CN115084480A - Metal oxide-metal sulfide heterojunction material and preparation method and application thereof - Google Patents

Metal oxide-metal sulfide heterojunction material and preparation method and application thereof Download PDF

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CN115084480A
CN115084480A CN202210851470.3A CN202210851470A CN115084480A CN 115084480 A CN115084480 A CN 115084480A CN 202210851470 A CN202210851470 A CN 202210851470A CN 115084480 A CN115084480 A CN 115084480A
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metal oxide
lithium
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sulfur
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曾攀
王清远
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Chengdu University
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Abstract

The invention discloses a metal oxide-metal sulfide heterojunction material and a preparation method and application thereof. The method of the invention prepares the precursor Na of the metal oxide 0.67 Ni x Mn 1‑x O 2 (0<x<1) Directly used as a sulfur carrier material and assembled into a lithium sulfur battery, and the metal oxide Na is realized by regulating and controlling the charge cut-off voltage 0.67 Ni x Mn 1‑x O 2 (0<x<1) In-situ reconstruction to generate metal oxide-metal sulfide heterojunction (Na) 0.67 Ni x Mn 1‑x O 2 ‑MnS 2 ‑Ni 3 S 4 ，0<x<1) The complex hydrothermal and high-temperature sulfide processes are avoided, and the preparation period of the metal oxide-metal sulfide heterojunction is shortened. The invention also provides application of the metal oxide-metal sulfide heterojunction material as a positive electrode material of a lithium-sulfur battery, so that polysulfide can be effectively adsorbed and catalytically converted, and the electrochemical performance of the lithium-sulfur battery can be remarkably improved.

Description

Metal oxide-metal sulfide heterojunction material and preparation method and application thereof
Technical Field
The invention belongs to the field of battery materials, and particularly relates to a lithium-sulfur battery positive electrode material and a preparation method thereof
Background
The theoretical specific capacity of the lithium-sulfur battery is up to 1675mAh g -1 Theoretical energy density can reach 2600Wh kg -1 Meanwhile, the lithium-sulfur battery has the advantages of low cost, environmental friendliness and the like by taking elemental sulfur as an active material, so that the lithium-sulfur battery is considered to be one of novel secondary battery systems with development prospects. However, polysulfide shuttling and its slow redox conversion during charging and discharging can lead to loss of sulfur active species, low coulombic efficiency and poor cycling performance, which severely hampers the commercial application of lithium sulfur batteries. Therefore, designing a catalytic material that can effectively adsorb polysulfides and accelerate the redox conversion of polysulfides is critical to the commercial application of lithium sulfur batteries. However, metal-based catalytic materials such as metal oxides (NiO, TiO) have been reported so far 2 、Co 3 O 4 、Mg 0.6 Ni 0.4 O), metal sulfides (CoS) 2 、MoS 2 ) Metal nitride (TiN, Ni) 3 N) and metal phosphides (FeP, CoFeP, MnP) etc. generally only adsorb polysulfides or catalytically convert polysulfides, but do not simultaneously fulfill the function of efficiently adsorbing and catalytically converting polysulfides. The construction of the metal oxide-metal sulfide heterojunction can integrate active centers with different catalytic functions into one structure, thereby realizing the conversion from a single-function catalyst to a multifunctional catalyst and further realizing the effective adsorption and catalytic conversion of polysulfide. For example, Yang et al prepared TiO 2 -Ni 3 S 2 Heterojunction of TiO in which 2 Effectively adsorb polysulfide dissolved in electrolyte and Ni 3 S 2 Promoting the conversion of adsorbed polysulfides. However, in the field of lithium-sulfur battery research, metal oxide-sulfide heterogeneityThe preparation of junctions typically requires two steps: firstly, preparing a metal oxide precursor, and then carrying out hydrothermal coating on the precursor or carrying out high-temperature vulcanization on the precursor. The method has the advantages of complex preparation process, long preparation period and need of introducing an additional sulfur source in the preparation process. Therefore, the development of a fast and efficient method for preparing a metal oxide-sulfide heterojunction is crucial to the development of lithium-sulfur batteries.
Disclosure of Invention
The invention aims to provide a metal oxide-metal sulfide heterojunction material, a preparation method and application thereof aiming at the problems in the prior art so as to simplify the preparation process of metal oxide-sulfide heterogeneity, shorten the preparation period and reduce the manufacturing cost; the material is used as a lithium-sulfur battery anode material to realize effective polysulfide adsorption and catalytic conversion, so that the electrochemical performance of the lithium-sulfur battery is remarkably improved.
