CN111554888B - Anode material containing rabbit hair hollow carbon fibers for lithium-sulfur battery and preparation method thereof - Google Patents
Anode material containing rabbit hair hollow carbon fibers for lithium-sulfur battery and preparation method thereof Download PDFInfo
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- CN111554888B CN111554888B CN202010272832.4A CN202010272832A CN111554888B CN 111554888 B CN111554888 B CN 111554888B CN 202010272832 A CN202010272832 A CN 202010272832A CN 111554888 B CN111554888 B CN 111554888B
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Abstract
The invention discloses a positive electrode material containing rabbit hair hollow carbon fibers for a lithium-sulfur battery and a preparation method thereof, wherein the positive electrode material is prepared from four components of a sulfur/rabbit hair hollow carbon fiber composite material, a carbon nano tube, Super P and polyvinylidene fluoride; the rabbit hair hollow carbon fiber is prepared by the steps of pretreatment, heat treatment, carbonization, cleaning and drying of rabbit hair, soaking the rabbit hair hollow carbon fiber in a phosphoric acid solution for acidification before preparing a positive electrode material, forming a composite material with molten liquid sulfur at high temperature, and uniformly mixing the composite material with a carbon nano tube, super P and polyvinylidene fluoride; the anode material for the lithium-sulfur battery utilizes rabbit hair with a hollow carbon fiber structure as a sulfur elementary substance storage unit, and achieves the purposes of improving the charge-discharge specific capacity, the thermal stability and the cycle life of the lithium-sulfur battery by compounding with other components; in addition, the preparation method is simple and easy to control, and effectively solves the problem of thermal shrinkage of the rabbit hair in the carbonization process, so that the appearance of the carbon fiber is completely maintained.
Description
Technical Field
The invention relates to the technical field of fiber preparation and electrode materials, in particular to a positive electrode material containing rabbit hair hollow carbon fibers for a lithium-sulfur battery and a preparation method thereof.
Background
Among biomass materials, goat hair is widely distributed around the world as an environmentally friendly, low-cost, easily available, sustainable biomass material. It is composed of abundant crude protein (keratin) and amino acids. The method shows that the goat hair is a promising carbon source, can be used for preparing intrinsic heteroatom-doped porous carbon materials, and can be widely applied to the fields of energy storage, decomposition, adsorption and the like. Juan Ren et al prepared in-situ nitrogen, oxygen and phosphorus doped goat wool hierarchical porous carbon (NOPC) by using phosphoric acid activation and high temperature carbonization. Compared with a representative synthetic route for preparing porous carbon (such as pyrolysis of polymer, CVD, template method), the method is relatively simple, safe, economical and environment-friendly. More importantly, the activated precursor is subjected to heat treatment at 600 ℃, the product yield is high (31.2%), and the method is favorable for large-scale production of carbon materials.
Besides wool, rabbit hair also has the characteristics of wide sources and low cost, however, according to statistics, dozens of tons of rabbit hair waste in China can be directly discarded in a refuse landfill every year. Although rabbit hair is a common rabbit hair, compared with other protein biomass fibers such as wool and human hair, rabbit hair is a biomass raw material with a natural hollow structure and containing nitrogen sulfur phosphorus element, the rabbit hair converted into carbon fiber by adopting the existing technical means can cause severe thermal shrinkage of the fiber and presents a scorched state, and rabbit hair carbon fiber with good fiber appearance preservation cannot be obtained. Therefore, the research on the carbonization of rabbit hair to prepare the carbon fiber with a natural hollow structure is an important research direction for effectively utilizing the natural resources, exerting the potential huge value of wool and rabbit hair and applying the carbon fiber to the actual life of people.
Currently, lithium sulfur batteries are affected by the shuttling effect of polysulfides in their positive electrode materials during charge and discharge cycles, resulting in lower cycle life and coulombic efficiency of the batteries. And a key factor to solve this problem is how to fix polysulfides in the cathode material.
The lithium-sulfur battery has the advantages that the selected sulfur exists in a large amount in the nature, the lithium-sulfur battery is non-toxic and low in cost, lithium metal naturally has the lowest standard potential (-3.04Vvs. SHE), the lowest density (0.53 g.cm < -3 >) and chemical equivalent (0.26 g.A < -1 >. h < -1 >) and the highest theoretical specific capacity (3861mAh < -1 >), and the battery has high theoretical specific capacity (1675mAh < -1 >) and energy density (2600Wh kg < -1 >), so that the lithium-sulfur battery becomes one of the first choice for high-performance battery research. Although the lithium-sulfur battery has a relatively high energy density in theory, the rapid decay of the battery capacity caused by the shuttle effect of the battery in the charging and discharging process restricts the popularization of the lithium-sulfur battery in practical application. By "shuttle effect" is meant that long-chain polysulfides reduced by elemental sulfur during discharge of the battery pass from the positive electrode of the battery, through the battery separator, and to the negative electrode of the battery. In the process, polysulfide is dissolved in an electrolyte, and a series of corresponding reactions occur between a positive electrode and a negative electrode of the lithium-sulfur battery, so that positive and negative active materials are lost, and serious self-discharge of the battery is brought. The reaction that will occur in this process will consume the active sulfur compound and lithium on the negative electrode and it generates Li2S2 and Li2S on the negative electrode covering the surface layer of the negative electrode lithium, causing the lithium negative electrode to be severely polarized. Secondly, the electronic ionic conductivity and the conductivity of the elemental sulfur are very low, so that the electrochemical activity and the utilization rate of the anode material are low. In addition, the great volume change of the cathode material in the charging and discharging process also enables the specific discharge capacity of the lithium-sulfur battery to be rapidly reduced.
