CN112551574A - Sulfur-nitrogen doped porous carbon-coated Li4Ti5O12Lithium ion battery cathode material and preparation method thereof - Google Patents

Sulfur-nitrogen doped porous carbon-coated Li4Ti5O12Lithium ion battery cathode material and preparation method thereof Download PDF

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CN112551574A
CN112551574A CN202011456210.3A CN202011456210A CN112551574A CN 112551574 A CN112551574 A CN 112551574A CN 202011456210 A CN202011456210 A CN 202011456210A CN 112551574 A CN112551574 A CN 112551574A
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顾建荣
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Tongxiang Hongxin Technology Partnership LP
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Abstract

The invention relates to the technical field of lithium ion battery materials, and discloses a sulfur-nitrogen doped porous carbon coated Li4Ti5O12The lithium ion battery cathode material is prepared by hydrothermal reaction and replacement of Na by Li ions2Ti3O7Na ion to obtain linear nano Li4Ti5O12Polymerizing 3-formaldehyde benzothiophene, resorcinol and melamine serving as raw materials to obtain porous phenolic resin coated Li4Ti5O12Nano-wire, carbonizing to obtain Li coated with S-N doped porous carbon4Ti5O12The lithium ion battery cathode material is coated by porous carbon so that linear nano Li4Ti5O12Uniform dispersion, low charge transfer resistance and high Li content4Ti5O12Conductivity and cycle performance, suppressing polarization, and increasing Li4Ti5O12The cathode material has the advantages of low charge transfer resistance, high reaction kinetics, and excellent conductivity, rate capability, cycle performance and theoretical specific capacity.

Description

Sulfur-nitrogen doped porous carbon-coated Li4Ti5O12Lithium ion battery cathode material and preparation method thereof
Technical Field
The invention relates to the technical field of lithium ion battery materials, in particular to a sulfur-nitrogen doped porous carbon-coated Li4Ti5O12The lithium ion battery cathode material and the preparation method.
Background
In order to solve the problems of energy shortage and environmental pollution in the automobile industry due to the fact that a large amount of traditional energy is used, the development of new energy automobiles is a new solution, the problems of energy shortage and environmental pollution can be effectively relieved, the ideal power source of the new energy automobiles is a lithium ion battery, the lithium ion battery has high energy density and long service life, and meanwhile, the lithium ion battery has application prospects in the fields of wind power generation energy storage, solar power generation energy storage and the like, the negative electrode material of the lithium ion battery comprises graphite, lithium titanate, tin dioxide and the like, but the multiplying power performance of the graphite is low, and the volume effect of the tin dioxide is serious, so that the development is restricted.
Lithium titanate can effectively avoid forming a solid electrolyte interface film and 'lithium dendrites', the safety performance of a lithium ion battery is improved, the volume is almost unchanged in the process of inserting and removing lithium ions, the lithium titanate has excellent cycle performance, but the electronic conductivity and the diffusion coefficient of the lithium ions are low, so that the rate performance of the lithium titanate is poor, the application of the lithium titanate is limited, the carbon material has excellent conductivity, the cost is low, the preparation is simple, the source is wide, and the lithium titanate is suitable for large-scale commercial application, so that sulfur-nitrogen doped porous carbon is adopted to coat Li4Ti5O12In order to solve the above problems.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides the sulfur-nitrogen doped porous carbon coated Li4Ti5O12The lithium ion battery cathode material and the preparation method solve the problems of poor conductivity of lithium titanate,Poor rate capability.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: sulfur-nitrogen doped porous carbon-coated Li4Ti5O12The lithium ion battery cathode material is prepared by coating Li on sulfur-nitrogen doped porous carbon4Ti5O12The preparation method of the lithium ion battery negative electrode material comprises the following steps:
