CN115566161B - Preparation method of sulfur-rich polymer hierarchical pore carbon nano cage composite material and application of sulfur-rich polymer hierarchical pore carbon nano cage composite material in lithium sulfur battery - Google Patents
Preparation method of sulfur-rich polymer hierarchical pore carbon nano cage composite material and application of sulfur-rich polymer hierarchical pore carbon nano cage composite material in lithium sulfur battery Download PDFInfo
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Abstract
The invention provides a preparation method of a sulfur-rich polymer hierarchical pore carbon nano-cage composite material and application thereof in a lithium sulfur battery, wherein the high conductivity of the carbon nano-cage material is utilized to improve the conductivity of the material, simultaneously, carbon-sulfur bonds formed in the sulfur-rich polymer are utilized to chemically fix sulfur, and the sulfur-rich polymer is regulated and packaged by regulating and controlling a carbon nano-cage structure to realize the production of long-chain polysulfide and NiCo loading 2 S 4 The nanoparticles catalyze polysulfides to achieve good electrochemical performance. The invention highlights the synergistic effect of two materials in graphene oxide, polydopamine and transition metal carbide, realizes the respective effects, and simultaneously can better exert the respective effects through the synergy of the graphene oxide, polydopamine and transition metal carbide, thereby constructing the high-performance lithium sulfur battery.
Description
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to a sulfur-rich polymer hierarchical pore carbon nano cage composite material and application thereof in a lithium-sulfur battery.
Background
Along with the continuous development of technology and the continuous progress of new energy automobile technology, the lithium ion battery has been widely applied in the fields of unmanned aerial vehicle, wireless earphone, hearing aid, mobile phone, computer and other high-end equipment because of the advantages of high energy density, long cycle life, low self-discharge rate and the like. However, with the rapid development of portable electronic products, the degree of intellectualization of the portable electronic products is also higher and higher, and the energy density of a power supply is also higher and higher, so that a new energy storage system must be developed to adapt to the development needs of new situations. The lithium-sulfur battery is an electrochemical energy storage device which takes metal lithium as a negative electrode and elemental sulfur as a positive electrode, and a diaphragm and an organic liquid electrolyte are arranged between the negative electrode and the positive electrode, wherein the theoretical specific energy of the electrochemical energy storage device can reach 2600Wh/kg, and is 4-5 times of the capacity density of the lithium ion battery. In addition, sulfur constituting the positive electrode is abundant in nature, and has outstanding advantages of low price, high safety, high environmental friendliness, and the like, and thus is considered as one of the next-generation energy storage devices having the most commercial application value.
However, there are still many problems to be solved in the large-scale industrialization of lithium sulfur batteries, such as low conductivity of sulfur and its final discharge product lithium sulfide, shuttle effect of polysulfide in lithium sulfur batteries, resulting in poor cycle life, cycle stability and safety hazards of lithium sulfur batteries. However, among the above drawbacks, the shuttle effect of lithium-sulfur batteries is the most fatal. During the discharge and charge cycles, long chain polysulfides (Li 2 S x ,4<x.ltoreq.8) moves toward the negative electrode and reacts with lithium metal to form short chain polysulfides (Li) insoluble in the electrolyte 2 S x ,2<x.ltoreq.4), and the diffusion of short chain polysulfides back into the positive electrode again yields long chain polysulfides. This process generally results in irreversible loss of active material and low coulombic efficiency, which are major reasons for rapid decay of capacity, low energy efficiency, severe self-discharge, and poor cycling stability.
In view of the above problems, particularly the shuttle effect, researchers at home and abroad generally compound sulfur by using a carbon material with high conductivity and abundant pore structure such as porous carbon, graphene and the like, and encapsulate sulfur in pores of the carbon material as much as possible, limit polysulfide dissolution and shuttle by means of multi-stage pores, and buffer volume change of the sulfur anode in the circulation process. However, these solutions mainly rely on physical adsorption methods to obtain good electrochemical performance at the initial stage of charge and discharge, but as charge and discharge are repeated, sulfur bound in the pores generates polysulfide and slowly dissolves, and rapid capacity fading and coulombic efficiency reduction occur. Thus, there remains a need to develop new cathode materials to improve the performance of lithium sulfur batteries.