In view of the above problems, fibers having specific properties and carbon materials having specific structures have attracted attention. The rabbit hair hollow carbon fiber is simple in preparation process, has a natural hollow structure, can adapt to volume change of a positive electrode and provide a good conductive path, contains natural nitrogen, phosphorus and sulfur elements, can effectively inhibit shuttle effect of polysulfide, and has a great application prospect when being used as a positive electrode material of a lithium-sulfur battery.
Disclosure of Invention
The invention aims to provide rabbit hair hollow carbon fibers for a lithium-sulfur battery positive electrode material.
The invention also aims to provide a positive electrode material for a lithium-sulfur battery, which comprises the rabbit hair hollow carbon fiber.
Another object of the present invention is to provide a method for preparing the above-mentioned positive electrode material for lithium-sulfur batteries.
Therefore, the technical scheme of the invention is as follows:
the rabbit hair hollow carbon fiber is prepared by four steps of pretreatment, heat treatment, carbonization, cleaning and drying of rabbit hair; the method comprises the following steps of pretreatment of rabbit hair: 1) boiling rabbit hair in boiling water for 1-3 h; 2) after the rabbit hair is naturally cooled, washing the rabbit hair with deionized water for 3-5 times to remove impurities in the rabbit hair; 3) placing the cleaned rabbit hair in a 60 ℃ oven, drying for 8-12 h, and drying the rabbit hair; 4) soaking the dried rabbit hair in methyl silicone oil for 3-5 h; 5) and (3) drying the rabbit hair soaked with the methyl silicone oil in a 60 ℃ drying oven for 6-10 h. The pretreatment step can effectively solve the problem of thermal shrinkage of the rabbit hair in the carbonization process, and is particularly suitable for the rabbit hair with the natural hollow structure fiber, so that the appearance of the rabbit hair is kept.
Further, the heat treatment comprises the following specific steps: placing the pretreated rabbit hair in a muffle furnace, uniformly heating to 300-350 ℃ at a heating rate of 0.5-2 ℃/min in an air gas environment, preserving heat for 1-3 h, and cooling to room temperature. The heat treatment step is used for effectively removing grease and other impurities contained in the rabbit hair, and meanwhile, on the basis of soaking of methyl silicone oil in the pretreatment process, the heat resistance of the rabbit hair is further improved, so that the problem of thermal shrinkage of the rabbit hair in the carbonization process is effectively solved, and the intact preservation of the appearance of carbonized fibers is facilitated.
Further, the specific steps of the carbonization of the carbon fiber are as follows: placing the rabbit hair subjected to heat treatment in a tube furnace, uniformly heating to 700-1000 ℃ at a heating rate of 1-3 ℃/min in a nitrogen gas environment, preserving heat for 1-3 h, and cooling to room temperature. The carbon fibrillation step is used for efficiently converting rabbit hair fibers into solid carbon fibers or hollow carbon fibers with high stability and crystallinity.
Further, the specific steps of cleaning and drying are as follows: washing the carbon-fibrillated rabbit hair with deionized water for at least 3 times, and then placing the rabbit hair in a vacuum drying oven at 50-80 ℃ for drying for 3-6 hours. The cleaning and drying step is used for cleaning impurities in the rabbit hair carbon fibers and then drying and dewatering the impurities.
A positive electrode material of a lithium-sulfur battery is prepared from four components, namely a sulfur/rabbit hair hollow carbon fiber composite material, a carbon nano tube, Super P and polyvinylidene fluoride; the sulfur/rabbit hair hollow carbon fiber composite material is formed by compounding rabbit hair hollow carbon fibers and sulfur at a high temperature, wherein the weight ratio of the rabbit hair hollow carbon fibers to the sulfur is (3-4): 1; the weight ratio of the carbon nano tube to the rabbit hair hollow carbon fiber is 1: 1; the weight ratio of the mixture of the sulfur/rabbit hair hollow carbon fiber composite material and the carbon nano tube, Super P and polyvinylidene fluoride is 8:1: 1.
In the positive electrode material, compared with other protein biomass fibers such as wool, human hair and the like, rabbit hair is a biomass raw material with a natural hollow structure and containing nitrogen-sulfur-phosphorus elements, the sulfur storage of the hollow carbon fiber prepared by carbonizing the rabbit hair can enhance the affinity of the hollow carbon fiber with polar polysulfide and a nonpolar carbon skeleton by utilizing the nitrogen, oxygen and phosphorus heteroatoms contained in the rabbit hair carbon fiber, and the surface of the rabbit hair carbon fiber contains a large amount of hydroxyl groups after being acidified, so that the shuttling effect of the polysulfide is effectively inhibited; meanwhile, the rabbit hair carbon fiber has the characteristics of convenient material acquisition and environment-friendly preparation method, and is suitable for industrial production.