(1) adding ethanol and titanium dioxide into a reaction bottle, uniformly stirring, adding a sodium hydroxide aqueous solution, uniformly stirring, transferring the mixture into a reaction kettle, placing the reaction kettle in an oven, carrying out a hydrothermal process, cooling, washing and drying to obtain linear nano Na2Ti3O7；
(2) Adding deionized water, lithium hydroxide and linear nano Na into a reaction bottle2Ti3O7The mass ratio of the two is 20-22:100, the mixture is evenly stirred, the mixture is moved into a reaction kettle and placed in a drying oven to carry out hydrothermal reaction, the mixture is cooled, washed and dried, the dried product is placed in a tube furnace and calcined for 3-5h at the temperature of 550-650 ℃ to obtain the linear nano Li4Ti5O12；
(3) Adding deionized water, 3-formaldehyde benzothiophene, resorcinol, melamine and linear nano Li into a reaction bottle4Ti5O12Uniformly dispersing by ultrasonic at 55-65 ℃, cooling, adding sodium carbonate, adjusting pH to 8-9, reacting at 55-65 ℃ for 20-40min, adding emulsifier Tween 20 and toluene as oil phase, fully stirring, adding catalyst phosphoric acid, uniformly stirring, pouring the solution into a mold, sealing, standing at 70-80 ℃ for 2-4 days, washing with acetone, and drying to obtain porous phenolic resin coated Li4Ti5O12A nanowire;
(4) coating porous phenolic resin with Li4Ti5O12The nanowire is placed in a tube furnace and is calcined to obtain the Li coated with the sulfur-nitrogen doped porous carbon4Ti5O12The lithium ion battery negative electrode material of (1);
(5) adding N-methyl pyrrolidone and sulfur-nitrogen doped porous carbon coated Li into a reaction bottle4Ti5O12The lithium ion battery negative electrode material, acetylene black and polyvinylidene fluoride are dispersed uniformly by ultrasonic, and the solution is coated on copper foil by a scraper and dried to obtain the lithium ion battery negative electrode working electrode.
Preferably, the hydrothermal process in the step (1) is a reaction at 190 ℃ for 36-60h at 170-.
Preferably, the hydrothermal reaction process in the step (2) is carried out at 170-190 ℃ for 12-36 h.
Preferably, in the step (3), 3-formaldehyde benzothiophene, resorcinol, melamine and linear nano Li4Ti5O12The mass ratio of the Tween 20 to the phosphoric acid is 400-480:100:30-60:3500-7000:120-150: 38-43.
Preferably, the tubular furnace in step (4) comprises a main body, a workbench is movably connected to the bottom of the main body, a heating device is movably connected to the middle of the workbench, gear teeth are movably connected to the top of the workbench, a furnace tube is movably connected to the middle of the main body, end covers are movably connected to the two sides of the furnace tube, an air hole is movably connected to the left side of each end cover, a gear is movably connected to the middle of the air hole, a crucible is movably connected to the middle of the furnace tube, and a universal wheel is movably connected to the bottom of the.
Preferably, the calcination process in the step (4) is pyrolysis at 600-650 ℃ in a nitrogen atmosphere for 1-3 h.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the sulfur-nitrogen doped porous carbon-coated Li4Ti5O12The negative electrode material of the lithium ion battery is TiO in alkaline environment2The sodium titanate which is corroded and peeled off in a single piece is curled to form linear nano Na in order to keep the lowest energy state2Ti3O7Adding lithium hydroxide, performing hydrothermal reaction to replace Na ions in sodium titanate by Li ions, and calcining to obtain linear nano Li4Ti5O123-A ofAldehyde benzothiophene is taken as a sulfur source, resorcinol is taken as a carbon source, melamine is taken as a nitrogen source, and under the catalysis of phosphoric acid, porous phenolic resin coated Li containing nitrogen and sulfur groups is obtained through emulsion polymerization in an alkaline environment4Ti5O12The nano-wire and the phenolic resin containing the nitrogen-sulfur group are further carbonized to obtain the Li coated with the sulfur-nitrogen doped porous carbon4Ti5O12The lithium ion battery cathode material.
