CN110729438A - 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

Info

Publication number
CN110729438A
CN110729438A CN201810785068.3A CN201810785068A CN110729438A CN 110729438 A CN110729438 A CN 110729438A CN 201810785068 A CN201810785068 A CN 201810785068A CN 110729438 A CN110729438 A CN 110729438A
Authority
CN
China
Prior art keywords
carbon fiber
heteroatom
fiber paper
doped porous
porous graphene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201810785068.3A
Other languages
Chinese (zh)
Other versions
CN110729438B (en
Inventor
付永胜
陈鹏
汪信
朱俊武
吴震
陈佳琪
周焱
刘青
孙蕴桦
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nanjing Tech University
Original Assignee
Nanjing Tech University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nanjing Tech University filed Critical Nanjing Tech University
Priority to CN201810785068.3A priority Critical patent/CN110729438B/en
Publication of CN110729438A publication Critical patent/CN110729438A/en
Application granted granted Critical
Publication of CN110729438B publication Critical patent/CN110729438B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • 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
    • 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 new battery systems, lithium-sulfur batteries are considered to be a potential next-generation high-energy battery system due to their advantages such as high theoretical energy density, and become a worldwide research hotspot. Although lithium-sulfur batteries have great advantages such as high energy density, some key problems still exist to restrict the marketable application 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. In 2012, the Manthiram topic group first proposed the concept of "barriers". 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 CO2Activating to obtain the carbon nanofiber interlayer with rich pore channel structures and applying the PAN-Nafion nanofiber interlayer to lithium sulfurOn the battery, the carbon fiber interlayer not only can reduce electrochemical impedance, but also can fix dissolved lithium polysulfide. Through the optimized design of the thickness and the pore structure of the interlayer, the first discharge capacity of the battery is up to 1549 mAh/g (Journal of materials chemistry A, 2015, 3(8): 4530-.
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-. 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 scheme for achieving the purpose of the invention is that 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.
Further, the amount of heteroatom doping in the heteroatom-doped porous graphene is between 1% and ~ 10%.
Further, the loading of the heteroatom-doped porous graphene is between 10% ~ 30%.
Further, the heteroatoms are 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 ~ 2h in an inert atmosphere to obtain the heteroatom-doped porous graphene modified carbon fiber paper, wherein the roasting temperature is 500 ~ 1000 ℃, and the heating and cooling rates are 1 ~ 10 ℃/min.
Further, in the first step, graphite oxide is ultrasonically dispersed in deionized water, and 30wt% of H is added2O2And heating in a water bath at 95 ℃ for 8 hours to react to obtain the porous graphite oxide.
Further, in the first step, the organic material containing a hetero atom 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.
Furthermore, in the first step, the temperature of water bath heating is 30 ~ 60 ℃, preferably not higher than the decomposition temperature of organic substances, and the reaction time is 0.5 ~ 2h, so as to form a stable dispersion.
Furthermore, in the second step, the natural cellulose is filter paper or cotton and other substances containing the natural cellulose, and the soaking time is 3 ~ 48 h.
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 synthesis of the present invention.
Fig. 2 is SEM pictures of pure carbon fiber papers (a, b) and N, S co-doped porous graphene modified carbon fiber papers (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 when 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) are used as the 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 water bath at 95 ℃ for 8h to obtain porous graphite oxide;
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 graphene is 0.5 ~ 5, and heating in a water bath for reacting for a certain time to form a stable dispersion liquid;
thirdly, ultrasonically cleaning and drying natural cellulose materials by deionized water and ethanol, soaking the natural cellulose materials into the dispersion liquid prepared in the second step for 3 ~ 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 ~ 2 hours in an inert atmosphere to obtain the heteroatom-doped porous graphene modified carbon fiber paper, wherein the roasting temperature is 500 ~ 1000 ℃, and the heating and cooling rates are 1 ~ 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 ℃ for 8h to obtain porous 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 24 hours, and then 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 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 SEM pictures of pure carbon fiber papers (a, b) and N, S co-doped porous graphene modified carbon fiber papers (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 shows a Carbon Cellulose Paper (CCP) and a reduced graphite oxide composite carbon cellulose paper (RGO-CCP)And (3) a charge-discharge cycle curve contrast diagram under 1C when the porous reduced graphite oxide composite carbon cellulose paper (RHGO-CCP) and the NS co-doped porous reduced graphite oxide composite carbon cellulose paper (NS-RHGO-CCP) are used as interlayer materials. 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. The NS-RHGO-CCP is obtained after N and S heteroatom co-doping is carried out on the RHGO-CCP, when the material is used as an interlayer material, the material not only has good inhibition effect on shuttle penetrating effect, but also does not block the transmission of lithium ions, the material is circulated for 300 circles under 1C, the discharge capacity is still 820mAh g-1The capacity retention rate was 85.4%, and the capacity fade 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 ℃ 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 48 hours, and then taken out and dried;
and fourthly, placing the filter paper obtained in the third step into a tubular furnace, and roasting for 2 hours in an inert atmosphere 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 battery is cycled for 300 circles at 1C, the capacity of 840.3 mAh/g is still maintained at 2C, and the battery has good cycling stability and rate capability.
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 ℃ 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 for 1h in an inert atmosphere 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 battery is cycled for 300 circles at 1C, the capacity of 850.4 mAh/g is still maintained at 2C, and the battery has good cycling stability and rate capability.
Example 4 of implementation:
firstly, graphite oxide is dispersed in deionized water by ultrasonic, and 30% of H is added2O2Heating in water bath at 95 ℃ 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 for 24 hours, and then 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 battery is cycled for 300 circles at 1C, the capacity of 849.3 mAh/g is still maintained at 2C, and the battery has good cycling stability and rate capability.
Example 5 was carried out:
firstly, graphite oxide is dispersed in deionized water by ultrasonic, and 30% of H is added2O2Heating in water bath at 95 ℃ 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 24 hours, and then 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 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 at 1C, the capacity of 832.1 mAh/g is still maintained at 2C, and the battery has good cycling stability and rate capability.
Example 6 of implementation:
firstly, graphite oxide is dispersed in deionized water by ultrasonic, and 30% of H is added2O2Heating in water bath at 95 ℃ 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 24 hours, and then taken out and dried;
and fourthly, placing the filter paper obtained in the third step into a tubular furnace, and roasting for 1h in an inert atmosphere 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 battery is cycled for 300 circles at 1C, the capacity of 823.4 mAh/g is still maintained at 2C, and the battery has good cycling stability and rate capability.

