CN115036592B - Double-site clay mineral-based sulfur reduction catalyst and preparation method and application thereof - Google Patents

Double-site clay mineral-based sulfur reduction catalyst and preparation method and application thereof Download PDF

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CN115036592B
CN115036592B CN202210702260.8A CN202210702260A CN115036592B CN 115036592 B CN115036592 B CN 115036592B CN 202210702260 A CN202210702260 A CN 202210702260A CN 115036592 B CN115036592 B CN 115036592B
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sulfur
reduction catalyst
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clay
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杨华明
高睿杰
张强
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China University of Geosciences
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
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    • H—ELECTRICITY
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    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
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    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
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Abstract

The invention discloses a double-site clay mineral-based sulfur reduction catalyst, and a preparation method and application thereof. The preparation method comprises the following steps: s1, calcining clay minerals, performing thermally activated dissociation treatment, and screening thermally activated clay; s2, uniformly mixing metal salt and activated clay in the step S1, and loading nano metal ions on the activated clay through a solid phase reaction of ball milling; and S3, grinding and mixing the activated clay and the sulfur powder of the S2 uniformly, and vulcanizing in a protective atmosphere to obtain the catalyst. The catalyst and the sulfur powder are ground and mixed uniformly, and are melted in a protective atmosphere to prepare the sulfur-carrying anode material of the double-site clay mineral-based sulfur reduction catalyst. The invention overcomes the limitation that the existing lithium sulfur battery anode only has single adsorption or single catalytic capability, can simultaneously enhance the adsorption capability and catalytic conversion capability to polysulfide, and has the characteristic of integrating multiple functions, thereby effectively inhibiting the shuttle effect of the lithium sulfur battery and improving the cycling stability of the lithium sulfur battery.

Description

Double-site clay mineral-based sulfur reduction catalyst and preparation method and application thereof
Technical Field
The invention relates to the technical field of catalysts, in particular to a double-site clay mineral-based sulfur reduction catalyst and a preparation method and application thereof.
Background
With the gradual development of the energy industry, the development and utilization of renewable energy sources such as solar energy, wind energy and the like have greatly advanced. At the same time, the implementation of these intermittent energy storage systems also places higher demands on battery technology. Among the numerous candidate batteries, lithium ion batteries, while having high energy density, have limited their large-scale use due to their toxicity to organic electrolytes, potential safety hazards, scarce lithium resources, and increasing costs.
Compared with the current commercial lithium ion battery, the lithium sulfur battery has obvious performance and cost advantages: in one aspect, a sulfur positive electrodeHas a mAh.g of up to 1675 mAh.g -1 Can be well matched with the ultrahigh capacity of lithium metal, and has the theoretical energy density of 2600 Wh.kg -1 Is ten times of theoretical energy density of the lithium iron phosphate battery. On the other hand, the sulfur element has the characteristics of environmental friendliness, low cost and large conservation amount, and the anode material does not pollute the environment in the use of the battery. For the above reasons, lithium sulfur battery systems are considered by the academia and industry as one of the most potential next-generation commercial lithium battery systems.
In the current research, wang and the like (grant publication number CN 110323447B) solve the problem of volume effect in the sulfur cycle process and improve the reaction kinetics of polysulfide by providing a lithium sulfur battery positive electrode framework material with a mesoporous structure; li Zhen (grant publication No. CN 109950472B) is used for researching and designing a lithium-sulfur battery positive electrode material with higher sulfur content, so that the battery energy density and the sulfur utilization rate are improved, the stable circulation of the battery is realized, and the production cost is reduced; yao Shanshan (grant publication No. CN 104752702B) is to add porous metal oxide micro-nanotubes into the positive electrode material of the lithium-sulfur battery to rapidly adsorb polysulfide and effectively prolong the cycle life of the lithium-sulfur battery.
Through the above search, the current technology is mainly to improve the cycling stability of the lithium sulfur battery by improving the adsorptivity of the positive electrode material of the lithium sulfur battery to polysulfide, but has few reports and applications for improving the catalytic conversion of the positive electrode material of the lithium sulfur battery to polysulfide in the cycling process and improving the ion diffusion rate and the electronic conductivity of the positive electrode material; in addition, the preparation process of the electrode is commonly used in a liquid phase system, is tedious and time-consuming, and is difficult to meet the requirements of mass and industrialized preparation.
Disclosure of Invention
The invention aims at overcoming the defects in the prior art and provides a double-site clay mineral-based sulfur reduction catalyst capable of simultaneously enhancing the adsorption capacity and the catalytic conversion capacity of polysulfide, and a preparation method and application thereof.
