CN117559074A - Porous carbon nanofiber film for lithium-sulfur battery and preparation method and application thereof - Google Patents
Porous carbon nanofiber film for lithium-sulfur battery and preparation method and application thereof Download PDFInfo
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- CN117559074A CN117559074A CN202311562054.2A CN202311562054A CN117559074A CN 117559074 A CN117559074 A CN 117559074A CN 202311562054 A CN202311562054 A CN 202311562054A CN 117559074 A CN117559074 A CN 117559074A
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- 239000002133 porous carbon nanofiber Substances 0.000 title claims abstract description 48
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000012528 membrane Substances 0.000 claims abstract description 36
- GPBUGPUPKAGMDK-UHFFFAOYSA-N azanylidynemolybdenum Chemical compound [Mo]#N GPBUGPUPKAGMDK-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 22
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 208000012886 Vertigo Diseases 0.000 claims abstract description 16
- 239000000835 fiber Substances 0.000 claims abstract description 16
- 239000011229 interlayer Substances 0.000 claims abstract description 16
- 238000009987 spinning Methods 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 239000002121 nanofiber Substances 0.000 claims abstract description 12
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims abstract description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 10
- 239000011733 molybdenum Substances 0.000 claims abstract description 10
- 239000002019 doping agent Substances 0.000 claims abstract description 7
- 238000010000 carbonizing Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- 229910021389 graphene Inorganic materials 0.000 claims description 8
- 238000002347 injection Methods 0.000 claims description 7
- 239000007924 injection Substances 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 238000001523 electrospinning Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 5
- 239000005077 polysulfide Substances 0.000 abstract description 10
- 229920001021 polysulfide Polymers 0.000 abstract description 10
- 150000008117 polysulfides Polymers 0.000 abstract description 10
- 239000011148 porous material Substances 0.000 abstract description 5
- 230000003746 surface roughness Effects 0.000 abstract description 5
- 238000003756 stirring Methods 0.000 abstract description 4
- 239000010408 film Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 239000002134 carbon nanofiber Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910003003 Li-S Inorganic materials 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 239000012464 large buffer Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 150000007517 lewis acids Chemical group 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000014233 sulfur utilization Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
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- D01F9/24—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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- D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
- D06C7/00—Heating or cooling textile fabrics
- D06C7/04—Carbonising or oxidising
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- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
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Abstract
The invention provides a porous carbon nanofiber membrane for a lithium-sulfur battery, and a preparation method and application thereof. The porous carbon nanofiber membrane is a porous carbon nanofiber membrane containing molybdenum nitride, and the preparation raw materials comprise PMMA, PAN and PI. The preparation method comprises the following steps: (1) Adding a doping agent containing molybdenum acetylacetonate into N, N-dimethylformamide, sequentially adding PMMA, PAN and PI, stirring to form a spinning solution, and carrying out electrostatic spinning to obtain a primary spinning nanofiber film; (2) Heating and solidifying the as-spun nanofiber film in an air atmosphere to obtain a pre-oxidized fiber film; (3) Pre-oxidized fiber film in NH 3 And (3) heating and carbonizing in Ar mixed atmosphere to obtain the porous carbon nanofiber film. The porous carbon nanofiber membrane provided by the invention has pore diameters with different sizes, has higher surface roughness and higher porosity on the surface, can improve the doping content of molybdenum nitride, can be used as a functional interlayer to inhibit shuttling of polysulfide with higher efficiency, and can improve the electrochemical performance of a lithium-sulfur battery.
Description
Technical Field
The invention relates to the technical field of lithium-sulfur battery materials, in particular to a porous carbon nanofiber film for a lithium-sulfur battery, and a preparation method and application thereof.
