CN114162876B - Preparation method and application of Co9S8@ carbon nanotube @ graphene composite material - Google Patents

Preparation method and application of Co9S8@ carbon nanotube @ graphene composite material Download PDF

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CN114162876B
CN114162876B CN202111505061.XA CN202111505061A CN114162876B CN 114162876 B CN114162876 B CN 114162876B CN 202111505061 A CN202111505061 A CN 202111505061A CN 114162876 B CN114162876 B CN 114162876B
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孙林
刘宴秀
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Yancheng Institute of Technology
Yancheng Institute of Technology Technology Transfer Center Co Ltd
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Abstract

The invention provides a preparation method and application of a Co9S8@ carbon nanotube @ graphene composite material, wherein the preparation method comprises the following steps: s1: preparing a graphene oxide aqueous solution; s2: dispersing ZIF-67 powder and thioacetamide into a graphene oxide aqueous solution, and uniformly stirring and mixing to obtain a first mixed solution; s3: adding pyrrole into the first mixed solution, and uniformly stirring and mixing to obtain a second mixed solution; s4: and transferring the second mixed solution into a reaction kettle with a polytetrafluoroethylene lining for heating, naturally cooling, and then sequentially carrying out freeze-drying treatment and heat treatment under an Ar atmosphere to obtain a sample Co9S8@ CNTs @ Gr. The preparation method of the Co9S8@ carbon nanotube @ graphene composite material and the application of the lithium-sulfur battery have the advantages of simple preparation process, no pollution and good flexibility, and show high capacity performance, excellent rate capability and long cycle performance when being applied to the anode material of the lithium-sulfur battery.

Description

Preparation method and application of Co9S8@ carbon nanotube @ graphene composite material
Technical Field
The invention relates to the technical field of functional materials of lithium-sulfur batteries, and particularly relates to a preparation method and application of a Co9S8@ carbon nanotube @ graphene composite material.
Background
At present, lithium-sulfur batteries (Li-S batteries) are widely concerned due to rich sulfur resources, low cost and particularly ultra-high theoretical energy density (2600mA h g < -1 >). However, the insulating properties of the S8 molecule, as well as the shuttling effect during charging and discharging and the solubility of lithium polysulfides, limit the application of lithium-sulfur batteries. Currently, cobalt metal doped carbon-based materials have been widely used as sulfur-fixing hosts to immobilize soluble polysulfides, mitigate shuttling effects, and accelerate electrochemical kinetics of lithium sulfur batteries. Such as: oriented growth of ZIF-67 on the surface of ZnAl-LDH by Jianbo Li et al (adv. energy Mater.2019,1901935), and then pyrolysis and acid etching are carried out to obtain mesoporous carbon nanosheets (MC-NC) with rich defects and Co-NC catalytic sites; weiwei Sun et al (Nano Res.2020,13(8): 2143-; songqi iao Niu et al (Nanomaterials 2021,11,1910) obtained Co-doped carbon skeleton with mesoporous structure by direct thermal treatment with ZIF-67 as precursor. The method can enhance the adsorption capacity to polysulfide to a certain extent and catalyze electrochemical reaction, but has the problems of time-consuming template removal, environmental harm, complex preparation process, unobvious capacity improvement, insufficient rate capability and long cycle performance and the like;
nano Energy 38(2017) 239-248, a Nano Energy university school team, reports a hollow carbon Nano-polyhedron embedded with Co9S8 nanocrystals synthesized from a template. Taking ZIF-67 as a precursor and thioacetamide as a vulcanizing agent, vulcanizing Co by a solvothermal method to form Co9S8 nano-crystals, and then preparing the hollow nano-polyhedron with the carbon shell and the embedded polar Co9S8 nano-crystals by pyrolysis. The hollow structure can accommodate high sulfur loads and buffer volume changes; co9S8 can bind to polysulfides, limiting their out-diffusion; the polar Co9S8/C shell can improve the redox reaction kinetics and rate capability; the three-dimensional conductive and porous Co9S8/C shell facilitates Li + and electron transport. Therefore, the resulting composite exhibits high capacity and long cycle life as a positive electrode of a lithium sulfur battery. Jianan Ye et al (J. Taiwan Inst. chem. Eng.112(2020)202-211) reported a new epitaxial growth pyrolysis strategy to fabricate N-doped CNTs assembled hollow frames (CoNC/CNTs) by core-shell/ZIF-8 pyrolysis with Co nanoparticles as catalysts to promote the formation of Co/N Co-doped CNTs. The composite material shows good adsorption capacity to methyl blue, acid fuchsin and malachite green. Tao Chen et al (Nano Lett.17(2017),437-444) reported a method based on the "sea urchin" -like cobalt nanoparticle embedding and nitrogen doping of carbon nanotubes/nanopolyheddles (Co-NCNT/NP). The graded micropores in Co-NCNT/NP can effectively impregnate sulfur and prevent diffusion of soluble sulfide through physical limitation, and the combination of embedded Co nanoparticles and nitrogen doping can synergistically improve polysulfide adsorption. At the same time, the conductive network of Co-NCNT/NP interconnected by the nitrogen-doped carbon nanotubes can facilitate electron transport and electrolyte permeation. The composite material exhibits excellent electrochemical properties as a positive electrode of a lithium sulfur battery. However, these methods are cumbersome steps and the material is not flexible.
