 B CN 114583130B
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sulfur
mxene
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lithium
battery
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CN114583130A (en
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杨树斌
张迪
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Beihang University
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract

The application discloses an MXene-coated sulfur composite material, a preparation method of a lithium sulfur battery positive electrode material and a battery, wherein the MXene-coated sulfur composite material has a core-shell structure of an MXene material-coated sulfur ball. The composite material can be used as a positive electrode material of a lithium sulfur battery, and the application also comprises a preparation method of the positive electrode material of the lithium sulfur battery, which comprises the steps of further mixing the composite material with an initiator to obtain a composite material of MXene and polysulfide; the composite material or the positive electrode material of the lithium sulfur battery is applied to the lithium sulfur battery, wherein MXene can effectively promote the kinetics of a sulfur oxidation-reduction reaction, is used in the positive electrode material of the lithium sulfur battery, can play a role in adsorbing polysulfide in a liquid phase to avoid a shuttle effect caused by dissolution of the polysulfide into an organic electrolyte, and can also promote the kinetics reaction of the positive electrode material sulfur, so that the cycle and the rate capability of the lithium sulfur battery are improved.

Description

MXene coated sulfur composite material, preparation method of lithium sulfur battery positive electrode material and battery
The application relates to a divisional application, and the main application is an application patent application of which the application date is 3/13/2020, the application number is 202010175425.1, and the application name is a sulfur-carrying material and a positive electrode material of a lithium sulfur battery.
Technical Field
The application relates to the field of energy storage, in particular to a MXene coated sulfur composite material, a preparation method of a lithium sulfur battery positive electrode material and a battery.
Background
The lithium-sulfur battery is a lithium battery with sulfur element as a battery anode and metal lithium as a battery cathode, and the reaction mechanism of the lithium-sulfur battery is different from the ion deintercalation mechanism of the lithium ion battery, but is an electrochemical mechanism. The lithium-sulfur battery using sulfur as the positive electrode material has higher theoretical specific capacity and higher battery theoretical specific energy which respectively reach 1675mAh g -1 And 2600Wh kg -1 Far higher than the capacity of lithium ion batteries in widespread commercial use. In addition, the elementary sulfur is abundant in the earth, has the characteristics of low price, environmental friendliness and the like, is regarded as one of ideal choices of next-generation high-energy-density battery systems, is highly concerned by the scientific research world and the industry world, and is also one of important research directions of layout of various countries in the future.
In practical applications, the sulfur positive electrode of lithium sulfur batteries generally exhibits serious capacity fade and low rate capability due to the following:
(1) The electron conductivity and ion conductivity of elemental sulfur are poor, and the conductivity of sulfur materials at room temperature is extremely low (5.0X10) -30 Scm -1 ) Final product of the reaction Li 2 S 2 And Li (lithium) 2 S is also an electronic insulator, which is not beneficial to the high rate performance of the battery;
(2) The densities of sulfur and lithium sulfide were 2.07 and 1.66g cm, respectively -3 Up to 79% of the volume expands/contracts during charge and discharge, which causes changes in the morphology and structure of the positive electrode, resulting in separation of sulfur from the conductive backbone, and thus capacity decay;
(3) Intermediate discharge products of lithium-sulfur batteries (soluble polysulfides, liPS, li 2 S n N is more than or equal to 4 and less than or equal to 8) can be dissolved into the organic electrolyte, so that the viscosity of the electrolyte is increased, the ion conductivity is reduced, polysulfide ions can migrate between the anode and the cathode, and the loss of active substances and the waste of electric energy (shuttle effect) are caused;
(4) The discharge process of the sulfur positive electrode is from solid sulfur to soluble polysulfideLi 2 S n And solid Li 2 S (solid-liquid-solid) heterogeneous conversion has low kinetic reactivity.
The first two problems are solved, and at present, active substance sulfur is compounded with conductive carbon materials, such as mesoporous carbon, carbon nano tubes and graphene, so as to improve the conductivity of a sulfur positive electrode and limit volume change. To suppress the shuttle effect of LiPS, electrode materials having high affinity for LiPS, such as heteroatom-doped carbon, transition metal compounds and polymers, were introduced into the sulfur positive electrode, and studies have demonstrated that strong interactions between them are very effective in suppressing soluble LiPS in the sulfur positive electrode.
For the problem of slower kinetic activity of the heterogeneous conversion reaction of sulfur, studies have found that this slow kinetic reaction comes mainly from the rate limiting step: li (Li) 2 S 2 →Li 2 S, the Gibbs free energy ΔG=0.6 to 1.3eV of this step is approximately 3 to 4 times that of the other steps (e.g., step: li 2 S 8 →Li 2 S 4 To promote the rate-limiting reaction, various catalysts such as noble metals (e.g., pt), transition metals (e.g., co, fe, ni, etc.), and metal compounds (oxides, disulfides, and phosphides) are currently mainly added to the sulfur positive electrode to promote the rate-limiting reaction. At present, research on a catalyst with high electrocatalytic activity is still in a starting stage, and development of the catalyst with high activity has important significance for improving the electrochemical performance of a sulfur positive electrode and even further commercialization of a lithium sulfur battery.
Disclosure of Invention
In order to solve the technical problem of the sulfur positive electrode in the lithium sulfur battery, the application provides a sulfur carrying material of the lithium sulfur battery, wherein the sulfur carrying material is an MXene material with a two-dimensional lamellar structure, and the chemical general formula of the sulfur carrying material is M n+1 X n Wherein M denotes a transition group metal element, X denotes a C and/or N element, and N is 1 to 3, wherein the two-dimensional lamellar structure has doping atoms dispersed therein, and the doping atoms have electrocatalytic activity for promoting a heterogeneous conversion reaction of sulfur.
In some embodiments, the doping atoms are metallic elements, the atomic outer layer of which has d-orbital electrons; or the doping atoms are nonmetallic elements, and the outer atomic layers of the nonmetallic elements are provided with lone pair electrons.
