CN113839024B - Self-supporting spinning sulfur anode host material uniformly loaded with small-size catalyst, preparation method and application thereof - Google Patents
Self-supporting spinning sulfur anode host material uniformly loaded with small-size catalyst, preparation method and application thereof Download PDFInfo
- Publication number
- CN113839024B CN113839024B CN202111107866.9A CN202111107866A CN113839024B CN 113839024 B CN113839024 B CN 113839024B CN 202111107866 A CN202111107866 A CN 202111107866A CN 113839024 B CN113839024 B CN 113839024B
- Authority
- CN
- China
- Prior art keywords
- nitrogen
- self
- nickel
- carbon quantum
- sulfur
- 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.)
- Active
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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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 belongs to the technical field of preparation of a lithium-sulfur battery anode host material, and particularly discloses a self-supporting spinning sulfur anode host material uniformly loaded with a small-size catalyst, a preparation method and application thereof. The invention provides a self-supporting spinning sulfur anode host material uniformly loading a small-size catalyst based on the confinement effect of carbon quantum dots, integrates the advantages of a small-size efficient catalyst and an easily-infiltrated self-supporting structure, and has the following advantages: the small-size catalyst of the carbon quantum dot confinement is uniformly and stably distributed in the carbon fiber, can efficiently catalyze polysulfide conversion, effectively relieve a shuttle effect and improve the cycle stability; the material is easy to infiltrate, is suitable for the conditions of ultrahigh sulfur loading and poor electrolyte, and shows excellent capacity performance and coulombic efficiency under severe conditions. The invention combines Ni @ NCDs with an electrostatic spinning technology, has the advantages of few synthesis process steps, simple operation and high cost performance, and can effectively improve the performance of LSBs under the condition of poor electrolyte.
Description
Technical Field
The invention belongs to the technical field of preparation of a lithium-sulfur battery anode host material, and particularly relates to a self-supporting spinning sulfur anode host material uniformly loaded with a small-size catalyst, a preparation method and application thereof, in particular to a self-supporting spinning sulfur anode host material suitable for a high-sulfur-loading and electrolyte-poor lithium-sulfur battery, and a preparation method and application thereof.
Background
Lithium Sulfur Batteries (LSBs) have received extensive research and attention due to having theoretical energy densities as high as 2600 Wh/kg. Since the Narza group of subjects utilized carbon as a host material of sulfur to significantly improve the performance of sulfur anodes in 2009, researchers designed many sulfur anodes with excellent electrochemical performance by further optimizing the host material, and greatly promoted the development of LSBs. However, positive electrodes based on these host materials generally need to be in an electrode solution-rich condition>20μL/mg s ) The electrochemical performance is excellent, the energy density of the LSBs is seriously affected, and the method is one of the main reasons for hindering the practical application of the LSBs.
In poor electrolytes LSBs, small amounts of dissolved polysulfides can cause large concentration variations, exacerbating the "shuttling effect", and thus require host materials with sufficient adsorption surface to inhibit the "shuttling effect", ensuring its cycling stability. However, host materials with sufficient surface cannot be infiltrated by small amounts of electrolyte; and sulfur can not react with lithium ions at the non-wetted part, thereby seriously affecting the specific capacity of the lithium ion battery. In addition, the electrode solution is difficult to permeate in the traditional powder electrode structure, and the problem of infiltration of the surface of the host material in the poor electrolyte LSBs is further aggravated. Therefore, reducing the amount of electrolyte requires effective suppression of the "shuttle effect" based on host materials that are easily wetted and have a low adsorption area.
The slow conversion process of polysulfides is the root cause for the polysulfide to accumulate in the electrolyte and cause a "shuttle effect". Thus, catalytic materials that can accelerate this process can effectively suppress the "shuttling effect" based on a low adsorption area. However, the catalytic material is easy to agglomerate and run off in the low specific surface area material, and the catalytic performance of the catalytic material is influenced. Therefore, achieving uniform loading of the catalyst on the low specific surface area material is one of the key approaches to reducing the amount of electrolyte used.
Chinese patent CN109037554A discloses a Ni/C composite nanofiber membrane applied to lithium sulfur batteries, the preparation method comprises the following steps: (1) adding polyacrylonitrile and nickel salt into an N, N-dimethylacetamide solution to be completely dissolved to obtain a spinning solution; (2) preparing the spinning solution into a precursor fiber film by adopting an electrostatic spinning technology, and sequentially carrying out pre-oxidation treatment and heat treatment on the precursor fiber film to obtain the Ni/C composite nanofiber film. When the nanofiber membrane is applied to a lithium-sulfur battery, the rate performance of the lithium-sulfur battery can be synergistically improved by utilizing the adsorption of porous carbon to polysulfide and the catalysis of metal Ni to polysulfide during charging and discharging. However, the Ni/C composite nanofiber membrane prepared by the patent is only used for membrane intercalation and cannot be directly used as a self-supporting anode host material, the process is complex, and the use cost is high.
Disclosure of Invention
The invention aims to provide a self-supporting spinning sulfur anode host material uniformly loading a small-size catalyst, which has the following advantages: the small-size catalyst of the carbon quantum dot confinement is uniformly and stably distributed in the carbon fiber; secondly, polysulfide can be efficiently catalyzed and converted, and the circulation stability is improved; thirdly, the electrolyte is easy to infiltrate and is suitable for the conditions of ultra-high sulfur-carrying and poor electrolyte (low E/S: low electrolyte/sulfur); fourthly, the synthesis process has less steps, simple operation and high cost performance.
Meanwhile, the invention also provides a preparation method of the self-supporting spinning sulfur anode host material uniformly loading the small-size catalyst.
Finally, the invention further provides an application of the self-supporting spinning sulfur anode host material uniformly loading the small-size catalyst in the preparation of Lithium Sulfur Batteries (LSBs).
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a self-supporting spinning sulfur positive host material (Ni @ NCDs-CNF) of a uniformly-supported small-size catalyst, which comprises self-supporting spinning Carbon Nanofibers (CNF) and nickel-supported nitrogen-doped carbon quantum dots (Ni @ NCDs) uniformly distributed in the self-supporting spinning carbon nanofibers; in the nickel-loaded nitrogen-doped carbon quantum dots, Ni-N bonds exist between nickel and nitrogen-doped carbon quantum dots (NCDs).
In a preferred embodiment, the mass ratio of the nickel-supported nitrogen-doped carbon quantum dots to the self-supporting spun carbon nanofibers is 0.1-1: 1.2. Further preferably, the mass ratio of the nitrogen-doped carbon quantum dots loaded with nickel to the self-supporting spun carbon nanofibers is 1: 2.4.
In a preferred embodiment, in the nickel-supported nitrogen-doped carbon quantum dot, the mass ratio of nickel (elemental nickel) to the nitrogen-doped carbon quantum dot is 1: 1-5. Further preferably, the mass ratio of the nickel to the nitrogen-doped carbon quantum dots is 1: 3.
As a preferred embodiment, the nickel-loaded nitrogen-doped carbon quantum dots have a size <20 nm. The nitrogen-doped carbon quantum dots comprise N, C, O and the like.
The invention provides a self-supporting spinning carbon nano material uniformly loading a small-size catalyst based on the confinement effect of carbon quantum dots, integrates the advantages of a small-size efficient catalyst and an easily-infiltrated self-supporting structure, and can be used as an LSBs (localized surface plasmon resonance) anode host material.
A preparation method of a self-supporting spinning sulfur anode host material uniformly loaded with a small-size catalyst comprises the following steps:
(1) preparation of nitrogen-doped carbon quantum dots (NCDs)
Preparing nitrogen-doped carbon quantum dots by using citric acid as a carbon source and ethylenediamine as a nitrogen source by adopting a hydrothermal method;
(2) preparation of nitrogen-doped carbon quantum dots (Ni @ NCDs) loaded with nickel
Dissolving nitrogen-doped carbon quantum dots and soluble nickel salt in water, and preparing the nickel-loaded nitrogen-doped carbon quantum dots by adopting a hydrothermal method;
(3) preparation of self-supporting spinning sulfur positive host material (Ni @ NCDs-CNF)
Mixing the nickel-loaded nitrogen-doped carbon quantum dots, polyvinylpyrrolidone (PVP) and a solvent to prepare a spinning solution, and then preparing the composite nanofiber by adopting an electrostatic spinning technology;
and carrying out pre-oxidation stabilization treatment on the composite nanofiber tabletting, and then carrying out heat treatment to obtain the composite nanofiber.
As a preferable embodiment, in the step (1), the reaction temperature for preparing the nitrogen-doped carbon quantum dots by the hydrothermal method is 180-. Further preferably, the reaction temperature is 200 ℃ and the hydrothermal time is 5 hours.
In a preferred embodiment, in step (1), the mass ratio of citric acid to ethylenediamine is 2-4: 1. Further preferably, the mass ratio of citric acid to ethylenediamine is 3.2: 1.