The invention discloses a preparation method of a double-site clay mineral-based sulfur reduction catalyst, which comprises the following steps:
s1, calcining clay minerals, so as to perform thermally activated dissociation treatment, and selecting thermally activated clay with proper granularity and size by screening;
s2, uniformly mixing a proper amount of metal salt with the activated clay in the step S1, and loading nano metal ions on the activated clay through a solid phase reaction of ball milling;
and S3, grinding and uniformly mixing the activated clay loaded with nano metal ions and sulfur powder in a certain mass ratio in the step S2, and vulcanizing in a protective atmosphere to obtain the metal-oxygen double-site clay mineral-based sulfur reduction catalyst.
Further, in step S1, clay mineral types include, but are not limited to, halloysite, kaolinite, sepiolite, vermiculite, rectorite, bentonite, and pyrophyllite; the purity of the clay mineral powder raw ore is more than 90 percent.
Further, in the step S1, the calcination temperature of the thermal activation is 400-600 ℃, and the calcination time of the thermal activation is 2-6 hours; the sieving granularity is 200-500 meshes, and the microscopic size of the thermally activated clay particles obtained by sieving is 0.1-2 mu m.
Further, the metal ion of the metal salt includes, but is not limited to, iron ion, cobalt ion, nickel ion, titanium ion, manganese ion, copper ion; the purity of the metal salts was analytically pure.
Further, in step S2, the clay is thermally activated: metal element=1g:10-100 mmol.
In the step S2, the mass ratio of the ball materials in the ball milling tank is 10-30:1, the rotating speed of the ball milling tank is 150-300 rpm, and the ball milling time is 12-48 h.
Further, in step S3, the ratio of activated clay loaded with nano metal ions to sulfur powder is the activated clay loaded with nano metal ions: sulfur powder = 1g:0.01 to 0.3mol; in the step S3, the vulcanization temperature is 300-600 ℃, and the vulcanization time is 2-4 h.
The double-site clay mineral-based sulfur reduction catalyst prepared by the double-site clay mineral-based sulfur reduction catalyst preparation method.
The preparation method of the sulfur-carrying anode material of the two-site clay mineral-based sulfur reduction catalyst comprises the steps of grinding and mixing the two-site clay mineral-based sulfur reduction catalyst and sulfur powder uniformly according to design components, and melting under a protective atmosphere to obtain the sulfur-carrying anode material of the two-site clay mineral-based sulfur reduction catalyst.
Further, the mass ratio of the two-site clay mineral-based sulfur reduction catalyst to the sulfur powder is 1:2-4, and the solid state melting temperature is 140-170 ℃; protective atmospheres include, but are not limited to, argon, nitrogen, hydrogen argon mixtures.
The invention has the following beneficial effects:
1. the material overcomes the defects of the prior synthesis technology, overcomes the defects of the prior lithium-sulfur battery cathode material in liquid phase reaction synthesis, prepares the double-site clay mineral-based sulfur reduction catalyst through solid phase reaction in the whole process, does not relate to a liquid phase system, has simple preparation flow and short time consumption, and is beneficial to large-scale commercial production.
2. The double-site sulfur reduction catalyst overcomes the limitation that the existing lithium sulfur battery anode only has single adsorption or single catalytic capability, can simultaneously enhance the adsorption capability and catalytic conversion capability to polysulfide, and has the characteristic of integrating multiple functions, thereby effectively inhibiting the shuttle effect of the lithium sulfur battery and improving the cycling stability of the lithium sulfur battery.
3. The double-site sulfur reduction catalyst has electrophilic property, can effectively solve the problems of poor ion diffusivity and low electron conductivity of a positive electrode material, promotes electrochemical conversion reaction, and improves the electrochemical performance of a lithium-sulfur battery.
4. In the process of absorbing and catalyzing polysulfide conversion, the metal site and the oxygen site of the interface can absorb polysulfide simultaneously, and when the conversion is completed and desorption is carried out, lithium sulfide products are desorbed from the metal site and then from the oxygen site, so that the rapid separation of polysulfide and the proceeding of chemical reaction of a battery are promoted.
5. The invention has low raw materials and very wide sources, and the preparation cost of the lithium-sulfur battery electrode is greatly reduced; the electrode material has high component safety, is environment-friendly, and accords with the national policy of green sustainable development.
