CN108767228B - Double-carbon-based single titanium-based sulfur composite cathode material and preparation method thereof - Google Patents
Double-carbon-based single titanium-based sulfur composite cathode material and preparation method thereof Download PDFInfo
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 48
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 40
- 239000011593 sulfur Substances 0.000 title claims abstract description 40
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 29
- 239000010936 titanium Substances 0.000 title claims abstract description 29
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000010406 cathode material Substances 0.000 title claims description 18
- 230000004927 fusion Effects 0.000 claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001694 spray drying Methods 0.000 claims abstract description 13
- 229910021385 hard carbon Inorganic materials 0.000 claims abstract description 12
- 239000012467 final product Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000011164 primary particle Substances 0.000 claims abstract description 9
- 239000011163 secondary particle Substances 0.000 claims abstract description 9
- 238000007873 sieving Methods 0.000 claims abstract description 9
- 229910021384 soft carbon Inorganic materials 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims description 110
- 239000007788 liquid Substances 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 29
- 239000012298 atmosphere Substances 0.000 claims description 14
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000010000 carbonizing Methods 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 239000004576 sand Substances 0.000 claims description 7
- 239000001307 helium Substances 0.000 claims description 6
- 229910052734 helium Inorganic materials 0.000 claims description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- 239000010426 asphalt Substances 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052744 lithium Inorganic materials 0.000 abstract description 9
- 238000007599 discharging Methods 0.000 abstract description 8
- 229920001021 polysulfide Polymers 0.000 abstract description 7
- 239000005077 polysulfide Substances 0.000 abstract description 7
- 150000008117 polysulfides Polymers 0.000 abstract description 7
- 239000007774 positive electrode material Substances 0.000 abstract description 7
- 239000010405 anode material Substances 0.000 abstract description 6
- 238000004090 dissolution Methods 0.000 abstract description 6
- 239000011148 porous material Substances 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 238000005469 granulation Methods 0.000 abstract description 2
- 230000003179 granulation Effects 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 abstract description 2
- 238000000197 pyrolysis Methods 0.000 abstract description 2
- 239000012300 argon atmosphere Substances 0.000 description 12
- 239000002245 particle Substances 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a double-carbon-based single titanium-based sulfur composite positive electrode material and a preparation method thereof, wherein the single-carbon-based single titanium-based primary particle submicron and secondary particle micron spherical sulfur composite material is obtained by using the in-situ decomposition of an organic carbon source and tetrabutyl titanate and the spray drying granulation control technology through the process means of high-speed mixing, spray drying, roasting treatment and the like; then obtaining spongy multi-micron pore structure hard carbon or soft carbon by utilizing pyrolysis of an organic carbon source; and finally, the spherical sulfur composite material is fused into a porous structure of hard carbon or soft carbon by utilizing a high-energy fusion technology, the binding force of the hard carbon or the soft carbon is increased by utilizing a post-treatment process, and oversize products are removed by utilizing a sieving process to obtain a final product. The main benefits of the invention are: the double-carbon-based structure can not only improve the conductivity of the sulfur anode material, but also inhibit the dissolution of lithium polysulfide in the charging and discharging processes; the mono-titanium-based structure can inhibit the dissolution of lithium polysulfide in the charging and discharging processes, and can ensure that the composite material maintains higher specific capacity.
Description
Technical Field
The invention relates to the field of lithium secondary battery anode materials, in particular to a double-carbon single-titanium-based sulfur composite anode material and a preparation method thereof.
Background
The key to the popularization and application of new energy automobiles is to realize that the economy and the use convenience of the new energy automobiles are equivalent to those of the traditional fuel oil automobiles. The current new energy automobile has great gap with traditional fuel automobile, promotes economic nature and use convenience and is the main direction of new energy automobile development in a long period of time in the future. The economy and the use convenience of the new energy automobile are improved, and the increase of the endurance mileage of pure electric drive driving is key. In order to increase the endurance mileage, the energy stored by the onboard power battery system must be increased, and the specific energy and energy density of the power battery must be increased on the premise of not obviously increasing the weight and volume of a new-energy automobile. The requirements of the technical route map of energy-saving and new energy automobiles are as follows: the specific energy density of the single battery in 2025 reaches 400Wh/kg, and the specific energy density of the single battery in 2030 reaches 500 Wh/kg. The specific energy density of the existing lithium ion battery system is difficult to meet the technical requirements, so a novel battery system must be developed.
