CN110729438B - Heteroatom-doped porous graphene-modified carbon fiber paper and preparation method and application thereof - Google Patents

Heteroatom-doped porous graphene-modified carbon fiber paper and preparation method and application thereof Download PDF

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CN110729438B
CN110729438B CN201810785068.3A CN201810785068A CN110729438B CN 110729438 B CN110729438 B CN 110729438B CN 201810785068 A CN201810785068 A CN 201810785068A CN 110729438 B CN110729438 B CN 110729438B
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carbon fiber
fiber paper
doped porous
graphite oxide
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付永胜
陈鹏
汪信
朱俊武
吴震
陈佳琪
周焱
刘青
孙蕴桦
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Nanjing University of Science and Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/44—Fibrous material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a preparation method of heteroatom-doped porous graphene modified carbon fiber paper as a lithium-sulfur battery interlayer. The heteroatom-doped porous graphene-modified carbon fiber paper with the self-supporting characteristic is prepared by a simple dipping and roasting method. The carbon fiber paper can be used as a spacer material of a lithium-sulfur battery, the shuttle effect of polysulfide can be inhibited through the effects of physical constraint and chemical adsorption, the doping of hetero atoms has a certain catalytic effect on the conversion reaction from polysulfide to lithium sulfide, and the conversion from polysulfide to lithium sulfide can be promoted, so that the reaction kinetics of the lithium-sulfur battery is improved, and the electrochemical performance of the lithium-sulfur battery is further improved.

Description

Heteroatom-doped porous graphene-modified carbon fiber paper and preparation method and application thereof
Technical Field
The invention relates to heteroatom-doped porous graphene modified carbon fiber paper and a preparation method and application thereof, and belongs to the field of chemical power sources.
Background
With the rapid development of the world economy, the non-renewable energy sources are gradually exhausted and the problem of environmental pollution seriously threatens the survival and development of human beings. Therefore, the research and development of new energy and environment-friendly functional materials have important significance. Among the new battery systems, lithium-sulfur batteries are considered to be the utmost due to their advantages such as high theoretical energy densityThe potential next generation high energy battery system becomes a research hotspot all over the world. Although lithium-sulfur batteries have the great advantages of high energy density, some key problems still exist to restrict the marketability of the batteries. Polysulfide generated by elemental sulfur in the discharging process is easily dissolved in electrolyte, is subjected to migration and diffusion, and shuttles back and forth between the anode and the cathode, so that the utilization rate of the anode material of the battery is reduced, the capacity attenuation is fast, and the shuttle effect is realized. The key point of improving the cycling stability of the lithium-sulfur battery by inhibiting the shuttle effect is that the shuttle effect is reduced. 2012. The Manthiram topic group first proposed the concept of "barriers" in the year. The interlayer is positioned between the positive electrode and the diaphragm, slows down the diffusion of lithium polysulfide, reuses the captured sulfur-containing phase, prevents the loss of active substance sulfur, improves the long cycle life of the lithium-sulfur battery, and improves the utilization rate of the active substance sulfur. The Manthiram group reported that multi-walled carbon nanotube paper (MWCNT) was used as a lithium sulfur battery separator to obtain self-supporting MWCNT by simple dispersion and vacuum filtration. The flexible carbon interlayer has good conductivity, can reduce interface impedance, provides an electron transmission channel and plays a role of a secondary current collector. (Accounts of Chemical Research, 2012, 46 (5): 1125-1134.). Singhal adopts electrostatic spinning technology to obtain PAN nano-fiber paper, and then the PAN nano-fiber paper is carbonized and subjected to CO2And activating to obtain the carbon nanofiber interlayer with rich pore structure and the PAN-Nafion nanofiber interlayer which are applied to the lithium-sulfur battery, wherein the carbon fiber interlayer can reduce electrochemical impedance and can fix dissolved lithium polysulfide. Through the optimized design of the interlayer thickness and the pore structure, the first discharge capacity of the battery is up to 1549 mAh/g (Journal of Materials Chemistry A, 2015, 3 (8): 4530-4538).
In order to further inhibit polysulfide diffusion, the barrier is far from sufficient by using a physical method, and researchers use modification on the surface of the barrier, such as introducing functional groups on the surface of the barrier to increase the adsorption capacity for polysulfide ions. Vizintin et al chemically prepare rGO interlayers with different fluorine-containing functional groups, and the interlayer material has strong hydrophobicity, inhibits polysulfide from diffusing to a lithium cathode, and improves the cycling stability of the battery (ChemSusChem, 2014, 7 (6): 1655-1661). However, the preparation method is complex and high in cost, so that a large-scale, low-cost and simple synthesis method for preparing the high-performance lithium-sulfur battery separator material is urgently needed.
Disclosure of Invention
The invention aims to provide heteroatom-doped porous graphene modified carbon fiber paper, a preparation method and application thereof as a lithium-sulfur battery interlayer.
The technical solution for realizing the purpose of the invention is as follows: the self-supporting heteroatom-doped porous graphene modified carbon fiber paper takes a 3D network-shaped structure formed by mutually intertwining hollow carbon tubes with the diameter of 1-10 mu m as a support, and the surface of the structure is loaded with heteroatom-doped porous graphene.
Furthermore, the doping amount of the heteroatoms in the heteroatom-doped porous graphene is 1% -10%.
Furthermore, the load capacity of the heteroatom-doped porous graphene is 10% -30%.
Further, the heteroatom is one or more of N, P, S, B, F.
The preparation method of the heteroatom-doped porous graphene modified carbon fiber paper comprises the following steps:
dissolving an organic matter containing heteroatoms in a solvent, dropwise adding the organic matter containing heteroatoms into porous graphite oxide, wherein the mass ratio of the organic matter containing heteroatoms to the porous graphite oxide is 1~5, and heating in a water bath for reacting for a certain time to form a stable dispersion liquid;
secondly, ultrasonically cleaning natural cellulose by deionized water and ethanol, drying, soaking in the dispersion liquid prepared in the first step for 3-48 h, taking out, drying, and repeating the soaking and drying steps for 2~3 times;
and thirdly, roasting the product obtained in the second step for 0.5 to 2h in an inert atmosphere to prepare the heteroatom-doped porous graphene modified carbon fiber paper, wherein the roasting temperature is 500 to 1000 ℃, and the heating and cooling rates are 1 to 10 ℃/min.
Further, in the first step, the graphite oxide is dispersed ultrasonically in the deionizationAdding 30wt% of H into the seawater2O2And heating in a water bath at 95 ℃ for 8 hours to react to obtain the porous graphite oxide.
In the first step, the organic material containing a heteroatom is a small-molecular organic compound containing a nonmetallic element such as N, P, S, B, F, preferably urea, dimethylimidazole, mercaptobenzothiazole, boric acid, phosphoric acid, or the like, and can be bonded to the porous graphite oxide by a weak interaction force such as a hydrogen bond to modify the surface and the interlayer of the porous graphite oxide.
Further, in the first step, the solvent is deionized water, ethanol, methanol, or the like.
Further, in the first step, the temperature of water bath heating is 30 to 60 ℃, the decomposition temperature of the organic matters is preferably not more than, and the reaction time is 0.5 to 2 hours, so that a stable dispersion liquid is formed.
Furthermore, in the second step, the natural cellulose is made of substances containing the natural cellulose, such as filter paper or cotton, and the soaking time is 3 to 48 hours.
And the heteroatom-doped porous graphene modified carbon fiber paper is used as a lithium-sulfur battery interlayer.
Compared with the prior art, the invention has the advantages that: (1) The method has simple synthesis steps, is easy to operate and convenient for industrialization; (2) the synthetic raw materials have wide sources and no pollution; (3) The synthesized carbon fiber paper has good conductivity, high toughness and self-supporting property; (4) The material is used for the interlayer material of the lithium-sulfur battery, does not need to add a bonding agent and a conductive agent, does not contain metal ions, has low cost and no pollution to the environment, is convenient to use (5), can inhibit the shuttle effect and improves the capacity and the cycling stability of the lithium-sulfur battery.
