CN114361454B - Composite carbon material for lithium-sulfur battery, preparation method of composite carbon material and lithium-sulfur battery comprising composite carbon material - Google Patents
Composite carbon material for lithium-sulfur battery, preparation method of composite carbon material and lithium-sulfur battery comprising composite carbon material Download PDFInfo
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Abstract
The application discloses a composite carbon material for a lithium-sulfur battery, a preparation method thereof and a lithium-sulfur battery containing the composite carbon material. The composite carbon material comprises a carbon matrix inner core, a first protective layer and a second protective layer; the first protective layer is coated on the outer surface of the carbon matrix inner core, is of a porous structure and comprises metal ions; the second protective layer is positioned on the outer side of the first protective layer, and a hollow layer is arranged between the second protective layer and the first protective layer. In the composite carbon material, the carbon core can increase the conductivity of the composite material and adsorb lithium polysulfide; the metal ions contained in the first protective layer can adsorb the lithium polysulfide and promote the conversion of elemental sulfur to the lithium sulfide; the hollow layer provides a buffer space for volume expansion; in order to improve the adsorption capacity of the composite carbon material to sulfur, a second protective layer is further arranged to further adsorb lithium polysulfide, inhibit the shuttling of polysulfide and improve the utilization rate of sulfur.
Description
Technical Field
The application belongs to the field of chemical power sources, and particularly relates to a composite carbon material for a lithium-sulfur battery, a preparation method of the composite carbon material and the lithium-sulfur battery containing the composite carbon material.
Background
A lithium sulfur (Li-S) battery is a very promising new generation of batteries because of its high theoretical specific capacity (1675 mAh-g -1 ) Energy density (2600 Wh kg) -1 ) And high raw material abundance. However, li-S batteries suffer from drawbacks such as diffusion of polysulfide, slow oxidation-reduction reaction rate, and volume expansion of active materials in electrochemical reactions, resulting in problems such as rapid decay of battery capacity, slow reaction kinetics rate, poor charge-discharge cycle performance, and the like. In order to obtain a high performance Li-S battery, the carbon matrix in the S/C composite is usually polar (polar carbon with good sulfur carrying effect, tiO 2 Modifying the carbon surface), catalytic effect (accelerating the reaction rate, promoting lithium polysulfideConversion to lithium sulfide, VS 2 、CoS 2 、TiS 2 And FeS modified carbon matrix) and a large specific surface area (sulfur loading is large). Particularly, nanocarbon materials having unique nanostructures, such as core-shell carbon spheres, two-dimensional core-shell carbon nanoplatelets, and the like, are designed as a high sulfur-loaded host to realize a high-performance Li-S battery. The core-shell structure is generally made of carbon nanomaterial, the inner core is made of high molecular polymer, and the outer shell is made of high molecular polymer, however, most core-shell structure composite materials have limited conductivity and cannot provide enough adsorption sites to prevent soluble polysulfide from shuttling.
Disclosure of Invention
In order to solve the problems, a composite carbon material for a lithium-sulfur battery, a preparation method thereof and a lithium-sulfur battery comprising the composite carbon material are provided.
The application provides a composite carbon material for a lithium-sulfur battery, which is characterized by comprising a carbon matrix inner core, a first protective layer and a second protective layer; the first protective layer is coated on the outer surface of the carbon matrix inner core, is of a porous structure and comprises metal ions; the second protective layer is positioned on the outer side of the first protective layer, and a hollow layer is arranged between the second protective layer and the first protective layer.
In another aspect, the present application provides a method for preparing a composite carbon material for a lithium-sulfur battery, comprising: s1, forming the first protective layer on the carbon matrix inner core; s2, forming a template layer on the first protective layer; s3, forming a precursor layer of a second protective layer on the surface of the template; and S4, etching to remove the template layer.
The application also provides a lithium sulfur battery containing the composite carbon material.