As a preferred embodiment, in step (1), the nitrogen-doped carbon quantum dots are prepared by a bottom-up hydrothermal method: firstly weighing 4.8g of anhydrous citric acid, completely dissolving the anhydrous citric acid in 50mL of deionized water, then using a pipettor to transfer 1.675mL of ethylenediamine, quickly adding the anhydrous citric acid solution, stirring uniformly, transferring the mixed solution into a 100mL reaction kettle with a polytetrafluoroethylene lining, heating for 5 hours at 200 ℃, naturally cooling the reacted solution to room temperature, concentrating the solution by using a vacuum rotary evaporator, placing the concentrated solution in a refrigerator for freezing for 12 hours, and then freeze-drying to obtain a dark reddish brown powder sample, namely the nitrogen-doped carbon quantum dots (NCDs).
In a preferred embodiment, in the step (2), the mass ratio of the nitrogen-doped carbon quantum dots to the soluble nickel salt is 1-5: 1. Further preferably, the mass ratio of the nitrogen-doped carbon quantum dots to the soluble nickel salt is 3: 1.
In a preferred embodiment, in step (2), the soluble nickel salt is one or more of nickel chloride, nickel nitrate, nickel acetate, nickel sulfate, and the like. Further preferably, the soluble nickel salt is nickel chloride.
In a preferable embodiment, in the step (2), the reaction temperature of the hydrothermal method for preparing the nitrogen-doped carbon quantum dots loaded with nickel is 180-220 ℃, and the hydrothermal time is 5-10 h. Further preferably, the reaction temperature is 200 ℃ and the hydrothermal time is 8 h.
As a preferred embodiment, in the step (2), the specific operation of preparing the nickel-loaded nitrogen-doped carbon quantum dots by the hydrothermal method is as follows: weighing 1g of nitrogen-doped carbon quantum dot powder, dissolving in 50mL of deionized water, and stirring to obtain a solutionHomogenizing; 0.33g of nickel chloride hexahydrate (NiCl) was weighed out 2 ·6H 2 O) adding the solution, stirring uniformly, transferring to a 100mL reaction kettle with a polytetrafluoroethylene lining, heating for 8h at 200 ℃, naturally cooling the solution after reaction to room temperature, concentrating by using a vacuum rotary evaporator, placing in a refrigerator for freezing for 12h, and then freeze-drying to obtain a dark brown powder sample, namely the nickel-loaded nitrogen-doped carbon quantum dots (Ni @ NCDs).
In a preferred embodiment, in the step (3), the mass ratio of the nickel-supported nitrogen-doped carbon quantum dots to the polyvinylpyrrolidone is 0.1-1: 1.2. Further preferably, the mass ratio of the nitrogen-doped carbon quantum dots supporting nickel to the polyvinylpyrrolidone is 1: 2.4.
In a preferred embodiment, in the step (3), the solvent is an aqueous solvent, specifically a mixed solution of anhydrous ethanol and water, and the volume ratio of the two is 2-1: 1; preferably 3: 2. The concentration of polyvinylpyrrolidone in the spinning solution is 0.1 to 0.2g/mL, preferably 0.12 g/mL.
As a preferred embodiment, in the step (3), the technical parameters of the composite nanofiber prepared by the electrospinning technology are as follows: the environmental humidity is 35-45%, and the temperature is about 30-40 ℃; the voltage is 10-20kV, the push speed is 0.5-1.0mL/h, the receiving distance is 10-20cm, and the receiving rotating speed is 20-40 rpm. Further preferably, the technical parameters are: ambient humidity about 40%, temperature about 35 ℃; the voltage is 16kV, the push speed is 0.8mL/h, the receiving distance is 15cm, and the receiving rotating speed is 30 rpm. Other technical parameters include: the syringe is 20mL gauge, stainless steel needle N23, oiled paper as the receiver.
As a preferred embodiment, in the step (3), the pre-oxidation stabilizing treatment is: under the air atmosphere, the temperature is raised to 130-170 ℃ from the room temperature at the heating rate of 0.5-2 ℃/min, and the temperature is kept for 2-4 h; then raising the temperature to 200-300 ℃ at a heating rate of 0.5-2 ℃/min, and keeping the temperature for 20-50 min. Further preferably, under the air atmosphere, the temperature is increased to 150 ℃ from room temperature at the heating rate of 1 ℃/min, and the temperature is kept for 3 h; then, the temperature is raised to 250 ℃ at a heating rate of 1 ℃/min, and the temperature is kept for 30 min.