Background
Energy is a necessary condition for social development, and technical progress and human cultural development are closely related to huge energy consumption. However, with uncontrolled exploitation of the world, conventional fossil energy has been exhausted. Therefore, the development of a novel environment-friendly energy storage system has important significance. Among all the existing energy storage systems, the lithium ion battery has the advantages of high working voltage, long cycle life, small environmental pollution and the like. Since the successful commercialization in the 90 s of the 20 th century, they have been dominant in the energy storage system market. However, the energy density of the traditional lithium ion battery has reached the theoretical limit after many years of development, and the higher requirements of the current society on the electrochemical energy storage system cannot be met. Therefore, there is interest in developing energy storage systems with high energy density and low cost. The lithium-sulfur battery has higher theoretical specific capacity (1675 mAh/g) and energy density (2600 Wh/kg) and is far higher than the existing lithium ion battery. In addition, the method has rich sulfur resource, low cost and environmental protection. Therefore, lithium sulfur batteries are considered to be a powerful competitor to the next generation of new energy storage systems. However, the commercialization process of lithium sulfur batteries still faces a number of problems, such as: the insulation property of the sulfur anode, the volume expansion in the charge and discharge process, the shuttle effect of polysulfide, dendrite of the lithium cathode and the like, wherein the shuttle effect of polysulfide is one of key factors for restricting the development of the lithium sulfur battery.
Disclosure of Invention
In view of the problems existing in the background art, the invention aims to provide a porous carbon nanofiber membrane for a lithium sulfur battery, a preparation method and application thereof, wherein the porous carbon nanofiber membrane has pore diameters with different sizes, has higher surface roughness and higher porosity on the surface, can improve the doping content of molybdenum nitride, can be used as a functional interlayer to inhibit shuttling of polysulfide with higher efficiency and improve the electrochemical performance of the lithium sulfur battery.
In order to achieve the above object, the present invention provides a porous carbon nanofiber membrane for a lithium sulfur battery, which is a porous carbon nanofiber membrane comprising molybdenum nitride; the preparation raw materials of the porous carbon nanofiber membrane comprise PMMA, PAN and PI.
The invention provides a preparation method of a porous carbon nanofiber membrane for a lithium-sulfur battery, which comprises the following steps: (1) Adding a doping agent containing molybdenum acetylacetonate into N, N-dimethylformamide, and carrying out ultrasonic treatment for 2-3.5 hours to obtain a mixed solution, wherein the mass volume ratio of the molybdenum acetylacetonate to the N, N-dimethylformamide is 1.5g (5-15) mL; then PMMA, PAN and PI with the total mass of 0.6-1.2g are added into the mixed solution in sequence, and then the mixed solution is stirred for 8-24 hours at room temperature to form uniform spinning solution, wherein the mass ratio of PMMA, PAN and PI is (0.5-1): 8 (2-4), and the mass volume ratio of the total mass of PMMA, PAN and PI to the mixed solution is (0.6-1.2) g (6-12) mL; the spinning solution is subjected to electrostatic spinning to obtain the as-spun nanofiberA film; (2) The collected as-spun nanofiber membrane is solidified for 4 to 6 hours in air atmosphere at a heating rate of 4 to 8 ℃/min to 160 to 200 ℃ so as to obtain a pre-oxidized fiber membrane; (3) Subjecting the collected pre-oxidized fiber film to NH 3 And (3) in the Ar mixed atmosphere, heating to 700-900 ℃ at a heating rate of 3-10 ℃/min, and carbonizing for 3-5 hours to finally obtain the molybdenum nitride doped porous carbon nanofiber film.
Optionally, in the step (1), the conditions of electrospinning are: the voltage is 10-20kV, the injection speed is 0.5-1.0mL/h, and the distance between the spinneret and the receiver is 10-20cm.
Optionally, in the step (1), the conditions of electrospinning are: the voltage was 15kV, the injection speed was 0.8mL/h, and the distance between the spinneret and the receiver was 15cm.
Optionally, in step (3), NH 3 NH/Ar mixed atmosphere of 10-30mL/min 3 And 10-30mL/min Ar.