A preparation method for preparing the cathode material for the lithium-sulfur battery comprises the following steps:
s1, soaking the rabbit hair hollow carbon fiber in a phosphoric acid solution for acidification;
in this step, the purpose of the acidification treatment is mainly to remove impurities in the rabbit hair hollow carbon fiber and make the surface of the rabbit hair hollow carbon fiber have more micropores and a large number of hydroxyl groups, and the hydroxyl groups on the surface can form chemical bonds with polysulfide during the charge-discharge cycle of the lithium-sulfur battery, so that the shuttle effect of the polysulfide can be greatly inhibited. In addition, the rabbit hair hollow carbon fiber has the characteristics of environmental friendliness, simple process, high production efficiency and easy implementation of industrial production;
s2, uniformly mixing the acidized rabbit hair hollow carbon fiber with sulfur powder, and then placing the mixture in a vacuum drying oven to heat the mixture for 24 hours at the constant temperature of 156 ℃ to obtain the sulfur/rabbit hair hollow carbon fiber composite material;
the step S2 is to flow liquid sulfur into the rabbit hair hollow carbon fiber at a temperature of 156 ℃ to fill the hollow part of the rabbit hair hollow carbon fiber, so as to form a sulfur/rabbit hair hollow carbon fiber composite material;
s3, uniformly mixing the sulfur/rabbit hair hollow carbon fiber composite material, the carbon nano tube, the super P and the polyvinylidene fluoride to obtain the positive electrode material for the lithium-sulfur battery.
The step aims to cooperatively construct short or long-range electron and ion channels of different levels by applying the ultra-long high conductivity characteristic of the carbon nanotube mixed with the sulfur/rabbit hair hollow carbon fiber composite material, so that the conductivity of the anode of the lithium-sulfur battery is greatly improved; the conductive agent Super P is added to enhance the conductive performance of the positive electrode material; the polyvinylidene fluoride adhesive is added to fully bond the components into a whole;
further, in step S1, the rabbit hair hollow carbon fiber is soaked in 40-60 wt.% phosphoric acid solution at 60 ℃ for acidification treatment for 8-12 h.
In summary, in the positive electrode material for the lithium-sulfur battery, the rabbit hair hollow carbon fiber contains nitrogen, oxygen and phosphorus heteroatoms, which are beneficial to enhancing the affinity of polar polysulfide and a nonpolar carbon skeleton, so that the shuttle effect of polysulfide is effectively inhibited, more sulfur storage space and convenient conductive channels are provided after acidification, the hydroxyl contained on the surface of the rabbit hair hollow carbon fiber after acidification further greatly inhibits the shuttle effect of polysulfide, and the hollow structure of the rabbit hair hollow carbon fiber can adapt to large volume change of the battery in the circulation process; the carbon nano tube uses the ultra-long high conductivity characteristic to cooperatively construct short or long-range electron and ion channels of different levels; therefore, the lithium-sulfur battery has more excellent electrochemical performance, the method can improve the charge-discharge specific capacity, the thermal stability and the cycle life of the lithium-sulfur battery, and meanwhile, a new way is provided for the development of the high-performance lithium-sulfur battery by taking the rabbit hair hollow carbon fiber as a raw material and compounding the raw material with sulfur.
Compared with the prior art, the cathode material for the lithium-sulfur battery containing carbon of the rabbit hair hollow carbon fiber adopts the rabbit hair with a hollow carbon fiber structure as a sulfur simple substance storage unit, so that the shuttle effect of polysulfide is inhibited by utilizing the affinity of nitrogen, oxygen and phosphorus heteroatoms naturally contained in the carbon fiber to enhance polar polysulfide and a nonpolar carbon skeleton, and the purposes of improving the charge-discharge specific capacity, the thermal stability and the cycle life of the lithium-sulfur battery are realized by matching with other components; specifically, the lithium-sulfur battery assembled by the positive electrode material has good thermal stability, the specific discharge capacity of the first circle can reach 837mAh/g, the battery can still maintain about 600mAh/g after being cycled for 300 times, and the cycle life is long; in addition, the preparation method of the cathode material for the lithium-sulfur battery is simple, the preparation conditions are mild and easy to control, and meanwhile, the preparation method of the rabbit hair hollow carbon fiber can effectively solve the problem of thermal shrinkage of rabbit hair in the carbonization process, and is beneficial to retention of the morphology of the rabbit hair so as to obtain the nitrogen-phosphorus-sulfur doped hollow carbon fiber.
Drawings
Fig. 1 is a scanning electron microscope picture of a nitrogen-phosphorus-sulfur three-element doped hollow carbon fiber prepared in example 1 of the present invention;
FIG. 2 is an enlarged view of a portion of FIG. 1;
fig. 3 is a scanning electron microscope picture of the nitrogen-phosphorus-sulfur three-element doped hollow carbon fiber prepared in example 2 of the present invention;
FIG. 4 is an EDAX spectrum of a NPS triple-doped hollow carbon fiber prepared in example 2 of the present invention;
FIG. 5 is a scanning electron microscope image of the NPS doped hollow carbon fiber prepared in example 3 of the present invention;
FIG. 6 is a scanning electron microscope image of the NPS doped hollow carbon fiber prepared in example 4 of the present invention;
FIG. 7 is a scanning electron microscope image of a NPS triple-doped hollow carbon fiber prepared in comparative example 1 of the present invention;
FIG. 8 is a scanning electron microscope image of a NPS triple-doped hollow carbon fiber prepared in comparative example 2 of the present invention;
fig. 9 is a test chart of discharge cycle performance at a rate of 0.2C, 0.5C, 1C, 2C of a lithium sulfur battery assembled using the cathode materials prepared in example 5 of the present invention and comparative example 3, respectively;
fig. 10 is a discharge cycle test chart of 300 discharge cycles of a lithium sulfur battery assembled by using the cathode material prepared in example 5 of the present invention at a rate of 0.5C;
fig. 11 is a discharge cycle performance test chart of a lithium sulfur battery assembled by using the cathode material prepared in comparative example 4 of the present invention.
