CN110729436B - Heteroatom-doped carbon nanotube modified carbon fiber paper and preparation method and application thereof - Google Patents
Heteroatom-doped carbon nanotube modified carbon fiber paper and preparation method and application thereof Download PDFInfo
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- 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
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- 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
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- H—ELECTRICITY
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- 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
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Abstract
The invention discloses heteroatom-doped carbon nanotube modified carbon fiber paper and a preparation method and application thereof. And (3) forming uniform carbon nanotube dispersion liquid by using the non-covalent bond modified carbon nanotube, soaking natural cellulose in the uniform carbon nanotube dispersion liquid, and drying and carbonizing the natural cellulose to obtain the heteroatom-doped carbon nanotube modified carbon fiber paper. 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
Technical Field
The invention relates to heteroatom-doped carbon nanotube modified carbon fiber paper, a preparation method and application thereof, which can be applied to an interlayer of a lithium-sulfur battery 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. For example, sulfur is an insulator and is inert to electrochemical reactions with electrode materials; the generation of intermediate polysulfide can be dissolved in the electrolyte and shuttled between the anode and the cathode, so that the irreversible loss of sulfur is caused, the coulombic efficiency and the cycle stability are seriously influenced, and the internal resistance of the battery is increased; li 2 S（1.66 g cm -3 ) With S (2.03 g cm) -3 ) The density difference is large and the volume expansion generated rapidly attenuates the capacity of the battery. How to enrich and reuse soluble polysulfides in the positive electrode region becomes the key for future practical applications of lithium-sulfur batteries.
In view of the above problems, researchers have found that the immobilization of sulfur active materials in electrodes by physical/chemical methods through the control of electrode structure and composition is an effective solution, among which the immobilization of sulfur positive electrodes in host materials such as carbon materials, conductive polymers, metal oxides, and metal/covalent organic frameworks is one of the most effective methods. Although the method can well inhibit the shuttle effect and improve the cycle stability of the lithium-sulfur battery, the preparation cost of the composite material is high, the process is complex, and the practical application of the lithium-sulfur battery is also hindered. Therefore, researchers have searched for a method of fixing polysulfides by adding a functional interlayer having good conductivity and self-supporting characteristics between the S positive electrode and the separator, which is convenient and more cost-effective, and the interlayer material becomes a new S carrier material during charge and discharge, thereby increasing the conductivity of S and binding polysulfides. The existing interlayer material is difficult to bind polysulfide due to the overlarge pore diameter of the interlayer material, but when a dense material such as graphene is used as the interlayer, the polysulfide is blocked, and the lithium ion transmission is also blocked, so that the capacity is low, and how to design and develop the interlayer which can bind polysulfide shuttle and does not block lithium ion transmission becomes the key point of research.
Disclosure of Invention
The invention aims to provide self-supporting heteroatom-doped carbon nanotube modified carbon fiber paper, a preparation method and application of the paper as a lithium-sulfur battery interlayer.
The technical solution for realizing the purpose of the invention is as follows: a self-supporting heteroatom-doped carbon nanotube modified carbon fiber paper takes a 3D network structure formed by mutually intertwining hollow carbon tubes with the diameter of 1 to 10 mu m as a support, and the surface of the structure is loaded with heteroatom-doped carbon nanotubes.
Furthermore, the doping amount of the heteroatoms in the heteroatom-doped carbon nanotube is 1% -10%.
Furthermore, the load capacity of the heteroatom-doped carbon nano tube is 20-40%.
Furthermore, the heteroatom is one or more of N, P and S.
The preparation method of the heteroatom-doped carbon nanotube modified carbon fiber paper comprises the following steps:
firstly, ultrasonically dispersing a carbon nano tube in de-ethanol for 1 hour to prepare dispersion liquid with a certain concentration;
secondly, dissolving a linear polymer containing heteroatoms in a solvent, dropwise adding the solvent into the carbon nanotube dispersion liquid obtained in the first step, and performing ultrasonic dispersion for a certain time to form a stable dispersion liquid, wherein the mass ratio of the linear polymer containing heteroatoms to the carbon nanotubes is 0.5-5;
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 prepare the heteroatom-doped carbon nanotube modified carbon fiber paper, wherein the roasting temperature is 500 to 1000 ℃, and the heating and cooling rates are 1 to 10 ℃/min.