Drawings
FIG. 1 is a schematic diagram of the synthesis of the present invention.
Fig. 2 is an SEM picture of pure carbon fiber paper (a, b) and N, S co-doped porous graphene modified carbon fiber paper (c, d).
Fig. 3 is a Map of N, S co-doped porous graphene modified carbon fiber paper.
FIG. 4 is a graph showing charge and discharge cycle curves at 1C in comparison with those of a Carbon Cellulose Paper (CCP), a reduced graphite oxide composite carbon cellulose paper (RGO-CCP), a porous reduced graphite oxide composite carbon cellulose paper (RHGO-CCP), and an NS co-doped porous reduced graphite oxide composite carbon cellulose paper (NS-RHGO-CCP) as a separator material.
Detailed Description
The heteroatom-doped porous graphene modified carbon fiber paper prepared by the invention has excellent electrochemical performance as a lithium sulfur battery interlayer, which is mainly attributed to the fact that the carbon fiber paper has a 3D conductive network, so that the charge transmission resistance in the battery can be greatly reduced, meanwhile, the heteroatom-doped porous graphite oxide can adsorb and block polysulfide from being transmitted to a negative electrode, meanwhile, the polysulfide is promoted to be converted into lithium sulfide, the reaction kinetics of the battery is increased, and the capacity and the cycle stability of the lithium sulfur battery are improved.
As shown in fig. 1, the heteroatom-doped porous graphene-modified carbon fiber paper of the present invention is prepared by the following steps:
firstly, graphite oxide is dispersed in deionized water by ultrasonic, and 30% of H is added2O2Heating in a water bath at 95 ℃ to react for 8h to obtain porous graphite oxide;
and secondly, dissolving the organic matter containing the heteroatom in a solvent, and dropwise adding the organic matter containing the heteroatom into the porous graphite oxide, wherein the mass ratio of the organic matter containing the heteroatom to the graphene is 0.5-5. Heating in water bath for reaction for a certain time to form stable dispersion liquid;
thirdly, ultrasonically cleaning and drying the natural cellulose material by deionized water and ethanol, soaking the natural cellulose material into the dispersion liquid prepared in the second step for 3 to 48 hours, taking out and drying;
and fourthly, placing the filter paper obtained in the third step into a tubular furnace, and roasting for 0.5 to 2 hours in an inert atmosphere to obtain the heteroatom-doped porous graphene modified carbon fiber paper. The baking temperature is 500 to 1000 ℃, and the heating and cooling rates are 1 to 10 ℃/min.
Example 1 was carried out:
firstly, graphite oxide is dispersed in deionized water by ultrasonic, and 30% of H is added2O2Heating in water bath at 95 ℃ to react 8h to obtain the polysaccharidePorous graphite oxide;
and secondly, dissolving mercaptobenzothiazole in ethanol and dropwise adding the mercaptobenzothiazole into porous graphite oxide, wherein the mass ratio of mercaptobenzothiazole to graphene is 1. Heating in water bath for 1h to form stable dispersion;
thirdly, after the qualitative filter paper is ultrasonically cleaned and dried by deionized water and ethanol, the qualitative filter paper is soaked in the dispersion liquid prepared in the second step for soaking 24 h, and then the qualitative filter paper is taken out and dried;
and fourthly, placing the filter paper obtained in the third step in a tubular furnace, and roasting the filter paper in an inert atmosphere for 0.5h to obtain N, S co-doped porous graphene modified carbon fiber paper. The roasting temperature is 900 ℃, and the heating and cooling rates are 5 ℃/min.
Fig. 2 is an SEM picture of pure carbon fiber paper (a, b) and N, S co-doped porous graphene modified carbon fiber paper (c, d). It can be seen from the figure that the surface of the unmodified carbon paper is relatively smooth, and after modification, the surface has many wrinkles, which indicates that the porous graphene is successfully adsorbed to the surface of the carbon cellulose paper. Fig. 3 is a Map of N, S co-doped porous graphene modified carbon fiber paper. It can be seen from the figure that the N and S atoms are uniformly distributed on the surface of the sample, and the doping amounts are 0.9% and 4.2%, respectively.