Detailed Description
The invention will be further described with reference to the following figures and specific examples, which are not intended to limit the invention in any way.
Example 1
A method for preparing nitrogen-phosphorus-sulfur three-element doped hollow carbon fiber by taking rabbit hair as a precursor is realized by the following steps in sequence:
pretreatment: boiling rabbit hair in boiling water for 2h, naturally cooling, and washing the rabbit hair with deionized water for 4 times to remove impurities in the rabbit hair; then, putting the cleaned rabbit hair into a 60 ℃ oven, and drying for 8 hours to dry the rabbit hair; soaking the dried rabbit hair in methyl silicone oil for 3h, taking out, and drying in a vacuum drying oven at 60 ℃ for 6 h;
and (3) heat treatment: putting the pretreated dry rabbit hair into a muffle furnace, uniformly heating to 300 ℃ at the speed of 1 ℃/min in the air gas environment, preserving heat for 1h, and naturally cooling to room temperature;
carbonizing treatment: placing the rabbit hair subjected to heat treatment in a tubular furnace, uniformly heating to 800 ℃ at the speed of 3 ℃/min in a nitrogen environment, preserving heat for 1h, and naturally cooling to room temperature;
cleaning and drying: and (3) washing the carbonized product with deionized water for at least 3 times, then placing the product into a drying oven at 50 ℃, and drying the product for 6 hours to obtain the nitrogen-phosphorus-sulfur triple-element doped hollow carbon fiber.
Fig. 1 shows a scanning electron microscope image of the nitrogen-phosphorus-sulfur triple-element doped hollow carbon fiber prepared by the preparation method of this example 1. Fig. 2 is a partially enlarged view of fig. 1. As is apparent from fig. 1 and 2, the carbon fiber prepared in example 1 has a hollow tubular structure and a complete structural morphology, and it can be seen that the preparation method can effectively solve the problem of thermal shrinkage of rabbit hair during carbonization, and prepare the complete rabbit hair carbon fiber having a hollow tubular structure.
Example 2
A method for preparing nitrogen-phosphorus-sulfur three-element doped hollow carbon fiber by taking rabbit hair as a precursor is realized by the following steps in sequence:
pretreatment: boiling rabbit hair in boiling water for 2h, naturally cooling, and washing the rabbit hair with deionized water for 3 times to remove impurities in the rabbit hair; then, putting the cleaned rabbit hair into a 60 ℃ oven, and drying for 8 hours to dry the rabbit hair; soaking the dried rabbit hair in methyl silicone oil for 3h, taking out, and drying in a vacuum drying oven at 60 ℃ for 6 h;
and (3) heat treatment: putting the pretreated dry rabbit hair into a muffle furnace, uniformly heating to 300 ℃ at the speed of 1.5 ℃/min in the air gas environment, preserving the heat for 1h, and naturally cooling to room temperature;
carbonizing treatment: placing the rabbit hair subjected to heat treatment in a tubular furnace, uniformly heating to 900 ℃ at the speed of 2 ℃/min in a nitrogen environment, preserving heat for 1h, and naturally cooling to room temperature;
cleaning and drying: and (3) washing the carbonized product with deionized water for at least 3 times, then placing the product into a drying oven at 50 ℃, and drying the product for 6 hours to obtain the nitrogen-phosphorus-sulfur triple-element doped hollow carbon fiber.
Fig. 3 is a scanning electron microscope image of the nitrogen-phosphorus-sulfur triple-element doped hollow carbon fiber prepared by the preparation method of this example 2. As is apparent from fig. 3, the carbon fiber prepared in example 2 can also be observed to have a hollow tubular structure and a complete structural morphology, and it can be seen that the method can effectively solve the problem of thermal shrinkage of rabbit hair during carbonization, and prepare the complete rabbit hair carbon fiber having a hollow tubular structure. As shown in fig. 4, an EDAX map of the nitrogen-phosphorus-sulfur triple-doped hollow carbon fiber shows that three elements, i.e., nitrogen, phosphorus and sulfur, are uniformly distributed on the hollow carbon fiber according to the EDAX map.
Example 3
A method for preparing nitrogen-phosphorus-sulfur three-element doped hollow carbon fiber by taking rabbit hair as a precursor is realized by the following steps in sequence:
pretreatment: boiling rabbit hair in boiling water for 1h, naturally cooling, and washing the rabbit hair with deionized water for 4 times to remove impurities in the rabbit hair; then, putting the cleaned rabbit hair into a 60 ℃ oven, and drying for 10 hours to dry the rabbit hair; soaking the dried rabbit hair in methyl silicone oil for 4h, taking out, and drying in a vacuum drying oven at 60 ℃ for 8 h;
and (3) heat treatment: putting the pretreated dry rabbit hair into a muffle furnace, uniformly heating to 330 ℃ at the speed of 0.5 ℃/min in the air gas environment, preserving heat for 2h, and naturally cooling to room temperature;
carbonizing treatment: placing the rabbit hair subjected to heat treatment in a tubular furnace, uniformly heating to 700 ℃ at a speed of 1 ℃/min in a nitrogen environment, preserving heat for 3h, and naturally cooling to room temperature;
cleaning and drying: and (3) washing the carbonized product with deionized water for at least 3 times, then placing the product into an oven at 70 ℃, and drying the product for 6 hours to obtain the nitrogen-phosphorus-sulfur triple-element doped hollow carbon fiber.