Different from the traditional preparation method that the prepared metal oxide precursor is vulcanized or hydrothermally coated to obtain the metal oxide-metal sulfide heterojunction, the method of the invention prepares the metal oxide precursor Na 0.67 Ni x Mn 1-x O 2 (0<x<1) Directly used as a sulfur carrier material and assembled into a lithium sulfur battery, and the metal oxide Na is realized by regulating and controlling the charge cut-off voltage 0.67 Ni x Mn 1-x O 2 (0<x<1) In-situ reconstruction to generate metal oxide-metal sulfide heterojunction (Na) 0.67 Ni x Mn 1-x O 2 -MnS 2 -Ni 3 S 4 ，0<x<1). The method avoids complicated hydrothermal and high-temperature sulfide processes, shortens the preparation period of the metal oxide-metal sulfide heterojunction, does not need to introduce an additional sulfur source in the preparation process, and reduces the manufacturing cost.
The chemical formula of the metal oxide-metal sulfide heterojunction material provided by the invention is Na 0.67 Ni x Mn 1-x O 2 -MnS 2 -Ni 3 S 4 (0<x<1)。
Further, the heterogeneous natureThe junction material is prepared by adding metal oxide precursor Na 0.67 Ni x Mn 1-x O 2 (0<x<1) Directly used as a sulfur carrier material, assembled into a lithium sulfur battery and adjusted and controlled in charge cut-off voltage to realize metal oxide Na 0.67 Ni x Mn 1-x O 2 (0<x<1) In situ reconstruction.
The invention provides a metal oxide-metal sulfide heterojunction and a preparation method thereof, wherein the preparation method comprises the following steps:
step 1: metal oxide Na 0.67 Ni x Mn 1-x O 2 (0<x<1) Preparation of
(1) Dissolving citric acid in a certain amount of glycol solvent, and stirring uniformly at room temperature, wherein the mass ratio of citric acid to glycol is 1: (1-8) adding;
(2) adding a certain amount of metal Na salt, Ni salt and Mn salt into the solution obtained in the step (1), and continuously stirring uniformly, wherein the amount of the metal Na salt, the amount of the metal Ni salt and the amount of the metal Mn salt are added according to the molar ratio of Na, Ni and Mn elements of 0.67: x (1-x);
(3) placing the solution obtained in the step (2) in an oil bath kettle, stirring for 2-48 h at 40-80 ℃, then heating to 100-260 ℃, and preserving heat for 2-48 h to obtain brown-black xerogel;
(4) calcining the obtained gel in a tubular furnace at 700-1200 ℃ for 1-72 h under the atmosphere of high-purity nitrogen or argon to obtain black metallic oxide Na 0.67 Ni x Mn 1-x O 2 And (3) powder.
And 2, step: na (Na) 0.67 Ni x Mn 1-x O 2 @S(0<x<1) Preparation of the Positive electrode
(1) Mixing Na 0.67 Ni x Mn 1-x O 2 Weighing and mixing the powder, the carbon material and the sulfur material according to the mass ratio of 1 (1-5) to (1-9) and grinding uniformly; placing the obtained mixture in a closed container, heating to 120-300 ℃, and preserving heat for 3-72 hours to obtain Na 0.67 Ni x Mn 1-x O 2 The @ S complex;
(2) mixing Na 0.67 Ni 0.25 Mn 0.75 O 2 @ S composite, carbon material, binder matrixThe quantity ratio (6-12): (1-6): 1 grinding and mixing uniformly, adding a solvent, grinding to form uniform slurry, wherein the dosage of the solvent is limited to completely dissolve the adhesive and uniformly disperse the carbon material to form the slurry; uniformly coating the slurry on an aluminum foil or a carbon-coated aluminum foil, drying at 60-80 ℃, and cooling to room temperature to obtain Na 0.67 Ni x Mn 1-x O 2 @ S positive electrode.