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 the surface of the structure is loaded with heteroatom-doped porous graphene.
2. The carbon fiber paper of claim 1, wherein the amount of heteroatom doping in the heteroatom-doped porous graphene is between 1% ~ 10%.
3. The carbon fiber paper according to claim 1 or 2, wherein the loading of the heteroatom-doped porous graphene is between 10% ~ 30% and 30%.
4. The carbon fiber paper according to claim 1, 2 or 3, wherein the heteroatom is one or more of N, P, S, B, F.
5. The preparation method of the heteroatom-doped porous graphene-modified carbon fiber paper according to any one of claims 1 to 3, 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 ~ 2h in an inert atmosphere to obtain the heteroatom-doped porous graphene modified carbon fiber paper, wherein the roasting temperature is 500 ~ 1000 ℃, and the heating and cooling rates are 1 ~ 10 ℃/min.
6. The method of claim 5, 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.
7. The method according to claim 5, wherein the organic substance containing a hetero atom in the first step is a small molecule organic compound containing N, P, S, B, F nonmetallic elements.
8. The method according to claim 5, 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.
9. The method according to claim 5, wherein the solvent is any one of deionized water, ethanol, and methanol in the first step.
10. The process of claim 5, wherein in the first step, the temperature of the water bath is 30 ~ 60 ℃ and the reaction time is 0.5 ~ 2 h.
CN201810785068.3A 2018-07-17 2018-07-17 Heteroatom-doped porous graphene-modified carbon fiber paper and preparation method and application thereof Active CN110729438B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810785068.3A CN110729438B (en) 2018-07-17 2018-07-17 Heteroatom-doped porous graphene-modified carbon fiber paper and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810785068.3A CN110729438B (en) 2018-07-17 2018-07-17 Heteroatom-doped porous graphene-modified carbon fiber paper and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN110729438A true CN110729438A (en) 2020-01-24
CN110729438B CN110729438B (en) 2022-11-01

Family

ID=69217460

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810785068.3A Active CN110729438B (en) 2018-07-17 2018-07-17 Heteroatom-doped porous graphene-modified carbon fiber paper and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN110729438B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111697188A (en) * 2020-06-23 2020-09-22 南京理工大学 Lithium-sulfur battery interlayer with flame retardant property and preparation method thereof
CN112133902A (en) * 2020-10-10 2020-12-25 山东省科学院能源研究所 Sodium metal negative electrode deposition matrix and preparation method and application thereof
CN117638107A (en) * 2024-01-18 2024-03-01 湖南隆深氢能科技有限公司 Preparation method of carbon fiber paper for fuel cell