As a preferable embodiment, in the step (3), the heat treatment is: raising the temperature to 600-750 ℃ at the heating rate of 3-10 ℃/min under the protection of Ar atmosphere, and keeping the temperature for 2-5 h. Further preferably, the temperature is increased to 700 ℃ at the temperature rising rate of 5 ℃/min under the protection of Ar atmosphere, and the temperature is kept for 3 h.
As a preferred embodiment, in step (3), the specific operation of preparing the composite nanofiber by using the electrospinning technology is as follows: firstly, preparing a solvent required by a spinning solution: 4mL of deionized water and 6mL of absolute ethyl alcohol are uniformly mixed; weighing 0.5g of nickel-loaded nitrogen-doped carbon quantum dots, uniformly dissolving the nickel-loaded nitrogen-doped carbon quantum dots in the solvent, then weighing 1.2g of polyvinylpyrrolidone (PVP), slowly adding the solution, and stirring for 12 hours; during the electrostatic spinning process, the ambient humidity is kept at about 40 percent, and the temperature is kept at about 35 ℃; the voltage is 16kV, the push speed is 0.8mL/h, the receiving distance is 15cm, and the receiving rotating speed is 30 rpm; the syringe is 20mL standard, stainless steel needle N23, oiled paper as the receiver, composite nanofiber was obtained. After spinning is finished, drying for 12h at 40 ℃, and then carrying out preoxidation stabilization treatment on the composite nanofiber tabletting: under the air atmosphere, the temperature is increased to 150 ℃ from the room temperature at the heating rate of 1 ℃/min, the temperature is maintained for 3h, then the temperature is increased to 250 ℃ at the heating rate of 1 ℃/min, and the temperature is maintained for 30 min; then carrying out heat treatment: heating to 700 ℃ at a heating rate of 5 ℃/min in a tubular furnace under the protection of Ar atmosphere, and keeping for 3h to obtain the catalyst.
The nitrogen-doped carbon quantum dots used in the invention are used as a zero-dimensional material, have the advantages of easy synthesis, doping and the like, rich functional groups of the nitrogen-doped carbon quantum dots can be coordinated with metal ions with empty d tracks such as Ni to form bonds, and the nitrogen-doped carbon quantum dots can limit the agglomeration and growth of metal particles in the heat treatment process to form M @ NCDs; and metal-loaded nitrogen-doped carbon material (NC) is a highly efficient catalyst. The electrostatic spinning carbon nanofiber is a self-supporting conductive material with high yield and simple process, and has the characteristics of low adsorption area and easy infiltration of electrolyte. According to the invention, Ni @ NCDs and an electrostatic spinning technology are combined to realize uniform loading of the catalyst in the material with easy infiltration and low adsorption area, so that the performance of LSBs under the condition of poor electrolyte is improved.
The invention prepares the self-supporting spinning carbon material Ni @ NCDs-CNF of the uniformly-loaded quantum dot high-efficiency catalyst based on the domain limiting effect of carbon quantum dots on metal particles and an electrostatic spinning technology, and has the following advantages: firstly, uniformly and stably distributing a metal quantum dot catalyst in a carbon quantum dot limited domain in carbon fibers; host materials can efficiently catalyze polysulfide conversion, shuttle effect is effectively relieved, and coulombic efficiency is improved; thirdly, the host material is very easy to infiltrate and is suitable for the conditions of ultrahigh sulfur carrying capacity and low electrolyte consumption; fourthly, the synthesis process has less steps, simple operation and high cost performance.
An application of a self-supporting spinning sulfur positive host material uniformly loading a small-size catalyst in the preparation of a lithium sulfur battery.
As a preferred embodiment, the lithium sulfur battery is prepared by first compounding sulfur with the self-supporting spun sulfur positive host material uniformly supporting the small-sized catalyst and then assembling the composite into the lithium sulfur battery.
The invention has the beneficial effects that:
the invention provides a self-supporting spinning sulfur anode host material uniformly loaded with a small-size catalyst, which has the following advantages compared with the traditional lithium sulfur battery anode host material: 1) the catalyst has high-efficiency catalytic performance in polysulfide catalytic conversion, and effectively relieves shuttle effect; 2) the electrolyte shows excellent capacity performance and coulombic efficiency under the severe conditions of ultrahigh sulfur loading and poor electrolyte.