Drawings
FIG. 1 is an XRD diffraction spectrum of halloysite before and after heat treatment;
FIG. 2 is an XRD diffraction spectrum of a sulfur-loaded positive electrode material of a two-site clay mineral-based sulfur reduction catalyst;
FIG. 3a is a graph of contact angle of a sulfur-loaded positive electrode material of a dual-site clay mineral-based sulfur reduction catalyst prepared in example 1;
FIG. 3b is a graph of contact angle of a sulfur-loaded positive electrode material of a dual-site clay mineral-based sulfur reduction catalyst prepared in example 2;
FIG. 3c is a graph of contact angle of a sulfur-loaded positive electrode material of comparative catalyst B prepared in comparative example 2;
FIG. 4a is a graph showing the cycle performance of the sulfur-supported anode material of the two-site clay mineral-based sulfur reduction catalyst prepared in example 1;
FIG. 4b is a graph showing the cycle performance of the sulfur-supported anode material of the dual-site clay mineral-based sulfur reduction catalyst prepared in example 2;
FIG. 4c is a graph showing the cycle performance of the sulfur-supported anode material of the dual-site clay mineral-based sulfur reduction catalyst prepared in example 3;
FIG. 4d is a graph showing the cycle performance of the sulfur-supported anode material of the dual-site clay mineral-based sulfur reduction catalyst prepared in example 4;
FIG. 4e is a graph showing the cycle performance of the sulfur-supported anode material of the dual-site clay mineral-based sulfur reduction catalyst prepared in example 5;
FIG. 4f is a graph showing the cycle performance of the sulfur-supported positive electrode material of comparative catalyst A prepared in comparative example 1;
FIG. 4g is a graph showing the cycle performance of the sulfur-supported positive electrode material of comparative catalyst B prepared in comparative example 2;
FIG. 5 is a schematic illustration of the catalytic conversion of polysulfide by a dual site clay mineral based sulfur reduction catalyst prepared in accordance with the present invention.
Detailed Description
The following are specific embodiments of the present invention and the technical solutions of the present invention will be further described with reference to the accompanying drawings, but the present invention is not limited to these embodiments.
The metal salt and the hydrochloric acid are analytically pure, and the clay in the clay raw ore in the following cases should be more than 90 percent except the special statement, and the average particle size is 200-500 meshes.
Example 1
(1) Thermal activation of halloysite: the halloysite Raw ore is processed for 2 hours at 400 ℃, and then is ground to 300 meshes for standby, the halloysite structure is basically unchanged before and after heat activation treatment, and XRD diffraction patterns of the Raw ore halloysite (Raw Hal) and the heat activated halloysite (A-Hal) are shown in the attached figure 1.
(2) Preparation of a two-site clay mineral-based sulfur reduction catalyst: mixing cobalt nitrate with the clay after heat activation to heat activate the clay: after being uniformly mixed in the ratio of cobalt element=1g:20mmol, the mixture is poured into a planetary ball mill for high-energy ball milling, the ball mass ratio in a ball milling tank is 10:1, the rotating speed of the ball milling tank is 200rpm, and the ball milling time is 24 hours. Collecting a sample after ball milling is finished, and according to the design components, the proportion of activated clay loaded with nano cobalt ions to sulfur powder is cobalt-loaded clay: sulfur powder = 1g:0.01mol, and then, under the argon atmosphere, vulcanizing for 2 hours at 450 ℃ to obtain the metal-oxygen double-site clay mineral-based sulfur reduction catalyst;
(3) Preparing a sulfur-loaded positive electrode material of a double-site clay mineral-based sulfur reduction catalyst: according to the design components, the catalyst: sulfur powder=1:4, and melting under argon atmosphere to obtain sulfur-carrying anode material of the two-site clay mineral-based sulfur reduction catalyst, wherein the diffraction pattern is shown in figure 2.
(4) Contact angle test: and (3) carrying out a contact angle test on the two-site clay mineral-based sulfur reduction catalyst positive electrode material obtained in the step (3), wherein the contact angle of the electrolyte drop on the surface of the composite positive electrode material is 25.81 degrees according to a three-site method, and the electrolyte drop has excellent hydrophilicity as shown in figure 3 a.
(5) Assembling a lithium-sulfur battery: firstly, mixing the sulfur-loaded positive electrode material of the two-site clay mineral-based sulfur reduction catalyst obtained in the step (3) with conductive carbon black and polyvinylidene fluoride (PVDF) according to the mass ratio of 7:2:1, dropwise adding nitrogen, grinding nitrogen-dimethylformamide (NMP) into slurry, coating the slurry on an aluminum foil, drying, and cutting into wafers with the diameter of 12mm for later use; secondly, in a glove box, placing a round lithium sheet with the diameter of 12mm as a negative electrode in a battery negative electrode shell, then dripping 3 drops of commercial lithium sulfur electrolyte, then placing a battery diaphragm, dripping 3 drops of commercial lithium sulfur electrolyte, and then placing a composite positive electrode material wafer which is just cut; and finally, covering the positive electrode shell of the battery, placing the battery into a special battery press for maintaining pressure for 30s, and wiping off redundant electrolyte to obtain the lithium-sulfur battery.
(6) The double-site clay mineral-based sulfur reduction catalyst positive electrode material prepared in the embodiment has excellent electrochemical performance after being applied to a lithium sulfur battery, and has 905.7 mAh.g after 100 circles of charge and discharge cycles under the current of 0.2C -1 The specific capacity of (2) and the capacity retention rate of 97% are shown in FIG. 4 a.
(7) A schematic diagram of the catalytic conversion of polysulfide in the electrochemical reaction process of a lithium sulfur battery using the two-site clay mineral-based sulfur reduction catalyst prepared in the example is shown in fig. 5.
Example 2
(1) Thermal activation of halloysite: the halloysite raw ore is treated for 3 hours at 500 ℃ and then is ground to 200 meshes for standby.
(2) Preparation of a two-site clay mineral-based sulfur reduction catalyst: mixing manganese sulfate with the clay after heat activation to heat activate the clay: manganese element=1g:50mmol, and then pouring the mixture into a planetary ball mill for high-energy ball milling, wherein the ball mass ratio in a ball milling tank is 20:1, the rotating speed of the ball milling tank is 300rpm, and the ball milling time is 24 hours. Collecting samples after ball milling is finished, and according to the design components, the proportion of activated clay loaded with nano manganese ions to sulfur powder is manganese-loaded clay: sulfur powder = 1g:0.1mol, after being uniformly mixed, the mixture is vulcanized for 3 hours at 450 ℃ in the argon atmosphere, and then the metal-oxygen double-site clay mineral-based sulfur reduction catalyst is obtained;
(3) Preparing a sulfur-loaded positive electrode material of a double-site clay mineral-based sulfur reduction catalyst: according to the design components, the catalyst: and (3) grinding and mixing the sulfur powder with the ratio of 1:3 uniformly, and melting the mixture in an argon atmosphere to obtain the sulfur-loaded anode material of the double-site clay mineral-based sulfur reduction catalyst.
(4) Contact angle test: and (3) carrying out a contact angle test on the two-site clay mineral-based sulfur reduction catalyst positive electrode material obtained in the step (3), wherein the contact angle of the electrolyte drop on the surface of the composite positive electrode material is 24.42 degrees according to a three-site method, and the electrolyte drop has excellent hydrophilicity as shown in a figure 3 b.
(5) Assembling a lithium-sulfur battery: firstly, mixing the two-site clay mineral-based sulfur reduction catalyst anode material obtained in the step (3) with conductive carbon black and polyvinylidene fluoride (PVDF) according to the mass ratio of 7:2:1, dropwise adding nitrogen, grinding nitrogen-dimethylformamide (NMP) into slurry, coating the slurry on an aluminum foil, drying, and shearing the slurry into a wafer with the diameter of 12mm for later use; secondly, in a glove box, placing a round lithium sheet with the diameter of 12mm as a negative electrode in a battery negative electrode shell, then dripping 3 drops of commercial lithium sulfur electrolyte, then placing a battery diaphragm, dripping 3 drops of commercial lithium sulfur electrolyte, and then placing a composite positive electrode material wafer which is just cut; and finally, covering the positive electrode shell of the battery, placing the battery into a special battery press for maintaining pressure for 30s, and wiping off redundant electrolyte to obtain the lithium-sulfur battery.
(6) The double-site clay mineral-based sulfur reduction catalyst positive electrode material prepared in the embodiment has excellent electrochemical performance after being applied to a lithium sulfur battery, and has 897.4 mAh.g after 100 cycles of charge and discharge under the current of 0.2C -1 The specific capacity of (2) and the capacity retention of 96% are shown in FIG. 4 b.
Example 3
(1) Thermal activation of kaolin: the kaolin crude ore is treated for 4 hours at 400 ℃ and then is ground to 200 meshes for standby.
(2) Preparation of a double-site clay mineral-based sulfur reduction catalyst positive electrode material: mixing ferric nitrate with the clay after heat activation to heat activate the clay: iron element=1g:30mmol, and then pouring the mixture into a planetary ball mill for high-energy ball milling, wherein the ball mass ratio in a ball milling tank is 30:1, the rotating speed of the ball milling tank is 200rpm, and the ball milling time is 36h. Collecting a sample after ball milling is finished, and according to the design components, the proportion of activated clay loaded with nano cobalt ions to sulfur powder is cobalt-loaded clay: sulfur powder = 1g:0.2mol, and then, under the argon atmosphere, vulcanizing for 3 hours at 500 ℃ to obtain the metal-oxygen double-site clay mineral-based sulfur reduction catalyst;
(3) Preparing a sulfur-loaded positive electrode material of a double-site clay mineral-based sulfur reduction catalyst: according to the design components, the catalyst: sulfur powder=1:4, and melting under argon atmosphere to obtain the double-site clay mineral-based sulfur reduction catalyst anode material.