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105529464A (en) * 2016-01-22 2016-04-27 南京航空航天大学 Lithium-sulfur battery
CN105762337A (en) * 2016-01-22 2016-07-13 三峡大学 Silicon/graphene/carbon fiber composite cathode material and preparation method thereof
CN106450104A (en) * 2016-10-09 2017-02-22 中国人民解放军63971部队 Novel positive electrode isolation layer applied to lithium-sulfur battery, and preparation method for novel positive electrode isolation layer
CN106684389A (en) * 2016-12-30 2017-05-17 温州大学 Sulfur-nitrogen dual-doped graphene nano material and preparation method and application thereof
US20180142114A1 (en) * 2015-05-26 2018-05-24 The Regents Of The University Of California Dispersions of holey graphene materials and applications thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180142114A1 (en) * 2015-05-26 2018-05-24 The Regents Of The University Of California Dispersions of holey graphene materials and applications thereof
CN105529464A (en) * 2016-01-22 2016-04-27 南京航空航天大学 Lithium-sulfur battery
CN105762337A (en) * 2016-01-22 2016-07-13 三峡大学 Silicon/graphene/carbon fiber composite cathode material and preparation method thereof
CN106450104A (en) * 2016-10-09 2017-02-22 中国人民解放军63971部队 Novel positive electrode isolation layer applied to lithium-sulfur battery, and preparation method for novel positive electrode isolation layer
CN106684389A (en) * 2016-12-30 2017-05-17 温州大学 Sulfur-nitrogen dual-doped graphene nano material and preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
杨铁军: "《产业专利分析报告第44册》", 30 June 2016, 知识产权出版社 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111697188A (en) * 2020-06-23 2020-09-22 南京理工大学 Lithium-sulfur battery interlayer with flame retardant property and preparation method thereof
CN112133902A (en) * 2020-10-10 2020-12-25 山东省科学院能源研究所 Sodium metal negative electrode deposition matrix and preparation method and application thereof
CN117638107A (en) * 2024-01-18 2024-03-01 湖南隆深氢能科技有限公司 Preparation method of carbon fiber paper for fuel cell
CN117638107B (en) * 2024-01-18 2024-04-09 湖南隆深氢能科技有限公司 Preparation method of carbon fiber paper for fuel cell

Also Published As

Publication number Publication date
CN110729438B (en) 2022-11-01

Similar Documents

Publication Publication Date Title
Zhang et al. Cellulose-based material in lithium-sulfur batteries: A review
CN110323451B (en) Multifunctional composite material based on graphene and polymer fibers and preparation method and application thereof
CN104201389B (en) A kind of preparation method of lithium selenium cell positive pole
CN108807808B (en) Preparation method of biomass carbon aerogel modified lithium-sulfur battery diaphragm
CN112490446B (en) Preparation method of Co-CNT @ CF three-dimensional self-supporting lithium-sulfur battery positive electrode material
CN108232369A (en) A kind of integrated form flexible electrode of biomass derived and preparation method thereof
CN110416546A (en) The preparation method and application of three-dimensional self-supporting nitrogen-doped carbon sodium ion negative electrode material
CN111362254A (en) Preparation method and application of nitrogen-doped carbon nanotube-loaded phosphorus-doped cobaltosic oxide composite material
CN105529192A (en) Preparing method of copper quantum dot/activated carbon composite material applied to super capacitor
CN110729438B (en) Heteroatom-doped porous graphene-modified carbon fiber paper and preparation method and application thereof
KR102139318B1 (en) Sodium ion battery electrode material and manufacturing method thereof
CN110517900B (en) Preparation method of nitrogen-doped low-temperature carbon nanofiber electrode material for supercapacitor
CN111969164A (en) Composite modified diaphragm for lithium-sulfur battery and preparation method thereof
CN110212180B (en) Preparation method of lithium sulfide self-supporting carbon sphere/carbon nanofiber composite material and lithium-sulfur battery
CN112117444A (en) Carbon-coated cobalt sulfide positive electrode material, preparation method, positive electrode and aluminum ion battery
CN113422153A (en) Preparation method of positive electrode side interlayer material for lithium-sulfur battery
CN106450423A (en) High-specific-energy flexible integrated electrode and preparation method therefor
Wang et al. Recent advances in inhibiting shuttle effect of polysulfide in lithium-sulfur batteries
CN113270275B (en) Composite electrode derived from metal organic framework and nanofiber and preparation method thereof
Zhou et al. Advanced cathodic free-standing interlayers for lithium–sulfur batteries: understanding, fabrication, and modification
CN111974430B (en) Preparation method of monoatomic copper catalyst and application of monoatomic copper catalyst in positive electrode of lithium-sulfur battery
CN113148975A (en) Preparation method of nitrogen self-doped porous carbon electrode
CN110504450B (en) Preparation method of heteroatom-doped hierarchical pore carbon material and application of heteroatom-doped hierarchical pore carbon material in lithium battery negative electrode slurry
CN109449008B (en) Preparation method and application of self-supporting hollow core-shell structure electrode material
CN113725444A (en) Ruthenium/carbon nanotube flexible positive electrode material and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant