CN114361454A - Composite carbon material for lithium-sulfur battery, preparation method thereof and lithium-sulfur battery comprising same - Google Patents
Composite carbon material for lithium-sulfur battery, preparation method thereof and lithium-sulfur battery comprising same Download PDFInfo
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Abstract
The invention discloses a composite carbon material for a lithium-sulfur battery, a preparation method thereof and the lithium-sulfur battery comprising the same. 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 inner core of the carbon substrate, is of a porous structure and comprises metal ions; the second protective layer is located the first protective layer outside, be provided with hollow layer between the second protective layer with 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 lithium polysulfide and promote the conversion of elemental sulfur into 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, so that polysulfide shuttling is inhibited, and the utilization rate of sulfur is improved.
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 comprising the composite carbon material.
Background
Lithium-sulfur (Li-S) batteries are a promising new generation because of their high theoretical specific capacity (1675mAh g)-1) Energy density (2600Wh kg)-1) And high raw material richness. However, Li-S batteries suffer from disadvantages of diffusion of polysulfides in electrochemical reactions, slow redox reaction rate, volume expansion of active materials, and the like, resulting in problems of rapid capacity fade, slow reaction kinetics, poor charge-discharge cycle performance, and the like. To obtain high performance Li-S cells, the carbon matrix in the S/C composite is typically polar (polar carbon has good sulfur loading effect, TiO2Modification of carbon surface), catalytic effects (increase of reaction rate, promotion of conversion of lithium polysulfide to lithium sulfide, VS2、CoS2、TiS2And FeS modified carbon substrate) and a large specific surface area (large sulfur loading). In particular, nanocarbon materials having unique nanostructures, such as core-shell carbon spheres, two-dimensional core-shell carbon nanosheets, and the like, are designed as a host of high-loading sulfur to achieve high-performance Li-S batteries. The core-shell structure is generally a core made of carbon nanomaterial and a shell made of high molecular polymer, but most core-shell structure composites have limited electrical conductivity and cannot provide enough adsorption sites to prevent shuttle of soluble polysulfide.
Disclosure of Invention
In order to solve the above problems, a composite carbon material for a lithium sulfur battery, a method for preparing the same, and a lithium sulfur battery including the composite carbon material are provided.
The invention provides a composite carbon material for a lithium-sulfur battery, which is characterized by comprising a carbon substrate core, a first protective layer and a second protective layer; the first protective layer is coated on the outer surface of the inner core of the carbon substrate, is of a porous structure and comprises metal ions; the second protective layer is located the first protective layer outside, be provided with hollow layer between the second protective layer with the first protective layer.
In another aspect, the present invention provides a method for preparing a composite carbon material for a lithium sulfur battery, including: s1, forming the first protective layer on the carbon matrix 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.
In another aspect, the present invention also provides a lithium sulfur battery comprising the above 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 adsorb lithium polysulfide and promote the conversion of elemental sulfur to lithium sulfide, and the porous structure of the first protective layer provides a space for the conversion of elemental sulfur to lithium sulfide, so that larger volume expansion can be generated in the process of converting elemental sulfur to 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, so that polysulfide shuttling is inhibited, and the utilization rate of sulfur is improved.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The composite carbon material for a 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 inner core of the carbon substrate, is of a porous structure and comprises metal ions; the second protective layer is located the first protective layer outside, is provided with 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 adsorb lithium polysulfide and promote the conversion of elemental sulfur to lithium sulfide, and the porous structure of the first protective layer provides a space for the conversion of elemental sulfur to lithium sulfide, so that larger volume expansion can be generated in the process of converting elemental sulfur to 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, so that polysulfide shuttling is inhibited, and the utilization rate of sulfur is improved.
In alternative embodiments, the carbon matrix core may be any carbon material suitable for use in a lithium sulfur battery negative electrode material, 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 20-50 nm. If the grain diameter of the inner core is less 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; the particle size of the inner core is larger than 50nm, the volume expansion capacity of the sulfur-based material tolerated by the composite carbon material is weakened.