Optionally, in step (3), NH 3 NH with Ar mixed atmosphere of 20mL/min 3 And 20mL/min Ar.
Optionally, the dopant comprises graphene oxide or carbon nanotubes.
Optionally, the mass ratio of the graphene oxide or the carbon nano tube to the molybdenum acetylacetonate in the doping agent is 1:500.
The invention provides a porous carbon nanofiber functional interlayer for a lithium sulfur battery, which comprises the porous carbon nanofiber film or the porous carbon nanofiber film prepared by the preparation method, wherein the porous carbon nanofiber functional interlayer is arranged between a sulfur anode and a diaphragm of the battery.
The invention provides an application of the porous carbon nanofiber membrane for a lithium-sulfur battery or the porous carbon nanofiber membrane prepared by the preparation method in the battery.
The beneficial effects of the invention are as follows:
1. the flexible carbon nanofiber membrane with high porosity and high molybdenum nitride content and uniform dispersion is used as an interlayer of the lithium sulfur battery, so that the shuttle of polysulfide can be restrained more efficiently, and the electrochemical performance of the lithium sulfur battery can be improved.
2. Most of the existing molybdenum nitride and carbon composite materials are powder materials, and an additional binder needs to be added in the preparation process, and the additional binder is used as an inert part to reduce the energy density of the battery; or energy consumption is caused by an additional deposition process during preparation. The invention does not need extra binder or complex process, thereby realizing the preparation of the functional interlayer of the lithium-sulfur battery.
3. In the sandwich material, the carbon nano-fibers prepared from PMMA, PAN and PI are matched and used in a specific proportion, and practice proves that the synergistic addition of PMMA and PI can ensure that the carbon fiber has the advantages of higher surface roughness or porosity in a larger pore size range and higher specific surface area compared with the single PAN, and can accommodate higher molybdenum nitride content; the carbon nanofibers are interwoven among the nanofibers to form a film with a three-dimensional conductive network structure, and the film has excellent conductivity and flexibility. In addition, the added or generated redox graphene or carbon nano tube has an improvement effect on mechanical stability, flexibility and conductivity.
4. The invention introduces high-content molybdenum nitride into the porous carbon-based material, enhances the adsorption of polysulfide and accelerates the redox kinetics in the reaction process. The Mo atoms which do not occupy the orbit on the surface of the molybdenum nitride serve as the positions of Lewis acid and can be used as a good polysulfide adsorbent. Theoretical calculations demonstrate that molybdenum nitride has an extremely low Li ion diffusion barrier, which allows for rapid ion transport. Combined with its high conductivity (4.55X10) 6 S/m), strong polysulfide adsorption and Li adsorption can be achieved by the action of molybdenum nitride 2 Rapid oxidation of S. And molybdenum nitride can effectively catalyze Li 2 The break of the Li-S bond in S promotes migration of the generated lithium ions.
5. According to the invention, PMMA, PAN and PI are used as raw materials, and a flexible porous carbon nanofiber membrane with uniform dispersion and high molybdenum nitride content can be prepared through an electrostatic spinning technology and a carbonization process. The carbon fiber has different pore diameters due to the gasification of PMMA in the carbonization process and the generation of ammonia gas and the like by PAN and PI, and the surface of the carbon fiber has higher surface roughness and higher porosity, so that a multi-layer porous structure and a high specific surface area are obtained, and the ammonia gas can increase the N doping content, so that more MoN is obtained. The sheet structure of PI can improve the strength of the carbon nanofiber after carbonization, and the problem of strength reduction caused by the increase of the porosity after PMMA pore-forming is avoided.
Drawings
Fig. 1 is a scanning electron microscope image of the molybdenum nitride doped porous carbon nanofiber thin film prepared in example 3.
Fig. 2 is a scanning electron microscope image of the molybdenum nitride doped porous carbon nanofiber thin film prepared in comparative example 1.
Fig. 3 is a graph of the rate performance test of the batteries in example 3 and comparative example 1.