The theoretical specific capacity of a sulfur-based positive electrode material in the lithium-sulfur battery is 1675mAh/g, the theoretical specific energy is 2600Wh/kg, the theoretical specific capacity is far higher than that of the existing lithium-ion battery system, the sulfur storage capacity is rich, the environment is not polluted, the sulfur-based positive electrode material is a very promising positive electrode material, and a plurality of domestic companies and research institutions invest certain energy to research the sulfur-based positive electrode material in nearly five years. However, the conductivity of the sulfur-based positive electrode material is poor, and the polysulfide compound formed in the lithium intercalation process is easily dissolved in the electrolyte, so that the wide application of the sulfur-based positive electrode material is limited.
Disclosure of Invention
In order to solve the technical problems, the invention provides a double-carbon-based single titanium-based sulfur composite cathode material and a preparation method thereof, wherein a double-carbon-based structure not only can improve the conductivity of the sulfur cathode material, but also can inhibit the dissolution of lithium polysulfide in the charging and discharging processes; the mono-titanium-based structure can inhibit the dissolution of lithium polysulfide in the charging and discharging processes, and can ensure that the composite material maintains higher specific capacity.
The technical scheme of the invention is as follows: a preparation method of a double-carbon-based single titanium-based sulfur composite cathode material comprises the following steps:
1) uniformly mixing single-mass sulfur powder, an organic carbon source, tetrabutyl titanate and an organic solvent in a high-speed mixer to obtain a solid-liquid mixture I, wherein the mass of the organic carbon source/the mass of the sulfur powder is 5-10%, the mass of the tetrabutyl titanate/the mass of the sulfur powder is 2-5%, and the mass of the organic solvent/(the mass of the sulfur powder + the mass of the organic carbon source + the mass of the tetrabutyl titanate) is 4-5: 1;
2) sanding the solid-liquid mixture I in a sand mill to obtain the solid-liquid mixtureII, particle size D of solid-liquid mixture II50≤100nm；
3) Spray drying the solid-liquid mixture II in an inert atmosphere at the spray drying temperature of 150-180 ℃ to obtain a material III, wherein the particle size D of the material III50The particle size is 9-15 mu m, and the particle size has a spherical structure with submicron primary particles and micron secondary particles;
4) roasting the material III in an inert atmosphere at the roasting temperature of 600-700 ℃ for 2-8 hours to obtain a material IV, wherein the material IV is a single-carbon-based single titanium-based sulfur composite material;
5) carbonizing an organic carbon source in an inert atmosphere at the temperature of 750-850 ℃ for 4-8 h to obtain a material V, wherein the material V is spongy multi-micron porous structure hard carbon or soft carbon;
6) adding the material IV and the material V into a fusion machine for high-energy fusion, wherein the rotating speed of the fusion machine is 500-800 r/min, the fusion time is 4-8 h, and the material IV enters a porous structure of the material V to obtain a material VI, wherein the mass of the material IV/the mass of the material V is (5-6): 1;
7) and (3) carrying out post-treatment on the material VI in an inert atmosphere, wherein the post-treatment temperature is 400-450 ℃, the post-treatment time is 2-4 h, so as to obtain a material VII, and sieving the material VII to obtain a final product.
Further: the organic carbon source in the step 1) is polyvinylpyrrolidone or polyethylene glycol.
Further: the organic solvent in the step 1) is ethanol or propanol.
Further, the inert atmosphere in steps 3), 4), 5) and 7) is nitrogen, argon or helium.
Further, the organic carbon source in the step 5) is glucose, sucrose, polyvinylpyrrolidone, phenolic resin or asphalt.