Therefore, the preparation method of the Co9S8@ carbon nanotube @ graphene composite material is simple in preparation process, the template is not required to be removed, acid-base treatment is not required, the environment is not polluted, and a sample obtained by a hydrothermal method is calcined after being freeze-dried to obtain the sample; meanwhile, the graphene oxide and the carbon nano tube can endow the sample with good flexibility, and the synergistic effect of the graphene oxide and the carbon nano tube can enable the prepared sample to show excellent rate capability when being applied to the positive electrode material of the lithium-sulfur battery, and meanwhile, the sample also shows good cycle performance when being applied to the positive electrode material of the lithium-sulfur battery.
Disclosure of Invention
The invention aims to provide a preparation method and application of a Co9S8@ carbon nanotube @ graphene composite material.
In order to solve the technical problem, the preparation method of the Co9S8@ carbon nanotube @ graphene composite material provided by the embodiment of the invention comprises the following steps:
s1: preparing a graphene oxide aqueous solution;
s2: dispersing ZIF-67 powder and thioacetamide into the graphene oxide aqueous solution, and uniformly stirring and mixing to obtain a first mixed solution;
s3: adding pyrrole into the first mixed solution, and uniformly stirring and mixing to obtain a second mixed solution;
s4: and transferring the second mixed solution into a reaction kettle with a polytetrafluoroethylene lining for heating, naturally cooling, and then sequentially performing freeze-drying treatment and heat treatment under an Ar atmosphere to obtain a sample Co9S8@ CNTs @ Gr.
Preferably, the dosage of the graphene oxide aqueous solution is 10-60ml, and the concentration is 20-80%.
Preferably, the amount of the ZIF-67 powder is 10-2000mg, the amount of the thioacetamide is 5-2000mg, and the mass ratio of the ZIF-67 powder to the thioacetamide is 1:1-8: 1.
Preferably, the stirring time period for stirring in step S2 is 10 min.
Preferably, the amount of pyrrole used is 2-8 ml.
Preferably, the stirring time period for stirring in step S3 is 5 min.
Preferably, the heating temperature of the second mixed solution in the reaction kettle with the polytetrafluoroethylene lining in the step S4 is 100-200 ℃, and the heating time is 2-10 h.
Preferably, the treatment temperature of the heat treatment under the Ar atmosphere in the step S4 is 700-1200 ℃, and the treatment time is 2-10 h.
Preferably, in step S4, the reaction kettle includes:
the kettle body is vertically arranged, and the inner wall of the kettle body is connected with polytetrafluoroethylene;
the steam jacket is connected to the surface of the kettle body;
the kettle cover is arranged at the top end of the kettle body;
the window is arranged on the kettle body;
the uniformly heated mechanism is arranged at the bottom end of the kettle cover;
wherein, the thermally equivalent mechanism includes:
the rotary motor is arranged on the kettle cover, and the output end of the rotary motor extends out of the bottom end of the kettle cover;
the rotating frame is positioned in the kettle body and is arranged at the output end of the rotating motor;
the shaft end of the traverse roller is arranged on the rotating frame;
the transverse moving chute is spirally arranged on the transverse moving roller;
the spline shaft is arranged on the rotating frame, is positioned below the transverse moving rollers and is arranged in parallel with the transverse moving rollers;
the transverse sliding block is connected in the transverse sliding chute in a sliding manner;
the transverse moving seat is sleeved on the spline shaft through a spline sleeve, and the transverse moving slider is fixedly connected with the transverse moving seat;
the power chamber is arranged in the transverse moving seat, and the spline shaft penetrates through the power chamber;
the rotating rod is vertically arranged at the end, far away from the transverse sliding block, of the transverse sliding seat;
the first chain wheel is arranged in the power chamber and is mounted on the spline sleeve;
the transmission chamber is arranged in the rotating rod and communicated with the power chamber;
the second chain wheel is connected into the transmission chamber through a mounting shaft;
the transmission chain is sleeved on the first chain wheel and the second chain wheel;
the incomplete gear is arranged in the transmission chamber, and the incomplete gear and the second chain wheel are coaxially arranged on the mounting shaft;
the offset rod is hinged to the rotating rod through a connecting shaft and far away from the transverse moving seat end, and the connecting shaft extends into the transmission chamber;
the straight gear is arranged in the transmission chamber, the straight gear is arranged on the connecting shaft, and the straight gear is meshed with the incomplete gear;
the transmission gear ring is fixedly connected to the bottom end of the kettle cover, and the rotating frame is sleeved in the transmission gear ring;
the two rotating gears are symmetrically arranged at the shaft end of the transverse moving roller by taking the output end of the rotating motor as a center, and are meshed with the transmission gear ring;
and the driving belt is sleeved on the two belt wheels, one belt wheel is arranged on the spline shaft, and the other belt wheel is arranged at the shaft end of the traverse roller.