In the composite carbon material, the carbon core can increase the conductivity of the composite material and adsorb lithium polysulfide; the metal ions contained in the first protective layer can absorb the lithium polysulfide and promote the conversion of the elemental sulfur to the lithium sulfide at the same time, the porous structure of the first protective layer provides a space for the conversion of the elemental sulfur to the lithium sulfide, and larger volume expansion can be generated in the process of converting the elemental sulfur to the lithium polysulfide; the hollow layer provides a buffer space for volume expansion; in order to improve the adsorption capacity of the composite carbon material to sulfur, a second protective layer is further arranged to further adsorb lithium polysulfide, inhibit the shuttling of polysulfide and improve the utilization rate of sulfur.
Detailed Description
The present application will be described in detail with reference to the following embodiments.
The composite carbon material for the lithium-sulfur battery comprises a carbon matrix inner core, a first protective layer and a second protective layer; the first protective layer is coated on the outer surface of the carbon matrix inner core, is of a porous structure and comprises metal ions; the second protective layer is located the first protective layer outside, is provided with the hollow layer between second protective layer and the first protective layer.
In the composite carbon material, the carbon core can increase the conductivity of the composite material and adsorb lithium polysulfide; the metal ions contained in the first protective layer can absorb the lithium polysulfide and promote the conversion of the elemental sulfur to the lithium sulfide at the same time, the porous structure of the first protective layer provides a space for the conversion of the elemental sulfur to the lithium sulfide, and larger volume expansion can be generated in the process of converting the elemental sulfur to the lithium polysulfide; the hollow layer provides a buffer space for volume expansion; in order to improve the adsorption capacity of the composite carbon material to sulfur, a second protective layer is further arranged to further adsorb lithium polysulfide, inhibit the shuttling of polysulfide and improve the utilization rate of sulfur.
In alternative embodiments, the carbon matrix core may be any carbon material suitable for use in a negative electrode material for a lithium sulfur battery, such as, but not limited to, pigment carbon black and the like. Carbon nanotubes, carbon nanofibers, graphene, and the like may also be included. The particle size of the carbon matrix core may be 20-50nm. If the grain diameter of the inner core is smaller than 20nm, the supporting effect of the inner core on the outer layer is insufficient, a composite structure is not easy to form, and the structure is easy to collapse; and if the particle size of the inner core is larger than 50nm, the volume expansion capacity of the sulfur-based material of the composite carbon material is weakened.
In an alternative embodiment, the carbon matrix core surface has polar functional groups; preferably, the polar functional group includes at least one of a hydroxyl group and a carboxyl group. Polar functional groups on the surface of the carbon matrix core may increase the ability of the carbon matrix to adsorb polysulfides.
In an alternative embodiment, the metal ion in the first protective layer may be one or more of cobalt ion, copper ion, zinc ion, sodium ion, iron ion, and nickel ion. Still further, the first protective layer includes a transition metal-based metal-organic framework compound (MOF). The metal organic framework compound is of a porous structure, wherein metal ions can absorb lithium polysulfide into pores, meanwhile, conversion of elemental sulfur into lithium sulfide is promoted, and the porous structure of the first protective layer provides space for conversion of elemental sulfur into lithium sulfide. Including transition metal-based metal organic framework compounds may be, but are not limited to, one or more of ZIF-67, ZIF-8, ZIF-7 (zinc nitrate and benzimidazole), ZIF-1 (zinc nitrate and isopyrazole), ZIF-12 (cobalt nitrate and benzimidazole), ZIF-90 (zinc nitrate and imidazole acid-2-formaldehyde), ZIF-62 (zinc nitrate and imidazole and benzimidazole), ZIF-78 (zinc nitrate and 2-nitroimidazole and 5-nitrobenzimidazole), ZIF-71 (zinc nitrate and 4, 5-dichloroimidazole), MOF-5 (zinc nitrate and terephthalic acid), MOF-74 (manganese chloride and 2, 5-dihydroxyterephthalic acid), MOF-2 (zinc nitrate and terephthalic acid). The first protective layer may also be a metal covalent organic framework Material (MCOFs). The COFs has regular structure, uniform pore canal and high thermal stability, and when the COFs is used as a first protective layer, metal ions adsorb lithium polysulfide in the pore canal, and meanwhile, the conversion of elemental sulfur into lithium sulfide can be promoted. For metal covalent organic framework materials, the COFs can be COF102 (tetra (4-dihydroxy-borophenyl) methane self-condensation), COF-103 (tetraphenyl methane boric acid self-condensation), COF-105 (condensation reaction of tebipenem and hexahydroxybenzophenanthrene), COF-108 (hexahydroxy benzophenanthrene and tetraphenyl methane boric acid condensation).