And step 3: na (Na) 0.67 Ni x Mn 1-x O 2 Assembly of @ S lithium-sulfur battery
Sealing the positive plate, the negative plate, the diaphragm and the ether electrolyte in the battery shell to form Na 0.67 Ni x Mn 1-x O 2 @ S lithium sulfur batteries;
and 4, step 4: formation of metal oxide-metal sulfide heterojunction Na by regulating and controlling charging voltage 0.67 Ni x Mn 1-x O 2 -MnS 2 -Ni 3 S 4
Na to be assembled 0.67 Ni x Mn 1-x O 2 The @ S lithium sulfur battery was first charged to different voltages, over Na 0.67 Ni x Mn 1-x O 2 Self electrochemical reconstruction preparation of metal oxide-metal sulfide heterojunction Na 0.67 Ni x Mn 1-x -MnS 2 -Ni 3 S 4 (ii) a Wherein, the first circle of charging voltage range sets up at 3 ~ 4.5V.
Further, after step 4, the battery is disassembled and Na is taken out 0.67 Ni x Mn 1-x O 2 Washing the/S electrode with dimethyl ether for several times, and naturally drying the electrode in a glove box for 2-72 hours; scraping off substances on the electrode slice, soaking the scraped substances in ethylene glycol dimethyl ether mixed solution, performing ultrasonic treatment for 0.5-72 h, centrifuging to remove floating carbon material suspension, and repeating soaking-centrifuging operation for multiple times to obtain Na 0.67 Ni x Mn 1-x O 2 -MnS 2 -Ni 3 S 4 Heterostructure powder.
Further, in step 1, the metal Na salt is selected from CH 3 COONa、Na 2 SO 4 、NaCl、Na 2 CO 3 、NaHCO 3 One or more of the above; the metal Ni salt is selected from Ni (CH) 3 COO) 2 、NiSO 4 、NiCl 2 One or more of the above; the metal Mn salt is selected from Mn (CH) 3 COO) 2 、MnSO 4 、MnCl 2 、MnCO 3 One or more of them.
Further, the carbon material in the step 2 is preferably one of conductive carbon black, acetylene black, ketjen carbon, activated carbon, carbon nanotubes, graphene, porous carbon and carbon nanofibers; the sulfur material is preferably sublimed sulfur.
Further, the binder in step 2 is preferably polyvinylidene fluoride or polytetrafluoroethylene.
Further, in the step 2, the uniformly dispersed slurry is coated on one side of the aluminum foil or the carbon-coated aluminum foil, preferably by one of spraying, blade coating, coating roll and coating brush.
Further, the solvent in step 2 is preferably one of N-methylpyrrolidone, dimethylformamide and dimethylacetamide.
Further, the negative electrode plate in the step 3 contains lithium metal or lithium alloy; the diaphragm is a polyolefin or polypropylene porous diaphragm; the ether electrolyte is formed by dissolving LiTFSI in mixed ether obtained by mixing dioxolane and ethylene glycol dimethyl ether.
The invention also provides an application of the metal oxide-metal sulfide heterojunction material, wherein the application is used as a positive electrode material of a lithium-sulfur battery.
The invention also provides a positive electrode material Na of the lithium-sulfur battery 0.67 Ni x Mn 1-x O 2 -MnS 2 -Ni 3 S 4 (0<x<1) The catalyst has irregular polygonal shape, high catalytic activity and catalytic stability, and can be used as a lithium sulfur battery cathode material to accelerate the conversion of polysulfide so as to obtain a high-performance lithium sulfur battery.
Compared with the prior art, the invention has the following technical effects:
different from the traditional preparation method (namely, the preparation method is to be implementedThe prepared metal oxide precursor is subjected to sulfuration or hydrothermal coating to obtain a metal oxide-sulfide heterojunction), and the method realizes the metal oxide Na by regulating and controlling the charge cut-off voltage 0.67 Ni x Mn 1-x O 2 In-situ reconstruction to generate metal oxide-metal sulfide heterojunction (Na) 0.67 Ni x Mn 1-x O 2 -MnS 2 -Ni 3 S 4 ) The complex hydrothermal and high-temperature sulfide processes are avoided, the preparation period of the metal oxide-metal sulfide heterojunction is shortened, an additional sulfur source is not required to be introduced in the preparation process, and the manufacturing cost is reduced, so that the industrial production is easy to realize. Meanwhile, the prepared metal oxide-metal sulfide heterojunction can simultaneously realize effective adsorption of polysulfide and continuous and rapid reduction and conversion of polysulfide, and the assembled lithium-sulfur battery has excellent rate performance and cycle stability.