FIG. 4 is a graph showing charge and discharge cycle curves at 1C in comparison with those of a Carbon Cellulose Paper (CCP), a reduced graphite oxide composite carbon cellulose paper (RGO-CCP), a porous reduced graphite oxide composite carbon cellulose paper (RHGO-CCP), and an NS co-doped porous reduced graphite oxide composite carbon cellulose paper (NS-RHGO-CCP) as a separator material. CCP is a three-dimensional network structure in which carbon fibers are interlaced with each other, and has good conductivity, but the capacity decreases rapidly because the gap is large and the effect of suppressing the shuttle effect is not good. After the CCP is modified with RGO, the RGO has good inhibition effect on shuttle of polysulfide when used as a spacer layer, but also obstructs the transmission of lithium ions, so that the capacity is lower under a large multiplying power. After modification of the CCP with RHGO, the barrier is good for ion transport, but the barrier effect on polysulfides is reduced, and after 200 cycles, a large drop in capacity occurs. NS-When the RHGO-CCP is used as an interlayer material, the RHGO-CCP not only has good inhibition effect on shuttle penetration effect, but also does not block the transmission of lithium ions, the RHGO-CCP still has 820mAh g of discharge capacity after circulating for 300 circles under 1C-1The capacity retention rate was 85.4%, and the capacity attenuation rate per cycle was 0.0487%. Has high capacity and cycle stability.
Example 2 was carried out:
firstly, graphite oxide is dispersed in deionized water by ultrasonic, and 30% of H is added2O2Heating in water bath at 95 ℃ to react for 8h to obtain porous graphite oxide;
and secondly, dissolving dimethylimidazole in deionized water and dropwise adding the dimethylimidazole into the porous graphite oxide, wherein the mass ratio of the dimethylimidazole to the graphene is 0.5. Heating in water bath for 1h to form stable dispersion;
thirdly, after the qualitative filter paper is ultrasonically cleaned and dried by deionized water and ethanol, the qualitative filter paper is soaked in the dispersion liquid prepared in the second step for soaking 48 h, and then the qualitative filter paper is taken out and dried;
and fourthly, placing the filter paper obtained in the third step in a tubular furnace, and roasting the filter paper in the tubular furnace under inert atmosphere for 2h to obtain the N-doped porous graphene modified carbon fiber paper. The roasting temperature is 700 ℃, and the heating and cooling rates are 5 ℃/min.
The prepared N-doped porous graphene modified carbon fiber paper is used as an interlayer to assemble a lithium-sulfur battery, the capacity retention rate is 81.9% after the N-doped porous graphene modified carbon fiber paper is cycled for 300 circles under 1C, the capacity of 840.3 mAh/g is still available under 2C, and the N-doped porous graphene modified carbon fiber paper has good cycling stability and rate performance.
Example 3 of implementation:
firstly, graphite oxide is dispersed in deionized water by ultrasonic, and 30% of H is added2O2Heating in water bath at 95 ℃ to react for 8h to obtain porous graphite oxide;
and secondly, dissolving n-dodecyl mercaptan in ethanol and dropwise adding the n-dodecyl mercaptan into the porous graphite oxide, wherein the mass ratio of the n-dodecyl mercaptan to the graphene is 2. Heating in water bath for 1h to form stable dispersion;
thirdly, after the qualitative filter paper is ultrasonically cleaned and dried by deionized water and ethanol, the qualitative filter paper is soaked in the dispersion liquid prepared in the second step for 12 hours, and then taken out and dried;
and fourthly, placing the filter paper obtained in the third step into a tubular furnace, and roasting the filter paper in an inert atmosphere for 1h to obtain the S co-doped porous graphene modified carbon fiber paper. The roasting temperature is 800 ℃, and the heating and cooling rates are 5 ℃/min.
The prepared S-doped porous graphene modified carbon fiber paper is used as an interlayer to assemble a lithium-sulfur battery, the capacity retention rate is 82.3% after the S-doped porous graphene modified carbon fiber paper is cycled for 300 circles under 1C, the capacity of 850.4 mAh/g is still available under 2C, and the S-doped porous graphene modified carbon fiber paper has good cycling stability and rate performance.