The sulfur-rich polymer is prepared by reacting positive elemental sulfur with unsaturated functional groups to form R-S through a reverse vulcanization process n Carbon-sulphur bonds in the form of R "to achieve co-fixation in the polymer backbone, the formation of carbon-sulphur covalent chemical bonds is stronger, i.e. more limiting of the sulphur element, than physical adsorption and chemisorption, thus inhibiting dissolution and shuttling effects of intermediate polysulphides. Sulfur-rich polymers are therefore an emerging direction in the field of lithium sulfur batteries.
While lithium sulfur batteries with sulfur-rich polymers as the host for sulfur positive electrode fix polysulfides by covalent S-S bonds to address the shuttle effect, sulfur-rich polymers have inherent drawbacks such as: ion-electron insulators, readily soluble and poorly conductive, have poor capacity at high discharge rates.
Therefore, it is an important issue how to improve the conductivity and stability of a positive electrode material for a lithium-sulfur battery using a sulfur-rich polymer as a matrix.
In the prior art, graphene, ferrocene and elemental sulfur are simply mixed and compounded to form an interconnected sulfur-rich copolymer cross-linked network, but the conductivity of a positive electrode material of a lithium-sulfur battery is only solved, but the most critical problem of lithium polysulfide shuttle phenomenon of the lithium-sulfur battery and the problem that the huge volume expansion damages an electrode structure in the charging and discharging process are not solved well. In addition, the battery cycle performance test can only be carried out at 0.5C small current, the cycle times can reach 500 circles, and the specific capacity can only reach 400mAh/g.
It can be seen that the specific capacity is improved, the cycle performance is still unstable, the synthesis process condition is complex, and the energy consumption is high. If the sulfur-rich polymer composite hierarchical pore carbon material is prepared by a simple method, the sulfur-rich polymer composite hierarchical pore carbon material is prepared by a low-cost raw material preparation method, polysulfide is enriched, packaged and fixedly linked with each other through chemical bonds, and then energy storage and release are realized through breaking and linking of S-S bonds, so that the generation of small molecule polysulfide discharge products is effectively reduced, the dissolution of sulfur sources and discharge products by electrolyte is more effectively protected, and electrode plates are prevented from corroding and collapsing, so that the high-performance lithium sulfur battery is constructed.
Disclosure of Invention
In view of the above, it is an object of the present invention to provide a sulfur-rich polymer/NiCo 2 S 4 The invention utilizes the high conductivity of the carbon nano cage material to improve the conductivity of the material, and utilizes the carbon-sulfur bonds formed in the sulfur-rich polymer to chemically fix sulfur, and controls and encapsulates the sulfur-rich polymer by controlling the carbon nano cage structure to limit the generation of long-chain polysulfide and the loaded NiCo 2 S 4 The nanoparticles catalyze polysulfides to achieve good electrochemical performance. The invention highlights the synergistic effect of two materials in graphene oxide, polydopamine and transition metal carbide, realizes the respective effects, and simultaneously can better exert the respective effects through the synergy of the graphene oxide, polydopamine and transition metal carbide, thereby constructing the high-performance lithium sulfur battery.
In order to achieve the above purpose, the following technical scheme is adopted:
a preparation method of a sulfur-rich polymer hierarchical pore carbon nano cage composite material comprises the following steps:
step S1: preparing a sulfur-rich polymer, heating sublimed sulfur under the protection of inert gas to obtain an orange-red solution, adding an alkenyl modifier, continuously stirring, and cooling to room temperature after the reaction is finished to obtain a sulfur-rich polymer solution;
step S2: niCo 2 S 4 Preparing a hierarchical pore carbon nanocage, namely dissolving a nano carbon-based material in a tris (hydroxymethyl) aminomethane solution, continuously stirring, cooling to room temperature after the reaction is finished, and adding a mixed solution of Ni salt and Co salt dissolved in ethanol and water according to a certain molar ratio; adding sulfur source into the mixed solution, ultrasonic dissolving thoroughly, sealing the obtained mixed solution, reacting in oven, cooling to room temperature, and sequentially using the obtained solidWashing with absolute ethanol, concentrated hydrochloric acid and deionized water, and drying to obtain NiCo 2 S 4 A@hierarchical pore carbon nanocage material;
step S3: sulfur-rich polymer/NiCo 2 S 4 Preparing a composite material of a hierarchical pore carbon nano cage, and slowly adding NiCo obtained in the step S2 into the sulfur-rich polymer solution obtained in the step S1 2 S 4 After fully stirring the @ hierarchical pore carbon nano cage material, regulating the reaction temperature, continuously stirring, synthesizing a sulfur-rich polymer through interfacial polymerization, and simultaneously packaging the sulfur-rich polymer into NiCo 2 S 4 The porous carbon nano-cage with the@hierarchical pores is arranged in a pore canal; then cooled to room temperature and then passed through CS 2 Repeatedly cleaning and dispersing by ultrasonic wave to finally obtain the sulfur-rich polymer/NiCo 2 S 4 A composite material of a hierarchical pore carbon nanocage.