Drawings
FIG. 1 is Na prepared in example 1 0.67 Ni 0 .25Mn 0.75 O 2 XRD characterization pattern of (a);
FIG. 2 is Na prepared in example 1 0.67 Ni 0.25 Mn 0.75 O 2 SEM characterization of (a);
FIG. 3 is Na prepared in example 1 0.67 Ni 0.25 Mn 0.75 O 2 A TEM representation of (D);
FIG. 4 is the original Na prepared in example 1 0.67 Ni 0.25 Mn 0.75 O 2 XRD representation patterns of the/S positive electrode and the positive electrode charged to 4V;
FIG. 5 is Na prepared in example 1 0.67 Ni 0.25 Mn 0.75 O 2 TEM representation of the/S positive electrode charged to 4V;
FIG. 6 is a cyclic voltammogram of a symmetric cell assembled from different materials as in example 1;
FIG. 7 is a first cyclic voltammogram of a lithium sulfur cell assembled from different materials as in example 1;
FIG. 8 is a graph of rate performance at room temperature for a lithium sulfur battery assembled from different materials in example 1;
fig. 9 is a graph of the cycling performance at room temperature of a lithium sulfur battery assembled with different materials in example 1.
Detailed Description
The invention is further illustrated by the following examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and those skilled in the art can make certain insubstantial modifications and adaptations of the present invention based on the above disclosure and still fall within the scope of the present invention.
EXAMPLE 1
Step 1: metal oxide Na 0.67 Ni 0.25 Mn 0.75 O 2 Preparation of
(1) 0.06mol of citric acid is dissolved in 60ml of glycol solvent and stirred evenly at room temperature.
(2) 0.02mol of CH 3 COONa、0.02mol Mn(CH 3 COO) 2 、0.0075mol Ni(CH 3 COO) 2 Adding into the solvent, and continuously stirring.
(3) And (3) placing the solution in an oil bath kettle, stirring for 12h at 80 ℃, then heating to 150 ℃, and preserving heat for 24h to obtain brown-black xerogel.
(4) Transferring the obtained gel into a porcelain boat, calcining at 900 ℃ for 12h in a tubular furnace under the atmosphere of high-purity nitrogen or argon to obtain black metallic oxide Na 0.67 Ni 0.25 Mn 0.75 O 2 And (3) powder.
FIG. 1 shows prepared Na 0.67 Ni 0.25 Mn 0.75 O 2 XRD characterization pattern of (a). As can be seen from the XRD pattern, all diffraction peaks are consistent with those of the typical layered transition metal oxide, and no impurity peak is found, indicating that the expected Na is obtained by the preparation method 0.67 Ni 0.25 Mn 0.75 O 2 And (3) precursor. SEM of FIG. 2 and TEM image of FIG. 3 show, Na 0.67 Ni 0.25 Mn 0.75 O 2 Has hexagonal morphology and a size of about 2 μm.
Step 2: na (Na) 0.67 Ni 0.25 Mn 0.75 O 2 Of the positive electrode @ SPreparation of
Mixing Na 0.67 Ni 0.25 Mn 0.75 O 2 Weighing and mixing the powder, the acetylene black and the sulfur according to the mass ratio of 1:1:6, and uniformly grinding; placing the obtained mixture in a closed container, heating to 155 deg.C, and keeping the temperature for 6h to obtain Na 0.67 Ni 0.25 Mn 0.75 O 2 The @ S complex; mixing Na 0.67 Ni 0.25 Mn 0.75 O 2 The @ S composite, the graphene and the polyvinylidene fluoride binder are mixed according to the mass ratio of 6: 3: 1 grinding and mixing uniformly, and then adding a proper amount of N-methyl pyrrolidone solvent for grinding for 0.5 h; then, uniformly coating the uniformly dispersed slurry on a carbon-coated aluminum foil by using a scraper; drying the carbon-coated aluminum foil coated with the mixed slurry at 60 ℃, and cooling to room temperature to obtain Na 0.67 Ni 0.25 Mn 0.75 O 2 @ S positive electrode.