Preferably, in step S4, during the heat treatment in the Ar atmosphere, the reaction monitoring is further performed, which specifically includes:
arranging a plurality of image acquisition point positions in a hearth;
transferring the second mixed solution after freeze-drying treatment into the hearth;
filling Ar atmosphere into the hearth;
acquiring preparation parameters for preparing the second mixed solution, and acquiring the heating temperature of the hearth to be subjected to heat treatment;
acquiring a preset acquisition opportunity determining model, and inputting the preparation parameters and the heating temperature into the acquisition opportunity determining model to acquire acquisition opportunities;
controlling the hearth to start heating, and recording the heating time length;
when the heating time reaches the acquisition time, triggering the image acquisition point position to be opened, and dynamically acquiring a reaction image of the second mixed solution subjected to freeze-drying treatment subjected to heat treatment in an Ar atmosphere;
performing feature extraction on the reaction image to obtain a plurality of first image features;
randomly combining the first image features to obtain a plurality of first image combination features;
setting a first item to be matched, wherein the item to be matched comprises: the first image feature and the first image combination feature;
acquiring a preset value feature library, performing feature matching on the first item to be matched and a first matching item in the value feature library, and acquiring a value degree corresponding to the first matching item matched if matching is matched;
accumulating and summarizing the value degrees to obtain a value degree sum;
when the sum of the value degrees is greater than or equal to a preset first value degree threshold value, acquiring a preset switching opportunity determination model, and inputting the newly generated reaction image into the switching opportunity determination model;
if the value degree sum is larger than or equal to a preset second value degree threshold and/or the switching time determines that a model outputs a switching time and the heating time reaches the switching time, performing feature extraction on the newly generated reaction image to obtain a plurality of second image features;
randomly combining the second image features to obtain a plurality of second image combination features;
setting a second item to be matched, wherein the item to be matched comprises: the second image feature and the second image combination feature;
acquiring a preset incomplete reaction feature library, performing feature matching on the second item to be matched and a second matching item in the incomplete reaction feature library, and if the matching is in accordance, acquiring the corresponding representation degree of the second matching item in accordance with the matching;
and when the value degree and the representation degree obtained in a preset time period are both less than or equal to a preset representation degree threshold value, determining that the reaction is complete, and outputting a sample Co9S8@ CNTs @ Gr.
The sample Co9S8@ CNTs @ Gr provided by the embodiment of the invention is applied to a lithium-sulfur battery.
The invention has the beneficial effects that:
1. the preparation process is simple: the preparation method comprises the steps of taking ZIF-67 as a precursor and pyrrole as a nitrogen source, preparing cobalt and nitrogen co-doped graphene by a simple hydrothermal method, further performing pyrolysis, and growing a carbon nano tube in situ under the catalytic action of cobalt without a template, namely removing the template;
2. no pollution to the environment: acid-base treatment is not needed;
3. when the lithium-sulfur battery positive electrode material is applied to a lithium-sulfur battery, the performance is improved: the pyrrole is used as a nitrogen source, so that the conductivity is improved, and the high-capacity performance, the excellent rate performance and the long cycle performance are also shown;
4. the material has flexibility: the graphene oxide and the carbon nano tube can endow a sample with good flexibility, can be easily stripped from a current collector, can be easily folded, and the unfolded pole piece is intact and cannot be broken;
5. the preparation quality is improved: the reaction kettle is heated uniformly, and the growth conditions of the carbon nano tube, namely the heating time and the heating temperature, can be accurately controlled when the heat treatment is carried out under the Ar atmosphere.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
The technical solution of the present invention is further described in detail by the accompanying drawings and embodiments.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a flow chart of a preparation method of a Co9S8@ carbon nanotube @ graphene composite material in an embodiment of the invention;
FIG. 2 is a graph of the cycle curve of the Co9S8@ CNTs @ Gr composite material used for a lithium sulfur battery positive electrode material in battery tests;
FIG. 3 is an electron micrograph of the Co9S8/Gr composite after lyophilization and before heat treatment in an Ar atmosphere;
FIG. 4 is an electron micrograph of a Co9S8@ CNTs @ Gr composite;
FIG. 5 is a graph of the cycling curves at different current densities for the Co9S8@ CNTs @ Gr composite used for battery testing of a lithium sulfur battery positive electrode material;
FIG. 6 is a schematic view of a reaction vessel according to an embodiment of the present invention;
FIG. 7 is an enlarged view of reference character A in FIG. 6;
in the figure: 11. a kettle body; 12. a steam jacket; 13. a kettle cover; 14. a window; 15. a uniformly heated mechanism; 16. rotating the motor; 17. a rotating frame; 18. a traversing roller; 19. a transverse sliding chute; 10. a spline shaft; 21. transversely moving the sliding block; 22. a traversing seat; 23. rotating the rod; 24. a first sprocket; 25. a transmission chamber; 26. a second sprocket; 27. an incomplete gear; 28. an offset lever; 29. a spur gear; 20. a transmission gear ring; 31. a rotating gear; 32. a pulley.
Detailed Description
The preferred embodiments of the present invention will be described in conjunction with the accompanying drawings, and it will be understood that they are described herein for the purpose of illustration and explanation and not limitation.