Example 4 of implementation:
firstly, graphite oxide is dispersed in deionized water by ultrasonic, and 30 percent of H is added2O2Heating in water bath at 95 ℃ to react for 8h to obtain porous graphite oxide;
and secondly, dissolving urea in deionized water and dropwise adding the urea into the porous graphite oxide, wherein the mass ratio of the urea to the graphene is 1. Heating in water bath for 1h to form stable dispersion;
thirdly, after the qualitative filter paper is ultrasonically cleaned and dried by deionized water and ethanol, the qualitative filter paper is soaked in the dispersion liquid prepared in the second step to be soaked in 24 h, and the qualitative filter paper is taken out and dried;
and fourthly, placing the filter paper obtained in the third step into a tubular furnace, and roasting for 0.5h in an inert atmosphere to obtain the N-doped porous graphene modified carbon fiber paper. The roasting temperature is 800 ℃, and the heating and cooling rates are 5 ℃/min.
The prepared N-doped porous graphene modified carbon fiber paper is used as an interlayer to assemble a lithium-sulfur battery, the capacity retention rate is 83.2% after the N-doped porous graphene modified carbon fiber paper is cycled for 300 circles under 1C, the capacity of 849.3 mAh/g is still available under 2C, and the N-doped porous graphene modified carbon fiber paper has good cycling stability and rate performance.
Example 5 was carried out:
firstly, graphite oxide is dispersed in deionized water by ultrasonic, and 30% of H is added2O2Heating in a water bath at 95 ℃ to react for 8h to obtain porous graphite oxide;
and secondly, dissolving boric acid in deionized water and dropwise adding the boric acid into the porous graphite oxide, wherein the mass ratio of the boric acid to the graphene is 0.5. Heating in water bath for 1h to form stable dispersion;
thirdly, after the qualitative filter paper is ultrasonically cleaned and dried by deionized water and ethanol, the qualitative filter paper is soaked in the dispersion liquid prepared in the second step for soaking 24 h, and then the qualitative filter paper is taken out and dried;
and fourthly, placing the filter paper obtained in the third step into a tubular furnace, and roasting the filter paper in an inert atmosphere for 0.5h to obtain the B-doped porous graphene modified carbon fiber paper. The roasting temperature is 800 ℃, and the heating and cooling rates are 5 ℃/min.
The prepared B-doped porous graphene modified carbon fiber paper is used as an interlayer to assemble a lithium-sulfur battery, the capacity retention rate is 80.1% after the battery is cycled for 300 circles under 1C, the capacity of 832.1 mAh/g is still available under 2C, and the battery has good cycling stability and rate performance.
Example 6 of implementation:
firstly, graphite oxide is dispersed in deionized water by ultrasonic, and 30% of H is added2O2Heating in a water bath at 95 ℃ to react for 8h to obtain porous graphite oxide;
and secondly, dissolving phosphoric acid in deionized water and dropwise adding the phosphoric acid into the porous graphite oxide, wherein the mass ratio of the phosphoric acid to the graphene is 1. Heating in water bath for 1h to form stable dispersion;
thirdly, after the qualitative filter paper is ultrasonically cleaned and dried by deionized water and ethanol, the qualitative filter paper is soaked in the dispersion liquid prepared in the second step for soaking 24 h, and then the qualitative filter paper is taken out and dried;
and fourthly, placing the filter paper obtained in the third step in a tubular furnace, and roasting the filter paper in the tubular furnace under inert atmosphere for 1h to obtain the P-doped porous graphene-decorated carbon fiber paper. The roasting temperature is 800 ℃, and the heating and cooling rates are 5 ℃/min.
The prepared P-doped porous graphene modified carbon fiber paper is used as an interlayer to assemble a lithium-sulfur battery, the capacity retention rate is 80.1% after the circulation is performed for 300 circles under 1C, the capacity of 823.4 mAh/g is still available under 2C, and the battery has good circulation stability and rate performance.