(4) Assembling a lithium-sulfur battery: firstly, mixing the two-site clay mineral-based sulfur reduction catalyst anode material obtained in the step (3) with conductive carbon black and polyvinylidene fluoride (PVDF) according to the mass ratio of 7:2:1, dropwise adding nitrogen, grinding nitrogen-dimethylformamide (NMP) into slurry, coating the slurry on an aluminum foil, drying, and shearing the slurry into a wafer with the diameter of 12mm for later use; secondly, in a glove box, placing a round lithium sheet with the diameter of 12mm as a negative electrode in a battery negative electrode shell, then dripping 3 drops of commercial lithium sulfur electrolyte, then placing a battery diaphragm, dripping 3 drops of commercial lithium sulfur electrolyte, and then placing a composite positive electrode material wafer which is just cut; and finally, covering the positive electrode shell of the battery, placing the battery into a special battery press for maintaining pressure for 30s, and wiping off redundant electrolyte to obtain the lithium-sulfur battery.
(5) After the double-site clay mineral-based sulfur reduction catalyst positive electrode material prepared in the embodiment is applied to a lithium sulfur battery, the material has 1085 mAh.g after 100 cycles of charge and discharge under the current of 0.2C -1 The specific capacity of (2) and the capacity retention of 95.8%, and the test results are shown in FIG. 4 c.
Example 4
(1) Thermal activation of sepiolite: the sepiolite raw ore is treated for 3 hours at 600 ℃ and then is ground to 200 meshes for standby.
(2) Preparation of a double-site clay mineral-based sulfur reduction catalyst positive electrode material: nickel nitrate and the clay after heat activation are used for heat activation of the clay: after being uniformly mixed in the ratio of nickel element=1g:60 mmol, the mixture is poured into a planetary ball mill for high-energy ball milling, the ball mass ratio in a ball milling tank is 10:1, the rotating speed of the ball milling tank is 300rpm, and the ball milling time is 48 hours. Collecting a sample after ball milling is finished, and according to the design components, the proportion of activated clay loaded with nano cobalt ions to sulfur powder is cobalt-loaded clay: sulfur powder = 1g:0.3mol, and then vulcanizing for 3 hours at 500 ℃ under the argon atmosphere to obtain the metal-oxygen double-site clay mineral-based sulfur reduction catalyst.
(3) Preparing a sulfur-loaded positive electrode material of a double-site clay mineral-based sulfur reduction catalyst: according to the design components, the catalyst: and (3) grinding and mixing the sulfur powder with the ratio of 1:4 uniformly, and melting the mixture in an argon atmosphere to obtain the sulfur-loaded anode material of the double-site clay mineral-based sulfur reduction catalyst.
(4) Assembling a lithium-sulfur battery: firstly, mixing the clay mineral-based lithium sulfur battery composite anode material obtained in the step (3) with conductive carbon black and polyvinylidene fluoride (PVDF) according to the mass ratio of 7:2:1, dropwise adding nitrogen, grinding nitrogen-dimethylformamide (NMP) into slurry, coating the slurry on an aluminum foil, drying, and cutting into wafers with the diameter of 12mm for later use; secondly, in a glove box, placing a round lithium sheet with the diameter of 12mm as a negative electrode in a battery negative electrode shell, then dripping 3 drops of commercial lithium sulfur electrolyte, then placing a battery diaphragm, dripping 3 drops of commercial lithium sulfur electrolyte, and then placing a composite positive electrode material wafer which is just cut; and finally, covering the positive electrode shell of the battery, placing the battery into a special battery press for maintaining pressure for 30s, and wiping off redundant electrolyte to obtain the lithium-sulfur battery.
(5) After the double-site clay mineral-based sulfur reduction catalyst positive electrode material prepared in the embodiment is applied to a lithium sulfur battery, the material has 786.1 mAh.g after 100 cycles of charge and discharge under the current of 0.2C -1 The specific capacity of 93.9% capacity retention, and the test results are shown in fig. 4 d.
Example 5
(1) Thermal activation of halloysite: the halloysite raw ore is treated for 3 hours at 500 ℃ and then is ground to 200 meshes for standby.
(2) Preparation of a two-site clay mineral-based sulfur reduction catalyst: mixing cobalt chloride with the clay after heat activation to heat activate the clay: after being uniformly mixed in a ratio of cobalt element=1g:50 mmol, the mixture is poured into a planetary ball mill for high-energy ball milling, the ball mass ratio in a ball milling tank is 20:1, the rotating speed of the ball milling tank is 300rpm, and the ball milling time is 24 hours. Collecting a sample after ball milling is finished, and according to the design components, the proportion of activated clay loaded with nano cobalt ions to sulfur powder is cobalt-loaded clay: sulfur powder = 1g:0.1mol, after being uniformly mixed, the mixture is vulcanized for 3 hours at 450 ℃ in the argon atmosphere, and then the metal-oxygen double-site clay mineral-based sulfur reduction catalyst is obtained;
(3) Preparing a sulfur-loaded positive electrode material of a double-site clay mineral-based sulfur reduction catalyst: according to the design components, the catalyst: and (3) grinding and mixing the sulfur powder with the ratio of 1:3 uniformly, and melting the mixture in an argon atmosphere to obtain the sulfur-loaded anode material of the double-site clay mineral-based sulfur reduction catalyst.