And 3, step 3: na (Na) 0.67 Ni 0.25 Mn 0.75 O 2 Assembly of @ S lithium sulfur battery
With Na 0.67 Ni 0.25 Mn 0.75 O 2 And the @ S is the anode, the lithium sheet is the cathode, the polypropylene diaphragm Celgard 2500 is the diaphragm, the lithium sulfur battery is placed into the lithium sulfur battery shell, electrolyte is dropwise added, and the lithium sulfur battery is assembled after sealing. The electrolyte component is DME/DOL (V: V ═ 1:1) and contains 1M LiTFSI and 2 wt% LiNO 3 。
And 4, step 4: formation of metal oxide-metal sulfide heterojunction Na by regulating and controlling charging voltage 0.67 Ni 0.25 Mn 0.75 O 2 -MnS 2 -Ni 3 S 4
Na to be assembled 0.67 Ni 0.25 Mn 0.75 O 2 The @ S lithium sulfur battery was first charged to 4V over Na 0.67 Ni 0.25 Mn 0.75 O 2 Preparation of metal oxide-metal sulfide heterojunction Na by self electrochemical reconstruction 0.67 Ni 0.25 Mn 0.75 O 2 -MnS 2 -Ni 3 S 4 。
FIG. 4 shows Na in assembly 0.67 Ni 0.25 Mn 0.75 O 2 XRD spectrum of positive electrode after charging of/S lithium-sulfur battery to 4V.From XRD in FIG. 4, it can be seen that Na is present after charging to 4.0V 0.67 Ni 0.25 Mn 0.75 O 2 The signal intensity is significantly reduced, the sulfur signal almost disappears, and MnS 2 And Ni 3 S 4 Diffraction occurred indicating that a ternary heterojunction Na was likely to be formed 0.67 Ni 0.25 Mn 0.75 O 2 -MnS 2 -Ni 3 S 4 . From the high resolution TEM of FIG. 5, 0.33nm corresponds to Ni 3 S 4 Face (022) of (1), 0.28nm corresponds to Na 0.67 Ni 0.25 Mn 0.75 O 2 And 0.27nm corresponds to the (210) plane of MnS 2. When XRD analysis in FIG. 4 shows that Na 0.67 Ni 0.25 Mn 0.75 O 2 When the lithium-sulfur battery assembled by the/S is charged to 4V, heterojunction Na is formed in the positive pole piece 0.67 Ni 0.25 Mn 0.75 O 2 -Ni 3 S 4 -MnS 2 。
To prove the heterojunction Na 0.67 Ni 0.25 Mn 0.75 O 2 -Ni 3 S 4 -MnS 2 The catalytic activity of (1) is that firstly, the battery charged to 4V is disassembled and Na is taken out 0.67 Ni 0.25 Mn 0.75 O 2 @ S electrode, washed several times with dimethyl ether and dried naturally in a glove box for 12 h. And then scraping the active substances on the electrode slice, soaking in a dimethyl ether solution, performing ultrasonic treatment for 2 hours, and centrifuging to remove the floating graphene suspension. Repeating the above operation for several times, and centrifuging to obtain Na 0.67 Ni 0.25 Mn 0.75 O 2 -MnS 2 -Ni 3 S 4 Heterostructure powder, last NNMO-Ni 3 S 4 -MnS 2 The composite material is assembled into a symmetrical battery by the following method:
prepared Na 0.67 Ni 0.25 Mn 0.75 O 2 -Ni 3 S 4 -MnS 2 And weighing and mixing the heterojunction powder and the polyvinylidene fluoride binder according to the mass ratio of 4:1, manually grinding the mixture in an agate mortar for 10min, and then adding a proper amount of N-methylpyrrolidone solvent for grinding for 10min to obtain viscous slurry. The obtained slurry was coated on a carbon cloth with a doctor blade,then placed in a constant temperature drying oven and incubated at 70 ℃ overnight. The resulting electrode was punched out with a punch to be cut into a circular piece having a diameter of 14 mm. The resulting wafer was used as an electrode material, Celgard 2500 was used as a separator, and the electrolyte composition was DME/DOL (V: V ═ 1:1) containing 1M LiTFSI and 0.2M Li 2 S 6 And assembling the symmetrical battery.