Fig. 4 is a graph showing cycle performance test at a current density of 0.2C for the batteries of example 3 and comparative example 1.
Fig. 5 is an ac impedance graph of the batteries in example 3 and comparative example 1.
Detailed Description
The following detailed description of the present invention will provide further details in order to make the above-mentioned objects, features and advantages of the present invention more comprehensible.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways other than those described herein, and persons skilled in the art will readily appreciate that the present invention is not limited to the specific embodiments disclosed below.
The porous carbon nanofiber functional interlayer for the lithium sulfur battery, the preparation method and the application thereof are specifically described below with reference to specific examples.
Example 1
(1) 1.5g of molybdenum acetylacetonate and 3mg of graphene oxide are added into 5mLN, N-dimethylformamide for ultrasonic treatment for 2 hours to obtain a mixed solution; then adding PMMA, PAN and PI with the total mass of 0.6 to 6mL of mixed solution in sequence, and stirring for 8 hours at room temperature to form uniform spinning solution, wherein the mass ratio of PMMA to PAN to PI is 0.5:8:2; the spinning solution is subjected to electrostatic spinning to obtain a primary spinning nanofiber film; the conditions of the electrostatic spinning are as follows: the voltage was 10kV, the injection speed was 0.5mL/h, and the distance between the spinneret and the receiver was 10cm.
(2) The collected as-spun nanofiber membrane is solidified for 4 hours in air atmosphere at the temperature rising rate of 4 ℃/min to 160 ℃ to obtain a pre-oxidized fiber membrane;
(3) Subjecting the collected pre-oxidized fiber film to NH 3 In Ar mixed atmosphere, heating to 700 ℃ at a heating rate of 3 ℃/min, and carbonizing for 3 hours to finally obtain the molybdenum nitride doped porous carbon nanofiber film; NH (NH) 3 NH with Ar mixed atmosphere of 10mL/min 3 And 10mL/min Ar.
Example 2
(1) 1.5g of molybdenum acetylacetonate and 3mg of graphene oxide are added to 15mLN, N-dimethylformamide for ultrasonic treatment for 3.5 hours to obtain a mixed solution; then adding PMMA, PAN and PI with the total mass of 1.2g to 12mL of mixed solution in sequence, and stirring for 24 hours at room temperature to form uniform spinning solution, wherein the mass ratio of PMMA to PAN to PI is 1:8:4; the spinning solution is subjected to electrostatic spinning to obtain a primary spinning nanofiber film; the conditions of the electrostatic spinning are as follows: the voltage was 20kV, the injection speed was 1.0mL/h, and the distance between the spinneret and the receiver was 20cm.
(2) The collected as-spun nanofiber membrane is solidified for 6 hours in air atmosphere at the temperature rising rate of 8 ℃/min to 200 ℃ to obtain a pre-oxidized fiber membrane;
(3) Subjecting the collected pre-oxidized fiber film to NH 3 In Ar mixed atmosphere, heating to 900 ℃ at a heating rate of 10 ℃/min, and carbonizing for 5 hours to finally obtain the molybdenum nitride doped porous carbon nanofiber film; NH (NH) 3 NH/Ar mixed atmosphere of 30mL/min 3 And 30mL/min Ar.
Example 3
(1) 1.5g of molybdenum acetylacetonate and 3mg of graphene oxide are added into 10mLN, N-dimethylformamide for ultrasonic treatment for 3 hours to obtain a mixed solution; then adding PMMA, PAN and PI with the total mass of 0.9g to 9mL of mixed solution in sequence, and stirring for 16 hours at room temperature to form uniform spinning solution, wherein the mass ratio of PMMA to PAN to PI is 0.8:8:3; the spinning solution is subjected to electrostatic spinning to obtain a primary spinning nanofiber film; the conditions of the electrostatic spinning are as follows: the voltage was 15kV, the injection speed was 0.8mL/h, and the distance between the spinneret and the receiver was 15cm.