The sulfur-nitrogen doped porous carbon-coated Li4Ti5O12Lithium ion battery negative electrode material of, Li4Ti5O12Is a linear nano structure with smaller grain size, and is coated by porous carbon, so that linear nano Li is obtained4Ti5O12Uniform dispersion, reduced agglomeration, reduced charge transfer resistance, accelerated electron transfer, and enhanced Li4Ti5O12The conductivity of the alloy is improved4Ti5O12The cycle performance of the lithium ion battery is improved, the diffusion path of the lithium ions is shortened, the diffusion coefficient of the lithium ions is improved, the polarization in the electrochemical reaction process is inhibited, and the Li is improved4Ti5O12The carbon material has the advantages that the multiplying power performance and the theoretical specific capacity are realized, sulfur atoms and nitrogen atoms are doped into crystal lattices of the carbon material, more defects are introduced, the surface of the carbon material is highly bent, more folds are formed, the specific surface area is increased, a three-dimensional porous reticular structure is formed, the charge transfer impedance is further reduced, the adsorption speed and the diffusion degree of lithium ions are increased, the negative electrode material has lower charge transfer resistance and faster reaction kinetics, and the sulfur-nitrogen-doped porous carbon coated Li is endowed with4Ti5O12The lithium ion battery cathode material has excellent conductivity, rate capability, cycle performance and theoretical specific capacity, and widens the application range in the fields of new energy automobiles, energy storage and the like.
Drawings
FIG. 1 is a schematic sectional elevational view of a tube furnace;
fig. 2 is a schematic view of a gear structure.
1. A main body; 2. a work table; 3. a heating device; 4. gear teeth; 5. a furnace tube; 6. an end cap; 7. an end cap; 8. a gear; 9. a crucible; 10. a universal wheel.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: sulfur-nitrogen doped porous carbon-coated Li4Ti5O12The lithium ion battery cathode material is Li coated by sulfur-nitrogen doped porous carbon4Ti5O12The preparation method of the lithium ion battery negative electrode material comprises the following steps:
(1) adding ethanol and titanium dioxide into a reaction bottle, uniformly stirring, adding a sodium hydroxide aqueous solution, wherein the mass ratio of the titanium dioxide to the sodium hydroxide is 100:113-120, uniformly stirring, transferring into a reaction kettle, placing into an oven, performing a hydrothermal process, wherein the hydrothermal process is a reaction at 190 ℃ of 170 ℃ for 36-60h, cooling, washing and drying to obtain linear nano Na2Ti3O7；
(2) Adding deionized water, lithium hydroxide and linear nano Na into a reaction bottle2Ti3O7The mass ratio of the two is 20-22:100, the mixture is evenly stirred, the mixture is moved into a reaction kettle and placed in a drying oven to carry out the hydrothermal reaction process, the hydrothermal reaction process is carried out for 12-36h at the temperature of 170-190 ℃, the mixture is cooled, washed and dried, the dried product is placed in a tube furnace and calcined for 3-5h at the temperature of 550-650 ℃ to obtain the linear nano Li4Ti5O12；
(3) Adding deionized water, 3-formaldehyde benzothiophene, resorcinol, melamine and linear nano Li into a reaction bottle4Ti5O12Dispersing uniformly by ultrasonic at 55-65 deg.C, cooling, adding sodium carbonate, adjusting pH to 8-9, reacting at 55-65 deg.C for 20-40min, adding emulsifier Tween 20 and toluene as oil phase, stirring, adding catalyst phosphoric acid, wherein 3-formaldehyde benzothiophene, resorcinol, melamine, and linear nanometer Li4Ti5O12Tween 20 and phosphoric acid in the mass ratio of 400-480:100:30-60:3500-7000: 120-38-43, stirring uniformly, pouring the solution into a mold, sealing, standing for 2-4 days at 70-80 ℃, washing with acetone and removing the acetoneDrying to obtain porous phenolic resin coated Li4Ti5O12A nanowire;
(4) coating porous phenolic resin with Li4Ti5O12The nanowire is arranged in a tube furnace, the tube furnace comprises a main body, the bottom of the main body is movably connected with a workbench, the middle of the workbench is movably connected with a heating device, the top of the workbench is movably connected with gear teeth, the middle of the main body is movably connected with a furnace tube, the two sides of the furnace tube are movably connected with end covers, the left side of each end cover is movably connected with an air hole, the middle of each air hole is movably connected with a gear, the middle of the furnace tube is movably connected with a crucible, the bottom of the crucible is movably connected with a universal wheel, a calcination process is carried out, the calcination process is that pyrolysis is carried out for 1-3 hours at the temperature4Ti5O12The lithium ion battery negative electrode material of (1);
(5) adding N-methyl pyrrolidone and sulfur-nitrogen doped porous carbon coated Li into a reaction bottle4Ti5O12The lithium ion battery negative electrode material, acetylene black and polyvinylidene fluoride are dispersed uniformly by ultrasonic, and the solution is coated on copper foil by a scraper and dried to obtain the lithium ion battery negative electrode working electrode.