In some embodiments, the metal element comprises: zinc, nickel, cobalt, iron, platinum, copper, silver, gold, magnesium, calcium, gallium, indium, tin, silicon, germanium, antimony, bismuth, lead, or aluminum.
In some embodiments, the nonmetallic elements include: n, P, S, O, F, br or I.
In some embodiments, the transition group metal comprises: ti, mo, W, zr, hf, V, nb, ta, cr or Sc.
The application also provides a positive electrode material of a lithium sulfur battery, which comprises the following components: sulfur and the sulfur-carrying material of the present application described above.
In some embodiments, the sulfur is spherical shaped sphere, and the sulfur-bearing material coats the surface of the sphere.
In some embodiments, the sulfur is an amorphous polysulfide, and the sulfur-bearing material is dispersed within the polysulfide.
In some embodiments, the sulfur-bearing material is present in an amount of between 5wt.% and 20 wt.%.
The application also provides a lithium sulfur battery, and the anode of the lithium sulfur battery contains the sulfur carrying material.
The sulfur-carrying material is used for the anode of a lithium sulfur battery, and has the beneficial technical effects that:
(1) The MXene matrix of the sulfur-carrying material contains the doping atoms dispersed by single atoms, so that the adsorption effect on liquid phase polysulfide can be enhanced, and the problems of increased viscosity of electrolyte, reduced ion conductivity, polysulfide ion migration between anode and cathode, active material loss, electric energy waste and the like caused by the dissolution of the sulfur-carrying material into organic electrolyte are avoided;
(2) The MXene matrix of the sulfur-carrying material has high catalytic activity due to the fact that the single-atom dispersed doping atoms are contained, so that the energy barrier of polysulfide electrochemical conversion can be reduced, and the dynamic reaction of sulfur of the anode material is promoted;
(3) Due to the combined action of the adsorption effect and the high catalytic activity of the sulfur-carrying material, electrons can rapidly migrate between the sulfur-carrying material and the sulfur anode;
(4) Soluble polysulfide during discharge of sulfur positive electrode is converted into Li of solid phase 2 In the S process, the sulfur-carrying material can carry out nucleation and deposition by taking the doped atoms containing single-atom dispersion on the MXene matrix as the cores, and is favorable for the stability of the anode structure.
In addition, the matrix MXene material of the sulfur-carrying material also has excellent conductive performance, and the sulfur-carrying material is added into a sulfur positive electrode of a lithium sulfur battery, so that the problem of poor electronic conductivity and ion conductivity of elemental sulfur can be solved, and the conductivity of the sulfur positive electrode is improved, thereby improving the rate capability of the lithium sulfur battery. The MXene material is similar to the structural characteristics of a two-dimensional lamellar of graphene, so that when the sulfur-carrying material is dispersed in the sulfur anode, the sulfur-carrying material can play a role in buffering the volume change of sulfur, and the sulfur anode has the effect of structural stability in the charge and discharge process.
The sulfur-carrying material belongs to a novel catalytic material, can obviously improve the cycle and multiplying power performance of a lithium sulfur battery, and has important significance for further commercialization of the lithium sulfur battery.
Drawings
FIG. 1 is a transmission electron microscope (STEM) photograph of a sulfur-bearing material SA-Zn-MXene and energy spectrum (EDS) analysis of selected areas thereof in accordance with one embodiment of the present application;
FIG. 2 is an X-ray photoelectron Spectrometry (XPS) of a sulfur-bearing material SA-Zn-MXene according to one embodiment of the application;
FIG. 3 is a high angle annular dark field scanning transmission electron microscope (HAADF-STEM) photograph of aberration correction of sulfur-bearing material SA-Zn-Mxene in an embodiment of the application;
FIG. 4 is an SEM photograph (a) and XRD spectrum (b) of a ball according to one embodiment of the application;
FIG. 5 is a schematic illustration of a process for preparing a cathode material S@SA-Zn-MXene according to an embodiment of the application;
FIG. 6 is an SEM photograph of a positive electrode material S@SA-Zn-MXene according to one embodiment of the application;
FIG. 7 is a SEM photograph and EDS analysis of a positive electrode material cpS@SA-Zn-MXene according to an embodiment of the application;
FIG. 8 is a photograph of an adsorption test of SA-Zn-Mxene, MXene, and carbon black, and an ultraviolet-visible absorption spectrum according to an embodiment of the present application;
FIG. 9S under the influence of SA-Zn-MXene and MXene in one embodiment of the application 8 To Li 2 Free energy of reaction during the reaction of S (a) and binding energy with polysulfide (b);
FIG. 10 is a cyclic voltammetry test curve for a symmetrical cell containing SA-Zn-MXene and a comparison thereof in accordance with one embodiment of the present application;
FIG. 11 shows the results of a potentiostatic nucleation test for a test cell containing SA-Zn-Mxene and a control thereof according to one embodiment of the present application;
FIG. 12 solid Li 2 S 2 /Li 2 S scanning electron micrographs (a and b) of electrode plates deposited on SA-Zn-MXene under different magnifications;
FIG. 13 shows the charge and discharge curves (a) and the rate test results (b) of a lithium sulfur battery with a positive electrode material of S@SA-Zn-MXene and sulfur balls according to an embodiment of the application;
FIG. 14 is a graph of cycling performance at 4C for a lithium sulfur battery of cpS@SA-Zn-MXene according to one embodiment of the application;
FIG. 15 shows charge and discharge curves of lithium sulfur batteries with positive electrode materials of CPS@SA-Zn-MXene (a), CPS@MXene (b), CPS (C) and sulfur balls (d) at a magnification of 0.2C in an embodiment of the application;
FIG. 16 is a graph showing the rate performance test of lithium sulfur batteries with positive electrode materials of cps@SA-Zn-MXene (a), cps@MXene (b) cpS (c) and sulfur balls (d), respectively, according to an embodiment of the present application;
FIG. 17 thermal weight loss (TG) curves for the cathode materials cpS@SA-Zn-MXene, S@SA-Zn-MXene and cpS of the present application.
Detailed Description
The technical scheme of the application is described below through specific examples. It is to be understood that the reference to one or more steps of the application does not exclude the presence of other methods and steps before or after the described combined steps, or that other methods and steps may be interposed between these explicitly mentioned steps. It should also be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. Unless otherwise indicated, the numbering of the method steps is for the purpose of identifying the method steps only and is not intended to limit the order of arrangement of the method steps or to limit the scope of the application, which relative changes or modifications may be regarded as the scope of the application which may be practiced without substantial technical content modification.
The raw materials and instruments used in the examples are not particularly limited in their sources, and may be purchased on the market or prepared according to conventional methods well known to those skilled in the art.
For simplicity and clarity, zn-MXene in the drawings of the present application represents the sample SA-Zn-MXene. For the purpose of distinguishing lines in the drawings, reference numerals 1 to 7 in the drawings represent materials of Zn-MXene, S@Zn-MXene, ball, cpS@Zn-MXene, cpS@MXene and cpS in order, or positive electrode materials or lithium sulfur batteries containing the materials.
Transition metal nitrides, transition metal carbides, transition metal carbo-nitrides, also known as MXene materials, having a two-dimensional lamellar structure of the general chemical formula M n+1 X n Wherein M refers to a transition group metal (such as one or more of Ti, mo, W, zr, hf, V, nb, ta, cr, sc, etc.), X refers to a C and/or N element, and N is generally 1 to 3. Currently, MXene materials are mainly obtained by extracting weakly bound a-site elements (e.g., aluminum or silicon) in the MAX phase with HF acid or a mixed solution of hydrochloric acid and fluoride. Common MXene materials include MXene materials including but not limited to Mo 2 C、Mo 1.33 C、V 2 C、Nb 2 C、Ti 3 C 2 、Ti 4 C 3 、Mo 2 Ti 2 C 3 、Mo 2 TiC 2 、Ta 2 C、Ta 4 C 3 And TiNbC, etc., the MXene material is known to have the characteristics of high specific surface area and high conductivity similar to graphene at present. For clarity and depth of description, the sulfur-carrying material of the application is applied to the sulfur anode of the lithium sulfur battery, and the following are trueExample Ti dispersed as monoatomic Zn 3 C 2 For purposes of illustration, it is to be understood that the following examples are merely illustrative of the concepts and methods of the application and are not intended to limit the scope of the application.
Example 1
This example provides a single atom Zn dispersed Ti 3 C 2 The preparation method of the nano sheet (marked as SA-Zn-MXene) comprises the following steps:
step 1): first, 6g ZnCl 2 And 1g Ti 3 AlC 2 The powders were mixed and annealed at 550-600 ℃ for 5h under Ar atmosphere. After cooling to room temperature, the obtained product was added to HCl (2M) and stirred for 10 hours to obtain a dispersion, which was centrifuged and washed several times to remove residual salts and acids to obtain an intermediate product;
step 2): 1g of the intermediate product from step 1) was dispersed in 80mL of isopropanol, then sealed with Ar atmosphere and sonicated for 20h. After sonication, the dispersion was stirred at 2000rpm for min -1 Centrifuge for 15 min to remove residue, then spin at 10000rpm for min -1 Centrifuge for 10 minutes to give a precipitate, which was SA-Zn-MXene.
The preparation method in this example, step 1) 1g Ti 3 AlC 2 The dispersion obtained after addition of the powder to HCl (2M) and stirring for 10 hours was centrifuged and washed several times to remove residual salts and acids, yielding an intermediate; step 2) is unchanged, and Ti without doping atom Zn can be prepared 3 C 2 Nanoplatelets (also identified as Ti due to their surface containing-Cl functionality) 3 C 2 Cl 2 )。
FIG. 1 shows a Scanning Transmission Electron Microscope (STEM) photograph of a sample SA-Zn-MXene and energy spectrum analysis (EDS) of selected regions thereof, illustrating the presence of Ti, cl and Zn elements in the sample SA-Zn-MXene. X-ray photoelectron spectroscopy (XPS) analysis of FIG. 2 further demonstrates that the sample SA-Zn-MXene consists of Zn, ti, cl and C elements. To verify the distribution of Zn atoms, the sample SA-Zn-MXene was subjected to aberration correction by a high angle annular dark field scanning transmission electron microscope (HAADF-STEM), and as a result, as shown in FIG. 3, a large number of isolated and dispersed bright spots, which should be isolated Zn atoms according to the Z contrast difference of heavier Zn atoms and Ti atoms, were seen from FIG. 3, and the content of Zn atoms in the sample was evaluated to be 1.5wt.% by inductively coupled plasma atomic emission spectrometry (ICP-AES).
Example 2
This example provides another single atom Zn dispersed Ti 3 C 2 Preparation method of nanosheets by reacting ZnCl 2 Is introduced into a typical HCl-LiF system for preparation, and comprises the following steps:
step 1): first, 1.5g LiF and 8g ZnCl are reacted 2 Added to 20mL HCl (2M). After stirring for 15 minutes, 1g of Ti was added 3 AlC 2 The powder was added to the dispersion and maintained at 35℃for 35h. Then, the dispersion was centrifuged 6 times to remove the supernatant, resulting in a precipitate;
step 2): dispersing the precipitate obtained in step 1) in distilled water, followed by ultrasonic treatment (1 hour) at 2000rpm for min -1 After centrifugation for 15 minutes, a SA-Zn-MXene solution was obtained.
The preparation method in this example, step 1), does not add ZnCl 2 Can prepare Ti without doping atom Zn 3 C 2 A nano-sheet.
Example 3
The embodiment provides a positive electrode material of a lithium sulfur battery, which comprises sulfur and a sulfur carrying material, wherein the sulfur carrying material adopts SA-Zn-MXene obtained by the preparation method of the embodiment 1 or 2, the sulfur is spherical colored balls, the surface of the colored balls is coated with the sulfur carrying material SA-Zn-MXene, and the obtained positive electrode material is marked as S@SA-Zn-MXene.