(4) Assembling a lithium-sulfur battery: firstly, mixing the two-site clay mineral-based sulfur reduction catalyst anode material obtained in the step (3) with conductive carbon black and polyvinylidene fluoride (PVDF) according to the mass ratio of 7:2:1, dropwise adding nitrogen, grinding nitrogen-dimethylformamide (NMP) into slurry, coating the slurry on an aluminum foil, drying, and shearing the slurry into a wafer with the diameter of 12mm for later use; secondly, in a glove box, placing a round lithium sheet with the diameter of 12mm as a negative electrode in a battery negative electrode shell, then dripping 3 drops of commercial lithium sulfur electrolyte, then placing a battery diaphragm, dripping 3 drops of commercial lithium sulfur electrolyte, and then placing a composite positive electrode material wafer which is just cut; and finally, covering the positive electrode shell of the battery, placing the battery into a special battery press for maintaining pressure for 30s, and wiping off redundant electrolyte to obtain the lithium-sulfur battery.
(5) The double-site clay mineral-based sulfur reduction catalyst positive electrode material prepared in the embodiment has excellent electrochemical performance after being applied to a lithium sulfur battery, and has 997.4 mAh.g after 100 cycles of charge and discharge under the current of 0.2C -1 The specific capacity of 96% capacity retention rate, and the test results are shown in fig. 4 e.
The foregoing description is only illustrative of the preferred embodiments of the present invention and is not to be construed as limiting the scope of the invention, i.e., the invention is not to be limited to the details of the invention.
Comparative example 1
(1) Preparation of comparative catalyst a: mixing cobalt nitrate with clay which is not subjected to thermal activation, and mixing the clay with the cobalt nitrate: after being uniformly mixed in a ratio of cobalt element=1g:50 mmol, the mixture is poured into a planetary ball mill for high-energy ball milling, the ball mass ratio in a ball milling tank is 20:1, the rotating speed of the ball milling tank is 300rpm, and the ball milling time is 24 hours. Collecting a sample after ball milling is finished, and according to the design components, the proportion of activated clay loaded with nano cobalt ions to sulfur powder is cobalt-loaded clay: sulfur powder = 1g:0.1mol, and then, vulcanizing for 3 hours at 450 ℃ under the argon atmosphere to obtain the comparative catalyst A.
(2) Comparative example preparation of sulfur-loaded positive electrode material catalyst a: comparative example catalyst a: and (3) grinding and mixing the sulfur powder with the ratio of 1:3 uniformly, and melting the mixture in an argon atmosphere to obtain the sulfur-carrying anode of the lithium-sulfur battery.
(3) Assembling a lithium-sulfur battery: firstly, mixing the sulfur-carrying positive electrode material of the comparative catalyst A obtained in the step (2), conductive carbon black and polyvinylidene fluoride (PVDF) according to the mass ratio of 7:2:1, dropwise adding nitrogen, grinding nitrogen-dimethylformamide (NMP) into slurry, coating the slurry on an aluminum foil, drying, and cutting into wafers with the diameter of 12mm for later use; secondly, in a glove box, placing a round lithium sheet with the diameter of 12mm as a negative electrode in a battery negative electrode shell, then dripping 3 drops of commercial lithium sulfur electrolyte, then placing a battery diaphragm, dripping 3 drops of commercial lithium sulfur electrolyte, and then placing a wafer of the positive electrode material which is just cut; and finally, covering the positive electrode shell of the battery, placing the battery into a special battery press for maintaining pressure for 30s, and wiping off redundant electrolyte to obtain the lithium-sulfur battery.
(4) The lithium sulfur battery prepared by the sulfur-loaded positive electrode material of the catalyst A of the comparative example has poor electrochemical performance, the electrochemical capacity is rapidly reduced after 50 cycles of charge and discharge under the current of 0.2C, and the performance of the lithium sulfur battery is difficult to meet the practical application of the lithium sulfur battery when the two-site clay mineral-based sulfur reduction catalyst is not arranged in the positive electrode material, as shown in the figure 4 f.
Comparative example 2
(1) Preparation of comparative catalyst B: and pouring cobalt nitrate into a planetary ball mill for high-energy ball milling, wherein the mass ratio of ball materials in a ball milling tank is 20:1, the rotating speed of the ball milling tank is 300rpm, and the ball milling time is 24 hours. Collecting a sample after ball milling is finished, and according to the design components, the proportion of the supported cobalt oxide to the sulfur powder is as follows: sulfur powder = 1g:0.1mol, and then, vulcanizing for 3 hours at 450 ℃ under the argon atmosphere to obtain the comparative catalyst B.