Furthermore, in the first step, the concentration of the carbon nano tube dispersion liquid is 0.5 to 10mg/ml, the diameter of the carbon nano tube is 8 to 20 nm, and the length of the carbon nano tube is 5 to 50 mu m.
Furthermore, in the second step, the linear polymer containing hetero atoms, including single-stranded DNA, polyvinylpyrrolidone (PVP), polystyrene sulfonate (PSS) and the like, can be wound and coated on the surface of the carbon nanotube in a non-covalent bond manner, so that the dispersibility of the carbon nanotube in the solution is improved.
Furthermore, in the second step, the solvent is deionized water, ethanol, methanol and the like.
Further, in the third step, the natural cellulose substance is a substance containing natural cellulose, such as filter paper or cotton.
And the heteroatom-doped carbon nanotube modified carbon fiber paper is used as an interlayer of the lithium-sulfur battery.
Compared with the prior art, the invention has the advantages that: the method has simple synthesis steps and is easy to operate; (2) The method for modifying the carbon nano tube by using the non-covalent bond can realize the solubilization of the carbon nano tube and simultaneously maintain the integrity of the structure of the carbon nano tube, thereby ensuring that the carbon fiber paper has good conductivity; (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 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, P co-doped carbon nanotube modified carbon fiber papers (c, d).
FIG. 3 is a Map of carbon fiber paper modified by N and P co-doped carbon nanotubes.
FIG. 4 is a graph comparing the rate performance of a lithium sulfur battery when carbon fiber paper modified by N and P co-doped carbon nanotubes is used as a lithium sulfur battery separator.
Detailed Description
The heteroatom-doped carbon nanotube modified carbon fiber paper prepared by the invention has excellent electrochemical performance as a lithium sulfur battery interlayer, and is mainly due to the fact that the carbon nanotube modified carbon fiber paper has a 3D conductive network, so that the charge transmission resistance in the battery can be greatly reduced, and the carbon nanotube modified carbon fiber paper also has a physical barrier effect on polysulfide; the heteroatom doping can adsorb and block polysulfide to be 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.
Referring to fig. 1, the heteroatom-doped carbon nanotube modified carbon fiber paper of the present invention is prepared by the following steps:
firstly, ultrasonically dispersing a carbon nano tube in de-ethanol for 1h to prepare 1mg/ml dispersion liquid;
and secondly, dissolving the linear polymer containing the heteroatom in a solvent, dripping the linear polymer into the carbon nano tube dispersion liquid, and performing ultrasonic dispersion for a certain time to form stable dispersion liquid, wherein the mass ratio of the long-chain organic matter containing the heteroatom to the carbon nano tube is 0.5 to 5.
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 carbon nanotube 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, ultrasonically dispersing a carbon nano tube in de-ethanol for 1h to prepare 1mg/ml dispersion liquid;
and secondly, dissolving PVP in ethanol, dropwise adding the PVP into the carbon nano tube dispersion liquid, and performing ultrasonic dispersion for a certain time to form stable dispersion liquid, wherein the mass ratio of the PVP to the carbon nano tube is 1.
Thirdly, after the filter paper is ultrasonically cleaned and dried by deionized water and ethanol, the filter paper is soaked in the dispersion liquid prepared in the second step for 24 hours and then taken out for drying;
and fourthly, placing the filter paper obtained in the third step in a tubular furnace, and roasting for 0.5 h in an inert atmosphere to obtain the N-doped carbon nanotube modified carbon fiber paper. The roasting temperature is 900 ℃, and the heating and cooling rates are 5 ℃/min.
The prepared N-doped carbon nanotube modified carbon fiber paper is used as an interlayer to assemble a lithium-sulfur battery, the battery is cycled for 100 circles at 0.2 ℃, the discharge capacity of the first circle is 1224.5mAh/g, the capacity retention rate is 77.9%, the capacity of 820.1 mAh/g is still maintained at 2 ℃, and the battery has good cycling stability and rate capability.