In alternative embodiments, the carbon matrix inner core surface has polar functional groups; preferably, the polar functional group includes at least one of a hydroxyl group and a carboxyl group. The polar functional groups on the surface of the carbon matrix core can increase the ability of the carbon matrix to adsorb polysulfides.
In an alternative embodiment, the metal ions in the first protective layer may be one or more of cobalt ions, copper ions, zinc ions, sodium ions, iron ions, and nickel ions. Still further, the first protective layer includes a transition metal-based metal organic framework compound (MOF). The metal organic framework compound is a porous structure, wherein metal ions can adsorb lithium polysulfide into pores and promote the conversion of elemental sulfur into lithium sulfide, and the porous structure of the first protective layer provides a space for the conversion of elemental sulfur into lithium sulfide. Including the transition metal-based metal organic framework compounds may be, but is 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-2-carbaldehyde), 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 a regular structure, uniform pore channels and high thermal stability, and when the COFs is used as a first protective layer, lithium polysulfide is absorbed in the pore channels by metal ions, and the conversion of elemental sulfur to lithium sulfide can be promoted. For metal covalent organic framework materials, among others, COFs can be COF102 (tetra (4-dihydroxy-borylphenyl) methane self-condensation), COF-103 (tetraphenylmethaneboronic acid self-condensation), COF-105 (condensation reaction of tebipenem and hexahydroxytriphenylene), COF-108 (hexahydroxytriphenylene and tetraphenylmethaneboronic 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 hydrothermally synthesized from a metal salt and a covalent organic framework. After carbonization, the porosity of the original structure is still maintained, and the generated carbon can increase the conductivity, thereby improving the conductivity of the material.
In an alternative embodiment, the metal ion is present in the first protective layer in a molar amount of 0.02 to 4% based on the number of moles of core in the carbon matrix. At metal ion levels below 0.02%, there are insufficient adsorption sites available to prevent soluble polysulfide shuttling; when the content of the metal ions is higher than 4%, the content of the metal ions with positive charges in the first protective layer is higher, so that the metal ions are preferentially combined with pigment carbon black with negative charges through electrostatic attraction, and sedimentation may be formed in severe cases, which is not favorable for subsequent reactions. Any value within the above range can be selected by one 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 5-30 nm. 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 the improvement effect on shuttling of polysulfide is small; when the thickness of the first protective layer is greater 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 resistance of the material is increased, and the polarization of the battery performance is large, and the capacity is not utilized.
The first protective layer can promote the conversion of elemental sulfur to lithium polysulfide, can produce great volume expansion at the in-process of elemental sulfur to lithium polysulfide conversion, and the hollow layer provides the space for volume expansion this moment to can avoid negative electrode material to fall sediment, drop etc. thereby improve the cycle stability of battery. In alternative embodiments, the hollow layer may be 80-100nm thick. The "thickness of the hollow layer" in this patent means an 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, that is, if the hollow layer is formed by a template method (described below), the thickness of the hollow layer is the thickness of the template layer. This is because, as will be understood by those skilled in the art, the hollow core layer in the composite material may not be a uniform layer due to gravity, but rather the spatial structure of the first protective layer and the second protective layer in contact at some point, if the thickness of the hollow core layer is described above only to illustrate the volume occupied by the hollow core layer in the composite material. When the thickness of the hollow layer is less than 80nm, the effect of relieving expansion caused by the conversion of elemental sulfur into lithium polysulfide is insufficient; if the thickness of the hollow core layer is greater than 100nm, unnecessary space is wasted, and the second protective layer is not easily formed due to the large thickness of the hollow core layer.