Fig. 5 is a scanning electron microscope image of the nitrogen-phosphorus-sulfur triple-element doped hollow carbon fiber prepared by the preparation method of this embodiment 3. As is apparent from fig. 5, the carbon fiber prepared in example 3 also has a hollow tubular structure and a complete structural morphology, and thus the method can effectively solve the problem of thermal shrinkage of rabbit hair during carbonization, and prepare the complete rabbit hair carbon fiber having a hollow tubular structure.
Example 4
A method for preparing nitrogen-phosphorus-sulfur three-element doped hollow carbon fiber by taking rabbit hair as a precursor is realized by the following steps in sequence: :
pretreatment: boiling rabbit hair in boiling water for 3h, naturally cooling, and washing the rabbit hair with deionized water for 5 times to remove impurities in the rabbit hair; then, putting the cleaned rabbit hair into a 60 ℃ oven, and drying for 12 hours to dry the rabbit hair; soaking the dried rabbit hair in methyl silicone oil for 5h, taking out, and drying in a vacuum drying oven at 60 ℃ for 10 h;
and (3) heat treatment: putting the pretreated dry rabbit hair into a muffle furnace, uniformly heating to 350 ℃ at the speed of 2 ℃/min in an air gas environment, preserving heat for 3h, and naturally cooling to room temperature;
carbonizing treatment: placing the rabbit hair subjected to heat treatment in a tubular furnace, uniformly heating to 1000 ℃ at the speed of 3 ℃/min in a nitrogen environment, preserving heat for 2h, and naturally cooling to room temperature;
cleaning and drying: and (3) washing the carbonized product with deionized water for at least 3 times, then placing the product into an oven at 80 ℃, and drying for 5 hours to obtain the nitrogen-phosphorus-sulfur triple-element doped hollow carbon fiber.
Fig. 6 is a scanning electron microscope image of the nitrogen-phosphorus-sulfur triple-element doped hollow carbon fiber prepared by the preparation method of this embodiment 4. As is apparent from fig. 6, the carbon fiber prepared in example 4 also has a hollow tubular structure and a complete structural morphology, and thus the method can effectively solve the problem of thermal shrinkage of rabbit hair during carbonization, and prepare the complete rabbit hair carbon fiber having a hollow tubular structure.
Comparative example 1
A method for preparing nitrogen-phosphorus-sulfur three-element doped hollow carbon fiber by taking rabbit hair as a precursor is realized by the following steps in sequence: :
pretreatment: boiling rabbit hair in boiling water for 2h, naturally cooling, and washing the rabbit hair with deionized water for 4 times to remove impurities in the rabbit hair; then, putting the cleaned rabbit hair into a 60 ℃ oven, and drying for 8 hours to dry the rabbit hair;
and (3) heat treatment: putting the pretreated dry rabbit hair into a muffle furnace, uniformly heating to 300 ℃ at the speed of 1 ℃/min in the air gas environment, preserving heat for 1h, and naturally cooling to room temperature;
carbonizing treatment: placing the rabbit hair subjected to heat treatment in a tubular furnace, uniformly heating to 800 ℃ at the speed of 3 ℃/min in a nitrogen environment, preserving heat for 1h, and naturally cooling to room temperature;
cleaning and drying: and (3) washing the carbonized product with deionized water for at least 3 times, then placing the product into a drying oven at 50 ℃, and drying the product for 6 hours to obtain the nitrogen-phosphorus-sulfur triple-element doped hollow carbon fiber.
Compared with the preparation method of example 1, the preparation method of comparative example 1 omits the step of immersing methyl silicone oil in the pretreatment step, and it is obvious from fig. 7 that the morphology of the carbon fiber prepared in comparative example 1 is poorly preserved, and the prepared carbon fiber is fragmented.
Comparative example 2
A method for preparing nitrogen-phosphorus-sulfur three-element doped hollow carbon fiber by taking rabbit hair as a precursor is realized by the following steps in sequence: :
pretreatment: boiling rabbit hair in boiling water for 2h, naturally cooling, and washing the rabbit hair with deionized water for 4 times to remove impurities in the rabbit hair; then, putting the cleaned rabbit hair into a 60 ℃ oven, and drying for 8 hours to dry the rabbit hair; soaking the dried rabbit hair in methyl silicone oil for 3h, taking out, and drying in a vacuum drying oven at 60 ℃ for 6 h;
carbonizing treatment: placing the rabbit hair subjected to heat treatment in a tube furnace, uniformly heating to 800 ℃ at the speed of 3 ℃/min in a nitrogen environment, preserving heat for 1h, and naturally cooling to room temperature.
Cleaning and drying: and (3) washing the carbonized product with deionized water for at least 3 times, then placing the product into a drying oven at 50 ℃, and drying the product for 6 hours to obtain the nitrogen-phosphorus-sulfur triple-element doped hollow carbon fiber.
The production method of comparative example 2 omits the heat treatment step before the carbonization treatment, resulting in that the product after the carbonization treatment is severely thermally shrunk into a scorched state and has an appearance state of a coke state as shown in FIG. 8, as compared with the production method of example 1.
In the following examples and comparative examples, each of the components was purchased from commercially available materials and ground to a nano-scale material before use, except that the rabbit hair fibers were self-prepared materials and ground to a micro-scale material before use.