The preparation method of the colored ball comprises the following steps: first, 2g of Na 2 S 2 O 3 ·5H 2 O and 50mg of polyvinylpyrrolidone (m.w. =58000) were dissolved in 100mL of distilled water. Then, 50mL of HCl (0.3M) was added to the solution over 2 hours with stable stirring, kept stirring for 2 hours, centrifuged and dried to obtain sulfur balls. Fig. 4 shows SEM (a) and XRD (b) of the spheres, which can be seen to be in a uniform spherical or spheroid form.
The preparation method of S@SA-Zn-MXene comprises the following steps: the dispersion of the spheres was poured into an aqueous solution containing SA-Zn-MXene nanoplatelets, rapidly sonicated (5 minutes) and after filtration and freeze-drying the sample S@SA-Zn-MXene was obtained. Notably, the SA-Zn-MXene is mixed with the sulfur spheres in an aqueous solution, wherein the SA-Zn-MXene layer spontaneously coats the surface of the sulfur spheres, which is associated with adsorption between the SA-Zn-MXene and sulfur. FIG. 5 shows a schematic diagram of the S@SA-Zn-MXene preparation process. FIG. 6 shows an SEM photograph of a sample S@SA-Zn-MXene, from which it can be seen that SA-Zn-MXene coats the surface of the sphere to form a coating structure.
The same method is adopted, except that the aqueous solution of SA-Zn-MXene nano-sheets is replaced by Ti which does not contain doping atom Zn 3 C 2 The sample label S@MXene is prepared from the aqueous solution of the nano-sheet.
Example 4
The present example provides another positive electrode material for a lithium sulfur battery, including sulfur and a sulfur-carrying material, wherein the sulfur-carrying material adopts SA-Zn-MXene obtained by the preparation method of example 1 or 2, sulfur is amorphous polysulfide, the sulfur-carrying material SA-Zn-MXene is dispersed in the polysulfide, and the obtained positive electrode material is marked with cps@SA-Zn-MXene.
The preparation method of the cpS@SA-Zn-MXene comprises the following steps: the weight ratio of S@SA-Zn-MXene to Diisobutylene (DIB) prepared in example 3 was 9:1, sealing the mixed sample, and annealing for 10 minutes at 185 ℃ under the protection of Ar atmosphere, and obtaining the sample cpS@SA-Zn-MXene after natural cooling.
FIG. 7 shows a scanning electron micrograph (a) and an energy spectrum analysis chart (b, c) of a sample cpS@SA-Zn-MXene, wherein the sulfur is in an amorphous form as seen in SEM, and the sulfur element and the Ti element are uniformly distributed as seen in EDS analysis.
Using the same method, S@SA-Zn-MXene was replaced with S@MXene or a ball, and the resulting samples were labeled cpS@MXene or cpS, respectively, and used as comparative cathode materials in electrochemical performance tests.
In the embodiment, the additive DIB and heat treatment are added to convert the ball into cross-linked polysulfide, and sulfur is converted into amorphous form from spherical form, so that the volume density of the electrode can be increased, the mass capacity of the positive electrode material can be improved, and meanwhile, the sulfur is not easy to enter the electrolyte in the charging and discharging process due to the conversion of the sulfur into cross-linked polysulfide, and the electrochemical performance of the positive electrode material can be improved.
Example 5
In order to identify the interaction between the sulfur-carrying material and polysulfide of the present application, this example was conducted to perform a visual adsorption test using SA-Zn-MXene of example 1 to obtain a sample containing Ti of example 1 without doping atom Zn 3 C 2 Nanoplatelets (labeled MXene) and carbon black (Super P) were used as control samples, and the test methods were as follows: firstly, the volume is 1:1, 3-Dioxolane (DOL) and Dimethoxyethane (DME) as solvents for Li preparation 2 S 6 Solution, the same mass of Super P, MXene and SA-Zn-MXene (12 mg) were added to 3.5mL Li, respectively 2 S 6 In the solution (5 mM, dark yellow in appearance), after 8 hours of standing, li with different samples was observed 2 S 6 The solution, the supernatant was extracted and tested by UV-VIS-NIRS spectrometer (UV-3000). As a result of the test, as shown in FIG. 8, it can be seen from the photograph in FIG. 8 that Li of SA-Zn-MXene was added as a sample 2 S 6 The solution, supernatant, was clear, indicating Li in electrolyte 2 S 6 Absorbed onto the sheet of SA-Zn-MXene. In contrast, under the same test conditions, MXene Li was added 2 S 6 The supernatant of the solution still appeared pale yellow, while carbon black (Super P) Li was added 2 S 6 The supernatant of the solution remained dark yellow, indicating that the solution contains a single atom of Zn-doped SA-Zn-MXene vs. Li 2 S 6 Is superior to MXene doped with Zn without single atom, and carbon black of carbon material is superior to Li 2 S 6 Is poor in absorbency. As can also be seen from the ultraviolet-visible absorption spectrum (UV/vis) in FIG. 8, SA-Zn-MXene and MXene-added Li 2 S 6 The UV/vis spectrum of the solution versus Li of carbon black (Super P) 2 S 6 The solution is much weaker, which may be due to the transition metal elements contained in the SA-Zn-MXene and MXene materials,the transition metal atoms exposed on the surface of the material can generate an inter-bonding action with sulfur atoms, thereby showing better adsorptivity relative to carbon black, and the carbon atoms in the carbon black and the sulfur atoms have no such bonding action, while the MXene material (such as SA-Zn-MXene exemplified in the present embodiment) containing the monoatomically dispersed doping atoms can be formed by embedding in the crystal structure of the MXene material and forming a strong bond of the fixed sulfur atoms, which is equivalent to an "anchoring" action, so that the MXene material (such as SA-Zn-MXene exemplified in the present embodiment) containing the monoatomically dispersed doping atoms shows better sulfur adsorptivity relative to the MXene material without monoatomically doping.