Example 1
(1) Adding ethanol and titanium dioxide into a reaction bottle, stirring uniformly, adding a sodium hydroxide aqueous solution, wherein the mass ratio of the titanium dioxide to the sodium hydroxide is 100:113, stirring uniformly, transferring into a reaction kettle, placing in an oven, performing a hydrothermal process, wherein the hydrothermal process is a reaction at 170 ℃ for 36 hours, cooling, washing cleanly and drying to obtain linear nano Na2Ti3O7；
(2) Adding deionized water, lithium hydroxide and linear nano Na into a reaction bottle2Ti3O7The mass ratio of the two is 20:100, the mixture is evenly stirred, the mixture is moved into a reaction kettle and placed in a drying oven to carry out the hydrothermal reaction process, the hydrothermal reaction process is carried out for 12 hours at the temperature of 170 ℃, the mixture is cooled, washed and dried, the dried product is placed in a tube furnace and calcined for 3 hours at the temperature of 550 ℃, and the linear nano Li is obtained4Ti5O12；
(3) Adding deionized water, 3-formaldehyde benzothiophene, resorcinol, melamine and linear nano Li into a reaction bottle4Ti5O12Dispersing uniformly by ultrasonic at 55 deg.C, cooling, adding sodium carbonate, adjusting pH to 8, reacting at 55 deg.C for 20min, adding emulsifier Tween 20 and toluene as oil phase, stirring, adding catalyst phosphoric acid, wherein 3-formaldehyde benzothiophene, resorcinol, melamine, and linear nanometer Li4Ti5O12Uniformly stirring, pouring the solution into a mold, sealing, standing at 70 ℃ for 2 days, washing with acetone, and drying to obtain porous phenolic resin coated Li4Ti5O12A nanowire;
(4) coating porous phenolic resin with Li4Ti5O12The nano wire is arranged in the tube furnace, the tube furnace comprises a main body, the bottom of the main body is movably connected with a workbench, the middle of the workbench is movably connected with a heating device, the top of the workbench is movably connected with gear teeth, the middle of the main body is movably connected with a furnace tube, the two sides of the furnace tube are movably connected with end covers, the left side of the end covers is movably connected with air holes, the middle of the air holes is movably connected with a gear, the middle of the furnace tube is movably connected with a crucible, the bottom of the crucible is movably connected with a universal wheel, the calcining process is carried out, the calcining process is pyrolysis for 1h at 600 ℃ in4Ti5O12The lithium ion battery negative electrode material of (1);
(5) adding N-methyl pyrrolidone and sulfur-nitrogen doped porous carbon coated Li into a reaction bottle4Ti5O12The lithium ion battery negative electrode material, acetylene black and polyvinylidene fluoride are dispersed uniformly by ultrasonic, and the solution is coated on copper foil by a scraper and dried to obtain the lithium ion battery negative electrode working electrode.