Example 5
A positive electrode material for a lithium-sulfur battery is prepared by the following steps:
s1, soaking the rabbit hair hollow carbon fiber prepared in the example 1 in a 50 wt.% phosphoric acid solution at 60 ℃ for acidification treatment for 10 h;
s2, uniformly mixing the acidized rabbit hair hollow carbon fiber with sulfur powder, and then placing the mixture in a vacuum drying oven to heat the mixture for 24 hours at the constant temperature of 156 ℃ to obtain the sulfur/rabbit hair hollow carbon fiber composite material; wherein the weight ratio of the rabbit hair hollow carbon fiber to sulfur before acidification is 1: 3;
s3, uniformly mixing the sulfur/rabbit hair hollow carbon fiber/carbon nanotube composite material, super P and polyvinylidene fluoride to obtain a positive electrode material A for the lithium-sulfur battery; wherein the weight ratio of the carbon nano tubes to the rabbit hair hollow carbon fibers before acidification is 1:1, and the weight ratio of the mixture of the carbon nano tubes and the sulfur/rabbit hair hollow carbon fiber composite material, the super P and the polyvinylidene fluoride is 8:1: 1.
Example 6
A positive electrode material for a lithium-sulfur battery is prepared by the following steps:
s1, soaking the rabbit hair hollow carbon fiber prepared in the example 2 in 60 wt.% phosphoric acid solution at 60 ℃ for acidification treatment for 8 h;
s2, uniformly mixing the acidized rabbit hair hollow carbon fiber with sulfur powder, and then placing the mixture in a vacuum drying oven to heat the mixture for 24 hours at the constant temperature of 156 ℃ to obtain the sulfur/rabbit hair hollow carbon fiber composite material; wherein the weight ratio of the rabbit hair hollow carbon fiber to sulfur before acidification is 1: 3.5;
s3, uniformly mixing the sulfur/rabbit hair hollow carbon fiber/carbon nanotube composite material, super P and polyvinylidene fluoride to obtain a positive electrode material B for the lithium-sulfur battery; wherein the weight ratio of the carbon nano tubes to the rabbit hair hollow carbon fibers before acidification is 1:1, and the weight ratio of the mixture of the carbon nano tubes and the sulfur/rabbit hair hollow carbon fiber composite material, the super P and the polyvinylidene fluoride is 8:1: 1.
Example 7
A positive electrode material for a lithium-sulfur battery is prepared by the following steps:
s1, soaking the rabbit hair hollow carbon fiber prepared in the example 3 in 40 wt.% phosphoric acid solution at 60 ℃ for acidification treatment for 12 h;
s2, uniformly mixing the acidized rabbit hair hollow carbon fiber with sulfur powder, and then placing the mixture in a vacuum drying oven to heat the mixture for 24 hours at the constant temperature of 156 ℃ to obtain the sulfur/rabbit hair hollow carbon fiber composite material; wherein the weight ratio of the rabbit hair hollow carbon fiber to sulfur before acidification is 1: 4;
s3, uniformly mixing the sulfur/rabbit hair hollow carbon fiber/carbon nanotube composite material, super P and polyvinylidene fluoride to obtain a positive electrode material C for the lithium-sulfur battery; wherein the weight ratio of the carbon nano tubes to the rabbit hair hollow carbon fibers before acidification is 1:1, and the weight ratio of the mixture of the carbon nano tubes and the sulfur/rabbit hair hollow carbon fiber composite material, the super P and the polyvinylidene fluoride is 8:1: 1.
Comparative example 3
A positive electrode material for a lithium-sulfur battery is prepared by the following steps:
s1, soaking the carbon nano tube in 60 wt.% phosphoric acid solution at 60 ℃ for acidification treatment for 10 h;
s2, uniformly mixing the carbon nano tube subjected to acidification treatment and sulfur powder according to the weight ratio of 1:3, and then placing the mixture in a vacuum drying oven to heat for 24 hours at the constant temperature of 156 ℃ to obtain a sulfur/carbon nano tube composite material;
s3, uniformly mixing the sulfur/carbon nanotube composite material, the super P and the polyvinylidene fluoride in a weight ratio of 8:1:1 to obtain the positive electrode material D for the lithium-sulfur battery.
Comparative example 4
A positive electrode material for a lithium-sulfur battery is prepared by the following steps:
s1, soaking the rabbit hair hollow carbon fiber prepared in the example 1 in a 50 wt.% phosphoric acid solution at 60 ℃ for acidification treatment for 12 h;
s2, uniformly mixing the acidized rabbit hair hollow carbon fiber with sulfur powder, and then placing the mixture in a vacuum drying oven to heat the mixture for 24 hours at the constant temperature of 156 ℃ to obtain the sulfur/rabbit hair hollow carbon fiber composite material; wherein the weight ratio of the rabbit hair hollow carbon fiber to sulfur before acidification is 1: 5;
s3, uniformly mixing the sulfur/rabbit hair hollow carbon fiber/carbon nanotube composite material, super P and polyvinylidene fluoride to obtain a positive electrode material E for the lithium-sulfur battery; wherein the weight ratio of the carbon nano tubes to the rabbit hair hollow carbon fibers before acidification is 1:1, and the weight ratio of the mixture of the carbon nano tubes and the sulfur/rabbit hair hollow carbon fiber composite material, the super P and the polyvinylidene fluoride is 8:1: 1.