Drawings
FIG. 1 is a transmission electron microscope image of NCDs in example 1 of the present invention;
FIG. 2 is a graph showing UV and excitation-emission spectra of NCDs in example 1 of the present invention;
FIG. 3 is an XPS spectrum of Ni @ NCDs as in example 1 of the present invention;
FIG. 4 is XRD patterns of three materials Ni @ CDs-CNF and the like in example 1 and comparative examples 1-2 of the present invention;
FIG. 5 is a transmission electron microscope image of Ni @ NCDs-CNF in example 1 of the present invention;
FIG. 6 is a CV diagram (20mV/s) of a symmetrical battery made of three materials, Ni @ NCDs-CNF, in example 1 and comparative examples 1-2 of the present invention;
FIG. 7 is a CV diagram (1mV/s) of a symmetrical battery using three materials, Ni @ NCDs-CNF, etc., in example 1 and comparative examples 1-2 according to the present invention;
FIG. 8 is a CV diagram (0.1mV/s) of an asymmetric battery using three materials, Ni @ NCDs-CNF, etc., in example 1 and comparative examples 1-2 according to the present invention;
FIG. 9 is a graph of rate capability of three materials, Ni @ NCDs-CNF, etc., in example 1 and comparative examples 1-2 of the present invention;
FIG. 10 shows the high sulfur loading and low E/S performance of the three materials Ni @ NCDs-CNF, etc. in example 1 and comparative examples 1-2 of the present invention at different current densities.
In order to more clearly explain the technical solutions of the embodiments of the present invention, the drawings obtained in the embodiments and experimental examples are briefly described above. It is understood that the above-mentioned drawings only show some experimental examples of the present invention and should not be considered as limiting the scope of protection of the claims in any way. For those skilled in the art, it is obvious that other related drawings can be obtained from these drawings without creative efforts.
Detailed Description
In order to make the technical problems to be solved, the technical solutions adopted and the technical effects achieved by the present invention easier to understand, the technical solutions of the present invention are clearly and completely described below with reference to specific examples, comparative examples and experimental examples. It should be noted that the reagents, instruments and the like used in examples, comparative examples and experimental examples are commercially available. Wherein, the vacuum rotary evaporator is purchased from Zhengzhou Zhengzheng apparatus Limited company, and has the model number: RE-2000A; the freeze dryer was purchased from Ningbo Xinzhi Biotech GmbH; the electrostatic spinning machine is purchased from Changshana instrument science and technology limited company, model: JDF 05.
Example 1
The self-supporting spinning sulfur positive host material uniformly loading the small-size catalyst in the embodiment comprises a self-supporting spinning Carbon Nanofiber (CNF) and nickel-loaded nitrogen-doped carbon quantum dots (Ni @ NCDs) uniformly distributed on the self-supporting spinning carbon nanofiber, wherein in the nickel-loaded nitrogen-doped carbon quantum dots, a Ni-N bond exists between nickel and the nitrogen-doped carbon quantum dots (NCDs).
The preparation method of the self-supporting spinning sulfur cathode host material uniformly loaded with the small-size catalyst in the embodiment comprises the following steps:
(1) preparation of nitrogen-doped carbon quantum dots (NCDs)
Preparing nitrogen-doped carbon quantum dots by a bottom-up hydrothermal method: firstly weighing 4.8g of anhydrous citric acid, completely dissolving the anhydrous citric acid in 50mL of deionized water, then using a pipettor to transfer 1.675mL of ethylenediamine, quickly adding the anhydrous citric acid solution, stirring uniformly, transferring the mixed solution into a 100mL reaction kettle with a polytetrafluoroethylene lining, heating for 5 hours at 200 ℃, naturally cooling the reacted solution to room temperature, concentrating the solution by using a vacuum rotary evaporator, placing the concentrated solution in a refrigerator for freezing for 12 hours, and then freeze-drying to obtain a dark reddish brown powder sample, namely the nitrogen-doped carbon quantum dots (NCDs).
(2) Preparation of nitrogen-doped carbon quantum dots (Ni @ NCDs) loaded with nickel
Weighing 1g of nitrogen-doped carbon quantum dot powder, dissolving in 50mL of deionized water, and stirring until the solution is uniform; 0.33g of nickel chloride hexahydrate salt (NiCl) was weighed out 2 ·6H 2 O) adding the solution into the mixture, stirring the mixture evenly, transferring the mixture into a 100mL reaction kettle with a polytetrafluoroethylene lining, heating the mixture for 8 hours at 200 ℃, naturally cooling the reacted solution to room temperature, concentrating the solution by using a vacuum rotary evaporator, freezing the concentrated solution in a refrigerator for 12 hours, and then freezing and drying the frozen solution to obtain a dark brown powder sample, namely the nickel-loaded nitrogen-doped carbon quantum dots (Ni @ NCDs).