In this embodiment, only one Li of polysulfides 2 S 6 By way of example, the strong interaction between the sulfur-bearing material SA-Zn-MXene of the application and lithium polysulfide can be demonstrated by adsorption testing. The sulfur-carrying material is used in a sulfur positive electrode of a lithium sulfur battery, and solid sulfur is converted into liquid polysulfide Li during the discharging process of the sulfur positive electrode 2 S n The sulfur-carrying material has strong interaction to polysulfide, can adsorb liquid polysulfide, and can avoid the problems of increasing the viscosity of electrolyte, reducing ion conductivity, enabling polysulfide ions to migrate between anode and cathode, and the like caused by the fact that the polysulfide can be dissolved into the electrolyte.
Example 6
To further demonstrate the effect of promoting kinetic reactivity of sulfur-bearing materials comprising the present application, this example provides a theoretical analysis of the catalytic behavior and chemical interactions between SA-Zn-MXene and polysulfide by Density Functional Theory (DFT) calculations. All first principles spin polarization calculations were performed by simulation program Vienna ab initio Simulation Program (VASP), using a Generalized Gradient Approximation (GGA) in the form of Perdew-Burke-Ernzerhof (PBE) and a cutoff energy of 450eV for the planar wave basis set. In the structural calculation, the brillouin zone is sampled using a 5×5×1Monkhorst-Pack k grid. Ion-electron interactions are described using the projector enhanced wave (PAW) method. For a single layer Mxene (Ti) with 3×3 unit cells 3 C 2 Cl 2 ) Modeling is performed, andby exceedingTo avoid interactions between two periodic cells. The convergence criterion for the structural optimization is chosen because the maximum force on each atom is smaller than +.>The energy variation is less than 1 x 10 -5 eV (eV). Van der Waals (vdW) interactions in these systems are described using the Grimme DFT-D3 dispersion correction scheme.
The simulation results are shown in FIG. 9, and the results from S are shown in FIG. 9a 8 To Li 2 S(S 8 →Li 2 S 8 →Li 2 S 6 →Li 2 S 4 →Li 2 S 2 →Li 2 S) the calculated free energy spectrum of the main reaction, the effect of SA-Zn-MXene and MXene on sulfur in the electrochemical process can be seen. From the calculated Gibbs free energy ΔG, S 8 →Li 2 S 8 Is spontaneous, li 2 S 8 To Li 2 S 6 /Li 2 S 4 Is close to thermodynamic equilibrium, in the reaction step Li 2 S 2 Reduction to Li 2 S has the highest free energy of reaction, belongs to the limiting step of the reaction, has the free energy of reaction of 0.71eV which is lower than the free energy of reaction of MXene material (0.92 eV) in the case of sulfur-carrying material SA-Zn-MXene, and has been reported to be graphene (1.21 eV), which shows that the presence of single atom Zn on the MXene material can effectively reduce Li 2 S 2 →Li 2 S. While by comparing the binding energies between SA-Zn-MXene and polysulfide in FIG. 9b, it can be seen that the binding energy between SA-Zn-MXene and polysulfide is higher than that between MXene, which higher binding energy is shown by the fact that the MXene material with single atom Zn doping is capable of better adsorption to polysulfide, which is consistent with the adsorption experimental results in example 5.
The embodiment shows that the sulfur-carrying material contains large single-atom dispersed doping atoms, so that not only can the chemical interaction between the matrix MXene material and the lithium polysulfide be enhanced, but also the kinetics of sulfur redox reaction can be effectively promoted, and the sulfur-carrying material can be used in the anode material of the lithium sulfur battery, and can play a role in adsorbing polysulfide in liquid phase to avoid a shuttle effect caused by dissolution of the polysulfide in organic electrolyte, but also can promote the kinetics reaction of sulfur in the anode material, thereby improving the cycle and rate capability of the lithium sulfur battery. It should be noted that the adsorption effect not only avoids the problems of shuttle effect caused by dissolution of polysulfide, but also enables polysulfide to be closely attached to the surface of the sulfur-carrying material of the application, thereby facilitating the conduction of electrons from the surface of the sulfur-carrying material to polysulfide.
Example 7
To further evaluate the kinetics of polysulfide reduction and oxidation reactions on SA-Zn-MXene, we carried 0.2M Li 2 S 6 Cyclic Voltammetry (CV) measurements were performed in a symmetric cell with SA-Zn-MXene electrodes of the solution, as follows:
first, the mass ratio is 8:1, mixing sample SA-Zn-MXene and polyvinylidene fluoride (PVDF), coating on aluminum foil, vacuum drying at 80deg.C for 12 hr to obtain working electrode sheet, and assembling into CR2032 type symmetrical battery with the same working electrode sheet, wherein the electrolyte is 20mM Li 2 S 6 The solution is a mixed solution of DOL and DME in a volume ratio of 1:1. The sample SA-Zn-MXene was replaced with Ti containing no doping atom Zn by the same method 3 C 2 The assembled symmetrical battery is used as a comparison sample.
The obtained symmetrical cells were scanned at different rates between-1V and 1V (3 to 30mV s -1 ) The scanning was performed and the results are shown in FIG. 10, in which CV of SA-Zn-MXene showed four different redox peaks at-0.58, -0.07, 0.63 and 0.06V, respectively. The first main peak at 0.58V can be attributed to Li on the working electrode 2 S 6 Reduction to Li 2 S 2 /Li 2 S, while the second peak at-0.07V is due to Li on the same electrode 2 S 2 /Li 2 Oxidation of S to Li 2 S 6 . Likewise, the other two peaks at 0.63 and 0.06V are derived from Li on the working electrode, respectively 2 S 6 And oxidation and reduction between the elements S. For a symmetric cell containing sulfur-bearing material SA-Zn-MXene, the current density of the four peaks is higher than that of the comparative sample (MXene) (for a peak value of 0.63V, the current density of SA-Zn-MXene is 6 times that of MXene), and the existence of single-atom zinc on MXene greatly improves the power of the redox reactions, so that the efficient catalytic function is provided for electrochemical conversion of lithium polysulfide.