Example 1
S1: mixing 10mg of ZIF-67 powder and 5mg of thioacetamide according to a mass ratio of 2: 1, adding the mixture into 10ml of graphene oxide aqueous solution with the concentration of 40%, stirring for 10min, adding 2ml of pyrrole, and continuing stirring for 5 min;
s2: and transferring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining, and heating for 3 hours at 180 ℃. Naturally cooling and freeze-drying, and performing heat treatment at 700 ℃ for 3h in Ar atmosphere to obtain a sample Co9S8@ CNTs @ Gr;
s3: and (3) mixing the obtained sample with conductive graphite and PVDF according to the mass ratio of 8: 1:1, preparing uniform slurry, coating the slurry on an aluminum foil, drying the slurry in vacuum at 45 ℃ for 10 hours, cutting the slurry into disks with the diameter of 14mm, assembling the batteries by taking a lithium sheet as a counter electrode, and testing the batteries.
Example 2
S1: mixing 40mg of ZIF-67 powder and 60mg of thioacetamide according to a mass ratio of 2: 3, adding the mixture into 30ml of graphene oxide aqueous solution with the concentration of 40%, stirring for 10min, adding 6ml of pyrrole, and continuing stirring for 5 min;
s2: the mixed solution is transferred to a reaction kettle with a polytetrafluoroethylene lining and heated for 5 hours at 160 ℃. Naturally cooling and freeze-drying, and performing heat treatment at 700 ℃ for 3h in Ar atmosphere to obtain a sample Co9S8@ CNTs @ Gr;
s3: and (3) mixing the obtained sample with conductive graphite and PVDF according to the mass ratio of 8: 1:1, preparing uniform slurry, coating the slurry on an aluminum foil, drying the slurry in vacuum at 45 ℃ for 10 hours, cutting the slurry into disks with the diameter of 14mm, assembling the batteries by taking a lithium sheet as a counter electrode, and testing the batteries.
Example 3
S1: mixing 90mg of ZIF-67 powder and 30mg of thioacetamide according to a mass ratio of 3: 1, adding the mixture into 40ml of graphene oxide aqueous solution with the concentration of 50%, stirring for 10min, adding 4ml of pyrrole, and continuing stirring for 5 min;
s2: the mixed solution is transferred to a reaction kettle with a polytetrafluoroethylene lining and heated for 6 hours at 150 ℃. Naturally cooling and freeze-drying, and carrying out heat treatment for 5h at 700 ℃ in Ar atmosphere to obtain a sample Co9S8@ CNTs @ Gr;
s3: and mixing the obtained sample with conductive graphite and PVDF according to the mass ratio of 8: 1:1, preparing uniform slurry, coating the slurry on an aluminum foil, drying the slurry in vacuum at 45 ℃ for 10 hours, cutting the slurry into disks with the diameter of 14mm, assembling the batteries by taking a lithium sheet as a counter electrode, and testing the batteries.
Through tests, when the samples Co9S8@ CNTs @ Gr prepared in example 1, example 2 and example 3 are used for assembled batteries of lithium-sulfur battery cathode materials for battery tests, measured by a Neware battery tester, and the cycling curve graphs at different current densities are drawn by Origin software, and are shown in FIG. 5;
example 1 corresponds to graphs a and b in fig. 5, and as shown in graphs a and b, the sample Co9S8@ CNTs @ Gr prepared in example 1 shows good cycling performance at current densities of 0.2A g-1 and 0.5A g-1 for the assembled battery of the lithium-sulfur battery cathode material;
example 2 corresponds to graph c in fig. 5, and as shown in the graph c, the sample Co9S8@ CNTs @ Gr prepared in example 2 shows good cycling performance at a current density of 0.8A g-1 for a battery assembled by using the lithium sulfur battery cathode material;
example 3 corresponds to graph d in fig. 5, and as shown in the graph d, the sample Co9S8@ CNTs @ Gr prepared in example 3 shows good cycling performance at a current density of 1A g-1 for a battery assembled with a lithium sulfur battery cathode material.