Further, the molar ratio of sublimed sulfur to the alkenyl modifier in the step S1 is (8:1) - (10:1), the alkenyl modifier in the step S1 is one of 1, 3-diisopropenylbenzene, 1, 3-ethynylbenzene or divinylbenzene, and the sulfur content of the sulfur-rich polymer accounts for the sulfur-rich polymer/NiCo 2 S 4 50-80 wt% of hierarchical porous carbon nano cage composite material.
Further, the nanocarbon-based material in the step S2 is any two of graphene oxide, polydopamine and transition metal carbide, the Ni salt in the step S2 is nickel nitrate tetrahydrate, and the Co salt is cobalt nitrate hexahydrate.
Further, the sulfur source in the step S2 is one or more of thiourea, thioacetamide, thiocarbamide and phenylthiourea.
Further, in the step S2, the molar ratio of the Ni salt to the Co salt is (1:2) to (1:4).
Further, in the step S1, sublimed sulfur is heated at 185 ℃ to obtain orange-red solution, the reaction temperature is 185 ℃ after the alkenyl modifier is added, and stirring is continued for 0.5-1.0 hour, wherein the sulfur content in the sulfur-rich polymer is 50-90 wt%.
Further, the reaction condition of dissolving the nano carbon-based material in the tris (hydroxymethyl) aminomethane solution in the step S2 is that the reaction temperature is 60 ℃, and the stirring is continuously carried out for 12-24 hours under the rotating speed of 300-600 rpm; after the sulfur source is added, the reaction is carried out for 6 to 12 hours at 120 ℃ in the oven.
Further, in the step S3, the reaction temperature is adjusted to 200 ℃, and stirring is continued.
Further, in the step S3, mechanical stirring is adopted, the stirring speed is 400-600 r/min, and the stirring time is 1.0-2 h; the CS is described as 2 The repeated cleaning times are 2 to 5 times; the ultrasonic time is 0.5-5 h; the final product is obtained by freeze drying.
Sulfur-rich polymer/NiCo 2 S 4 Application method of hierarchical pore carbon nano-cage composite material, sulfur-rich polymer/NiCo prepared by the method 2 S 4 The composite material of the hierarchical pore carbon nano cage is used as an active substance of the positive electrode of the lithium sulfur battery, and is mixed with carbon black and a binder to prepare the positive electrode of the lithium sulfur battery.
The invention has the greatest characteristics with the prior art that:
1. structural layer: the invention relates to a sulfur-rich polymer/NiCo 2 S 4 The@hierarchical pore carbon nano cage composite material contains a sulfur-rich polymer, and the carbon nano material is NiCo 2 S 4 The @ hierarchical pore carbon nano cage form is relatively simple in composition because of only containing the combination of two materials, and the process implementation difficulty and cost are controllable;
2. the process level is as follows: the invention takes two carbon nano materials as raw materials, obtains the composite of the two carbon nano materials through self-polymerization in alkaline solution, and obtains NiCo through carbonization and metal ion catalysis by taking common nickel salt, cobalt salt and sulfur source as raw materials 2 S 4 A multi-level pore carbon nano cage material. Finally, encapsulating the sulfur-rich polymer into NiCo at high temperature by self-polymerization 2 S 4 Obtaining sulfur-rich polymer/NiCo in the porous carbon nano-cage of the@hierarchical pore 2 S 4 A composite material of a hierarchical pore carbon nanocage.
The beneficial effects are that:
the beneficial effects of the invention are as follows:
1. the invention creatively proposes to propose a sulfur-rich polymer/NiCo 2 S 4 A new preparation method of a hierarchical pore carbon nanocage.
2. The invention changes the lithium sulfur battery to take sulfur-carbon material as anode material, obtains sulfur-rich polymer to replace pure sulfur as active material through interfacial polymer action, and combines with NiCo 2 S 4 Composite formation of sulfur-rich polymer/NiCo by@hierarchical pore carbon nanocage 2 S 4 @hierarchical pore carbon nanocages.