Example 2
(1) Adding ethanol and titanium dioxide into a reaction bottle, uniformly stirring, adding a sodium hydroxide aqueous solution, uniformly stirring, transferring into a reaction kettle, placing into an oven, and performing a hydrothermal processThe process comprises reacting at 180 deg.C for 48h, cooling, washing and drying to obtain linear nanometer Na2Ti3O7；
(2) Adding deionized water, lithium hydroxide and linear nano Na into a reaction bottle2Ti3O7The mass ratio of the two is 21:100, the mixture is evenly stirred, the mixture is moved into a reaction kettle and placed in a drying oven to carry out the hydrothermal reaction process, the hydrothermal reaction process is carried out for 24 hours at 180 ℃, the mixture is cooled, washed and dried, the dried product is placed in a tube furnace and calcined for 4 hours at 600 ℃, and the linear nano Li is obtained4Ti5O12；
(3) Adding deionized water, 3-formaldehyde benzothiophene, resorcinol, melamine and linear nano Li into a reaction bottle4Ti5O12Dispersing uniformly at 60 deg.C by ultrasonic wave, cooling, adding sodium carbonate, adjusting pH to 9, reacting at 60 deg.C for 30min, adding emulsifier Tween 20 and toluene as oil phase, stirring, adding catalyst phosphoric acid, wherein 3-formaldehyde benzothiophene, resorcinol, melamine, and linear nanometer Li4Ti5O12The mass ratio of the Tween 20 to the phosphoric acid is 440:100:45:5250:135:40.5, the mixture is uniformly stirred, the solution is poured into a mold for sealing, the mold is kept stand for 3 days at the temperature of 75 ℃, acetone is used for washing and drying, and the porous phenolic resin coated Li is obtained4Ti5O12A nanowire;
(4) coating porous phenolic resin with Li4Ti5O12The nano wire is arranged in the tube furnace, the tube furnace comprises a main body, the bottom of the main body is movably connected with a workbench, the middle of the workbench is movably connected with a heating device, the top of the workbench is movably connected with gear teeth, the middle of the main body is movably connected with a furnace tube, the two sides of the furnace tube are movably connected with end covers, the left side of the end covers is movably connected with air holes, the middle of the air holes is movably connected with a gear, the middle of the furnace tube is movably connected with a crucible, the bottom of the crucible is movably connected with a universal wheel, the calcining process is carried out, the calcining process is pyrolysis for 2 hours at 625 ℃ in4Ti5O12The lithium ion battery negative electrode material of (1);
(5) adding N-methyl pyrrolidone and sulfur-nitrogen doped porous carbon coated Li into a reaction bottle4Ti5O12The lithium ion battery negative electrode material, acetylene black and polyvinylidene fluoride are dispersed uniformly by ultrasonic, and the solution is coated on copper foil by a scraper and dried to obtain the lithium ion battery negative electrode working electrode.
Example 3
(1) Adding ethanol and titanium dioxide into a reaction bottle, stirring uniformly, adding a sodium hydroxide aqueous solution, wherein the mass ratio of the titanium dioxide to the sodium hydroxide is 100:116, stirring uniformly, transferring into a reaction kettle, placing in an oven, performing a hydrothermal process, wherein the hydrothermal process is a reaction at 180 ℃ for 40 hours, cooling, washing cleanly and drying to obtain linear nano Na2Ti3O7；
(2) Adding deionized water, lithium hydroxide and linear nano Na into a reaction bottle2Ti3O7The mass ratio of the two is 20:100, the mixture is evenly stirred, the mixture is moved into a reaction kettle and placed in a drying oven to carry out hydrothermal reaction process, the hydrothermal reaction process is carried out for 18 hours at 175 ℃, the mixture is cooled, washed and dried, the dried product is placed in a tube furnace and calcined for 3 hours at 580 ℃, and the linear nano Li is obtained4Ti5O12；
(3) Adding deionized water, 3-formaldehyde benzothiophene, resorcinol, melamine and linear nano Li into a reaction bottle4Ti5O12Dispersing uniformly at 60 deg.C by ultrasonic wave, cooling, adding sodium carbonate, adjusting pH to 8, reacting at 55 deg.C for 25min, adding emulsifier Tween 20 and toluene as oil phase, stirring, adding catalyst phosphoric acid, wherein 3-formaldehyde benzothiophene, resorcinol, melamine, and linear nanometer Li4Ti5O12Uniformly stirring, pouring the solution into a mold, sealing, standing for 2 days at 75 ℃, washing with acetone, and drying to obtain porous phenolic resin coated Li4Ti5O12A nanowire;