Claims (10)

1. The heteroatom-doped porous graphene modified carbon fiber paper is characterized in that the carbon fiber paper takes a 3D network structure formed by mutually intertwining hollow carbon tubes with the diameter of 1-10 mu m as a support, and heteroatom-doped porous graphene is loaded on the surface of the structure;
wherein the doping amount of the heteroatoms in the heteroatom-doped porous graphene is 1% -10%;
the load capacity of the heteroatom-doped porous graphene is 10% -30%;
the preparation method comprises the following steps:
dissolving organic matter containing heteroatoms in a solvent, dropwise adding the organic matter containing heteroatoms into porous graphite oxide, wherein the mass ratio of the organic matter containing heteroatoms to the porous graphite oxide is 1~5, heating in a water bath for reacting for a certain time to form stable dispersion liquid, ultrasonically dispersing the graphite oxide in deionized water, and adding 30% of H2O2Heating in a 95 ℃ water bath to react for 8h to obtain porous graphite oxide, wherein the organic matter containing the heteroatom is a micromolecular organic compound containing N, P, S, B, F nonmetal elements, and the organic matter containing the heteroatom is selected from any one or more of urea, dimethyl imidazole, mercaptobenzothiazole, boric acid and phosphoric acid;
secondly, ultrasonically cleaning natural cellulose by deionized water and ethanol, drying, soaking in the dispersion liquid prepared in the first step for 3-48 h, taking out, drying, repeating the soaking and drying steps for 2~3 times, wherein the natural cellulose adopts filter paper or cotton;
and thirdly, roasting the product obtained in the second step for 0.5 to 2h in an inert atmosphere to prepare the heteroatom-doped porous graphene modified carbon fiber paper, wherein the roasting temperature is 500 to 1000 ℃, and the heating and cooling rates are 1 to 10 ℃/min.
2. The carbon fiber paper of claim 1, wherein the heteroatoms are one or more of N, P, S, B, F.
3. The preparation method of the heteroatom-doped porous graphene-modified carbon fiber paper according to claim 1 or 2, characterized by comprising the following steps:
dissolving an organic matter containing heteroatoms in a solvent, dropwise adding the organic matter containing heteroatoms into porous graphite oxide, wherein the mass ratio of the organic matter containing heteroatoms to the porous graphite oxide is 1~5, and heating in a water bath for reacting for a certain time to form a stable dispersion liquid;
secondly, ultrasonically cleaning natural cellulose by deionized water and ethanol, drying, soaking in the dispersion liquid prepared in the first step for 3-48 h, taking out, drying, and repeating the soaking and drying steps for 2~3 times;
and thirdly, roasting the product obtained in the second step for 0.5 to 2h in an inert atmosphere to prepare the heteroatom-doped porous graphene modified carbon fiber paper, wherein the roasting temperature is 500 to 1000 ℃, and the heating and cooling rates are 1 to 10 ℃/min.
4. The method of claim 3, wherein in the first step, the graphite oxide is ultrasonically dispersed in deionized water, and 30wt% H is added2O2And heating in a water bath at 95 ℃ for 8 hours to react to obtain the porous graphite oxide.
5. The method of claim 3, wherein in the first step, the heteroatom-containing organic compound is a small molecule organic compound containing N, P, S, B, F nonmetallic elements.
6. The method according to claim 3, wherein in the first step, the organic compound containing a hetero atom is one or more selected from urea, dimethylimidazole, mercaptobenzothiazole, boric acid, and phosphoric acid.
7. The method according to claim 3, wherein the solvent in the first step is any one of deionized water, ethanol, and methanol.
8. The preparation method according to claim 3, wherein in the first step, the temperature of water bath heating is 30 to 60 ℃, and the reaction time is 0.5 to 2 hours.
9. The preparation method according to claim 3, wherein in the second step, the natural cellulose is filter paper or cotton, and the soaking time is 3 to 48 hours.
10. Use of the heteroatom-doped porous graphene-modified carbon fiber paper of claim 1 or 2 as a lithium-sulfur battery separator.
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