Example 8
The embodiment proves that the single-atom dispersed doping atoms in the sulfur-carrying material are bonded with sulfur strongly and are nucleated and deposited on the matrix MXene material through a potentiostatic nucleation experiment, and the testing method comprises the following steps:
first, by setting the mass ratio to 7:2:1, sample SA-Zn-MXene, ketjen black and PVDF were mixed, followed by knife coating on aluminum foil and drying at 80 ℃ for 12 hours to prepare a positive electrode for nucleation measurement. Then, the prepared positive electrode and negative electrode lithium foil are assembled into a CR2032 button cell, and the positive electrode and the negative electrode are respectively provided with different electrolyte. The electrolyte on the negative electrode side was 10. Mu.L of lithium sulfur electrolyte (LiTFSI as electrolyte, DOL and DME mixed solution in a volume ratio of 1:1 as solvent, which contained 1wt.% LiNO) 3 ) The positive electrode electrolyte was 30. Mu.L of polysulfide electrolyte (electrolyte 20mM Li 2 S 6 The solvent is a mixture of DOL and DME in a volume ratio of 1:1). The battery operation was performed by discharging to 2.12V and then performing a potentiostatic step at 2.05V, during which the current was recorded simultaneously. Under the same conditions, the sample SA-Zn-MXene is replaced by MXene, and the assembled button cell is used as a comparison sample.
As a result of the test, as shown in FIG. 11, it can be seen that SA-Zn-MXene has a 1.45mA g -1 Higher than MXene (1.21 mA g) -1 ) Li of corresponding SA-Zn-MXene 2 The S precipitation capacity is 114mAh g -1 Specific MXene positive electrode (97 mAh g) -1 ) To be high, it is stated that the inclusion of monoatomically dispersed dopant atoms favors Li 2 S 2 /Li 2 S is deposited on the surface of the matrix MXene material by nucleation. By electrochemical deposition of Li 2 S 2 /Li 2 SEM photograph of the positive electrode after S (FIG. 12), all Li was also seen and confirmed 2 S 2 /Li 2 S is deposited on the sheet where SA-Zn-MXene is present. It is worth noting that the deposition capacity of the sulfur-carrying material of the application is higher than that of the polysulfide catalyst reported in the prior art by-103 mAh g -1 This benefits from the ability of the sulfur-bearing material of the present application to adsorb polysulfides and to promote the kinetic reactivity of sulfur. Furthermore, it can be demonstrated by this example that in the heterogeneous conversion of sulfur, soluble polysulfide Li 2 S n Conversion to solid Li 2 S 2 /Li 2 In the S process, doping atoms with single atom dispersion also have nucleation function, and solid Li 2 S 2 /Li 2 The S nucleation deposition mode is fixed on the sheet layer of SA-Zn-MXene, so that the structure of the sulfur positive electrode is more stable.
Example 9
This example provides a lithium sulfur battery for testing the electrochemical performance of the positive electrode material of the present application, and the battery was subjected to charge and discharge tests at various current densities of 2.8 to 1.6V through a constant current process. The positive electrode material was S@SA-Zn-MXene prepared as in example 3.
The preparation steps of the lithium sulfur battery comprise: first, by mixing the positive electrode material s@sa-Zn-MXe, conductive carbon black (ketjen black) and polyacrylic acid at a ratio of 7:2: mixing the materials in the mass ratio of 1 in water, coating the mixture on carbon fiber, and vacuum drying the mixture at 80 ℃ for 12 hours to prepare a positive plate for testing; then, the lithium foil was assembled as a negative electrode sheet into a CR2032 type button cell, wherein 20. Mu.L of lithium sulfur electrolyte (LiTFSI as electrolyte, 1:1 volume ratio of DOL to DME mixed solution containing 1wt.% LiNO) was added as the electrolyte 3 ). The same procedure was used to replace the positive electrode material with the ball prepared in example 3, and the assembled button cell was used as a comparative sample.
As shown in FIG. 13a, it can be seen that the lithium sulfur battery containing the positive electrode material S@SA-Zn-MXe of the application at a charge/discharge rate of 0.2CThe initial reversible capacity of (2) reaches 1222mAh g -1 Far higher than the comparative sample battery (790 mAh g) -1 ) It can also be seen from the discharge curve that the overpotential of the positive electrode material of the present application is 30mV, which is lower than that of the comparative sample cell (51 mV) in which the positive electrode material is a ball. It can also be seen from the multiplying power test results in fig. 13b that the lithium sulfur battery of the present application still maintains 550mAh g when the charge-discharge multiplying power is increased from 0.2C to 6.0C -1 Almost twice the reversible capacity of the control cell, and is also superior to the known reported composite positive electrode of sulfur and carbon materials, indicating that the positive electrode material of the present application exhibits excellent rate. This can be attributed to the fact that the sulfur-carrying material therein is capable of absorbing energy to adsorb polysulfides, and on the other hand, the monoatomically dispersed doping atoms having a catalytic function have a nucleation function and are capable of promoting the kinetic reactivity of sulfur.
Example 10
The present application provides another lithium sulfur battery, the test and assembly method is the same as example 9, except that the positive electrode material selected is cpS@SA-Zn-MXene prepared in example 4, the positive electrode material is replaced with sulfur balls (S), the battery assembled from cpS and cpS@MXene is a comparative battery, wherein the sulfur loading is about 1mg cm -2 。
The lithium sulfur battery with the four electrode materials is subjected to cycle performance test, and the initial reversible capacity of the lithium sulfur battery is 1210mAh g under the multiplying power of 0.2C -1 Maintained at 918mAh g after 50 cycles -1 Corresponding to a capacity retention of 75.8% and a capacity fade of 0.48%. In contrast, the comparative cells with the positive electrode material being ball, cpS and cps@mxene had capacities of 551.9, 649.2 and 783.7mAh g, respectively, after 50 cycles -1 The capacity and capacity retention are lower than the lithium sulfur battery of the present application. As can be seen from FIG. 14, the capacity of the lithium sulfur battery with the positive electrode material of cpS@SA-Zn-MXene is still higher than 500mAh g after 350 cycles at a rate of 4C -1 And the coulombic efficiency is close to 100%, and shows excellent cycle performance. As can also be seen from FIG. 15, the overpotential between the initial charge and discharge plateau of the lithium sulfur battery of the present application is 0.14V, lower than the potentials of CPS@MXene (0.18V), CPS (0.23V) and colored glazeBalls (0.23V) further demonstrate that the sulfur-bearing material of the present application can enhance catalysis, promoting the kinetic reactivity of sulfur. FIG. 16 shows the rate performance test, increasing the charge-discharge rate from 0.5C to 6C, and it can be seen that the lithium sulfur battery of the present application exhibits capacities of 888.0, 820.5, 732.7 and 658.3mAh g, respectively, when cycled at 0.5, 1.0, 2.0 and 4.0C -1 641.2mAh g was still obtained at a high current density increased to 6.0C -1 The high capacity of the battery is far higher than that of other three comparative batteries, and the battery shows excellent rate performance.