In an alternative embodiment, the first protective layer comprises a carbonized transition metal-based metal-organic framework compound or a carbonized metal ion containing porous material synthesized from a metal salt and a covalent organic framework by hydrothermal synthesis. After carbonization, the original structure porosity is still maintained, and meanwhile, the generated carbon can increase the conductivity, so that the conductivity of the material is improved.
In an alternative embodiment, the molar content of metal ions in the first protective layer is 0.02 to 4% based on the number of moles of the carbon matrix core. At a metal ion level below 0.02%, sufficient adsorption sites cannot be provided to prevent shuttling of soluble polysulfides; when the content of the metal ions is higher than 4%, the content of the positively charged metal ions in the first protective layer is large, which leads to preferential and negatively charged pigment carbon black, and in severe cases, sedimentation may be formed by electrostatic attraction, which is unfavorable for subsequent reactions. Any number within the above range may be selected by those skilled in the art according to actual needs, such as, but not limited to, 0.02%, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, etc.
In an alternative embodiment, the first protective layer has a thickness of 5-30nm. When the thickness of the first protective layer is less than 5nm, the content of metal ions is too small, the adsorption capacity to polysulfide is relatively weak, and thus the improvement effect on the shuttling of polysulfide is small; when the thickness of the first protective layer is larger than 30nm, if the first protective layer is made of a material with poor conductivity, the proportion of the first protective layer in the composite material is large, so that the conductivity of the composite material is poor, the material resistance is increased, and the battery performance is polarized to be larger, and the capacity is not utilized.
The first protective layer can promote the conversion of elemental sulfur to lithium polysulfide, and larger volume expansion can be generated in the process of converting the elemental sulfur to lithium polysulfide, and the hollow layer provides space for the volume expansion at the moment, so that the negative electrode material can be prevented from falling slag, falling off and the like, and the cycling stability of the battery is improved. In alternative embodiments, the hollow layer thickness may be 80-100nm. The "hollow layer thickness" in this patent refers to the average distance between the outer surface of the first protective layer and the inner surface of the second protective layer, assuming that the centers of the first protective layer and the second protective layer coincide, i.e., the thickness of the hollow layer is the thickness of the template layer if the hollow layer is formed by the template method (described later). This is because, as will be appreciated by those skilled in the art, the hollow layer in the composite may not be a uniform layer due to gravity, but rather the spatial structure of the first and second protective layers in contact at a point, if the thickness of the hollow layer is described only to illustrate the volume occupied by the hollow layer in the composite. When the thickness of the hollow layer is less than 80nm, the effect of relieving the expansion caused by the conversion of the elemental sulfur into lithium polysulfide is insufficient; if the thickness of the hollow layer is greater than 100nm, unnecessary space is wasted, and the second protective layer is not easily formed due to the fact that the thickness of the hollow layer is too large.
In alternative embodiments, the second protective layer comprises a carbon-based material, a metal compound, or a combination of both. The second protective layer can avoid polysulfide ions which are not adsorbed by the first protective layer from dissolving into the electrolyte, so that polysulfide shuttles. When the second protective layer comprises a metal compound, the metal compound acts as a catalyst to further adsorb polysulfides while promoting the conversion of elemental sulfur to polysulfides. The metal compound may be MoS 2 、TiO 2 、PtO 2 、Fe 2 O 3 、Co 9 S 8 、WS 2 、CeO 2 、Co 3 O 4 、TiN、VO x 、MnO x 、CeO x 、Fe 3 N、A x N (A is transition metal, X is 1-9), me x S y (Me is a transition metal, X is 1-9), M x P x (M is a transition metal, X is one or more of 1-9)
In an alternative embodiment, the molar content of the metal compound in the second protective layer is 0.1% -5% of the molar number of the core of the carbon matrix. When the content of the metal compound is less than 0.1%, adsorption and catalytic action on polysulfide are not ideal; if the content is more than 5%, unnecessary waste is caused. Any number within the above range may be selected by those skilled in the art according to actual needs, such as, but not limited to, 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, etc.
In an alternative embodiment, the second protective layer has a thickness of 1-25nm. The second protective layer is too thin: the corresponding catalyst content is low, so that the catalysis effect is weak, the speed of sulfur to lithium sulfide is low, and the discharge capacity is low; the second protective layer is too thick: one is unfavorable for the structural construction, easy collapse, and the second is that the sheet structure is easy to form a pile, too thick, and the conductivity, the porosity and the active sites are relatively weakened, so that the performance of the battery is unfavorable. Any number within the above range may be selected by those skilled in the art according to the actual needs, such as, but not limited to, 1nm, 5nm, 10nm, 15nm, 20nm, 25nm, etc.
The preparation method of the composite carbon material for the lithium-sulfur battery comprises the following steps: s1, forming a first protective layer on a carbon matrix inner core; s2, forming a template layer on the first protective layer; s3, forming a second protective layer on the surface of the template; and S4, etching to remove the template layer.
In the steps S1, S3, the method of forming the first protective layer and the second protective layer may be any suitable method. In step S2, the template layer formed may be any suitable template layer that does not affect subsequent steps, such as, but not limited to, silica, polystyrene microspheres, and the like. In step S4, the etching manner may be any suitable manner that does not affect the first protection layer and the second protection layer.
After step S3, a high temperature treatment step may be further included, by which the first protective layer and the second protective layer are further carbonized. The high temperature treatment step may be provided before the step S4 or after the step S4.
The application also discloses a lithium sulfur battery containing the composite carbon material.
The application is further described below by means of specific examples. These examples are merely exemplary and are not intended to limit the scope of the present application in any way.
In the following examples and comparative examples, reagents, materials and instruments used, unless otherwise specified, were commercially available.
Example 1
(1) 20g of pigment carbon black in 5M HNO 3 In (50 mL), reflux and heat preservation are carried out for 6h at 75 ℃, then a sample is taken out, the sample is washed by deionized water until the sample is neutral, and the sample is dried to obtain the oxygen-containing functionalized pigment carbon black;
(2) 1.1g of dimethyl imidazole and 0.25g of cobalt nitrate hexahydrate are respectively dissolved in 60mL of deionized water, then 20g of pigment carbon black is dispersed in cobalt nitrate solution, after the pigment carbon black is uniformly dispersed, the mixture is poured into dimethyl imidazole dispersion liquid, stirred for 4 hours at room temperature, and the pigment carbon black coated by ZIF-67 (ZIF-67@pigment carbon black) is obtained through filtration and washing;
(3) ZIF-67@pigment carbon black is put into a mixed solution composed of 180mL of ethanol and 20mL of deionized water, and stirred for 10min. Subsequently, 12mL of an aqueous ammonia solution and 8mL of tetraethyl orthosilicate were continuously added to the above solution, and SiO was grown on the surface of ZIF-67@pigment carbon black 2 The reaction was stirred at 30℃for 6h; the precipitate is centrifuged and washed to obtain SiO 2 Coated ZIF-67@pigment carbon black and redispersed in deionized water to obtain a solution dispersion (50 mL);
(4) 300mg of glucose, 80mg of ammonium heptamolybdate tetrahydrate ((NH) 4 ) 6 Mo 7 O 24 ·4H 2 O, AHT) and 210mg thiourea (CS (NH) 2 ) 2 TA) placing SiO 2 Coated ZIF-67@pigment carbon black dispersion. The mixed solution was then sealed into a polytetrafluoroethylene stainless steel autoclave, hydrothermally treated at 160 ℃ for 24 hours, and the precipitate was centrifuged, washed, and dried at 60 ℃. Finally, annealing the obtained product for 1h at 750 ℃ under argon atmosphere to obtain MoS 2 /C@SiO 2 Porous carbon @ pigment carbon black doped with @ Co-N;
(5) Etching MoS with HF acid solution (20%) 2 /C@SiO 2 Porous carbon @ pigment carbon black doped with @ Co-N to produce MoS 2 A/C@void@Co-N doped porous carbon@pigment carbon black heterostructure.
Example 2
The procedure was the same as in example 1, except for the step (2).
The step (2) is as follows: 1.3g of dimethyl imidazole and 0.2g of Zn (NO) 3 ) 2 ·6H 2 O is respectively dissolved in 60mL deionized water, then 20g of pigment carbon black is dispersed in zinc nitrate solution, after the pigment carbon black is uniformly dispersed, the mixture is poured into dimethyl imidazole dispersion liquid, stirred for 4 hours at room temperature, and the pigment carbon black (ZIF-8@pigment carbon black) coated by ZIF-8 is obtained through filtration and washing.
Example 3
The procedure was the same as in example 1, except for the step (2).
The step (2) is as follows: 1.5g Zn (NO) 3 ) 2 ·6H 2 O and 0.6g of terephthalic acid are respectively dissolved in 30mL of DMF, then 20g of pigment carbon black is dispersed in zinc nitrate solution, after the dispersion is uniform, the mixture is poured into terephthalic acid dispersion, 2.5mL of triethylamine is added under electromagnetic stirring, after stirring for 4 hours, the mixture is filtered and washed to obtain the pigment carbon black (MOF-5@pigment carbon black) coated by MOF-5.
Example 4
The procedure was the same as in example 1, except for the step (2).
The step (2) is as follows: 2g Cu (NO) 3 ) 2 And 2.1g of trimellitic acid were dissolved in 30mL of deionized water, respectively, and 20g of pigment carbon black was dispersed in Cu (NO) 3 ) 2 And after the solution is uniformly dispersed, pouring the solution into trimellitic acid dispersion liquid, stirring the solution for 0.5h, then preserving the temperature in a 140 ℃ oven for 8h, washing the precipitate with ethanol to remove redundant terephthalic acid, and filtering to obtain the MOF-199 coated pigment carbon black.
Example 5
Steps (1) - (3) are the same as in example 1.
The step (4) is as follows: preparing an alcohol-water mixed solution with the pH value of 8.5 and the alcohol-water ratio of 1:6, and pouring SiO 2 Adding 0.5ml tetrabutyl titanate into the coated ZIF-67@pigment carbon black dispersion liquid, performing ultrasonic dispersion for 30min, reacting for 1h, filtering, washing and drying to obtain TiO 2 @SiO 2 Pigment carbon black/ZIF-67. Finally, annealing the obtained product for 1h at 750 ℃ under argon atmosphere to obtain TiO 2 @SiO 2 Pigment carbon black @ Co-N-C@;
the step (5) is as follows: etching TiO with HF acid solution (20%) 2 @SiO 2 Porous carbon @ pigment carbon black doped with @ Co-N to produce TiO 2 A carbon black heterostructure of/C@void@Co-N doped porous carbon C@ pigment.
Example 6
Steps (1) - (3) are the same as in example 1.
The step (4) is as follows: 300mg of glucose was placed in a SiO2 coated ZIF-67@ pigment carbon black dispersion. The mixed solution was then sealed to polytetrafluoroethyleneIn a stainless steel autoclave, the precipitate was subjected to hydrothermal treatment at 160℃for 24 hours, centrifuged, washed and dried at 60 ℃. Finally, annealing the obtained product for 1h at 750 ℃ under argon atmosphere to obtain MoS 2 /C@SiO 2 Porous carbon @ pigment carbon black doped with @ Co-N;
the step (5) is as follows: etching C@SiO with HF acid solution (20%) 2 The @ Co-N doped porous carbon @ pigment carbon black produces a C @ void @ Co-N doped porous carbon @ pigment carbon black heterostructure.
Example 7
The procedure was the same as in example 1, except for the step (1).
The step (1) is as follows: 20g of carbon nanotubes in 5M HNO 3 In (50 mL), the mixture is refluxed and kept at 75 ℃ for 6 hours, then the sample is taken out, washed with deionized water to be neutral, and dried to obtain the oxygen-containing functionalized carbon nano tube.
Example 8
The procedure was the same as in example 1, except for the step (4).
The step (4) is as follows: 300mg of glucose, 80mg of ammonium heptamolybdate tetrahydrate ((NH) 4 ) 6 Mo 7 O 24 ·4H 2 O, AHT) and 210mg thiourea (CS (NH) 2 ) 2 TA) placing SiO 2 Coated ZIF-67@pigment carbon black dispersion. The mixed solution was then sealed into a polytetrafluoroethylene stainless steel autoclave, hydrothermally treated at 160 ℃ for 24 hours, and the precipitate was centrifuged, washed, and dried at 60 ℃.
Example 9
The procedure was the same as in example 1, except for the step (2).
The step (2) is as follows: 20g of pigment carbon black and commercially available polyarylether-linked COFs (300.0 mg) were stirred in a beaker at 40℃for 3h, then treated in the flask with 20% NaOH in ultrapure water and ethanol (1:1, 50 mL). The reaction mixture was heated and refluxed at 120 ℃ for three days. After cooling to 25 ℃, the solid was filtered and rinsed 3 times with ultra pure water. Then, the resulting solid was refluxed in ultrapure water at 100℃for 2 hours. The solution was filtered and the filter cake was rinsed with copious amounts of ultrapure water. Subsequently, the solids were immersed in ultrapure water, tetrahydrofuran and acetone, respectively, for 24 hours. Finally, the treated solid is dried under vacuum at 80 ℃ to obtain pure light yellow NaOOC COF@pigment carbon black powder.
Comparative example 1
Composite materials without ZIF-67 coating (first protective layer), i.e. preparation of MoS 2 And (2) a C@void@pigment carbon black heterostructure material.
The composite carbon materials prepared in examples 1 to 9 and comparative example 1 were tested. The test comprises the following steps:
and preparing the prepared composite carbon material into a positive plate, assembling the positive plate into a lithium sulfur battery, and performing performance test on the lithium sulfur battery.
Firstly taking the prepared composite carbon material and sublimed sulfur according to the following proportion of 25:75 mass ratio, and processing the mixture in inert gas for 12 hours at 155 ℃ to obtain the positive electrode material. Then preparing the obtained positive electrode material G4:SP:PVDF into slurry according to the mass ratio of 92:2:3:5, wherein the concrete process is as follows: firstly, dissolving a binder PVDF in a solvent NMP, grinding and blending a positive electrode material and a conductive agent, adding the mixture into the dissolved binder to mix the slurry, coating the synthesized slurry on a carbon-coated aluminum foil by using a scraper, and drying the slurry at 60 ℃ for 12 hours. Finally, the prepared positive electrode material is cut into a rectangle with the diameter of 45 mm and 60mm, a lithium foil with the diameter of 100 mu M is cut into a rectangle with the diameter of 50 mm and 65mm, PP is selected as a diaphragm, electrolyte is 1M LiTFSI and is dissolved in DOL/DME=1:1V/V, and the mass ratio of the electrolyte to active sulfur is E/S=10, so that the single-piece soft package is assembled.
The electrochemical performance test adopts blue electric testing equipment to carry out 0.2C discharge and 0.1C charge at 25 ℃, and the voltage window is 1.7-2.6V.