Simultaneously setting a control group Na 0.67 Ni 0.25 Mn 0.75 O 2 、MnS、Ni 3 S 2 And is free of Li 2 S 6 Group (I) wherein, Na 0.67 Ni 0.25 Mn 0.75 O 2 、MnS、Ni 3 S 2 Respectively adding Na 0.67 Ni 0.25 Mn 0.75 O 2 、MnS、Ni 3 S 2 The powder and the polyvinylidene fluoride binder are weighed and mixed according to the mass ratio of 4:1, the mixture is manually ground in an agate mortar for 10min, and then a proper amount of N-methyl pyrrolidone solvent is added for grinding for 10min, so as to obtain viscous slurry. The obtained slurry was coated on a carbon cloth with a doctor blade, and then placed in a constant temperature drying oven to be kept at 70 ℃ overnight. The resulting electrode was punched out with a punch to be cut into a circular piece having a diameter of 14 mm. The resulting wafer was used as an electrode material and 2500 was used as a separator, and the electrolyte composition was DME/DOL (V: V ═ 1:1) containing 1M LiTFSI and 0.2M Li 2 S 6 And assembling the symmetrical battery. Free of Li 2 S 6 Group assembly method and Na 0.67 Ni 0.25 Mn 0.75 O 2 -Ni 3 S 4 -MnS 2 Same except that 0.2M-free Li is used 2 S 6 DME/DOL (V: V ═ 1:1) and 1M LiTFSI as the electrolyte. Addition of this group of Li-free 2 S 6 To demonstrate that the response current in a symmetrical cell is derived from Li 2 S 6 Produced by conversion of (1), containing Li 2 S 6 All have response current generation, and no Li 2 S 6 The symmetric cell of (2) has no response current generation, which proves that the response current generation is caused by Li 2 S 6 And (4) converting the obtained product.
The cyclic voltammograms of the different symmetrical cells were tested separately and the results are shown in FIG. 6, which is a graphAs can be seen in (1), heterojunction Na 0.67 Ni 0.25 Mn 0.75 O 2 -Ni 3 S 4 -MnS 2 The assembled symmetric cell has the largest response current, which indicates the metal oxide-metal colored sulfide heterojunction Na 0.67 Ni 0.25 Mn 0.75 O 2 -Ni 3 S 4 -MnS 2 Has the best catalytic conversion effect on polysulfide.
Fig. 7 is a first cyclic voltammogram of a lithium sulfur battery assembled with different materials. As can be seen from FIG. 7, the metal oxide-metal sulfide heterojunction Na 0.67 Ni 0.25 Mn 0.75 O 2 -Ni 3 S 4 -MnS 2 The redox peaks of the assembled lithium sulfur cell have small polarization, which also demonstrates Na 0.67 Ni 0.25 Mn 0.75 O 2 -Ni 3 S 4 -MnS 2 The composite material has a catalytic effect on the redox conversion of polysulfides.
Fig. 8 is a graph of the cycling performance of lithium sulfur cells assembled with different materials at room temperature. As can be seen from FIG. 8, Na 0.67 Ni 0.25 Mn 0.75 O 2 -MnS 2 -Ni 3 S 4 the/S positive electrode exhibits a ratio of Ni 3 S 2 /S, MnS/S and Na 0.67 Ni 0.25 Mn 0.75 O 2 Higher rate capability of the/S anode. Even at 4C and 8C (1C ═ 1675mA g -1 ) At high magnification, Na 0.67 Ni 0.25 Mn 0.75 O 2 -MnS 2 -Ni 3 S 4 the/S positive electrode still keeps high specific capacity, namely 922mAh g-1 and 380mAh g -1 。
Fig. 9 is a graph of the cycling performance of lithium sulfur batteries assembled with different materials at room temperature. After circulating for 100 circles, Na 0.67 Ni 0.25 Mn 0.75 O 2 -MnS 2 -Ni 3 S 4 The specific capacity of the/S anode reaches 952mAh g -1 The corresponding capacity retention was 87% higher than that of comparative Ni 3 S 2 /S(709mAh g -1 ，75％)，MnS/S(690mAh g -1 71%) and Na 0.67 Ni 0.25 Mn 0.75 O 2 /S(550mAh g -1 67%) positive electrode.
EXAMPLE 2
Step 1: metal oxide Na 0.67 Ni 0.25 Mn 0.75 O 2 Preparation of
(1) 0.06mol of citric acid is dissolved in 60ml of glycol solvent and stirred evenly at room temperature.
(2) 0.02mol of CH 3 COONa、0.02mol Mn(CH 3 COO) 2 、0.0075mol Ni(CH 3 COO) 2 Adding into the solvent, and continuously stirring.
(3) And (3) placing the solution in an oil bath kettle, stirring for 12h at 80 ℃, then heating to 150 ℃, and preserving heat for 24h to obtain brown-black xerogel.
(4) Transferring the obtained gel into a porcelain boat, calcining at 900 ℃ for 12h in a tubular furnace under the atmosphere of high-purity nitrogen or argon to obtain black metallic oxide Na 0.67 Ni 0.25 Mn 0.75 O 2 And (3) powder.