(3) Preparation of self-supporting spinning sulfur positive host material (Ni @ NCDs-CNF)
Firstly, preparing a solvent required by a spinning solution: 4mL of deionized water and 6mL of absolute ethyl alcohol are uniformly mixed; weighing 0.5g of nickel-loaded nitrogen-doped carbon quantum dots, uniformly dissolving the nickel-loaded nitrogen-doped carbon quantum dots in the solvent, then weighing 1.2g of polyvinylpyrrolidone (PVP), slowly adding the solution, and stirring for 12 hours; during the electrostatic spinning process, the ambient humidity is kept at about 40 percent, and the temperature is kept at about 35 ℃; the voltage is 16kV, the push speed is 0.8mL/h, the receiving distance is 15cm, and the receiving rotating speed is 30 rpm; the needle cylinder is 20mL in specification, a stainless steel needle head N23 and oiled paper are used as a receiver, and the composite nanofiber is obtained;
after spinning is finished, drying the composite nanofiber at 40 ℃ for 12h, and then performing preoxidation stabilization treatment on a sample pressed sheet: under the air atmosphere, the temperature is increased to 150 ℃ from the room temperature at the heating rate of 1 ℃/min, the temperature is maintained for 3h, then the temperature is increased to 250 ℃ at the heating rate of 1 ℃/min, and the temperature is maintained for 30 min; then carrying out heat treatment: heating to 700 ℃ at a heating rate of 5 ℃/min in a tubular furnace under the protection of Ar atmosphere, and keeping for 3h to obtain the catalyst.
Example 2
The self-supporting spinning sulfur anode host material uniformly loaded with the small-size catalyst in the embodiment is prepared by the method comprising the following steps of:
(1) preparation of nitrogen-doped carbon quantum dots (NCDs)
Preparing nitrogen-doped carbon quantum dots by a bottom-up hydrothermal method: weighing 3.0g of anhydrous citric acid, completely dissolving the anhydrous citric acid in 50mL of deionized water, then using a pipettor to transfer 1.675mL of ethylenediamine, quickly adding the anhydrous citric acid solution, stirring uniformly, transferring the mixed solution to a 100mL reaction kettle with a polytetrafluoroethylene lining, heating for 8h at 180 ℃, naturally cooling the reacted solution to room temperature, concentrating the solution by using a vacuum rotary evaporator, placing the concentrated solution in a refrigerator for freezing for 12h, and then freeze-drying to obtain a dark reddish brown powder sample, namely nitrogen-doped carbon quantum dots (NCDs).
(2) Preparation of nitrogen-doped carbon quantum dots (Ni @ NCDs) loaded with nickel
Weighing 0.33g of nitrogen-doped carbon quantum dot powder, dissolving in 50mL of deionized water, and stirring until the solution is uniform; 0.33g of nickel chloride hexahydrate salt (NiCl) was weighed out 2 ·6H 2 O) adding the solution, stirring uniformly, transferring to a 100mL reaction kettle with a polytetrafluoroethylene lining, heating for 10h at 180 ℃, naturally cooling the solution after reaction to room temperature, concentrating by using a vacuum rotary evaporator, placing in a refrigerator for freezing for 12h, and then freeze-drying to obtain a dark brown powder sample, namely the nickel-loaded nitrogen-doped carbon quantum dots (Ni @ NCDs).
(3) Preparation of self-supporting spinning sulfur positive host material (Ni @ NCDs-CNF)
Firstly, preparing a solvent required by a spinning solution: 4mL of deionized water and 6mL of absolute ethyl alcohol are uniformly mixed; weighing 0.1g of nickel-loaded nitrogen-doped carbon quantum dots, uniformly dissolving the nickel-loaded nitrogen-doped carbon quantum dots in the solvent, then weighing 1.2g of polyvinylpyrrolidone (PVP), slowly adding the solution, and stirring for 12 hours; during the electrostatic spinning process, the ambient humidity is kept at about 40 percent, and the temperature is kept at about 35 ℃; the voltage is 18kV, the push speed is 1.0mL/h, the receiving distance is 15cm, and the receiving rotating speed is 35 rpm; the needle cylinder is 20mL in specification, a stainless steel needle head N23 and oiled paper are used as a receiver, and the composite nanofiber is obtained;
after spinning is finished, drying the composite nanofiber at 40 ℃ for 12h, and then performing preoxidation stabilization treatment on a sample tabletting: under the air atmosphere, the temperature is increased to 160 ℃ from the room temperature at the heating rate of 1.5 ℃/min, the temperature is kept for 2.5h, then the temperature is increased to 300 ℃ at the heating rate of 1 ℃/min, and the temperature is kept for 30 min; then carrying out heat treatment: heating to 650 ℃ at the heating rate of 10 ℃/min in a tube furnace under the protection of Ar atmosphere, and keeping for 4h to obtain the catalyst.