(2) The collected as-spun nanofiber membrane is solidified for 5 hours in air atmosphere at the temperature rising rate of 6 ℃/min to 180 ℃ to obtain a pre-oxidized fiber membrane;
(3) Subjecting the collected pre-oxidized fiber film to NH 3 In Ar mixed atmosphere, heating to 800 ℃ at a heating rate of 6 ℃/min, and carbonizing for 4 hours to finally obtain the molybdenum nitride doped porous carbon nanofiber film; NH (NH) 3 NH with Ar mixed atmosphere of 20mL/min 3 And 20mL/min Ar.
Comparative example 1
Except that PMMA is not used, other materials or processes are the same as in example 3, and the molybdenum nitride doped porous carbon nanofiber film is prepared.
Performance test and results
1. Scanning electron microscope test of samples:
fig. 1 is a scanning electron microscope image of a molybdenum nitride doped porous carbon nanofiber membrane prepared in example 3, which has a rough fiber surface, a high porosity, and a high content of MoN particles uniformly distributed on the fiber surface.
Fig. 2 is a scanning electron microscope image of a molybdenum nitride doped porous carbon nanofiber thin film prepared in comparative example 1, in which the surface roughness of the fiber surface is reduced and the diameter is flattened with respect to the fiber of fig. 1.
2. Lithium sulfur battery performance test:
the carbon nanofiber films of example 3 and comparative example 1 were used as functional interlayers, placed between the sulfur positive electrode and the separator of a lithium sulfur battery, and the lithium sulfur battery was subjected to electrochemical performance test, and the electrolyte was: 1.0M LiTFSI was dissolved in DOL/DME solution and 1% LiNO was added 3 An additive.
As shown in FIG. 3, example 3 is shown at 0.2C, 0.5C, 1C, 2C andthe discharge capacities at 3C were 1311, 1226, 1156, 1053 and 900.5mAhg, respectively -1 1264mAhg can still be obtained when the current density is returned to 0.2C -1 Is a reversible capacity of (2); whereas the discharge capacities of comparative example 1 at 0.2C, 0.5C, 1C, 2C and 3C were 1233, 1100.5, 1033.8, 910.9 and 804.2mAhg, respectively -1 When the current density returns to 0.2C, 1146mAhg can be obtained -1 Is a reversible capacity of (2); this means that the carbon nanofiber film of example 3 served as a functional interlayer, and the battery had excellent rate performance and stability.
Fig. 4 compares the cycling performance at 0.2C current density of two cells of the carbon nanofiber thin films of example 3 and comparative example 1. The initial capacity of the battery of example 3 was 1311mAhg -1 Is superior to the battery of comparative example 1 (1233 mAhg -1 ). The capacity of the battery of example 3 reached 1220mAhg even after 100 cycles -1 The capacity retention and capacity fade rates per turn were 93.1% and 0.07%, respectively. The initial discharge capacity of the battery of comparative example 1 was 1233mAh g -1 After 100 cycles, the discharge capacity is 1088mAh g -1 The capacity retention and capacity fade rates per turn were 88.2% and 0.12%, respectively. The functional interlayer of example 3 is described to give a battery with higher capacity stability, and the functional interlayer can better inhibit polysulfide and improve sulfur utilization.
Fig. 5 is an ac impedance plot. Through the test of alternating current impedance, it can be found that the use of the porous carbon nanofiber membrane (MoN/CNF (PMMA-PAN-PI)) of example 3 as a functional interlayer can significantly reduce the resistance of the battery. This is because the unique pore size porous structure of MoN/CNF (PMMA-PAN-PI) is more conducive to rapid permeation of electrolyte and provides a large buffer space, and its developed 3D conductive network provides a rapid channel for electron transport. In addition, moN can accelerate the reaction kinetics of polysulfides, and batteries containing the functional interlayer exhibit excellent electrochemical performance.