Through the electrochemical performance tests of examples 9 and 10, it is confirmed that the cycle and rate performance of the lithium-sulfur battery can be significantly improved by applying the sulfur-carrying material of the present application. The key point of the excellent electrochemical performance of the lithium sulfur battery is that the sulfur-carrying material can absorb polysulfide in liquid phase to avoid the polysulfide from being dissolved into organic electrolyte, and can promote the dynamic reaction of the sulfur in the positive electrode material. In addition, the sulfur-carrying material disclosed by the application is an MXene material, has excellent conductive performance, can be added into a sulfur positive electrode of a lithium sulfur battery, and can be used for solving the problem of poor electronic conductivity and ion conductivity of elemental sulfur, and improving the conductivity of the sulfur positive electrode, so that the rate performance of the lithium sulfur battery is improved. The MXene material is similar to the structural characteristics of a two-dimensional lamellar of graphene, so that when the sulfur-carrying material is dispersed in the sulfur anode, the sulfur-carrying material can play a role in buffering the volume change of sulfur, and the sulfur anode has the effect of structural stability in the charge and discharge process.
It should be noted that, in the implementation of the present application, the technical concept and solution of the present application are described only by the single-atom dispersed doped atom Zn, those skilled in the art should know that other catalysts having catalytic effect on heterogeneous reaction of sulfur, that is, catalysts capable of promoting the reaction power of sulfur, and also capable of achieving the technical effect of improving the electrochemical performance of lithium sulfur battery, the catalysts include metal elements and non-metal elements, the outer atomic layer of the metal elements usually has d-orbital electrons easy to conduct, such as Zn atoms for describing the present application, and has complete fillingCharged d track (3 d 10 4s 2 ) These metal elements also include: noble metals Pt, au, ag, transition metals such as one or more of Co, fe, ni, etc., the outer layers of atoms of these nonmetallic elements typically have lone pairs of electrons such as one or more of N, P, S, O, F, br or I, etc.
The sulfur-carrying material of the application is used in the sulfur positive electrode of the lithium sulfur battery, and has the advantages that the effect is equivalent to an additive, the additive does not have capacity, the effect of improving is not obvious due to the fact that the additive is too little, the specific capacity of the positive electrode is reduced and the redundant cost is increased due to the fact that the performance is improved due to the fact that the additive is too much, and preferably, the content of the sulfur-carrying material of the application in the positive electrode material of the lithium sulfur battery is between 2wt.% and 20 wt.%. The content of the additives can be characterized by thermogravimetric analysis TG testing, as shown in fig. 17, giving a thermal weight loss curve between 100 ℃ and 500 ℃ for different samples, wherein the mass content of SA-Zn-MXene in sample cps@sa-Zn-MXene is 13wt.%, and the mass content of SA-Zn-MXene in sample s@sa-Zn-MXene is 5wt.%.
In addition, in the known reported technology, graphene has a two-dimensional structure and good electrical conductivity, and a material doped with a single atom having catalytic activity (a catalyst of graphene) on a substrate of graphene also shows better catalytic activity than a catalyst existing in a non-single atom form (such as a metal wire shape, a metal sheet shape and the like). However, such graphene-based catalysts differ from the sulfur-bearing materials of the present application in that: since graphene consists of carbon atoms only, the atomic structure of graphene determines that doping atoms can only exist on defect sites of graphene, the number and distribution of the defect sites of graphene determine the number and distribution of doping atoms, and the defect sites of graphene are difficult to control in synthesis, so that uniform monoatomic dispersion of doping atoms on a graphene substrate can not be realized. The sulfur-carrying material is an MXene matrix, the atomic structure of the sulfur-carrying material contains transition metal elements, and doped atoms exist in the lattice structure of the MXene, so that uniform single-atom dispersion can be realized, the loading capacity of the doped atoms is not limited by defect sites, and high-loading single-atom doping can be realized. In addition, the sulfur-carrying material of the present application exhibits unexpectedly excellent adsorption capacity for polysulfides due to the exposure of transition metal atoms and the "anchoring" effect of doping atoms on the surface, while carbon atoms in graphene do not have such adsorption effect for polysulfides, and the problems of shuttle effect and the like caused by dissolution of polysulfides into an electrolyte during charge and discharge cannot be avoided, and conduction of electrons from the surface of graphene to polysulfides is also inevitably hindered due to the lack of a tight adsorption effect.
The sulfur-carrying material of the present application has different doping atoms, amounts of doping atoms and types of MXene matrix that affect the performance of the sulfur-carrying material of the present application, and the preferred embodiments can be selected by optimizing experimental conditions, so that it is only described in the embodiments of the present application, and it is possible for those skilled in the art to make several modifications and improvements without departing from the inventive concept of the present application.

Claims (11)

1. The preparation method of the MXene coated sulfur composite material is characterized by comprising the following steps: mixing and dispersing the MXene material and sulfur balls in the solution, filtering and drying to obtain a composite material with an MXene coated sulfur core-shell structure; the MXene material has single-atom dispersed doped metal atoms on lattice sites.
2. The method of claim 1, wherein the MXene is present in an amount of between 5 wt% and 20 wt% by mass;
and/or, the sulfur spheres are particles containing elemental sulfur and a binder.