In alternative embodiments, the second protective layer includes a carbon-based material, a metal compound, or a combination of both. The second protective layer can prevent polysulfide ions which are not adsorbed by the first protective layer from dissolving into the electrolyte and causing polysulfide shuttling. 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 MoS2、TiO2、PtO2、Fe2O3、Co9S8、WS2、CeO2、Co3O4、TiN、VOx、MnOx、CeOx、Fe3N、AxN (A is transition metal, X is 1-9) and MexSy(Me is a transition metal, X is 1-9), MxPx(M is transition metal, X is 1-9)
In an alternative embodiment, the molar content of the metal compound in the second protective layer is 0.1% to 5% of the number of moles of the core in the carbon matrix. When the content of the metal compound is less than 0.1%, adsorption and catalytic effects on polysulfides are not preferable; if the content is more than 5%, unnecessary waste is caused. Any value within the above range can be selected by one skilled in the art according to the 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 of1 to 25 nm. The second protective layer is too thin: the corresponding catalyst content is low, so that the catalytic action is weak, the speed from sulfur to lithium sulfide is slow, and the discharge capacity is low; the second protective layer is too thick: one is not favorable for the structure and is easy to collapse, and the other is that the sheet structure is easy to form stack and is too thick, so that the conductivity, the porosity and the active sites are relatively weakened, thereby being not favorable for the performance of the battery. Any value within the above range can be selected by one 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 the carbon substrate 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 the subsequent steps, such as, but not limited to, silica, polystyrene microspheres, and the like. In step S4, the etching manner may be any appropriate manner that does not affect the first protective layer and the second protective layer.
After the step of 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 processing step may be provided before the step of S4, or may be provided after the step of S4.
The invention also discloses a lithium-sulfur battery containing the composite carbon material.
The present invention is further described below by way of specific examples. However, these examples are only illustrative and do not set any limit to the scope of the present invention.
In the following examples and comparative examples, reagents, materials and instruments used therefor were commercially available unless otherwise specified.
Example 1
(1)20g of pigment carbon black in 5M HNO3In the medium (50mL), carrying out reflux heat preservation for 6h at 75 ℃, then taking out a sample, washing the sample to be neutral by using deionized water, and drying the sample to obtain the oxygen-containing functionalized pigment carbon black;
(2) respectively dissolving 1.1g of dimethylimidazole and 0.25g of cobalt nitrate hexahydrate in 60mL of deionized water, then dispersing 20g of pigment carbon black in a cobalt nitrate solution, pouring the mixture into a dimethylimidazole dispersion solution after uniform dispersion, stirring for 4 hours at room temperature, filtering and washing to obtain ZIF-67-coated pigment carbon black (ZIF-67@ pigment carbon black);
(3) ZIF-67@ pigment carbon black was added to a mixed solution of 180mL of ethanol and 20mL of deionized water, and stirred for 10 min. Subsequently, 12mL of aqueous ammonia solution and 8mL of tetraethyl orthosilicate were added successively to the above solution to grow SiO on the surface of ZIF-67@ pigment carbon black2Layer, reacting at 30 ℃ and stirring for 6 h; centrifuging and washing the precipitate to obtain SiO2Coated 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)6Mo7O24·4H2O, AHT) and 210mg Thiourea (CS (NH)2)2TA) into SiO2Coated ZIF-67@ pigment carbon black dispersion. The mixed solution was then sealed in 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 at 750 ℃ for 1h in argon atmosphere to obtain MoS2/C@SiO2@ Co-N doped porous carbon @ pigment carbon black;
(5) MoS was etched with HF acid solution (20%)2/C@SiO2@ Co-N doped porous carbon@ pigment carbon Black for MoS production2the/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 dimethylimidazole and 0.2g Zn (NO)3)2·6H2And O is respectively dissolved in 60mL of deionized water, then 20g of pigment carbon black is dispersed in a zinc nitrate solution, after uniform dispersion, the mixture is poured into a dimethyl imidazole dispersion solution, the mixture is stirred for 4 hours at room temperature, and the mixture is filtered and washed to obtain the ZIF-8 coated pigment carbon black (ZIF-8@ pigment carbon black).