(4) coating porous phenolic resin with Li4Ti5O12The nano wire is placed in a tube furnaceThe utility model discloses a tube furnace, the tube furnace includes the main part, the bottom swing joint of main part has the workstation, the middle swing joint of workstation has heating device, the top swing joint of workstation has the teeth of a cogwheel, the middle swing joint of main part has the boiler tube, the both sides swing joint of boiler tube has the end cover, the left side swing joint of end cover has the gas pocket, the middle swing joint of gas pocket has the gear, the middle swing joint of boiler tube has the crucible, the bottom swing joint of crucible has the universal wheel, carry out the calcination process, the calcination process is 620 ℃ of pyrolysis 1h down in the nitrogen atmosphere, obtain sulphur nitrogen doping porous carbon cladding Li4Ti5O12The lithium ion battery negative electrode material of (1);
(5) adding N-methyl pyrrolidone and sulfur-nitrogen doped porous carbon coated Li into a reaction bottle4Ti5O12The lithium ion battery negative electrode material, acetylene black and polyvinylidene fluoride are dispersed uniformly by ultrasonic, and the solution is coated on copper foil by a scraper and dried to obtain the lithium ion battery negative electrode working electrode.
Example 4
(1) Adding ethanol and titanium dioxide into a reaction bottle, uniformly stirring, adding a sodium hydroxide aqueous solution, wherein the mass ratio of the titanium dioxide to the sodium hydroxide is 100:120, uniformly stirring, transferring into a reaction kettle, placing in an oven, performing a hydrothermal process, wherein the hydrothermal process is to react for 60 hours at 190 ℃, cooling, washing and drying to obtain linear nano Na2Ti3O7；
(2) Adding deionized water, lithium hydroxide and linear nano Na into a reaction bottle2Ti3O7The mass ratio of the two is 22:100, the mixture is evenly stirred, the mixture is moved into a reaction kettle and placed in a drying oven to carry out the hydrothermal reaction process, the hydrothermal reaction process is carried out for 36 hours at 190 ℃, the mixture is cooled, washed and dried, the dried product is placed in a tube furnace and calcined for 5 hours at 650 ℃, and the linear nano Li is obtained4Ti5O12；
(3) Adding deionized water, 3-formaldehyde benzothiophene, resorcinol, melamine and linear nano Li into a reaction bottle4Ti5O12Dispersing uniformly by ultrasonic wave at 65 deg.C, cooling, adding sodium carbonate, adjusting pH to 9, and adjusting pH to 6Reacting at 5 deg.C for 40min, adding emulsifier Tween 20 and toluene as oil phase, stirring, adding catalyst phosphoric acid, wherein 3-formaldehyde benzothiophene, resorcinol, melamine, and linear nanometer Li4Ti5O12The mass ratio of the Tween 20 to the phosphoric acid is 480:100:60:7000:150:43, the mixture is uniformly stirred, the solution is poured into a die for sealing, the die is kept stand for 4 days at the temperature of 80 ℃, acetone is used for washing and drying, and the porous phenolic resin coated Li is obtained4Ti5O12A nanowire;
(4) coating porous phenolic resin with Li4Ti5O12The nano wire is arranged in the tube furnace, the tube furnace comprises a main body, the bottom of the main body is movably connected with a workbench, the middle of the workbench is movably connected with a heating device, the top of the workbench is movably connected with gear teeth, the middle of the main body is movably connected with a furnace tube, the two sides of the furnace tube are movably connected with end covers, the left side of the end covers is movably connected with air holes, the middle of the air holes is movably connected with a gear, the middle of the furnace tube is movably connected with a crucible, the bottom of the crucible is movably connected with a universal wheel, the calcining process is carried out, the calcining process is pyrolysis for 3 hours at 650 ℃ in4Ti5O12The lithium ion battery negative electrode material of (1);
(5) adding N-methyl pyrrolidone and sulfur-nitrogen doped porous carbon coated Li into a reaction bottle4Ti5O12The lithium ion battery negative electrode material, acetylene black and polyvinylidene fluoride are dispersed uniformly by ultrasonic, and the solution is coated on copper foil by a scraper and dried to obtain the lithium ion battery negative electrode working electrode.