The invention firstly obtains the single-carbon single-titanium-based primary particle submicron and secondary particle micron spherical sulfur composite material by technological means of high-speed mixing, spray drying, roasting treatment and the like and by utilizing the in-situ decomposition of an organic carbon source and tetrabutyl titanate and the spray drying granulation control technology; then obtaining spongy multi-micron pore structure hard carbon or soft carbon by utilizing pyrolysis of an organic carbon source; and finally, the spherical sulfur composite material is fused into a porous structure of hard carbon or soft carbon by utilizing a high-energy fusion technology, the binding force of the hard carbon or the soft carbon is increased by utilizing a post-treatment process, and oversize products are removed by utilizing a sieving process to obtain a final product. The main benefits of the invention are: the double-carbon-based structure can not only improve the conductivity of the sulfur anode material, but also inhibit the dissolution of lithium polysulfide in the charging and discharging processes; the mono-titanium-based structure can inhibit the dissolution of lithium polysulfide in the charging and discharging processes, and can ensure that the composite material maintains higher specific capacity.
Drawings
FIG. 1 is a process flow chart of the preparation method of the double-carbon-based single titanium-based sulfur composite cathode material.
Detailed Description
The technical solution of the present invention is described in detail below with reference to examples.
Example 1
A preparation method of a double-carbon-based single titanium-based sulfur composite cathode material comprises the following steps:
1) uniformly mixing 320g of single-substance sulfur powder, 16g of polyvinylpyrrolidone, 6.4g of tetrabutyl titanate and 1369.6 of ethanol in a high-speed mixer to obtain a solid-liquid mixture I;
2) sanding the solid-liquid mixture I in a sand mill to obtain a solid-liquid mixture II with the granularity D50＝80nm；
3) Spray-drying the solid-liquid mixture II in a nitrogen atmosphere at 150 ℃ to obtain a material III with the granularity D of the material III509 μm, a spherical structure with submicron primary particles and micron secondary particles;
4) roasting the material III in a nitrogen atmosphere at the roasting temperature of 600 ℃ for 8 hours to obtain a material IV, wherein the material IV is a single-carbon-based single-titanium-based sulfur composite material;
5) carbonizing 1000g of glucose in a nitrogen atmosphere at 750 ℃ for 4h to obtain a material V, wherein the material V is spongy multi-micron porous hard carbon;
6) 300g of the material IV and 60g of the material V are added into a fusion machine for high-energy fusion, the rotating speed of the fusion machine is 500 r/min, the fusion time is 8h, and the material IV enters a porous structure of the material V to obtain a material VI;
7) and (3) carrying out post-treatment on the material VI in a nitrogen atmosphere, wherein the post-treatment temperature is 400 ℃, and the post-treatment time is 4h to obtain a material VII, and sieving the material VII to obtain a final product.
Example 2
A preparation method of a double-carbon-based single titanium-based sulfur composite cathode material comprises the following steps:
1) uniformly mixing 320g of single sulfur powder, 32g of polyethylene glycol, 16g of tetrabutyl titanate and 1840g of propanol in a high-speed mixer to obtain a solid-liquid mixture I;
2) sanding the solid-liquid mixture I in a sand mill to obtain a solid-liquid mixture II with the granularity D50＝80nm；
3) Spray-drying the solid-liquid mixture II in an argon atmosphere at 180 ℃ to obtain a material III with a particle size D5015 μm, a spherical structure with submicron primary particles and micron secondary particles;
4) roasting the material III in an argon atmosphere at the roasting temperature of 700 ℃ for 2 hours to obtain a material IV, wherein the material IV is a single-carbon-based single-titanium-based sulfur composite material;
5) carbonizing 1000g of sucrose in an argon atmosphere at 850 ℃ for 4h to obtain a material V, wherein the material V is spongy multi-micron pore structure hard carbon;
6) 300g of the material IV and 60g of the material V are added into a fusion machine for high-energy fusion, the rotating speed of the fusion machine is 800 r/min, the fusion time is 4h, and the material IV enters a porous structure of the material V to obtain a material VI;
7) and (3) carrying out post-treatment on the material VI under the argon atmosphere, wherein the post-treatment temperature is 450 ℃, and the post-treatment time is 2 hours, so as to obtain a material VII, and sieving the material VII, so as to obtain a final product.