Example 2 was carried out:
firstly, ultrasonically dispersing carbon nano tubes in de-ethanol for 1h to prepare 5 mg/ml dispersion liquid;
and secondly, dissolving PVP in ethanol, dropwise adding the PVP into the carbon nano tube dispersion liquid, and performing ultrasonic dispersion for a certain time to form stable dispersion liquid, wherein the mass ratio of the PVP to the carbon nano tube is 2.
Thirdly, ultrasonically cleaning and drying cotton by deionized water and ethanol, soaking the cotton into the dispersion liquid prepared in the second step for 24 hours, taking out and drying;
and fourthly, clamping the cotton obtained in the third step, placing the cotton in a tube furnace, and roasting for 1h in an inert atmosphere to obtain the N-doped carbon nanotube modified carbon fiber paper. The roasting temperature is 800 ℃, and the heating and cooling rates are 5 ℃/min.
The prepared N-doped carbon nanotube modified carbon fiber paper is used as an interlayer to assemble a lithium-sulfur battery, the battery is cycled for 100 circles at 0.2 ℃, the first circle discharge capacity is 1235.6mAh/g, the capacity retention rate is 79.1%, the capacity of 825.2 mAh/g is still maintained at 2 ℃, and the battery has good cycling stability and rate capability.
Example 3 of implementation:
firstly, ultrasonically dispersing a carbon nano tube in de-ethanol for 1h to prepare 0.5 mg/ml dispersion liquid;
and secondly, dissolving the PSS in ethanol, dropwise adding the dissolved PSS into the carbon nanotube dispersion liquid, and ultrasonically dispersing for a certain time to form stable dispersion liquid, wherein the mass ratio of the PSS to the carbon nanotubes is 1.
Thirdly, ultrasonically cleaning and drying the filter paper by deionized water and ethanol, soaking the filter paper in the dispersion liquid prepared in the second step for 24 hours, taking out and drying the filter paper;
and fourthly, placing the filter paper obtained in the third step in a tubular furnace, and roasting for 1 hour under inert atmosphere to obtain the S-doped carbon nanotube modified carbon fiber paper. The roasting temperature is 800 ℃, and the heating and cooling rates are 5 ℃/min.
The prepared S-doped carbon nanotube modified carbon fiber paper is used as an interlayer to assemble a lithium-sulfur battery, the battery is cycled for 100 circles at 0.2 ℃, the discharge capacity of the first circle is 1245.3mAh/g, the capacity retention rate is 78.5%, the capacity of 813.1 mAh/g is still remained at 2 ℃, and the battery has good cycling stability and rate capability.
Example 4 of implementation:
firstly, ultrasonically dispersing a carbon nano tube in de-ethanol for 1h to prepare 0.5 mg/ml dispersion liquid;
and secondly, dissolving the PSS in ethanol, dropwise adding the dissolved PSS into the carbon nanotube dispersion liquid, and ultrasonically dispersing for a certain time to form stable dispersion liquid, wherein the mass ratio of the PSS to the carbon nanotubes is 0.5.
Thirdly, ultrasonically cleaning and drying cotton by deionized water and ethanol, soaking the cotton into the dispersion liquid prepared in the second step for 24 hours, taking out and drying;
and fourthly, clamping the cotton obtained in the third step, placing the cotton in a tube furnace, and roasting for 2 hours in an inert atmosphere to obtain the S-doped carbon nanotube modified carbon fiber paper. The roasting temperature is 700 ℃, and the heating and cooling rates are 5 ℃/min.
The prepared S-doped carbon nanotube modified carbon fiber paper is used as an interlayer to assemble a lithium-sulfur battery, the battery is cycled for 100 circles at 0.2 ℃, the discharge capacity of the first circle is 1215.4mAh/g, the capacity retention rate is 80.3%, the capacity of 824.3 mAh/g is still remained at 2 ℃, and the battery has good cycling stability and rate capability.