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)2·6H2O and 0.6g of terephthalic acid are respectively dissolved in 30mL of DMF, then 20g of pigment carbon black is dispersed in a zinc nitrate solution, after uniform dispersion, the mixture is poured into terephthalic acid dispersion liquid, 2.5mL of triethylamine is added under electromagnetic stirring, after stirring for 4h, the mixture is filtered and washed to obtain the MOF-5 coated pigment carbon black (MOF-5@ pigment carbon black).
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)2And 2.1g of trimellitic acid were dissolved in 30mL of deionized water, respectively, and then 20g of pigment carbon black was dispersed in Cu (NO)3)2After the solution is uniformly dispersed, pouring the solution into trimellitic acid dispersion, stirring for 0.5h, then keeping the temperature in a drying oven at 140 ℃ for 8h, then washing the precipitate with ethanol to remove redundant trimellitic acid, and filtering to obtain the MOF-199 coated carbon black pigment.
Example 5
Steps (1) to (3) are the same as in example 1.
The step (4) is as follows: preparing alcohol-water mixed solution with the pH value of 8.5, pouring SiO into the alcohol-water mixed solution with the alcohol-water ratio of 1:62Carrying out ultrasonic dispersion on the coated ZIF-67@ pigment carbon black dispersion for 30min, adding 0.5ml of tetrabutyl titanate for reaction for 1h, filtering, washing and drying to obtain TiO2@SiO2@ pigment carbon black/ZIF-67. Finally, annealing the obtained product at 750 ℃ for 1h in argon atmosphere to obtain TiO2@SiO2@ Co-N-C @ pigment carbon black;
the step (5) is as follows: etching of TiO with HF acid solution (20%)2@SiO2@ Co-N doped porous carbon @ pigment carbon black to produce TiO2the/C @ void @ Co-N doped porous carbon C @ pigment carbon black heterostructure.
Example 6
Steps (1) to (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 in 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 at 750 ℃ for 1h in argon atmosphere to obtain MoS2/C@SiO2@ Co-N doped porous carbon @ pigment carbon black;
the step (5) is as follows: etching of C @ SiO with HF acid solution (20%)2@ Co-N doped porous carbon @ pigment carbon black to produce 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 HNO3In 50mL, the mixture is refluxed and kept at 75 ℃ for 6h, then a sample is taken out, the sample is washed to be neutral by deionized water, and the sample is dried to obtain the carbon nano tube containing the oxygen functional group.
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)6Mo7O24·4H2O, AHT) and 210mg Thiourea (CS (NH)2)2TA) into SiO2Coated ZIF-67@ pigment carbon black dispersion. Then sealing the mixed solution into a polytetrafluoroethylene stainless steel autoclave, carrying out hydrothermal treatment at 160 ℃ for 24 hours, and separating precipitatesHeart, 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 (300.0mg) were stirred in a beaker at 40 ℃ for 3h, and then treated in the flask with 20% NaOH in a solution of 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 ultrapure water. The resulting solid was then refluxed in ultrapure water at 100 ℃ for 2 h. The solution was filtered and the filter cake was washed with copious amounts of ultrapure water. Subsequently, the solid was immersed in ultrapure water, tetrahydrofuran and acetone for 24 hours, respectively. Finally, the treated solid was dried under vacuum at 80 ℃ to give pure pale yellow NaOOC COF @ pigment carbon black powder.
Comparative example 1
Preparation of MoS without ZIF-67 coating (first protective layer) of the composite2a/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 pole piece, assembling the positive pole piece into a lithium-sulfur battery, and testing the performance of the lithium-sulfur battery.