Example 3
The self-supporting spinning sulfur anode host material uniformly loaded with the small-size catalyst in the embodiment is prepared by the method comprising the following steps of:
(1) preparation of nitrogen-doped carbon quantum dots (NCDs)
Preparing nitrogen-doped carbon quantum dots by a bottom-up hydrothermal method: firstly weighing 6.0g of anhydrous citric acid, completely dissolving the anhydrous citric acid in 50mL of deionized water, then using a pipette to remove 1.675mL of ethylenediamine, quickly adding the anhydrous citric acid solution, stirring uniformly, transferring the mixed solution into a 100mL reaction kettle with a polytetrafluoroethylene lining, heating for 3 hours at 220 ℃, naturally cooling the reacted solution to room temperature, concentrating the solution by using a vacuum rotary evaporator, then placing the concentrated solution into a refrigerator for freezing for 12 hours, and then freezing and drying to obtain a dark reddish brown powder sample, namely nitrogen-doped carbon quantum dots (NCDs).
(2) Preparation of nickel-loaded nitrogen-doped carbon quantum dots (Ni @ NCDs)
Weighing 1.65g of nitrogen-doped carbon quantum dot powder, dissolving in 50mL of deionized water, and stirring until the solution is uniform; 0.33g of nickel chloride hexahydrate salt (NiCl) was weighed out 2 ·6H 2 O) adding the solution, stirring uniformly, transferring to a 100mL reaction kettle with a polytetrafluoroethylene lining, heating for 5h at 220 ℃, naturally cooling the solution after reaction to room temperature, concentrating by using a vacuum rotary evaporator, placing in a refrigerator for freezing for 12h, and then freeze-drying to obtain a dark brown powder sample, namely the nickel-loaded nitrogen-doped carbon quantum dots (Ni @ NCDs).
(3) Preparation of self-supporting spinning sulfur positive host material (Ni @ NCDs-CNF)
Firstly, preparing a solvent required by a spinning solution: 4mL of deionized water and 6mL of absolute ethyl alcohol are uniformly mixed; weighing 1.0g of nickel-loaded nitrogen-doped carbon quantum dots, uniformly dissolving the nickel-loaded nitrogen-doped carbon quantum dots in the solvent, then weighing 1.2g of polyvinylpyrrolidone (PVP), slowly adding the solution, and stirring for 12 hours; during the electrostatic spinning process, the ambient humidity is kept at about 40 percent, and the temperature is kept at about 35 ℃; the voltage is 14kV, the push speed is 0.6mL/h, the receiving distance is 18cm, and the receiving rotating speed is 20 rpm; the needle cylinder is 20mL in specification, a stainless steel needle head N23 and oiled paper are used as a receiver, and composite nanofiber is obtained;
after spinning is finished, drying the composite nanofiber at 40 ℃ for 12h, and then performing preoxidation stabilization treatment on a sample pressed sheet: under the air atmosphere, the temperature is raised to 130 ℃ from the room temperature at the heating rate of 0.5 ℃/min, the temperature is kept for 4 hours, and then the temperature is raised to 280 ℃ at the heating rate of 1.5 ℃/min, and the temperature is kept for 20 minutes; then carrying out heat treatment: heating to 750 ℃ at a heating rate of 3 ℃/min in a tubular furnace under the protection of Ar atmosphere, and keeping for 4h to obtain the catalyst.
Comparative example 1
The preparation of Ni-CNF in this comparative example comprises the following steps: 0.1g of NiCl was weighed 2 ·6H 2 Dissolving O in 10mL of a special spinning solvent (4mL of deionized water and 6mL of absolute ethyl alcohol), slowly and gradually adding 1.2g of polyvinylpyrrolidone (PVP) while stirring, and stirring for 12 hours to obtain uniform slurry; the subsequent electrostatic spinning process, the high-temperature roasting process and the like are kept consistent with those of the embodiment 1, and the sample Ni-CNF roasted at 700 ℃ is obtained.