Example 3
A preparation method of a double-carbon-based single titanium-based sulfur composite cathode material comprises the following steps:
1) uniformly mixing 320g of single-substance sulfur powder, 16g of polyethylene glycol, 16g of tetrabutyl titanate and propyl alcohol 1408 in a high-speed mixer to obtain a solid-liquid mixture I;
2) sanding the solid-liquid mixture I in a sand mill to obtain a solid-liquid mixture II with the granularity D50＝80nm；
3) Spray-drying the solid-liquid mixture II in an argon atmosphere at 170 ℃ to obtain a material III, wherein the granularity D of the material III5012 μm, a spherical structure with submicron primary particles and micron secondary particles;
4) roasting the material III in an argon atmosphere at the roasting temperature of 700 ℃ for 2 hours to obtain a material IV, wherein the material IV is a single-carbon-based single-titanium-based sulfur composite material;
5) carbonizing 1000g of polyvinylpyrrolidone in an argon atmosphere at 850 ℃ for 4h to obtain a material V, wherein the material V is spongy multi-micron pore structure hard carbon;
6) 300g of the material IV and 60g of the material V are added into a fusion machine for high-energy fusion, the rotating speed of the fusion machine is 800 r/min, the fusion time is 4h, and the material IV enters a porous structure of the material V to obtain a material VI;
7) and (3) carrying out post-treatment on the material VI under the argon atmosphere, wherein the post-treatment temperature is 450 ℃, and the post-treatment time is 2 hours, so as to obtain a material VII, and sieving the material VII, so as to obtain a final product.
Example 4
A preparation method of a double-carbon-based single titanium-based sulfur composite cathode material comprises the following steps:
1) uniformly mixing 320g of single-substance sulfur powder, 32g of polyvinylpyrrolidone, 6.4g of tetrabutyl titanate and 1433.6g of propanol in a high-speed mixer to obtain a solid-liquid mixture I;
2) sanding the solid-liquid mixture I in a sand mill to obtain a solid-liquid mixture IIParticle size D of solid-liquid mixture II50＝80nm；
3) Spray-drying the solid-liquid mixture II in an argon atmosphere at 170 ℃ to obtain a material III, wherein the granularity D of the material III5010 μm, a spherical structure with submicron primary particles and micron secondary particles;
4) roasting the material III in an argon atmosphere at the roasting temperature of 700 ℃ for 2 hours to obtain a material IV, wherein the material IV is a single-carbon-based single-titanium-based sulfur composite material;
5) carbonizing 1000g of phenolic resin in an argon atmosphere at 850 ℃ for 4h to obtain a material V, wherein the material V is spongy multi-micron pore structure hard carbon;
6) adding 300g of the material IV and 50g of the material V into a fusion machine for high-energy fusion, wherein the rotating speed of the fusion machine is 800 revolutions per minute, the fusion time is 4 hours, and the material IV enters a porous structure of the material V to obtain a material VI;
7) and (3) carrying out post-treatment on the material VI under the argon atmosphere, wherein the post-treatment temperature is 450 ℃, and the post-treatment time is 4h to obtain a material VII, and sieving the material VII to obtain a final product.
Example 5
A preparation method of a double-carbon-based single titanium-based sulfur composite cathode material comprises the following steps:
1) uniformly mixing single-mass sulfur powder, polyvinylpyrrolidone, tetrabutyl titanate and ethanol in a high-speed mixer to obtain a solid-liquid mixture I, wherein the mass of the polyvinylpyrrolidone/the mass of the sulfur powder is 10%, the mass of the tetrabutyl titanate/the mass of the sulfur powder is 2%, and the mass of an organic solvent/(the mass of the sulfur powder + the mass of the polyvinylpyrrolidone + the mass of the tetrabutyl titanate) is 4: 1;
2) sanding the solid-liquid mixture I in a sand mill to obtain a solid-liquid mixture II with the granularity D50＝80nm；
3) Spray-drying the solid-liquid mixture II in a helium atmosphere at 170 ℃ to obtain a material III, wherein the granularity D of the material III5010 μm, has submicron primary particles,a spherical structure with micronized secondary particles;
4) roasting the material III in a helium atmosphere at 700 ℃ for 2 hours to obtain a material IV, wherein the material IV is a single-carbon-based single-titanium-based sulfur composite material;
5) carbonizing asphalt in a helium atmosphere at 850 ℃ for 4h to obtain a material V, wherein the material V is spongy multi-micron pore structure soft carbon;
6) adding the material IV and the material V into a fusion machine for high-energy fusion, wherein the rotating speed of the fusion machine is 800 revolutions per minute, the fusion time is 4 hours, and the material IV enters a porous structure of the material V to obtain a material VI, wherein the mass of the material IV/the mass of the material V is 6: 1;
7) and (3) carrying out post-treatment on the material VI under the helium atmosphere, wherein the post-treatment temperature is 450 ℃, and the post-treatment time is 4h to obtain a material VII, and sieving the material VII to obtain a final product.