Firstly, taking the prepared composite carbon material and sublimed sulfur according to the weight ratio of 25: 75, grinding and mixing, and treating in inert gas at 155 ℃ for 12h to obtain the cathode material. And preparing the obtained positive electrode material G4: SP:: PVDF into slurry according to the mass ratio of 92:2:3:5, wherein the specific process is as follows: firstly, dissolving PVDF (polyvinylidene fluoride) binder in NMP (N-methyl pyrrolidone) as a solvent, grinding and blending the positive electrode material and the conductive agent, adding the ground and blended binder into the slurry, coating the synthesized slurry on a carbon-coated aluminum foil by using a scraper, and drying the carbon-coated aluminum foil for 12 hours at 60 ℃. Finally, the prepared positive electrode material is cut into a rectangle of 45 × 60mm, a 100 μ M lithium foil is cut into a rectangle of 50 × 65mm, PP is selected as a diaphragm, 1M LiTFSI electrolyte is dissolved in DOL/DME (1: 1V/V), and the mass ratio E/S of the electrolyte to active sulfur is 10, so that a single soft package is assembled.
The electrochemical performance test adopts blue test equipment to carry out 0.2C discharge and 0.1C charge at 25 ℃, and the voltage window is 1.7-2.6V.
The results of the tests on the materials prepared in examples 1-9 and comparative example 1 are detailed in table 1.
TABLE 1
It can be seen from table 1 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 that of comparative example 1, which proves that the composite material of the present application indeed functions to inhibit the shuttling of sulfur so as to reduce the loss of sulfur, improve the utilization rate of sulfur, and improve the cycle life.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments 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 invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (11)
1. A composite carbon material for a lithium-sulfur battery is characterized by comprising a carbon substrate core, a first protective layer and a second protective layer;
the first protective layer is coated on the outer surface of the inner core of the carbon substrate, is of a porous structure and comprises metal ions; the second protective layer is located the first protective layer outside, be provided with hollow layer between the second protective layer with the first protective layer.
2. The composite carbon material for lithium sulfur batteries according to claim 1, wherein the carbon matrix inner core has a polar functional group on the surface; preferably, the polar functional group includes at least one of a hydroxyl group and a carboxyl group.
3. The composite carbon material for lithium sulfur batteries 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.
4. The composite carbon material for lithium sulfur batteries according to claim 1, wherein the first protective layer comprises a carbonized transition metal-based metal-organic framework compound or a carbonized metal-covalent-organic framework material.
5. The composite carbon material for a lithium-sulfur battery according to claim 1, wherein the particle diameter of the carbon-based core is 20 to 50nm, the thickness of the first protective layer is 5 to 30nm, the thickness of the hollow layer is 80 to 100nm, and the thickness of the second protective layer is 1 to 25 nm.
6. The composite carbon material for lithium-sulfur batteries according to claim 1, wherein the molar content of metal ions in the first protective layer is 0.02 to 4% by mol based on the number of moles of the core in the carbon matrix.
7. The composite carbon material for lithium sulfur batteries according to claim 1, wherein the second protective layer comprises a carbon-based material, a metal compound, or a combination of both; preferably, the metal compound is MoS2、TiO2、PtO2、Fe2O3、Co9S8、WS2、CeO2、Co3O4、TiN、VOx、MnOx、CeOx、Fe3N、AxN (A is transition metal, X is 1-9) and MexSy(Me is a transition metal, X is 1-9), MxPx(M is transition metal, X is 1-9).
8. The composite carbon material for lithium-sulfur batteries according to claim 7, wherein the molar content of the metal compound in the second protective layer is 0.1 to 5% by mol based on the number of moles of the core in the carbon matrix.
9. A method for producing the composite carbon material for lithium-sulfur batteries according to any one of claims 1 to 8, comprising:
s1, forming the first protective layer on the carbon matrix core;
s2, forming a template layer on the first protective layer;
s3, forming a second protective layer on the surface of the template; and
and S4, etching to remove the template layer.
10. The method of claim 9, further comprising a high temperature treatment step after the step of S3 to carbonize the first protective layer and the second protective layer.
11. A lithium-sulfur battery comprising the composite carbon material for lithium-sulfur batteries according to any one of claims 1 to 8.
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