Comparative example 1
(1) Adding ethanol and titanium dioxide into a reaction bottle, stirring uniformly, adding a sodium hydroxide aqueous solution, wherein the mass ratio of the titanium dioxide to the sodium hydroxide is 100:100, stirring uniformly, transferring into a reaction kettle, placing in an oven, performing a hydrothermal process, wherein the hydrothermal process is a reaction at 180 ℃ for 48 hours, cooling, washing cleanly and drying to obtain linear nano Na2Ti3O7；
(2) Adding deionized water, lithium hydroxide and linear nano Na into a reaction bottle2Ti3O7The mass ratio of the two is 18:100, the mixture is evenly stirred, the mixture is moved into a reaction kettle and placed in a drying oven to carry out the hydrothermal reaction process, the hydrothermal reaction process is carried out for 24 hours at 180 ℃, the mixture is cooled, washed and dried, the dried product is placed in a tube furnace and calcined for 4 hours at 600 ℃, and the linear nano Li is obtained4Ti5O12；
(3) Adding deionized water, 3-formaldehyde benzothiophene, resorcinol, melamine and linear nano Li into a reaction bottle4Ti5O12Dispersing uniformly at 60 deg.C by ultrasonic wave, cooling, adding sodium carbonate, adjusting pH to 8, reacting at 55 deg.C for 40min, adding emulsifier Tween 20 and toluene as oil phase, stirring, adding catalyst phosphoric acid, wherein 3-formaldehyde benzothiophene, resorcinol, melamine, and linear nanometer Li4Ti5O12The mass ratio of the Tween 20 to the phosphoric acid is 380:100:20:3000:100:35, the mixture is uniformly stirred, the solution is poured into a mold for sealing, the mold is kept stand for 2 days at the temperature of 80 ℃, acetone is used for washing and drying, and the porous phenolic resin coated Li is obtained4Ti5O12A nanowire;
(4) coating porous phenolic resin with Li4Ti5O12The nano wire is arranged in the tube furnace, the tube furnace comprises a main body, the bottom of the main body is movably connected with a workbench, the middle of the workbench is movably connected with a heating device, the top of the workbench is movably connected with gear teeth, the middle of the main body is movably connected with a furnace tube, the two sides of the furnace tube are movably connected with end covers, the left side of the end covers is movably connected with air holes, the middle of the air holes is movably connected with a gear, the middle of the furnace tube is movably connected with a crucible, the bottom of the crucible is movably connected with a universal wheel, the calcining process is carried out, the calcining process is pyrolysis for 2 hours at 600 ℃ in4Ti5O12The lithium ion battery negative electrode material of (1);
(5) adding N-methyl pyrrolidone and sulfur-nitrogen doped porous carbon coated Li into a reaction bottle4Ti5O12The lithium ion battery cathode material, acetylene black and polyvinylidene fluoride are dispersed uniformly by ultrasound, and the solution is coated by a scraperAnd drying on the copper foil to obtain the working electrode of the negative electrode of the lithium ion battery.
Lithium sheet is taken as a counter electrode, a polyethylene microporous membrane is taken as a diaphragm, and 1mol/L LiPF is dissolved in electrolyte6The volume ratio of the ethylene carbonate to the dimethyl carbonate is 1:1, the lithium ion battery negative working electrode obtained in the embodiment and the comparative example is added, and the lithium ion battery negative working electrode is assembled in a vacuum glove box to obtain the sulfur-nitrogen doped porous carbon-coated Li4Ti5O12The button type half cell carries out constant current charge and discharge test on the discharge specific capacity of the assembled cell on an MC8 type test system, and the test standard is GB/T36276-2018.