While certain specific embodiments of the invention have been described in detail by way of example, it will be appreciated by those skilled in the art that the above examples are for illustration only and are not intended to limit the scope of the invention. It will be appreciated by those skilled in the art that modifications may be made to the above embodiments without departing from the scope and spirit of the invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. The porous carbon nanofiber membrane for the lithium sulfur battery is characterized by comprising molybdenum nitride; the preparation raw materials of the porous carbon nanofiber membrane comprise PMMA, PAN and PI.
2. The method for preparing a porous carbon nanofiber membrane for a lithium sulfur battery as set forth in claim 1, comprising the steps of:
(1) Adding a doping agent containing molybdenum acetylacetonate into N, N-dimethylformamide, and carrying out ultrasonic treatment for 2-3.5 hours to obtain a mixed solution, wherein the mass volume ratio of the molybdenum acetylacetonate to the N, N-dimethylformamide is 1.5g (5-15) mL; then PMMA, PAN and PI with the total mass of 0.6-1.2g are added into the mixed solution in sequence, and then the mixed solution is stirred for 8-24 hours at room temperature to form uniform spinning solution, wherein the mass ratio of PMMA, PAN and PI is (0.5-1): 8 (2-4), and the mass volume ratio of the total mass of PMMA, PAN and PI to the mixed solution is (0.6-1.2) g (6-12) mL; the spinning solution is subjected to electrostatic spinning to obtain a primary spinning nanofiber film;
(2) The collected as-spun nanofiber membrane is solidified for 4 to 6 hours in air atmosphere at a heating rate of 4 to 8 ℃/min to 160 to 200 ℃ so as to obtain a pre-oxidized fiber membrane;
(3) Subjecting the collected pre-oxidized fiber film to NH 3 And (3) in the Ar mixed atmosphere, heating to 700-900 ℃ at a heating rate of 3-10 ℃/min, and carbonizing for 3-5 hours to finally obtain the molybdenum nitride doped porous carbon nanofiber film.
3. The method for producing a porous carbon nanofiber membrane for a lithium sulfur battery according to claim 2, wherein in the step (1), the conditions for electrospinning are: the voltage is 10-20kV, the injection speed is 0.5-1.0mL/h, and the distance between the spinneret and the receiver is 10-20cm.
4. The method for producing a porous carbon nanofiber membrane for a lithium sulfur battery according to claim 3, wherein in the step (1), the conditions for electrospinning are: the voltage was 15kV, the injection speed was 0.8mL/h, and the distance between the spinneret and the receiver was 15cm.
5. The method for producing a porous carbon nanofiber membrane for a lithium sulfur battery according to claim 2, wherein in step (3), NH 3 NH/Ar mixed atmosphere of 10-30mL/min 3 And 10-30mL/min Ar.
6. The method for producing a porous carbon nanofiber membrane for a lithium sulfur battery according to claim 5, wherein in step (3), NH 3 NH with Ar mixed atmosphere of 20mL/min 3 And 20mL/min Ar.
7. The method for producing a porous carbon nanofiber membrane for a lithium sulfur battery according to claim 2, wherein the dopant comprises graphene oxide or carbon nanotubes.
8. The method for preparing a porous carbon nanofiber functional interlayer for a lithium sulfur battery according to claim 7, wherein the mass ratio of graphene oxide or carbon nanotubes to molybdenum acetylacetonate in the dopant is 1:500.
9. The porous carbon nanofiber functional interlayer for the lithium sulfur battery is characterized by comprising the porous carbon nanofiber film according to claim 1 or the porous carbon nanofiber film prepared by the preparation method according to claims 2-8, and the porous carbon nanofiber functional interlayer is arranged between a sulfur anode and a diaphragm of the battery.
10. Use of the porous carbon nanofiber membrane for lithium sulfur batteries according to claim 1 or the porous carbon nanofiber membrane prepared by the preparation method according to any one of claims 2 to 8 in batteries.
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