Example 4
As shown in fig. 6 and 7, in step S4, the reaction kettle includes:
the kettle body 11 is vertically arranged, and the inner wall of the kettle body 11 is connected with polytetrafluoroethylene;
a steam jacket 12, wherein the steam jacket 12 is connected to the surface of the kettle body 11;
the kettle cover 13 is arranged at the top end of the kettle body 11;
the window 14, the said window 14 is set up on the said kettle body 11;
the uniformly-heated mechanism 15 is arranged at the bottom end of the kettle cover 13;
wherein, the even heating mechanism 15 includes:
the rotating motor 16 is arranged on the kettle cover 13, and the output end of the rotating motor 16 extends out of the bottom end of the kettle cover 13;
the rotating frame 17 is positioned in the kettle body 11, and the rotating frame 17 is installed at the output end of the rotating motor 16;
a traverse roller 18, wherein the shaft end of the traverse roller 18 is arranged on the rotating frame 17;
a traverse chute 19, the traverse chute 19 being spirally provided on the traverse roller 18;
the spline shaft 10 is installed on the rotating frame 17, the spline shaft 10 is positioned below the transverse moving rollers 18, and the spline shaft 10 is arranged in parallel with the transverse moving rollers 18;
the transverse sliding block 21 is connected in the transverse sliding chute 19 in a sliding manner;
the transverse moving seat 22 is sleeved on the spline shaft 10 through a spline sleeve, and the transverse moving slide block 21 is fixedly connected with the transverse moving seat 22;
the power chamber is arranged in the transverse moving seat 22, and the spline shaft 10 penetrates through the power chamber;
the rotating rod 23 is vertically arranged at the end, away from the transverse sliding block 21, of the transverse sliding seat 22;
the first chain wheel 24 is arranged in the power chamber, and the first chain wheel 24 is installed on the spline sleeve;
the transmission chamber 25 is arranged in the rotating rod 23, and the transmission chamber 25 is communicated with the power chamber;
a second sprocket 26, wherein the second sprocket 26 is connected to the transmission chamber 25 through a mounting shaft;
the transmission chain is sleeved on the first chain wheel 24 and the second chain wheel 26;
an incomplete gear 27, wherein the incomplete gear 27 is disposed in the transmission chamber 25, and the incomplete gear 27 and the second sprocket 26 are coaxially mounted on the mounting shaft;
the offset rod 28 is hinged to the end, far away from the transverse moving seat 22, of the rotating rod 23 through a connecting shaft, and the connecting shaft extends into the transmission chamber 25;
a spur gear 29, wherein the spur gear 29 is arranged in the transmission chamber 25, the spur gear 29 is mounted on the connecting shaft, and the spur gear 29 is meshed with the incomplete gear 27;
the transmission gear ring 20 is fixedly connected to the bottom end of the kettle cover 13, and the rotating frame 17 is sleeved in the transmission gear ring 20;
the two rotating gears 31 are symmetrically arranged at the shaft end of the traverse roller 18 by taking the output end of the rotating motor 16 as a center, and the rotating gears 31 are meshed with the transmission gear ring 20;
and the belt pulleys 32 are sleeved on the two belt pulleys 32, one belt pulley 32 is arranged on the spline shaft 10, and the other belt pulley 32 is arranged at the shaft end of the traverse roller 18.
The working principle and the beneficial effects of the technical scheme are as follows:
the second mixed solution is transferred into the kettle body 11, steam passes through the steam jacket 12 to heat the kettle body 11 at high temperature, the heating condition of the second mixed solution is observed through the window 14, meanwhile, the uniformly heated mechanism 15 works, the rotating motor 16 rotates to further drive the rotating frame 17 arranged at the output end of the rotating motor 16 to rotate, the rotating frame 17 drives the traverse roller 18 arranged on the rotating frame 17 and the spur gear 29 arranged at the end part of the traverse roller 18 to rotate on the transmission gear ring 20, under the matching of the transmission gear ring 20 and the spur gear 29, the spur gear 29 drives the traverse roller 18 to axially rotate, thereby driving the traverse chute 19 on the traverse roller 18, the traverse slide block 21 connected in the traverse chute 19 in a sliding way and the traverse seat 21 fixedly connected with the traverse slide block 21 to reciprocate left and right along the spline shaft 10, further driving the rotating rod 23 fixedly connected with the traverse seat 21 and the offset rod 28 hinged with the traverse seat 23 to reciprocate left and right, at this time, the rotating rod 23 and the offset rod 28 move left and right while rotating along with the rotating frame 17, so as to increase the contact area between the rotating rod 23 and the offset rod 28 and the second mixed solution, thereby improving the fluidity of the second mixed solution, so that the steam jacket 12 uniformly heats the second mixed solution, the traverse roller 18 drives the spline shaft 10 to rotate through the belt pulley 32 and the transmission belt, and further drives the first chain wheel 24 sleeved on the spline shaft 10 to rotate, the first chain wheel 24 drives the second chain wheel 26 to rotate through the transmission chain, the second chain wheel 26 drives the incomplete gear 27 to rotate through the mounting shaft, the incomplete gear 27 intermittently drives the spur gear 29 to rotate, when the spur gear 29 rotates, the offset rod 28 coaxially mounted on the connecting shaft with the spur gear 29 is driven to rotate, and further the offset rod 28 and the rotating rod 23 are turned downwards, when the spur gear 29 is not rotated, because the return coil spring is installed on the connecting shaft, the offset rod 28 is turned upwards to return under the action of the return coil spring, when the uniformly heated mechanism 15 stops working, the rotating rod 23 is arranged close to the inner wall of the kettle body 11, and the offset rod 28 is turned upwards to return so as to reduce the contact area with the second mixed solution, at the moment, the kettle cover 13 is opened through a crane, the second mixed solution is naturally cooled in the kettle body 11, and after the second mixed solution is pumped away by a pump, freeze-drying treatment is carried out, and then heat treatment is carried out under an Ar atmosphere.