And 2, step: na (Na) 0.67 Ni 0.25 Mn 0.75 O 2 Preparation of @ S cathode
Mixing Na 0.67 Ni 0.25 Mn 0.75 O 2 Weighing and mixing the powder, the acetylene black and the sulfur according to the mass ratio of 1:1:6, and uniformly grinding; placing the obtained mixture in a closed container, heating to 155 deg.C, and keeping the temperature for 6h to obtain Na 0.67 Ni 0.25 Mn 0.75 O 2 The @ S complex; mixing Na 0.67 Ni 0.25 Mn 0.75 O 2 The @ S composite, the graphene and the polyvinylidene fluoride binder are mixed according to the mass ratio of 6: 3: 1 grinding and mixing uniformly, and then adding a proper amount of N-methyl pyrrolidone solvent for grinding for 0.5 h; then, uniformly coating the uniformly dispersed slurry on a carbon-coated aluminum foil by using a scraper; drying the carbon-coated aluminum foil coated with the mixed slurry at 60 ℃, and cooling to room temperature to obtain Na 0.67 Ni 0.25 Mn 0.75 O 2 @ S positive electrode.
And 3, step 3: na (Na) 0.67 Ni 0.25 Mn 0.75 O 2 Assembly of @ S lithium sulfur battery
With Na 0.67 Ni 0.25 Mn 0.75 O 2 And the @ S is the anode, the lithium sheet is the cathode, the polypropylene diaphragm Celgard 2500 is the diaphragm, the lithium sulfur battery is placed into the lithium sulfur battery shell, electrolyte is dropwise added, and the lithium sulfur battery is assembled after sealing. The electrolyte component is DME/DOL (V: V ═ 1:1) and contains 1M LiTFSI and 2 wt% LiNO 3 。
And 4, step 4: formation of metal oxide-metal sulfide heterojunction Na by regulating and controlling charging voltage 0.67 Ni 0.25 Mn 0.75 O 2 -MnS 2 -Ni 3 S 4
Na to be assembled 0.67 Ni 0.25 Mn 0.75 O 2 The @ S lithium sulfur battery was first charged to 3.5V over Na 0.67 Ni 0.25 Mn 0.75 O 2 Preparation of metal oxide-metal sulfide heterojunction Na by self electrochemical reconstruction 0.67 Ni 0.25 Mn 0.75 O 2 -MnS 2 -Ni 3 S 4 。

Claims (10)

1. A metal oxide-metal sulfide heterojunction material is characterized in that the chemical formula of the material is Na 0.67 Ni x Mn 1-x O 2 -MnS 2 -Ni 3 S 4 (0<x<1)。
2. The metal oxide-metal sulfide heterojunction material of claim 1, wherein said heterojunction material is prepared by subjecting a metal oxide precursor Na 0.67 Ni x Mn 1-x O 2 (0<x<1) Directly used as a sulfur carrier material, assembled into a lithium sulfur battery and adjusted and controlled in charge cut-off voltage to realize metal oxide Na 0.67 Ni x Mn 1-x O 2 (0<x<1) In situ reconstruction.
3. The metal oxide-metal sulfide heterojunction as claimed in claim 1, comprising the steps of:
step 1: metal oxide Na 0.67 Ni x Mn 1-x O 2 (0<x<1) Preparation of
(1) Dissolving citric acid in a certain amount of glycol solvent, and stirring uniformly at room temperature, wherein the mass ratio of citric acid to glycol is 1: (1-8) adding;
(2) adding a certain amount of metal Na salt, Ni salt and Mn salt into the solution obtained in the step (1), and continuously stirring uniformly, wherein the metal Na salt, the metal Ni salt and the metal Mn salt are added according to the molar ratio of Na, Ni and Mn elements of 0.67: x (1-x) in sequence;
(3) placing the solution obtained in the step (2) in an oil bath kettle, stirring for 2-48 h at 40-80 ℃, then heating to 100-260 ℃, and preserving heat for 2-48 h to obtain brown-black xerogel;
(4) calcining the obtained gel in a tubular furnace at 700-1200 ℃ for 1-72 h under the atmosphere of high-purity nitrogen or argon to obtain black metallic oxide Na 0.67 Ni x Mn 1-x O 2 And (3) powder.