Example 5 was carried out:
firstly, ultrasonically dispersing carbon nano tubes in de-ethanol for 1 hour to prepare 1mg/ml dispersion liquid;
and secondly, dissolving single-stranded DNA in deionized water, dropwise adding the solution into the carbon nanotube dispersion solution, and ultrasonically dispersing for a certain time to form stable dispersion solution, wherein the mass ratio of the single-stranded DNA to the carbon nanotube is 2.
Thirdly, ultrasonically cleaning and drying cotton by deionized water and ethanol, soaking the cotton into the dispersion liquid prepared in the second step for 24 hours, taking out and drying;
and fourthly, clamping the cotton obtained in the third step, placing the cotton in a tubular furnace, and roasting for 0.5 h in an inert atmosphere to obtain the N and P co-doped carbon nanotube modified carbon fiber paper. The roasting temperature is 900 ℃, and the heating and cooling rates are 5 ℃/min.
The prepared S-doped carbon nanotube modified carbon fiber paper is used as an interlayer to assemble the lithium-sulfur battery, the battery is cycled for 100 circles at 0.2 ℃, the discharge capacity of the first circle is 1224.5mAh/g, the capacity retention rate is 78.6%, the capacity of 816.4 mAh/g is still kept at 2 ℃, and the lithium-sulfur battery has good cycle stability and rate capability.
Example 6 of implementation:
firstly, ultrasonically dispersing carbon nano tubes in de-ethanol for 1 hour to prepare 1mg/ml dispersion liquid;
and secondly, dissolving single-stranded DNA in deionized water, dropwise adding the solution into the carbon nanotube dispersion solution, and ultrasonically dispersing for a certain time to form stable dispersion solution, wherein the mass ratio of the single-stranded DNA to the carbon nanotube is 1.
Thirdly, ultrasonically cleaning and drying the filter paper by deionized water and ethanol, soaking the filter paper in the dispersion liquid prepared in the second step for 24 hours, taking out and drying the filter paper;
and fourthly, placing the filter paper obtained in the third step in a tubular furnace, and roasting for 0.5 h in an inert atmosphere to obtain the N and P co-doped carbon nanotube modified carbon fiber paper. The roasting temperature is 800 ℃, and the heating and cooling rates are 5 ℃/min.
Fig. 2 is SEM pictures of pure carbon fiber papers (a, b) and N, P co-doped carbon nanotube modified carbon fiber papers (c, d). As shown in the figure, the surface of the unmodified carbon fiber paper is smooth, and the carbon fiber paper modified by the heteroatom-doped carbon nanotubes has a plurality of carbon nanotubes on the surface, which proves that the carbon nanotubes are well modified on the surface of the carbon fibers.
FIG. 3 is a Map of carbon fiber paper modified by N and P co-doped carbon nanotubes. As shown, the N and P heteroatoms were uniformly distributed on the surface of the sample with doping amounts of 3.2% and 0.4%, respectively.
FIG. 4 is a graph comparing the rate performance of batteries when the carbon fiber paper modified by N and P co-doped carbon nanotubes and the unmodified carbon fiber paper are used as the lithium sulfur battery interlayer. It can be seen from the figure that at each rate, when the carbon fiber paper modified by the N and P co-doped carbon nanotubes is used as an interlayer, the discharge capacity of the first cycle is 1235.6mAh/g when the carbon fiber paper is cycled at 0.2C, and still has a capacity of 813.5 mAh/g at 2C. This is higher than unmodified carbon fiber paper and the stability is also better.