Figure BDA0002829235590000101
Figure BDA0002829235590000111

Claims (6)

1. Sulfur-nitrogen doped porous carbon-coated Li4Ti5O12The lithium ion battery cathode material is characterized in that: the sulfur-nitrogen doped porous carbon-coated Li4Ti5O12The preparation method of the lithium ion battery negative electrode material comprises the following steps:
(1) adding titanium dioxide into ethanol, stirring uniformly, adding a sodium hydroxide aqueous solution, wherein the mass ratio of the titanium dioxide to the sodium hydroxide is 100:113-120, stirring uniformly, transferring into a reaction kettle, placing in an oven, performing a hydrothermal process, cooling, washing and drying to obtain linear nano Na2Ti3O7；
(2) Adding lithium hydroxide and linear nano Na into deionized water2Ti3O7The mass ratio of the two is 20-22:100, the mixture is evenly stirred, the mixture is moved into a reaction kettle and placed in a drying oven to carry out hydrothermal reaction, the mixture is cooled, washed and dried, the dried product is placed in a tube furnace and calcined for 3-5h at the temperature of 550-650 ℃ to obtain the linear nano Li4Ti5O12；
(3) Adding 3-formaldehyde benzothiophene, resorcinol, melamine and linear nano Li into deionized water4Ti5O12Uniformly dispersing by ultrasonic at 55-65 ℃, cooling, adding sodium carbonate, adjusting pH to 8-9, reacting at 55-65 ℃ for 20-40min, adding emulsifier Tween 20 and toluene as oil phase, fully stirring, adding catalyst phosphoric acid, uniformly stirring, pouring the solution into a mold, sealing, standing at 70-80 ℃ for 2-4 days, washing and drying to obtain porous phenolic resin coated Li4Ti5O12A nanowire;
(4) coating porous phenolic resin with Li4Ti5O12The nanowire is placed in a tube furnace and is calcined to obtain the Li coated with the sulfur-nitrogen doped porous carbon4Ti5O12The lithium ion battery negative electrode material of (1);
(5) adding sulfur-nitrogen doped porous carbon-coated Li into N-methylpyrrolidone4Ti5O12The lithium ion battery negative electrode material, acetylene black and polyvinylidene fluoride are dispersed uniformly by ultrasonic, and the solution is coated on copper foil by a scraper and dried to obtain the lithium ion battery negative electrode working electrode.
2. The Li of claim 1, wherein Li is coated with porous carbon doped with S and N4Ti5O12The lithium ion battery cathode material is characterized in that: the hydrothermal process in the step (1) is a reaction at 170-190 ℃ for 36-60 h.
3. The Li of claim 1, wherein Li is coated with porous carbon doped with S and N4Ti5O12The lithium ion battery cathode material is characterized in that: the hydrothermal reaction process in the step (2) is reaction at 170-190 ℃ for 12-36 h.
4. The Li of claim 1, wherein Li is coated with porous carbon doped with S and N4Ti5O12The lithium ion battery cathode material is characterized in that: 3-formaldehyde benzothiophene, resorcinol, melamine and wire in the step (3)Nano Li like material4Ti5O12The mass ratio of the Tween 20 to the phosphoric acid is 400-480:100:30-60:3500-7000:120-150: 38-43.
5. The Li of claim 1, wherein Li is coated with porous carbon doped with S and N4Ti5O12The lithium ion battery cathode material is characterized in that: the tubular furnace in the step (4) comprises a main body, wherein the bottom of the main body is movably connected with a workbench, the middle of the workbench is movably connected with a heating device, the top of the workbench is movably connected with gear teeth, the middle of the main body is movably connected with a furnace tube, the two sides of the furnace tube are movably connected with end covers, the left side of each end cover is movably connected with an air hole, the middle of each air hole is movably connected with a gear, the middle of the furnace tube is movably connected with a crucible, and the bottom of the crucible is movably connected.
6. The Li of claim 1, wherein Li is coated with porous carbon doped with S and N4Ti5O12The lithium ion battery cathode material is characterized in that: the calcination process in the step (4) is pyrolysis for 1-3h at 600-650 ℃ in a nitrogen atmosphere.
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