Comparative example 5
A positive electrode material for a lithium-sulfur battery is prepared by the following steps:
s1, soaking the rabbit hair hollow carbon fiber prepared in the example 1 in a 50 wt.% phosphoric acid solution at 60 ℃ for acidification treatment for 12 h;
s2, uniformly mixing the acidized rabbit hair hollow carbon fiber with sulfur powder, and then placing the mixture in a vacuum drying oven to heat the mixture for 24 hours at the constant temperature of 156 ℃ to obtain the sulfur/rabbit hair hollow carbon fiber composite material; wherein the weight ratio of the rabbit hair hollow carbon fiber to sulfur before acidification is 1: 2;
s3, uniformly mixing the sulfur/rabbit hair hollow carbon fiber/carbon nanotube composite material, super P and polyvinylidene fluoride to obtain a positive electrode material F for the lithium-sulfur battery; wherein the weight ratio of the carbon nano tubes to the rabbit hair hollow carbon fibers before acidification is 1:1, and the weight ratio of the mixture of the carbon nano tubes and the sulfur/rabbit hair hollow carbon fiber composite material, the super P and the polyvinylidene fluoride is 8:1: 1.
And (3) performance testing:
the lithium-sulfur battery positive electrode materials prepared in examples 5 to 7 and comparative examples 3 to 5 were assembled into batteries, and the batteries were charged and discharged at a rate of 0.2 to 2C to test the discharge cycle performance. The lithium-sulfur battery assembly method comprises the following steps: respectively dispersing positive pole materials A to F of the lithium-sulfur battery in NMP (N-methyl-2-pyrrolidone) to prepare slurry, sequentially coating the slurry on six aluminum foils, naturally drying the six aluminum foils for 12 hours at room temperature, and then placing the six aluminum foils in a vacuum drying oven at 45 ℃ for 24 hours to prepare positive pole pieces A to F; six lithium sheets are taken as negative electrode sheets, 1M Li TFSI is dissolved in a solvent with the composition of DOL/DME (1/1) (v/v) to serve as an electrolyte, and a celgard 2400 diaphragm is arranged between each group of negative electrode sheets and each group of positive electrode sheets, so that the lithium-sulfur batteries A to F are prepared.
As shown in fig. 1, I is a discharge cycle performance test chart of the lithium-sulfur battery made of the cathode material prepared in example 5. As can be seen from fig. 9, the discharging specific capacities of the lithium-sulfur battery are relatively stable at the multiplying powers of 0.2C, 0.5C, 1C and 2C, which indicates that the stability of the battery is good; and as can be seen from fig. 9, the specific capacity of the battery is always maintained at a higher level, indicating that the cycle performance of the battery is good. The performance is shown due to the fact that the hollow structure of the rabbit hair hollow carbon fiber can effectively relieve the volume expansion of sulfur simple substance in the reaction process, and the nitrogen, oxygen and phosphorus heteroatoms contained in the rabbit hair hollow carbon fiber are beneficial to enhancing the affinity of polar polysulfide and a nonpolar carbon skeleton, so that the shuttle effect of polysulfide is effectively inhibited, and the stability and the specific discharge capacity of the battery are obviously increased.
Fig. 10 is a test chart of 300 discharge cycles of the lithium-sulfur battery made of the positive electrode material prepared in example 5 at a rate of 0.5C. As shown in fig. 10, the specific discharge capacity of the first loop of the battery can reach 837.4mAh/g, and can still be maintained at 600mAh/g after 300 cycles, which indicates that the lithium-sulfur battery has both good cycle stability and good cycle life.
The lithium sulfur batteries prepared from the cathode materials of examples 6 and 7 also showed good cycle performance, stability and cycle life in the discharge cycle performance test as the lithium sulfur battery prepared from the cathode material of example 5.
As shown in fig. 9, II is a discharge cycle performance test chart of the lithium-sulfur battery made of the cathode material prepared in comparative example 3. As can be seen from fig. 9, although the specific discharge capacity of the lithium-sulfur battery is relatively stable at the multiplying power of 0.2C, 0.5C, 1C, and 2C, the specific discharge capacity of the lithium-sulfur battery is lower than that of the lithium-sulfur battery prepared by using the positive electrode materials of examples 5 to 7, which is mainly caused by the shuttling effect of polysulfides, in the positive electrode materials of examples 5 to 7, the inclusion of the hetero atoms of nitrogen, oxygen, and phosphorus in the rabbit hair hollow carbon fibers is beneficial to enhancing the affinity of polar polysulfides with a non-polar carbon skeleton, thereby effectively inhibiting the shuttling effect of polysulfides.
Fig. 11 is a graph showing the discharge cycle performance test of the lithium-sulfur battery made of the cathode material prepared in comparative example 4. As can be seen from fig. 11, when the lithium-sulfur battery is charged and discharged at a rate of 0.5C, the specific discharge capacity is low, and after 10 cycles, the specific discharge capacity is greatly reduced, which indicates that the battery stability is poor, because the mixing ratio of elemental sulfur and rabbit hair carbon fibers is too large, the elemental sulfur cannot be sufficiently compounded with the carbon fibers.
The lithium sulfur battery prepared from the cathode material of comparative example 5 was also the same as the lithium sulfur battery prepared from the cathode material of comparative example 4 in the discharge cycle performance test, and the battery stability and cycle life were poor.