(2) Comparative example preparation of catalyst B sulfur-loaded positive electrode material: comparative example catalyst B: sulfur powder=1:4, and melting under argon atmosphere to obtain the sulfur-carrying cathode material of the comparative catalyst B.
(3) Contact angle test: and (3) carrying out a contact angle test on the sulfur-carrying positive electrode material of the comparative catalyst B obtained in the step (2), wherein the contact angle of the electrolyte drop on the surface of the composite positive electrode material is 46.82 degrees according to a three-point method, and the hydrophilicity is poor, as shown in a figure 3 c.
(4) Assembling a lithium-sulfur battery: firstly, mixing the sulfur-loaded positive electrode material of the comparative catalyst B obtained in the step (2) with conductive carbon black and polyvinylidene fluoride (PVDF) according to the mass ratio of 7:2:1, dropwise adding nitrogen, grinding nitrogen-dimethylformamide (NMP) into slurry, coating the slurry on an aluminum foil, drying, and cutting into wafers with the diameter of 12mm for later use; secondly, in a glove box, placing a round lithium sheet with the diameter of 12mm as a negative electrode in a battery negative electrode shell, then dripping 3 drops of commercial lithium sulfur electrolyte, then placing a battery diaphragm, dripping 3 drops of commercial lithium sulfur electrolyte, and then placing a wafer of the positive electrode material which is just cut; and finally, covering the positive electrode shell of the battery, placing the battery into a special battery press for maintaining pressure for 30s, and wiping off redundant electrolyte to obtain the lithium-sulfur battery.
(5) The sulfur-loaded positive electrode material of the comparative catalyst B has poor electrochemical performance after being applied to a lithium sulfur battery, and the electrochemical capacity is rapidly reduced after 50 cycles of charge and discharge under the current of 0.2C, as shown in figure 4 g.
The above is not relevant and is applicable to the prior art.
While certain specific embodiments of the present invention have been described in detail by way of example, it will be appreciated by those skilled in the art that the foregoing examples are provided for the purpose of illustration only and are not intended to limit the scope of the invention, and that various modifications or additions and substitutions to the described specific embodiments may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the invention as defined in the accompanying claims. It should be understood by those skilled in the art that any modification, equivalent substitution, improvement, etc. made to the above embodiments according to the technical substance of the present invention should be included in the scope of protection of the present invention.

Claims (8)

1. A preparation method of a double-site clay mineral-based sulfur reduction catalyst is characterized by comprising the following steps of: comprising the following steps:
s1, calcining clay minerals, so as to perform thermally activated dissociation treatment, and selecting thermally activated clay with proper granularity and size by screening;
s2, uniformly mixing a proper amount of metal salt with the activated clay in the step S1, and loading nano metal ions on the activated clay through a solid phase reaction of ball milling;
s3, grinding and uniformly mixing activated clay loaded with nano metal ions and sulfur powder in a certain mass ratio in the step S2, and vulcanizing in a protective atmosphere to obtain a metal-oxygen double-site clay mineral-based sulfur reduction catalyst;
in the step S3, the vulcanization temperature is 300-600 ℃, and the vulcanization time is 2-4 hours;
in step S2, the clay is thermally activated: metal element=1g, 10-100 mmol;
in the step S3, the proportion of activated clay loaded with nano metal ions to sulfur powder is the activated clay loaded with nano metal ions: sulfur powder = 1g:0.01 to 0.3mol.
2. The method for preparing a two-site clay mineral-based sulfur reduction catalyst according to claim 1, wherein: in step S1, clay mineral species include, but are not limited to halloysite, kaolinite, sepiolite, vermiculite, rectorite, bentonite, and pyrophyllite; the purity of the clay mineral powder raw ore is more than 90 percent.
3. The method for preparing a two-site clay mineral-based sulfur reduction catalyst according to claim 1, wherein: in the step S1, the calcination temperature of thermal activation is 400-600 ℃, and the calcination time of thermal activation is 2-6 hours; the sieving granularity is 200-500 meshes, and the microscopic size of the thermally activated clay particles obtained through sieving is 0.1-2 mu m.
4. The method for preparing a two-site clay mineral-based sulfur reduction catalyst according to claim 1, wherein: the metal ion of the metal salt includes, but is not limited to, iron ion, cobalt ion, nickel ion, titanium ion, manganese ion, copper ion; the purity of the metal salts was analytically pure.
5. The method for preparing a two-site clay mineral-based sulfur reduction catalyst according to claim 1, wherein: in the step S2, the mass ratio of the ball materials in the ball milling tank is 10-30:1, the rotating speed of the ball milling tank is 150-300 rpm, and the ball milling time is 12-48 h.