The test results for the materials prepared in examples 1-9 and comparative example 1 are detailed in Table 1.
TABLE 1
From table 1, it can be seen that examples 1 to 9 and comparative example 1 are not much different in the first discharge capacity and the first efficiency, but the capacity retention rate after 100 cycles of examples 1 to 9 is significantly better than comparative example 1, which proves that the composite material of the present application does play a role in inhibiting shuttling of sulfur, thereby reducing sulfur loss, improving sulfur utilization, and improving cycle life.
The preferred embodiments of the application disclosed above are intended only to assist in the explanation of the application. The preferred embodiments are not exhaustive or to limit the application to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the application and the practical application, to thereby enable others skilled in the art to best understand and utilize the application. The application is limited only by the claims and the full scope and equivalents thereof.
Claims (15)
1. The composite carbon material for the lithium-sulfur battery is characterized by comprising a carbon matrix inner core, a first protective layer and a second protective layer;
the first protective layer is coated on the outer surface of the carbon matrix inner core, is of a porous structure and comprises metal ions; the second protective layer is positioned on the outer side of the first protective layer, and a hollow layer is arranged between the second protective layer and the first protective layer.
2. The composite carbon material for lithium-sulfur batteries according to claim 1, wherein the surface of the carbon matrix core has polar functional groups.
3. The composite carbon material for lithium-sulfur batteries according to claim 2, wherein the polar functional group comprises at least one of a hydroxyl group and a carboxyl group.
4. The composite carbon material for lithium sulfur battery according to claim 1, wherein the first protective layer comprises a transition metal-based metal-organic framework compound or a metal-covalent organic framework material.
5. The composite carbon material for lithium sulfur batteries according to claim 1, wherein said first protective layer comprises a carbonized transition metal-based metal-organic framework compound or a carbonized metal-covalent organic framework material.
6. The composite carbon material for lithium-sulfur battery according to claim 1, wherein the carbon matrix inner core has a particle diameter of 20 to 50nm, the first protective layer has a thickness of 5 to 30nm, the hollow layer has a thickness of 80 to 100nm, and the second protective layer has a thickness of1 to 25nm.
7. The composite carbon material for lithium-sulfur battery according to claim 1, wherein the molar content of the metal ions in the first protective layer is 0.02 to 4% based on the number of moles of the core of the carbon matrix.
8. The composite carbon material for a lithium sulfur battery according to claim 1, wherein the second protective layer comprises a carbon-based material, a metal compound, or a combination of both.
9. The composite carbon material for lithium-sulfur battery according to claim 8, wherein the metal compound is a x N、Me y S z Wherein A is a transition metal, and x is 1-9; me is a transition metal, and y is 1-9.
10. The composite carbon material for lithium-sulfur battery according to claim 8, wherein the metal compound is MoS 2 、TiO 2 、PtO 2 、Fe 2 O 3 、Co 9 S 8 、WS 2 、CeO 2 、Co 3 O 4 、TiN、VO x 、MnO x 、Fe 3 One or more of N.
11. The method according to claim 8The composite carbon material for the lithium-sulfur battery is characterized in that the metal compound is CeO x 。
12. The composite carbon material for lithium-sulfur battery according to claim 8, wherein the molar content of the metal compound in the second protective layer is 0.1% to 5% based on the number of moles of the core of the carbon matrix.
13. A method for producing the composite carbon material for lithium-sulfur batteries according to any one of claims 1 to 12, characterized by comprising:
s1, forming the first protective layer on the carbon matrix inner core;
s2, forming a template layer on the first protective layer;
s3, forming a second protective layer on the surface of the template; a kind of electronic device with high-pressure air-conditioning system
S4, etching to remove the template layer.
14. The method for producing a composite carbon material for a lithium-sulfur battery according to claim 13, characterized by further comprising a high-temperature treatment step of carbonizing the first protective layer and the second protective layer after the step S3.
15. A lithium-sulfur battery comprising the composite carbon material for a lithium-sulfur battery according to any one of claims 1 to 12.
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