Experimental conditions:
table 1 shows the specific capacity of first cycle discharge and the cycle life of button cells made of the lithium secondary battery cathode materials prepared in examples 1-5.
The test conditions of the button cell are LR 2032, 0.1C, 1.5-3.0V, vs. Li+and/Li, the charging and discharging equipment used is a blue-charge charging and discharging instrument.
TABLE 1 comparison table of specific capacity of initial discharge and cycle life
The data in the table show that the first discharge specific capacity of the double-carbon single titanium-based sulfur composite anode material prepared by the invention reaches more than 800mAh/g, the cycle capacity retention rate of 50 weeks reaches more than 85 percent, and the double-carbon single titanium-based sulfur composite anode material has strong application performance.
In summary, the disclosure of the present invention is not limited to the above-mentioned embodiments, and persons skilled in the art can easily set forth other embodiments within the technical teaching of the present invention, but such embodiments are included in the scope of the present invention.
Claims (6)
1. A preparation method of a double-carbon-based single titanium-based sulfur composite cathode material is characterized by comprising the following steps:
1) uniformly mixing single-mass sulfur powder, an organic carbon source, tetrabutyl titanate and an organic solvent in a high-speed mixer to obtain a solid-liquid mixture I, wherein the mass of the organic carbon source/the mass of the sulfur powder is 5-10%, the mass of the tetrabutyl titanate/the mass of the sulfur powder is 2-5%, and the mass of the organic solvent/(the mass of the sulfur powder + the mass of the organic carbon source + the mass of the tetrabutyl titanate) is 4-5: 1;
2) sanding the solid-liquid mixture I in a sand mill to obtain a solid-liquid mixture II with the granularity D50≤100nm；
3) Spray drying the solid-liquid mixture II in an inert atmosphere at the spray drying temperature of 150-180 ℃ to obtain a material III, wherein the granularity D of the material III50A spherical structure having a primary particle submicron structure and a secondary particle micron structure, the spherical structure being 9 to 15 μm;
4) roasting the material III in an inert atmosphere at the roasting temperature of 600-700 ℃ for 2-8 hours to obtain a material IV, wherein the material IV is a single-carbon-based single titanium-based sulfur composite material;
5) carbonizing an organic carbon source in an inert atmosphere at the temperature of 750-850 ℃ for 4-8 h to obtain a material V, wherein the material V is spongy multi-micron porous structure hard carbon or soft carbon;
6) adding the material IV and the material V into a fusion machine for high-energy fusion, wherein the rotating speed of the fusion machine is 500-800 r/min, the fusion time is 4-8 h, and the material IV enters a porous structure of the material V to obtain a material VI, wherein the mass of the material IV/the mass of the material V is (5-6): 1;
7) and (3) carrying out post-treatment on the material VI in an inert atmosphere, wherein the post-treatment temperature is 400-450 ℃, the post-treatment time is 2-4 h, so as to obtain a material VII, and sieving the material VII to obtain a final product.
2. The preparation method of the double-carbon-based single titanium-based sulfur composite cathode material according to claim 1, wherein the organic carbon source in the step 1) is polyvinylpyrrolidone or polyethylene glycol.
3. The preparation method of the double-carbon single-titanium-based sulfur composite cathode material according to claim 1, wherein the organic solvent in the step 1) is ethanol or propanol.
4. The preparation method of the double-carbon single-titanium-based sulfur composite cathode material according to claim 1, wherein the inert atmosphere in the steps 3), 4), 5) and 7) is nitrogen, argon or helium.
5. The preparation method of the double-carbon-based single titanium-based sulfur composite cathode material according to claim 1, wherein the organic carbon source in the step 5) is glucose, sucrose, polyvinylpyrrolidone, phenolic resin or asphalt.
6. The double-carbon single titanium-based sulfur composite cathode material prepared by the preparation method of any one of claims 1 to 5.
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