Example 5
During the heat treatment under the Ar atmosphere, reaction monitoring is also carried out, and the method specifically comprises the following steps:
arranging a plurality of image acquisition point positions in a hearth;
transferring the second mixed solution after freeze-drying treatment into the hearth;
filling Ar atmosphere into the hearth;
acquiring preparation parameters for preparing the second mixed solution, and acquiring the heating temperature of the hearth to be subjected to heat treatment;
acquiring a preset acquisition opportunity determining model, and inputting the preparation parameters and the heating temperature into the acquisition opportunity determining model to acquire acquisition opportunities;
controlling the hearth to start heating, and recording the heating time length;
when the heating time reaches the acquisition time, triggering the image acquisition point position to be opened, and dynamically acquiring a reaction image of the second mixed solution subjected to freeze-drying treatment subjected to heat treatment in an Ar atmosphere;
performing feature extraction on the reaction image to obtain a plurality of first image features;
randomly combining the first image features to obtain a plurality of first image combination features;
setting a first item to be matched, wherein the item to be matched comprises: the first image feature and the first image combination feature;
acquiring a preset value feature library, performing feature matching on the first item to be matched and a first matching item in the value feature library, and acquiring a value degree corresponding to the first matching item matched if matching is matched;
accumulating and summarizing the value degrees to obtain a value degree sum;
when the sum of the value degrees is greater than or equal to a preset first value degree threshold value, acquiring a preset switching opportunity determination model, and inputting the newly generated reaction image into the switching opportunity determination model;
if the value degree sum is larger than or equal to a preset second value degree threshold and/or the switching time determines that a model outputs a switching time and the heating time reaches the switching time, performing feature extraction on the newly generated reaction image to obtain a plurality of second image features;
randomly combining the second image features to obtain a plurality of second image combination features;
setting a second item to be matched, wherein the item to be matched comprises: the second image feature and the second image combination feature;
acquiring a preset incomplete reaction feature library, performing feature matching on the second item to be matched and a second matching item in the incomplete reaction feature library, and if the matching is in accordance, acquiring the corresponding representation degree of the second matching item in accordance with the matching;
and when the value degree and the representation degree obtained in a preset time period are both less than or equal to a preset representation degree threshold value, determining that the reaction is complete, and outputting a sample Co9S8@ CNTs @ Gr.
The working principle and the beneficial effects of the technical scheme are as follows:
the heat treatment under Ar atmosphere is carried out in an atmosphere heat treatment furnace; arranging a plurality of image acquisition point positions (including a high-definition camera, a micro-camera and the like, and all provided with light supplementing devices and high-temperature resistant protection) in a hearth of the atmosphere heat treatment furnace; transferring the second mixed solution after freeze-drying treatment into a hearth, and filling Ar atmosphere into the hearth for heating; acquiring preparation parameters (concentration and dosage of a graphene oxide aqueous solution, dosage of ZIF-67 powder and thioacetamide, dosage of pyrrole and the like) for preparing a second mixed solution and heating temperature (manual setting) of a hearth to be subjected to heat treatment, inputting the preparation parameters and the heating temperature into a preset acquisition opportunity determination model (a model generated after learning a large amount of experimental records of manual experiments by using a machine learning algorithm, wherein the experimental records comprise records of starting growing carbon nanotubes through manual observation), and acquiring acquisition opportunities, wherein the acquisition opportunities are opportunities when the second mixed solution subjected to freeze-drying treatment possibly starts growing carbon nanotubes; starting heating, recording the heating time, and controlling the starting of an image acquisition point position to acquire a reaction image when the heating time reaches the acquisition time; extracting first image features from the reaction image, wherein the first image features are randomly combined to obtain first image combination features as some features of the grown carbon nanotubes may need different features to be presented together; respectively matching the first image characteristic and the first image combination characteristic (item to be matched) with a first matching item in a preset value characteristic library (containing a large number of characteristics capable of confirming that the carbon nano tube grows), if the matching is consistent, indicating that the characteristics of the carbon nano tube grows, and acquiring the value degree corresponding to the first matching item which is consistent with the matching, wherein the larger the value degree is, the more the carbon nano tube grows; summarizing the value degree, and when the summarized value degree sum is greater than or equal to a preset first value degree threshold value, indicating that the carbon nano tube starts to grow gradually; inputting a newly generated reaction image into a preset switching time determination model (a model generated after a large amount of manual observation of the growth condition of the carbon nano tubes is carried out by utilizing a machine learning algorithm and whether the record of observing the unreacted part needs to be learned or not is determined), and if the switching time determination model outputs the switching time and/or the value degree and a second value degree threshold value which is larger than or equal to a preset value degree threshold value, indicating that the growth of the carbon nano tubes is nearly complete, monitoring the unreacted part together; extracting second image characteristics of the newly generated reaction image, and performing random combination; matching the characteristics of the two characteristics with a second matching item in a preset incomplete reaction characteristic library (a database containing a large number of incompletely reacted image characteristics), and if the matching is consistent, acquiring a characterization degree, wherein the larger the characterization degree is, the larger the incomplete reaction degree is; when the value degree and the representation degree which is more than or equal to a preset third value degree threshold value and is obtained within a preset time period (for example: 1.2 seconds) are both less than or equal to a preset representation degree threshold value, the reaction is complete, and a sample Co9S8@ CNTs @ Gr can be output;
in the embodiment of the invention, when the heat treatment is carried out in the Ar atmosphere, the reaction monitoring is carried out, the characteristic that the second mixed solution after the freeze-drying treatment grows into the carbon nano tube after being heated in the hearth is accurately and timely captured, a mechanism for judging whether the reaction is complete is reasonably arranged, and the influence on the preparation quality of the sample Co9S8@ CNTs @ Gr due to too short or too long reaction time is avoided.