6. A dual site clay mineral-based sulfur reduction catalyst prepared using the method of preparing a dual site clay mineral-based sulfur reduction catalyst of any one of claims 1-5.
7. A preparation method of a sulfur-loaded anode of a double-site clay mineral-based sulfur reduction catalyst is characterized by comprising the following steps of: the sulfur-carrying anode of the two-site clay mineral-based sulfur reduction catalyst is prepared by grinding and uniformly mixing the two-site clay mineral-based sulfur reduction catalyst and sulfur powder according to designed components and melting the two-site clay mineral-based sulfur reduction catalyst in a protective atmosphere.
8. The method for preparing the sulfur-loaded positive electrode of the two-site clay mineral-based sulfur reduction catalyst according to claim 7, wherein the method comprises the following steps: the mass ratio of the two-site clay mineral-based sulfur reduction catalyst to the sulfur powder is 1:2-4, and the solid state melting temperature is 140-170 ℃; protective atmospheres include, but are not limited to, argon, nitrogen, hydrogen argon mixtures.
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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105609742A (en) * 2016-03-04 2016-05-25 河北工业大学 Positive electrode material for sulfur-based lithium ion battery and preparation method and application of positive electrode material
CN105932235A (en) * 2016-05-05 2016-09-07 北京化工大学 Halloysite-based positive electrode material of lithium-sulfur battery and preparation method for positive electrode material
WO2016192389A1 (en) * 2015-06-03 2016-12-08 中国地质大学（武汉） Lithium sulfur battery composite positive electrode material and preparation method thereof
CN108199030A (en) * 2018-01-11 2018-06-22 南开大学 The preparation method of lithium rechargeable battery Nano-porous Si/Graphite/C Composite Anode Materials
CN109755546A (en) * 2019-03-08 2019-05-14 湖南宸宇富基新能源科技有限公司 A kind of preparation method of lithium-ion-power cell silicon based composite material
CN111952594A (en) * 2020-08-25 2020-11-17 中南大学 Lithiated halloysite lithium-sulfur battery positive electrode material and preparation method thereof
CN112290162A (en) * 2020-09-29 2021-01-29 江汉大学 Cobalt-doped carbon nanotube composite diaphragm and preparation method thereof
CN112635726A (en) * 2020-12-10 2021-04-09 广东省科学院化工研究所 Bentonite-based composite material and preparation method and application thereof
CN113381120A (en) * 2021-06-11 2021-09-10 中国科学院兰州化学物理研究所 Preparation method of nitrogen-doped clay mineral-loaded cobalt hybrid material modified lithium-sulfur battery diaphragm
CN113381121A (en) * 2021-06-11 2021-09-10 中国科学院兰州化学物理研究所 Preparation method of tungsten oxide/clay mineral nano material modified diaphragm for lithium-sulfur battery

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7029794B2 (en) * 1998-03-31 2006-04-18 Celanese Ventures Gmbh Lithium battery and electrode

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016192389A1 (en) * 2015-06-03 2016-12-08 中国地质大学（武汉） Lithium sulfur battery composite positive electrode material and preparation method thereof
CN105609742A (en) * 2016-03-04 2016-05-25 河北工业大学 Positive electrode material for sulfur-based lithium ion battery and preparation method and application of positive electrode material
CN105932235A (en) * 2016-05-05 2016-09-07 北京化工大学 Halloysite-based positive electrode material of lithium-sulfur battery and preparation method for positive electrode material
CN108199030A (en) * 2018-01-11 2018-06-22 南开大学 The preparation method of lithium rechargeable battery Nano-porous Si/Graphite/C Composite Anode Materials
CN109755546A (en) * 2019-03-08 2019-05-14 湖南宸宇富基新能源科技有限公司 A kind of preparation method of lithium-ion-power cell silicon based composite material
CN111952594A (en) * 2020-08-25 2020-11-17 中南大学 Lithiated halloysite lithium-sulfur battery positive electrode material and preparation method thereof
CN112290162A (en) * 2020-09-29 2021-01-29 江汉大学 Cobalt-doped carbon nanotube composite diaphragm and preparation method thereof
CN112635726A (en) * 2020-12-10 2021-04-09 广东省科学院化工研究所 Bentonite-based composite material and preparation method and application thereof
CN113381120A (en) * 2021-06-11 2021-09-10 中国科学院兰州化学物理研究所 Preparation method of nitrogen-doped clay mineral-loaded cobalt hybrid material modified lithium-sulfur battery diaphragm
CN113381121A (en) * 2021-06-11 2021-09-10 中国科学院兰州化学物理研究所 Preparation method of tungsten oxide/clay mineral nano material modified diaphragm for lithium-sulfur battery

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