3. NiCo of the invention 2 S 4 The carbon nano cage with the multi-level holes not only has the performance of the carbon nano tube, but also has the multi-level hole structure, the capability of enriching, capturing, packaging and fixing polysulfide to be linked with each other through chemical bonds (carbon-sulfur bonds), and NiCo 2 S 4 The nano particles have strong catalytic capability on the polysulfide-converted high-activity intermediate, and the common effect can reduce the generation of small-molecule discharge products, effectively protect sulfur and the discharge products from being dissolved by electrolyte, thereby inhibiting the shuttle effect.
4. Single graphene oxide, polydopamine and transition metal carbide do not have good enough polysulfide capture capacity; according to the invention, two of graphene oxide, polydopamine and transition metal carbide are compounded in the tris (hydroxymethyl) aminomethane solution, so that the high conductivity of the nano carbon material can be utilized to improve the conductivity of the composite material, and meanwhile, the mechanical strength of the material can be improved. More favorable for exposing more surfaces with various functional groups and active sites, and can further improve the conductivity of the material and the capturing capability of polysulfide, thereby improving the multiplying power performance and the cycling stability.
5. The invention highlights the synergistic effect of two materials in graphene oxide, polydopamine and transition metal carbide, and can better exert the respective effects through the synergistic effect of the two materials while realizing the respective effects.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 shows a sulfur-rich polymer/NiCo in an embodiment of the invention 2 S 4 A manufacturing flow chart of the@hierarchical pore carbon nanocages;
FIG. 2 is a NiCo of example 1 of the present invention 2 S 4 Scanning electron micrographs of the graphene oxide-dopamine nanocage composite material with the multilevel pores;
FIG. 3 is a sulfur-rich polymer/NiCo of example 1 of the present invention 2 S 4 Scanning electron micrographs of the graphene oxide-dopamine nanocage composite material with the multilevel pores;
FIG. 4 is a sulfur-rich polymer/NiCo of example 1 of the present invention 2 S 4 The @ multi-level pore graphene oxide-dopamine nano-cage composite material is used as an anode for a rate performance test curve of a lithium sulfur battery;
FIG. 5 is a sulfur-rich polymer/NiCo of example 1 of the present invention 2 S 4 The @ hierarchical pore graphene oxide-dopamine nano-cage composite material is used as an anode for 1000-cycle performance curves under high current of a lithium-sulfur battery.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
According to FIG. 1, a sulfur-rich polymer/NiCo 2 S 4 And (3) preparing a composite material in the embodiment by a manufacturing flow chart of the hierarchical pore carbon nanocages.
Example 1
This example sulfur-rich polymer/NiCo 2 S 4 The preparation flow of the@hierarchical pore carbon nano-cage composite material is shown in a figure 1, and the specific preparation process is as follows:
4.5g of sublimed sulfur is weighed and put into a three-neck flask, under the protection of inert gas nitrogen,the oil bath is heated to 185 ℃, stirred until sublimed sulfur is changed into orange-red solution from pale yellow solid, then 0.5g of 1, 3-diisopropenylbenzene is added, stirring is continued for 0.5 hour, and the reaction is cooled to room temperature after completion, thus obtaining sulfur-rich polymer solution. Weighing graphene oxide 0.01g and dopamine 0.05g, dissolving the graphene oxide 0.01g and dopamine 0.05g in 200ml of a trimethylol aminomethane solution with the concentration of 10mol/L and the pH=8.5, continuously stirring for 12 hours at the reaction temperature of 60 ℃ and the rotating speed of 300rpm, cooling to room temperature after the reaction, and adding Ni (NO 3 ) 2 ·4H 2 O0.42 g and Co (NO) 3 ) 2 ·6H 2 O0.85 g of mixed solution of ethanol and water dissolved in 30mL, adding 0.2g of thiourea, fully dissolving in the mixed solution by ultrasonic, sealing, placing in an oven for reaction at 120 ℃ for 12 hours, cooling to room temperature, washing the obtained solid with absolute ethanol, concentrated hydrochloric acid and deionized water in sequence, and drying to obtain NiCo 2 S 4 Graphene oxide-dopamine nanocage composite material with@hierarchical pores, niCo 2 S 4 A scanning electron microscope photograph of the @ hierarchical pore graphene oxide-dopamine nanocage composite material is shown in FIG. 2. Weigh 0.1g NiCo 2 S 4 Adding the prepared sulfur-rich polymer solution into the hierarchical pore graphene oxide-dopamine nano cage material, regulating the reaction temperature to 200 ℃, continuously stirring for 1.0 hour, cooling to room temperature, centrifuging, freeze-drying, and then passing through CS 2 Repeatedly cleaning and dispersing by ultrasonic wave to finally obtain the sulfur-rich polymer/NiCo 2 S 4 The composite material is prepared from graphene oxide-dopamine carbon nanocage with multilevel holes. The prepared sulfur-rich polymer/NiCo 2 S 4 The sulfur content in the@hierarchical pore graphene oxide-dopamine nano cage composite material is 65wt%, and the sulfur-rich polymer is uniformly distributed in NiCo 2 S 4 The scanning electron microscope photograph of the composite material in the pore canal of the @ hierarchical pore graphene oxide-dopamine nanocage is shown in figure 3.