Example 6
When obtaining the value degree corresponding to the first matching item matched with the first matching item or obtaining the representation degree corresponding to the second matching item matched with the second matching item, setting an obtaining target, wherein the obtaining target comprises: matching the first matching item of the coincidence with the second matching item of the coincidence;
obtaining a plurality of target test records corresponding to the obtained target, wherein the target test records include: a test person, a test method and a test target value;
calculating a target value corresponding to the acquisition target based on the value degree test record, wherein the calculation formula is as follows:
Figure BDA0003403923830000141
where ρ is a target value corresponding to the acquisition target, O is a total number of the target test records corresponding to the acquisition target, αt,iThe experience value, l, of i test persons in the t-th target test record corresponding to the acquired targettThe total number of the test persons in the tth target test record corresponding to the acquired target, betatA method weight value, gamma, of the test method in the tth target test record corresponding to the acquired targett,jFor the jth test target value in the tth target test record corresponding to the acquired target, EtThe total number of the test target values, mu, in the tth target test record corresponding to the acquired target1And mu2Is a preset weight value.
The working principle and the beneficial effects of the technical scheme are as follows:
when obtaining the value degree corresponding to the first matching item matched and conformed to or the representation degree corresponding to the second matching item matched and conformed to, respectively setting the first matching item matched and conformed to and the second matching item matched and conformed to as obtaining targets, and obtaining target test records corresponding to the obtaining targets, wherein the target test records comprise testers, test methods (how to test the degree of the corresponding condition represented by the image characteristics) and test target values (the value degree or the representation degree obtained by the test)Degree of characterization); the tester has experience values correspondingly, and the greater the experience value is, the more sufficient the test experience is; the test method corresponds to a method weight value, and the larger the method weight value is, the more reliable the test result is; calculating a target value corresponding to the acquired target (when the acquired target is a first matching item, the target value is a value degree, otherwise, the target value is a representation degree) based on the empirical value, the method weight and the test target value; rapidly summarizing experimental results; in the formula, the empirical value αt,iMethod weight value betatAnd a test target value gammat,jThe ratio of the rho to the rho is reasonable.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.

Claims (7)

1. A preparation method of a Co9S8@ carbon nanotube @ graphene composite material is characterized by comprising the following steps:
s1: preparing a graphene oxide aqueous solution;
s2: dispersing ZIF-67 powder and thioacetamide into the graphene oxide aqueous solution, and uniformly stirring and mixing to obtain a first mixed solution;
s3: adding pyrrole into the first mixed solution, and uniformly stirring and mixing to obtain a second mixed solution;
s4: transferring the second mixed solution into a reaction kettle with a polytetrafluoroethylene lining for heating, and after natural cooling, sequentially carrying out freeze-drying treatment and heat treatment under an Ar atmosphere to obtain a sample Co9S8@ CNTs @ Gr;
the amount of the graphene oxide aqueous solution is 10-60ml, and the concentration is 20-80%;
the amount of the ZIF-67 powder is 10-2000mg, the amount of the thioacetamide is 5-2000mg, and the mass ratio of the ZIF-67 powder to the thioacetamide is 1:1-8: 1;
in the step S4, the heating temperature of the second mixed solution in the reaction kettle with the polytetrafluoroethylene lining is 100-200 ℃, and the heating time is 2-10 h;
the treatment temperature of the heat treatment under the Ar atmosphere in the step S4 is 700-1200 ℃, and the treatment time is 2-10 h;
the preparation method comprises the steps of taking ZIF-67 as a precursor and pyrrole as a nitrogen source, further preparing cobalt and nitrogen co-doped graphene by a hydrothermal method, and further growing the carbon nano tube in situ under the catalytic action of cobalt by pyrolysis.
2. The preparation method of the Co9S8@ carbon nanotube @ graphene composite material as claimed in claim 1, wherein the stirring time in the step S2 is 10 min.
3. The preparation method of the Co9S8@ carbon nanotube @ graphene composite material as claimed in claim 1, wherein the amount of pyrrole used is 2-8 ml.
4. The preparation method of the Co9S8@ carbon nanotube @ graphene composite material as claimed in claim 1, wherein the stirring time in the step S3 is 5 min.