3. The method of claim 2, wherein the dopant metal atoms are selected from one or more of zinc, nickel, cobalt, iron, platinum, copper, silver, gold, magnesium, calcium, gallium, indium, tin, silicon, germanium, antimony, bismuth, lead, or aluminum;
and/or the sulfur spheres have a particle size of 0.5 μm to 1 μm.
4. The method of any one of claims 2 or 3, wherein the method of producing MXene comprises:
mixing the metal salt doped with the metal with MAX phase material, annealing at a preset temperature, cooling to room temperature, adding the obtained product into acid liquor, stirring for a preset time to obtain a dispersion, centrifuging and washing for several times to remove residual salt and acid, thus obtaining an intermediate product; dispersing the intermediate product in a solvent, performing ultrasonic treatment, and collecting a dispersion in a liquid phase to obtain the MXene material;
or, mixing the metal salt doped with the metal, the etchant and the MAX phase material in the solution, and then keeping for a preset time to obtain the MXene material.
5. The method of claim 4, wherein the metal salt is a metal chloride;
and/or, the predetermined temperature is between 550 ℃ and 600 ℃;
and/or, the predetermined time is 10h; and/or the solvent is isopropanol.
6. The production method according to any one of claims 1 to 3, 5, wherein the production method of the sulfur ball comprises: na is mixed with 2 S 2 O 3 Dispersing the mixture and the binder in water to obtain a mixed solution; and (3) adding acid liquor into the mixed liquor to react under the stirring state, collecting a product obtained by the reaction, and drying to obtain the sulfur ball.
7. The method of claim 6, wherein the binder is polyvinylpyrrolidone; the acid liquid is hydrochloric acid.
8. Use of the MXene coated sulfur composite material obtained by the preparation method of any one of claims 1 to 7 as a positive electrode material for lithium sulfur battery.
9. The preparation method of the positive electrode material of the lithium-sulfur battery is characterized by comprising the following steps: the preparation method of any one of claims 1 to 5 is used for obtaining the MXene coated sulfur composite material, and the MXene coated sulfur composite material is mixed with an initiator and heated to polymerize sulfur in the composite material and convert the sulfur into cross-linked polysulfide, so that the positive electrode material of the lithium-sulfur battery is obtained.
10. The method of claim 9, wherein the initiator is: diisobutylene;
and/or, the mass ratio of the composite material to the initiator is 9:1;
and/or, the heating temperature is: 185 ℃;
and/or, the heating time is 10min.
11. A lithium sulfur battery comprising the MXene coated sulfur composite material obtained by the production method according to any one of claims 1 to 7;
or, the positive electrode material of the lithium-sulfur battery obtained by the preparation method of claim 9 or 10.
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101719545A (en) * 2009-12-16 2010-06-02 北京理工大学 Anode composite material of lithium sulfur battery and preparation method thereof
CN104332600A (en) * 2014-10-24 2015-02-04 东莞市翔丰华电池材料有限公司 Method for preparing graphene/sulfur/conductive polymer composite material used for lithium-sulfur battery positive electrode
CN105070895A (en) * 2015-09-24 2015-11-18 扬州大学 Method for preparing nanometer sulfur ball wrapped by manganese dioxide
WO2016012275A1 (en) * 2014-07-22 2016-01-28 Basf Se Composites comprising mxenes for cathodes of lithium sulfur cells
CN106450205A (en) * 2016-11-02 2017-02-22 南京工业大学 Two-dimensional transition metal carbide (nitride) and nano sulfur particle composite material and preparation and application thereof
KR20170106860A (en) * 2016-03-14 2017-09-22 한국에너지기술연구원 Mxene materials surface-modified with sulfur
CN109301227A (en) * 2018-10-30 2019-02-01 肇庆市华师大光电产业研究院 A kind of compound MXene material of ternary metal oxide and its application in lithium-sulfur cell
CN109449405A (en) * 2018-10-30 2019-03-08 肇庆市华师大光电产业研究院 A kind of sulphur-oxygen doping MXene- carbon nano tube compound material and its application in lithium-sulfur cell

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102024897B1 (en) * 2016-06-08 2019-09-24 주식회사 엘지화학 Self-assembled composite with Carbon Nitride and Graphene Oxide, Manufacturing Method Thereof, Cathode Applying the same, And Lithium-Sulfur Battery Comprising The Same
CN109437177B (en) * 2018-12-04 2021-10-26 中国科学院宁波材料技术与工程研究所 MXene material with Cl as surface group and preparation method and application thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101719545A (en) * 2009-12-16 2010-06-02 北京理工大学 Anode composite material of lithium sulfur battery and preparation method thereof
WO2016012275A1 (en) * 2014-07-22 2016-01-28 Basf Se Composites comprising mxenes for cathodes of lithium sulfur cells
CN104332600A (en) * 2014-10-24 2015-02-04 东莞市翔丰华电池材料有限公司 Method for preparing graphene/sulfur/conductive polymer composite material used for lithium-sulfur battery positive electrode
CN105070895A (en) * 2015-09-24 2015-11-18 扬州大学 Method for preparing nanometer sulfur ball wrapped by manganese dioxide
KR20170106860A (en) * 2016-03-14 2017-09-22 한국에너지기술연구원 Mxene materials surface-modified with sulfur
CN106450205A (en) * 2016-11-02 2017-02-22 南京工业大学 Two-dimensional transition metal carbide (nitride) and nano sulfur particle composite material and preparation and application thereof
CN109301227A (en) * 2018-10-30 2019-02-01 肇庆市华师大光电产业研究院 A kind of compound MXene material of ternary metal oxide and its application in lithium-sulfur cell
CN109449405A (en) * 2018-10-30 2019-03-08 肇庆市华师大光电产业研究院 A kind of sulphur-oxygen doping MXene- carbon nano tube compound material and its application in lithium-sulfur cell

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Synthesis of MXenes and MXenes-containing Composites for Energy Storage and Conversions;WU Weiming等;《应用化学》;第35卷(第3期);第317-327页 *
高性能锂硫电池正极用碳基材料的表、界面修饰;袁华栋;罗剑敏;金成滨;盛欧微;黄辉;张文魁;陶新永;;储能科学与技术(03);第57-87页 *

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