Step 2: na (Na) 0.67 Ni x Mn 1-x O 2 @S(0<x<1) Preparation of the Positive electrode
(1) Mixing Na 0.67 Ni x Mn 1-x O 2 Weighing and mixing the powder, the carbon material and the sulfur material according to the mass ratio of 1 (1-5) to (1-9) and grinding uniformly; placing the obtained mixture in a closed container, heating to 120-300 ℃, and preserving heat for 3-72 hours to obtain Na 0.67 Ni x Mn 1- x O 2 The @ S complex;
(2) mixing Na 0.67 Ni 0.25 Mn 0.75 O 2 The @ S composite, the carbon material and the binder are mixed according to the mass ratio (6-12): (1-6): 1 grinding and mixing uniformly, adding a solvent, grinding to form uniform slurry, wherein the dosage of the solvent is limited to completely dissolve the adhesive and uniformly disperse the carbon material to form the slurry; uniformly coating the slurry on an aluminum foil or a carbon-coated aluminum foil, drying at 60-80 ℃, and cooling to room temperature to obtain Na 0.67 Ni x Mn 1-x O 2 @ S positive electrode.
And step 3: na (Na) 0.67 Ni x Mn 1-x O 2 Assembly of @ S lithium-sulfur battery
Mixing positive plate, negative plate, diaphragm and ether electrolyteSealing the electrolyte in the battery case to form Na 0.67 Ni x Mn 1-x O 2 @ S lithium sulfur batteries;
and 4, step 4: formation of metal oxide-metal sulfide heterojunction Na by regulating and controlling charging voltage 0.67 Ni x Mn 1-x O 2 -MnS 2 -Ni 3 S 4
Na to be assembled 0.67 Ni x Mn 1-x O 2 The @ S lithium sulfur battery was first charged to different voltages, over Na 0.67 Ni x Mn 1-x O 2 Preparation of metal oxide-metal sulfide heterojunction Na by self electrochemical reconstruction 0.67 Ni x Mn 1-x -MnS 2 -Ni 3 S 4 (ii) a Wherein, the first circle of charging voltage range sets up at 3 ~ 4.5V.
4. The method of claim 3, wherein after step 4, the battery is disassembled and Na is removed 0.67 Ni x Mn 1-x O 2 Washing the/S electrode with dimethyl ether for several times, and naturally drying the electrode in a glove box for 2-72 hours; scraping off substances on the electrode slice, soaking the scraped substances in ethylene glycol dimethyl ether mixed solution, performing ultrasonic treatment for 0.5-72 h, centrifuging to remove floating carbon material suspension, and repeating soaking-centrifuging operation for multiple times to obtain Na 0.67 Ni x Mn 1-x O 2 -MnS 2 -Ni 3 S 4 Heterostructure powder.
5. The method according to claim 3, wherein the metal Na salt in step 1 is selected from CH 3 COONa、Na 2 SO 4 、NaCl、Na 2 CO 3 、NaHCO 3 One or more of the above; the metal Ni salt is selected from Ni (CH) 3 COO) 2 、NiSO 4 、NiCl 2 One or more of the above; the metal Mn salt is selected from Mn (CH) 3 COO) 2 、MnSO 4 、MnCl 2 、MnCO 3 One or more of them.
6. The method according to claim 3, wherein the carbon material in step 2 is preferably one of conductive carbon black, acetylene black, Keqin carbon, activated carbon, carbon nanotube, graphene, porous carbon and carbon nanofiber; the sulfur material is sublimed sulfur.
7. The method of claim 3, wherein the binder in step 2 is preferably polyvinylidene fluoride or polytetrafluoroethylene; the solvent in the step 2 is preferably one of N-methyl pyrrolidone, dimethylformamide and dimethylacetamide; and in the step 2, the uniformly dispersed slurry is coated on one surface of the aluminum foil or the carbon-coated aluminum foil in a spraying mode, a scraper coating mode, a coating roller mode and a coating brush mode.
8. The method according to claim 3, wherein the negative electrode sheet in step 3 contains lithium metal or lithium alloy; the diaphragm is a polyolefin or polypropylene porous diaphragm; the ether electrolyte is formed by dissolving LiTFSI in mixed ether obtained by mixing dioxolane ring and glycol dimethyl ether.
9. Use of the metal oxide-metal sulfide heterojunction material of claim 1 in a lithium-sulfur battery.
10. The positive electrode material of the lithium-sulfur battery is characterized in that the chemical formula of the positive electrode material is Na 0.67 Ni x Mn 1-x O 2 -MnS 2 -Ni 3 S 4 (0<x<1) Is a metal oxide-metal sulfide heterojunction material.
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