Claims (7)
1. The rabbit hair hollow carbon fiber for the lithium-sulfur battery positive electrode material is characterized in that the rabbit hair hollow carbon fiber is prepared by four steps of pretreatment, heat treatment, carbonization and cleaning and drying of rabbit hair; the method comprises the following steps of pretreatment of rabbit hair: 1) boiling rabbit hair in boiling water for 1-3 h; 2) after the rabbit hair is naturally cooled, washing the rabbit hair with deionized water for 3-5 times to remove impurities in the rabbit hair; 3) placing the cleaned rabbit hair in a 60 ℃ oven, drying for 8-12 h, and drying the rabbit hair; 4) soaking the dried rabbit hair in methyl silicone oil for 3-5 h; 5) and (3) drying the rabbit hair soaked with the methyl silicone oil in a 60 ℃ drying oven for 6-10 h.
2. The rabbit hair hollow carbon fiber for the positive electrode material of the lithium-sulfur battery as claimed in claim 1, wherein the heat treatment comprises the following specific steps: placing the pretreated rabbit hair in a muffle furnace, uniformly heating to 300-350 ℃ at a heating rate of 0.5-2 ℃/min in an air gas environment, preserving heat for 1-3 h, and cooling to room temperature.
3. The rabbit hair hollow carbon fiber for the positive electrode material of the lithium-sulfur battery as claimed in claim 2, wherein the step of carbonizing the carbon fiber is as follows: placing the rabbit hair subjected to heat treatment in a tube furnace, uniformly heating to 700-1000 ℃ at a heating rate of 1-3 ℃/min in a nitrogen gas environment, preserving heat for 1-3 h, and cooling to room temperature.
4. The rabbit hair hollow carbon fiber for the positive electrode material of the lithium-sulfur battery as claimed in claim 3, wherein the specific steps of washing and drying are as follows: washing the carbon-fibrillated rabbit hair with deionized water for at least 3 times, and then placing the rabbit hair in a vacuum drying oven at 50-80 ℃ for drying for 3-6 hours.
5. The positive electrode material for the lithium-sulfur battery is prepared from the rabbit hair hollow carbon fiber as defined in any one of claims 1 to 4, and is characterized by being prepared from four components of a sulfur/rabbit hair hollow carbon fiber composite material, carbon nanotubes, Super P and polyvinylidene fluoride; the sulfur/rabbit hair hollow carbon fiber composite material is formed by compounding rabbit hair hollow carbon fibers and sulfur at a high temperature, wherein the weight ratio of the rabbit hair hollow carbon fibers to the sulfur is (3-4): 1; the weight ratio of the carbon nano tube to the rabbit hair hollow carbon fiber is 1: 1; the weight ratio of the mixture of the sulfur/rabbit hair hollow carbon fiber composite material and the carbon nano tube, Super P and polyvinylidene fluoride is 8:1: 1.
6. A method for preparing a positive electrode material for a lithium-sulfur battery according to claim 5, comprising the steps of:
s1, soaking the rabbit hair hollow carbon fiber in a phosphoric acid solution for acidification;
s2, uniformly mixing the acidized rabbit hair hollow carbon fiber with sulfur powder, and then placing the mixture in a vacuum drying oven to heat the mixture for 24 hours at the constant temperature of 156 ℃ to obtain the sulfur/rabbit hair hollow carbon fiber composite material;
s3, uniformly mixing the sulfur/rabbit hair hollow carbon fiber composite material, the carbon nano tube, the super P and the polyvinylidene fluoride to obtain the positive electrode material for the lithium-sulfur battery.
7. The method of claim 6, wherein in step S1, the rabbit hair hollow carbon fiber is soaked in 40-60 wt.% phosphoric acid solution at 60 ℃ and then acidified for 8-12 h.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN106006638A (en) * | 2016-05-25 | 2016-10-12 | 绍兴文理学院 | Preparation method of high-penetration microporous granular active carbon |
| CN106450191A (en) * | 2016-10-11 | 2017-02-22 | 天津工业大学 | Positive electrode material of lithium-sulfur battery |
| CN107978741A (en) * | 2017-11-17 | 2018-05-01 | 中南大学 | A kind of preparation method of lithium-sulfur cell anode composite material |
| CN109860571A (en) * | 2019-02-28 | 2019-06-07 | 蜂巢能源科技有限公司 | Lithium sulfur battery anode material and its preparation method and application |
| CN109913980A (en) * | 2019-02-25 | 2019-06-21 | 南开大学 | A kind of Heteroatom doping flexibility carbon fiber and its preparation method and application |
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| FR3071361B1 (en) * | 2017-09-15 | 2019-09-13 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | PROCESS FOR PRODUCING LITHIUM-SULFUR ACCUMULATOR ELECTRODE USING LI2S AS ACTIVE MATERIAL |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130056731A (en) * | 2011-11-22 | 2013-05-30 | 현대자동차주식회사 | Metal-sulfur electrode for litium-sulfur battery and its preparing mathod |
| CN106006638A (en) * | 2016-05-25 | 2016-10-12 | 绍兴文理学院 | Preparation method of high-penetration microporous granular active carbon |
| CN106450191A (en) * | 2016-10-11 | 2017-02-22 | 天津工业大学 | Positive electrode material of lithium-sulfur battery |
| CN107978741A (en) * | 2017-11-17 | 2018-05-01 | 中南大学 | A kind of preparation method of lithium-sulfur cell anode composite material |
| CN109913980A (en) * | 2019-02-25 | 2019-06-21 | 南开大学 | A kind of Heteroatom doping flexibility carbon fiber and its preparation method and application |
| CN109860571A (en) * | 2019-02-28 | 2019-06-07 | 蜂巢能源科技有限公司 | Lithium sulfur battery anode material and its preparation method and application |
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