5. The preparation method of the Co9S8@ carbon nanotube @ graphene composite material as claimed in claim 1, wherein in the step S4, the reaction kettle comprises:
the kettle body (11), the kettle body (11) is arranged vertically, and the inner wall of the kettle body (11) is connected with polytetrafluoroethylene;
a steam jacket (12), wherein the steam jacket (12) is connected to the surface of the kettle body (11);
the kettle cover (13), the kettle cover (13) is installed at the top end of the kettle body (11);
the window (14), the said window (14) is set up on the said kettle body (11);
the uniformly heated mechanism (15), the uniformly heated mechanism (15) is arranged at the bottom end of the kettle cover (13);
wherein the uniformly heated mechanism (15) comprises:
the rotary motor (16), the rotary motor (16) is installed on the kettle cover (13), and the output end of the rotary motor (16) extends out of the bottom end of the kettle cover (13);
the rotating frame (17), the rotating frame (17) is located in the kettle body (11), and the rotating frame (17) is installed at the output end of the rotating motor (16);
a traverse roller (18), wherein the shaft end of the traverse roller (18) is arranged on the rotating frame (17);
the transverse moving chute (19), the said transverse moving chute (19) is set up on the said transverse moving roller (18) in the form of heliciform;
the spline shaft (10) is mounted on the rotating frame (17), the spline shaft (10) is located below the transverse moving roller (18), and the spline shaft (10) and the transverse moving roller (18) are arranged in parallel;
the transverse sliding block (21), the transverse sliding block (21) is connected in the transverse sliding chute (19) in a sliding manner;
the transverse moving seat (22), the transverse moving seat (22) is sleeved on the spline shaft (10) through a spline sleeve, and the transverse moving slide block (21) is fixedly connected with the transverse moving seat (22);
the power chamber is arranged in the transverse moving seat (22), and the spline shaft (10) penetrates through the power chamber;
the rotating rod (23) is vertically arranged at the end, away from the transverse sliding block (21), of the transverse sliding seat (22);
the first chain wheel (24), the said first chain wheel (24) locates in the said power chamber, the said first chain wheel (24) is installed on the said spline housing;
the transmission chamber (25) is arranged in the rotating rod (23), and the transmission chamber (25) is communicated with the power chamber;
a second chain wheel (26), wherein the second chain wheel (26) is connected in the transmission chamber (25) through a mounting shaft;
the transmission chain is sleeved on the first chain wheel (24) and the second chain wheel (26);
an incomplete gear (27), wherein the incomplete gear (27) is arranged in the transmission chamber (25), and the incomplete gear (27) and the second chain wheel (26) are coaxially arranged on the mounting shaft;
the offset rod (28) is hinged to the end, far away from the transverse moving seat (22), of the rotating rod (23) through a connecting shaft, and the connecting shaft extends into the transmission chamber (25);
the straight gear (29) is arranged in the transmission chamber (25), the straight gear (29) is arranged on the connecting shaft, and the straight gear (29) is meshed with the incomplete gear (27);
the transmission gear ring (20), the transmission gear ring (20) is fixedly connected to the bottom end of the kettle cover (13), and the rotating frame (17) is sleeved in the transmission gear ring (20);
the two rotating gears (31) are symmetrically arranged at the shaft end of the traverse roller (18) by taking the output end of the rotating motor (16) as a center, and the rotating gears (31) are meshed with the transmission gear ring (20);
and the belt wheels (32) are sleeved on the two belt wheels (32), one belt wheel (32) is arranged on the spline shaft (10), and the other belt wheel (32) is arranged at the shaft end of the traverse roller (18).
6. The method for preparing a Co9S8@ carbon nanotube @ graphene composite material according to claim 1, wherein in step S4, during the heat treatment under Ar atmosphere, reaction monitoring is further performed, and the method specifically comprises:
arranging a plurality of image acquisition point positions in a hearth;
transferring the second mixed solution after freeze-drying treatment into the hearth;
filling Ar atmosphere into the hearth;
acquiring preparation parameters for preparing the second mixed solution, and acquiring the heating temperature of the hearth to be subjected to heat treatment;
acquiring a preset acquisition opportunity determining model, and inputting the preparation parameters and the heating temperature into the acquisition opportunity determining model to acquire acquisition opportunities;
controlling the hearth to start heating, and recording the heating time length;
when the heating time reaches the acquisition time, triggering the image acquisition point position to be opened, and dynamically acquiring a reaction image of the second mixed solution subjected to freeze-drying treatment subjected to heat treatment in an Ar atmosphere;
performing feature extraction on the reaction image to obtain a plurality of first image features;
randomly combining the first image features to obtain a plurality of first image combination features;
setting a first item to be matched, wherein the item to be matched comprises: the first image feature and the first image combination feature;
acquiring a preset value feature library, performing feature matching on the first item to be matched and a first matching item in the value feature library, and acquiring a value degree corresponding to the first matching item matched if matching is matched;
accumulating and summarizing the value degrees to obtain a value degree sum;
when the sum of the value degrees is greater than or equal to a preset first value degree threshold value, acquiring a preset switching opportunity determination model, and inputting the newly generated reaction image into the switching opportunity determination model;
if the value degree sum is larger than or equal to a preset second value degree threshold and/or the switching time determines that a model outputs a switching time and the heating time reaches the switching time, performing feature extraction on the newly generated reaction image to obtain a plurality of second image features;
randomly combining the second image features to obtain a plurality of second image combination features;
setting a second item to be matched, wherein the item to be matched comprises: the second image feature and the second image combination feature;
acquiring a preset incomplete reaction feature library, performing feature matching on the second item to be matched and a second matching item in the incomplete reaction feature library, and if the matching is in accordance, acquiring the corresponding representation degree of the second matching item in accordance with the matching;
and when the value degree and the representation degree obtained in a preset time period are both less than or equal to a preset representation degree threshold value, determining that the reaction is complete, and outputting a sample Co9S8@ CNTs @ Gr.
7. Use of the sample Co9S8@ CNTs @ Gr obtained according to the preparation method in claim 1 in lithium-sulfur batteries.
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