Claims (8)
1. A heteroatom-doped carbon nanotube modified carbon fiber paper is characterized in that a 3D network structure formed by mutually intertwining hollow carbon tubes with the diameters of 1 to 10 mu m is used as a support, and heteroatom-doped carbon nanotubes are loaded on the surface of the structure;
wherein the doping amount of the heteroatom in the heteroatom-doped carbon nanotube is 1-10%;
the load capacity of the heteroatom-doped carbon nano tube is 20-40%;
the preparation method comprises the following steps:
firstly, ultrasonically dispersing carbon nano tubes in de-ethanol, and ultrasonically preparing a dispersion liquid with a certain concentration;
secondly, dissolving a linear polymer containing heteroatoms in a solvent, dropwise adding the solvent into the carbon nanotube dispersion liquid obtained in the first step, and performing ultrasonic dispersion for a certain time to form a stable dispersion liquid, wherein the mass ratio of the linear polymer containing heteroatoms to the carbon nanotubes is 0.5-5;
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, taking out and drying;
fourthly, placing the filter paper obtained in the third step in a tubular furnace, and roasting for 0.5 to 2 hours in an inert atmosphere to prepare heteroatom doped carbon nanotube modified carbon fiber paper, wherein the roasting temperature is 500 to 1000 ℃, and the heating and cooling rates are 1 to 10 ℃/min;
in the second step, the linear polymer containing hetero atoms is selected from any one of single-stranded DNA, polyvinylpyrrolidone and polystyrene sulfonate;
and in the third step, the natural cellulose substance is filter paper or cotton, and the soaking time is 3 to 48 hours.
2. The carbon fiber paper according to claim 1, wherein the hetero atom is one or more of N, P, S.
3. The preparation method of the heteroatom-doped carbon nanotube modified carbon fiber paper as claimed in claim 1 or 2, which comprises the following steps:
firstly, ultrasonically dispersing carbon nano tubes in de-ethanol, and ultrasonically preparing a dispersion liquid with a certain concentration;
secondly, dissolving a linear polymer containing heteroatoms in a solvent, dropwise adding the solvent into the carbon nanotube dispersion liquid obtained in the first step, and performing ultrasonic dispersion for a certain time to form a stable dispersion liquid, wherein the mass ratio of the linear polymer containing heteroatoms to the carbon nanotubes is 0.5-5;
thirdly, ultrasonically cleaning and drying natural cellulose substances by deionized water and ethanol, soaking the natural cellulose substances into the dispersion liquid prepared in the second step, taking out and drying;
and fourthly, placing the filter paper obtained in the third step into a tube furnace, and roasting for 0.5 to 2 hours in an inert atmosphere to obtain the heteroatom-doped carbon nanotube 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 according to claim 3, wherein in the first step, the concentration of the carbon nanotube dispersion is 0.5 to 10mg/ml, the diameter of the carbon nanotube is 8 to 20 nm, and the length of the carbon nanotube is 5 to 50 μm.
5. The method according to claim 3, wherein in the second step, the linear polymer containing a hetero atom is any one selected from the group consisting of single-stranded DNA, polyvinylpyrrolidone and polystyrene sulfonate.
6. The method according to claim 3, wherein in the second step, the solvent is any one of deionized water, ethanol, and methanol.
7. The preparation method according to claim 3, wherein in the third step, the natural cellulose substance is filter paper or cotton, and the soaking time is 3 to 48 hours.
8. Use of the heteroatom-doped carbon nanotube modified carbon fiber paper of claim 1 or 2 as a lithium sulfur battery separator.
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| CN104900830A (en) * | 2015-06-29 | 2015-09-09 | 北京理工大学 | Lithium-sulfur battery with carbon fiber cloth as barrier layer |
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| 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 |
| KR20170136971A (en) * | 2016-06-02 | 2017-12-12 | 주식회사 엘지화학 | Carbon-based fiber sheet and lithium-sulfur battery comprising the same |
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| CN104900830A (en) * | 2015-06-29 | 2015-09-09 | 北京理工大学 | Lithium-sulfur battery with carbon fiber cloth as barrier layer |
| CN105762337A (en) * | 2016-01-22 | 2016-07-13 | 三峡大学 | Silicon/graphene/carbon fiber composite cathode material and preparation method thereof |
| KR20170136971A (en) * | 2016-06-02 | 2017-12-12 | 주식회사 엘지화학 | Carbon-based fiber sheet and lithium-sulfur battery comprising the same |
| CN106299282A (en) * | 2016-08-31 | 2017-01-04 | 合肥国轩高科动力能源有限公司 | A kind of nitrogen-doped carbon nanometer pipe sulfur composite and preparation method |
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