The obtained sulfur-rich polymer/NiCo 2 S 4 The@hierarchical pore graphene oxide-dopamine carbon nanocage composite material is directly used as a positive electrode of a lithium-sulfur battery for electrochemical performance test. Fig. 4 is a graph showing the rate performance test of a composite material as a positive electrode prepared electrode sheet for a lithium-sulfur battery. Drawing of the figureAnd 5, a 1000-cycle performance curve of the prepared pole piece under the condition of high current of a lithium sulfur battery.
Example 2
Example 2 is different from example 1 in the kind of precursor nanocarbon-based material.
Weighing 4.5g of sublimed sulfur, placing the sublimed sulfur into a three-neck flask, heating the three-neck flask to 185 ℃ in an oil bath under the protection of inert gas nitrogen, stirring until the sublimed sulfur is changed into orange-red solution from pale yellow solid, adding 0.5g of 1, 3-diisopropenylbenzene, continuously stirring for 0.5 hour, and cooling to room temperature after the reaction is finished to obtain a sulfur-rich polymer solution. Weighing graphene oxide 0.01g and transition metal carbide 0.08g, dissolving in 200ml of a tris (hydroxymethyl) aminomethane solution with the concentration of 10mol/L and the pH=8.5, continuously stirring for 12 hours at the temperature of 80 ℃ and the rotating speed of 300rpm, cooling to room temperature after the reaction, and adding Ni (NO 3 ) 2 ·4H 2 O0.42 g and Co (NO) 3 ) 2 ·6H 2 O0.85 g of mixed solution of ethanol and water dissolved in 30mL, adding 0.2g of thiourea, fully dissolving in the mixed solution by ultrasonic, sealing, placing in an oven for reacting at 150 ℃ for 12 hours, cooling to room temperature, washing the obtained solid with absolute ethanol, concentrated hydrochloric acid and deionized water in sequence, and drying to obtain NiCo 2 S 4 The composite material is prepared from a hierarchical porous graphene oxide-transition metal carbide nano cage composite material. Weigh 0.1g NiCo 2 S 4 Adding the prepared sulfur-rich polymer solution into the nano cage material of the hierarchical porous graphene oxide-transition metal carbide, regulating the reaction temperature to 200 ℃, continuously stirring for 1.0 hour, cooling to room temperature, centrifuging, freeze-drying, and then passing through CS 2 Repeatedly cleaning and dispersing by ultrasonic wave to finally obtain the sulfur-rich polymer/NiCo 2 S 4 The composite material is prepared from a hierarchical porous graphene oxide-transition metal carbide nano cage composite material. The prepared sulfur-rich polymer/NiCo 2 S 4 The sulfur content in the @ hierarchical pore graphene oxide-transition metal carbide nanocage composite material is 58wt%.
Example 3
Example 3 is different from example 1 in the kind of precursor nanocarbon-based material.
Weighing 4.5g of sublimed sulfur, placing the sublimed sulfur into a three-neck flask, heating the three-neck flask to 185 ℃ in an oil bath under the protection of inert gas nitrogen, stirring until the sublimed sulfur is changed into orange-red solution from pale yellow solid, adding 0.5g of 1, 3-diisopropenylbenzene, continuously stirring for 0.5 hour, and cooling to room temperature after the reaction is finished to obtain a sulfur-rich polymer solution. Weighing 0.05g dopamine and 0.08g transition metal carbide, dissolving in 200ml trimethylol aminomethane solution with concentration of 10mol/L and pH=8.5, reacting at 80deg.C and rotating speed of 300rpm, stirring continuously for 12 hr, cooling to room temperature after the reaction, adding Ni (NO 3 ) 2 ·4H 2 O0.42 g and Co (NO) 3 ) 2 ·6H 2 O0.85 g of mixed solution of ethanol and water dissolved in 30mL, adding 0.2g of thiourea, fully dissolving in the mixed solution by ultrasonic, sealing, placing in an oven for reacting at 150 ℃ for 12 hours, cooling to room temperature, washing the obtained solid with absolute ethanol, concentrated hydrochloric acid and deionized water in sequence, and drying to obtain NiCo 2 S 4 A multi-level pore dopamine-transition metal carbide nano-cage composite material. Weigh 0.1g NiCo 2 S 4 Adding the prepared sulfur-rich polymer solution into the nano-cage material of the dopamine-transition metal carbide with hierarchical pores, regulating the reaction temperature to 200 ℃, continuously stirring for 1.0 hour, cooling to room temperature, centrifuging, freeze-drying, and then passing through CS 2 Repeatedly cleaning and dispersing by ultrasonic wave to finally obtain the sulfur-rich polymer/NiCo 2 S 4 A multi-level pore dopamine-transition metal carbide nano-cage composite material. The prepared sulfur-rich polymer/NiCo 2 S 4 The sulfur content in the @ hierarchical pore dopamine-transition metal carbide nanocage composite material is 55wt%.
Example 4
Example 4 differs from example 1 in the types of alkenyl modifier and sulfur source.
Weighing 5.0g of sublimed sulfur, placing into a three-neck flask, heating to 185 ℃ in an oil bath under the protection of inert gas nitrogen, stirring until sublimed sulfur is changed into orange-red solution from pale yellow solid, adding 0.8g of 1, 3-ethynyl benzene, continuously stirring for 0.5 hour, and cooling to room temperature after the reaction is finished to obtain the rich sulfurSulfur polymer solution. Weighing graphene oxide 0.01g and dopamine 0.05g, dissolving the graphene oxide 0.01g and dopamine 0.05g in 200ml of a trimethylol aminomethane solution with the concentration of 10mol/L and the pH=8.5, continuously stirring for 12 hours at the reaction temperature of 60 ℃ and the rotating speed of 300rpm, cooling to room temperature after the reaction, and adding Ni (NO 3 ) 2 ·4H 2 O0.42 g and Co (NO) 3 ) 2 ·6H 2 O0.85 g of mixed solution of ethanol and water dissolved in 30mL of mixed solution, 0.15g of thioacetamide is added, ultrasonic treatment is carried out to fully dissolve the thioacetamide in the mixed solution, the mixed solution is placed in an oven for reaction at 120 ℃ for 12 hours after being sealed, then the mixed solution is cooled to room temperature, the obtained solid is washed by absolute ethanol, concentrated hydrochloric acid and deionized water in sequence, and NiCo is obtained after drying 2 S 4 The composite material is prepared from graphene oxide and dopamine nanocage with multilevel holes. Weigh 0.1g NiCo 2 S 4 Adding the prepared sulfur-rich polymer solution into the hierarchical pore graphene oxide-dopamine nano-cage composite material, regulating the reaction temperature to 200 ℃, continuously stirring for 1.0 hour, cooling to room temperature, centrifuging, freeze-drying, and then passing through CS 2 Repeatedly cleaning and dispersing by ultrasonic wave to finally obtain the sulfur-rich polymer/NiCo 2 S 4 The composite material is prepared from graphene oxide and dopamine nanocage with multilevel holes. The prepared sulfur-rich polymer/NiCo 2 S 4 The sulfur content in the @ hierarchical pore graphene oxide-dopamine nanocage composite material is 60wt%.
Example 5
Example 5 differs from example 1 in the types of alkenyl modifier and sulfur source.
6.0g of sublimed sulfur is weighed and placed into a three-neck flask, under the protection of inert gas nitrogen, the oil bath is heated to 185 ℃, after stirring is carried out until sublimed sulfur is changed into orange-red solution from pale yellow solid, 1.0g of divinylbenzene is added, stirring is continued for 0.5 hour, and after the reaction is finished, the temperature is cooled to room temperature, thus obtaining the sulfur-rich polymer solution. Weighing graphene oxide 0.01g and dopamine 0.05g, dissolving the graphene oxide 0.01g and dopamine 0.05g in 200ml of a trimethylol aminomethane solution with the concentration of 10mol/L and the pH=8.5, continuously stirring for 12 hours at the reaction temperature of 60 ℃ and the rotating speed of 300rpm, cooling to room temperature after the reaction, and adding Ni (NO 3 ) 2 ·4H 2 O0.42 g and Co (NO) 3 ) 2 ·6H 2 O0.85 g of mixed solution of ethanol and water dissolved in 30mL of mixed solution, 0.2g of phenylthiourea is added, the mixed solution is fully dissolved in ultrasonic wave, the mixed solution is placed in an oven for reaction at 120 ℃ for 12 hours after being sealed, then the mixed solution is cooled to room temperature, the obtained solid is washed by absolute ethanol, concentrated hydrochloric acid and deionized water in sequence, and NiCo is obtained after drying 2 S 4 The composite material is prepared from graphene oxide and dopamine nanocage with multilevel holes. Weigh 0.1g NiCo 2 S 4 Adding the prepared sulfur-rich polymer solution into the hierarchical pore graphene oxide-dopamine nano-cage composite material, regulating the reaction temperature to 200 ℃, continuously stirring for 1.0 hour, cooling to room temperature, centrifuging, freeze-drying, and then passing through CS 2 Repeatedly cleaning and dispersing by ultrasonic wave to finally obtain the sulfur-rich polymer/NiCo 2 S 4 The composite material is prepared from graphene oxide and dopamine nanocage with multilevel holes. The prepared sulfur-rich polymer/NiCo 2 S 4 The sulfur content in the @ hierarchical pore graphene oxide-dopamine nanocage composite material is 55wt%.
Experimental results show that the invention uses sulfur-rich polymer/NiCo 2 S 4 Technology of @ hierarchical pore graphene oxide-dopamine nanocage compounding, the capability of obtaining sulfur-rich polymer to replace pure sulfur as active substance by utilizing interfacial polymer action, enriching, capturing, packaging and fixing polysulfide through chemical bond (carbon-sulfur bond) and linking with each other, and NiCo 2 S 4 The nano particles have strong catalytic capability on the polysulfide-converted high-activity intermediate, the common effect can reduce the generation of small-molecule discharge products, effectively protect the dissolution of sulfur and discharge products by electrolyte, and further limit the shuttle effect; and the high conductivity of the nano carbon material is utilized to improve the conductivity of the composite material, and meanwhile, the mechanical strength of the material can be improved. More favorable for exposing more surfaces with various functional groups and active sites, and can further improve the conductivity of the material and the capturing capability of polysulfide, thereby improving the multiplying power performance and the cycling stability. The method is simple and convenient to operate, easy to structure control and easy to prepare in a large scale, and provides a wide prospect for the application of the sulfur-rich polymer in the aspect of lithium sulfur batteries.
In summary, the present invention provides a sulfur-rich polymer/NiCo 2 S 4 The invention utilizes the high conductivity of the carbon nano cage material to improve the conductivity of the material, and utilizes the carbon-sulfur bonds formed in the sulfur-rich polymer to chemically fix sulfur, and controls and encapsulates the sulfur-rich polymer by controlling the carbon nano cage structure to limit the generation of long-chain polysulfide and the loaded NiCo 2 S 4 The nanoparticles catalyze polysulfides to achieve good electrochemical performance. The invention highlights the synergistic effect of two materials in graphene oxide, polydopamine and transition metal carbide, realizes the respective effects, and simultaneously can better exert the respective effects through the synergy of the graphene oxide, polydopamine and transition metal carbide, thereby constructing the high-performance lithium sulfur battery.
The present invention is not limited to the above-mentioned embodiments, but is not limited to the above-mentioned embodiments, and any person skilled in the art can make some changes or modifications to the equivalent embodiments without departing from the scope of the technical solution of the present invention, but any simple modification, equivalent changes and modifications to the above-mentioned embodiments according to the technical substance of the present invention are still within the scope of the technical solution of the present invention.
Claims (6)
1. The preparation method of the sulfur-rich polymer hierarchical pore carbon nano cage composite material is characterized by comprising the following steps of:
step S1: preparing a sulfur-rich polymer, heating sublimed sulfur under the protection of inert gas to obtain an orange-red solution, adding an alkenyl modifier, continuously stirring, and cooling to room temperature after the reaction is finished to obtain a sulfur-rich polymer solution;
step S2: niCo 2 S 4 Preparing a nano carbon-based material, namely dissolving the nano carbon-based material in a tris (hydroxymethyl) aminomethane solution, continuously stirring, and finishing the reactionCooling to room temperature, adding a mixed solution of Ni salt and Co salt which are dissolved in ethanol and water according to a certain molar ratio; adding a sulfur source into the mixed solution, sufficiently dissolving the mixed solution by ultrasonic treatment, sealing the obtained mixed solution, then placing the mixed solution into a baking oven for reaction, cooling the mixed solution to room temperature, sequentially washing the obtained solid with absolute ethyl alcohol, concentrated hydrochloric acid and deionized water, and drying the solid to obtain NiCo 2 S 4 A@hierarchical pore carbon nanocage material;
step S3: sulfur-rich polymer/NiCo 2 S 4 Preparing a composite material of a hierarchical pore carbon nano cage, and slowly adding NiCo obtained in the step S2 into the sulfur-rich polymer solution obtained in the step S1 2 S 4 After fully stirring the @ hierarchical pore carbon nano cage material, regulating the reaction temperature, continuously stirring, synthesizing a sulfur-rich polymer through interfacial polymerization, and simultaneously packaging the sulfur-rich polymer into NiCo 2 S 4 The porous carbon nano-cage with the@hierarchical pores is arranged in a pore canal; then cooled to room temperature and then passed through CS 2 Repeatedly cleaning and dispersing by ultrasonic wave to finally obtain the sulfur-rich polymer/NiCo 2 S 4 Composite material of@hierarchical pore carbon nanocages;
the nano carbon-based material in the step S2 is any two of graphene oxide, polydopamine and transition metal carbide, the Ni salt in the step S2 is nickel nitrate tetrahydrate, and the Co salt is cobalt nitrate hexahydrate;
the sulfur source in the step S2 is one or more of thiourea, thioacetamide, thiocarbamide and phenylthiourea;
in the step S2, the molar ratio of Ni salt to Co salt is (1:2) - (1:4);
the reaction condition of dissolving the nano carbon-based material in the tris (hydroxymethyl) aminomethane solution in the step S2 is that the reaction temperature is 60 ℃, and the stirring is continuously carried out for 12-24 hours under the rotating speed of 300-600 rpm; after the sulfur source is added, the reaction is carried out for 6 to 12 hours at 120 ℃ in the oven.
2. The method for preparing a sulfur-rich polymer hierarchical pore carbon nanocage composite material according to claim 1, wherein the molar ratio of sublimed sulfur to alkenyl modifier in step S1 is (8:1) - (10:1), and the alkenyl group in step S1 isThe modifier is one of 1, 3-diisopropenylbenzene, 1, 3-ethynylbenzene or divinylbenzene, and the sulfur content of the sulfur-rich polymer accounts for sulfur-rich polymer/NiCo 2 S 4 50-80 wt% of hierarchical porous carbon nano cage composite material.
3. The method for preparing a sulfur-rich polymer hierarchical pore carbon nanocage composite material according to claim 1, wherein in the step S1, sublimed sulfur is heated at 185 ℃ to obtain an orange-red solution, and after an alkenyl modifier is added, the reaction temperature is 185 ℃, stirring is continued for 0.5-1.0 hours, and the sulfur content in the sulfur-rich polymer is 50-90 wt%.
4. The method for preparing a sulfur-rich polymer hierarchical pore carbon nanocage composite material according to claim 1, wherein the reaction temperature is adjusted to 200 ℃ in the step S3, and stirring is continued.
5. The method for preparing the sulfur-rich polymer hierarchical pore carbon nano cage composite material according to claim 1, wherein in the step S3, mechanical stirring is adopted, the stirring speed is 400-600 r/min, and the stirring time is 1.0-2 h; the CS is described as 2 The repeated cleaning times are 2 to 5 times; the ultrasonic time is 0.5-5 h; the final product is obtained by freeze drying.
6. An application method of the sulfur-rich polymer hierarchical pore carbon nano cage composite material is characterized in that the sulfur-rich polymer hierarchical pore carbon nano cage composite material prepared by the method of any one of claims 1-5 is used as a positive electrode active substance of a lithium sulfur battery, and is mixed with carbon black and a binder to prepare the positive electrode of the lithium sulfur battery.
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