It should be noted that: the present invention contemplates Ni-CNF as a comparative example intended to require large amounts of electrolyte for current high performance lithium sulfur batteries in general, i.e., high E/S: (C/S)>20μL/mg s ) This seriously affects the volumetric energy density, which is disadvantageous for industrialization. The invention is based on a low E/S (5. mu.L/mg) s ) Ultra-high sulfur loading under conditions (18mg S/cm) 2 ) The design of a positive host material provides a new idea of replacing Ni with small-size Ni catalysts (namely Ni @ NCDs) of carbon quantum dot restricted domains to uniformly distribute Ni on carbon nanofibers; compared with Ni-CNF, Ni @ NCDs are uniformly and stably distributed in the carbon fiber in an ultra-small size, the consumption of metal salt is greatly reduced, and the solventIs water and ethanol, is nontoxic and harmless, and is environment-friendly. Meanwhile, a coordination bond Ni-N exists between Ni and NCDs, polysulfide conversion can be efficiently catalyzed, the cycle stability is improved, and due to the application of the NCDs, the conductivity of a spinning material is obviously improved, and the electronic environment of an active site is effectively adjusted, so that the excellent performance can be achieved only by roasting at 700 ℃, and the energy consumption is obviously saved.
Comparative example 2
The preparation of CNF in this comparative example comprises the following steps: weighing 1.2g of Polyacrylonitrile (PAN), slowly adding the Polyacrylonitrile (PAN) into 10mL of N, N-Dimethylformamide (DMF) while stirring, and stirring for 12h to obtain uniform slurry; the subsequent electrostatic spinning process, the high-temperature roasting process and the like are kept consistent with those of the embodiment 1, and the sample CNF roasted at 700 ℃ is obtained.
It should be noted that: the nitrogen-doped carbon quantum dots (Ni @ NCDs) loaded with nickel prepared by the invention are water-soluble materials and are insoluble in toxic organic solvents such as N, N-dimethylformamide, N-dimethylacetamide and the like which pollute the environment, so that polyvinylpyrrolidone is selected as a carbon source in the invention, and the design is also based on the advantages of general non-toxicity, good biocompatibility and the like of CDs materials. Comparative example 2 polyacrylonitrile was used as a carbon source to represent a pure carbon fiber type material without a catalyst as a comparative scheme because polyvinylpyrrolidone is unstable and decomposed at an annealing temperature of 700 c when CNF is prepared.
Experimental example 1
(1) The results of transmission electron microscopy analysis of the NCDs of example 1 are shown in FIG. 1.
As can be seen from FIG. 1, the NCDs in example 1 are spherical particles having an average particle diameter of 4.7nm (particle diameter statistics is shown in the inset), and are uniformly dispersed.
(2) The NCDs from example 1 were taken for UV and excitation-emission spectroscopy (the inset is a 365nm UV light excitation image) and the results are shown in FIG. 2.
As can be seen from fig. 2, the uv absorption of NCDs at 230nm and 340nm in example 1 is characteristic of typical aromatic C ═ C bond pi-pi transition and conjugated C ═ O, C ═ N bond N-pi transition, with a maximum emission wavelength at 440nm, corresponding to an excitation wavelength of 360 nm.
(3) XPS analysis of Ni @ NCDs of example 1 was performed, and the results are shown in FIG. 3.
As can be seen from FIG. 3, Ni @ NCDs in example 1 have Ni-N bonds between Ni and NCDs.
(4) XRD analysis was performed on the Ni @ NCDs-CNF of example 1 and the Ni-CNF and CNF of comparative examples 1-2, and the results are shown in FIG. 4.
As can be seen from FIG. 4, the nickel of Ni @ NCDs-CNF in example 1 exists in elemental form, and its characteristic peak is weaker compared to Ni-CNF, indicating that the crystal size of nickel particles is smaller.
(5) The transmission electron microscope analysis was carried out using Ni @ NCDs-CNF of example 1, and the results are shown in FIG. 5 (A: 50nm, B: 200 nm).
As can be seen from FIG. 5, Ni @ NCDs-CNF in example 1 is a carbon fiber structure uniformly loaded with small-size nickel.
Experimental example 2
The performance of the composite material such as Ni @ NCDs-CNF carrying the nickel quantum dots is evaluated through the electrochemical performance and the battery performance.
Electrochemical performance evaluation method: cyclic voltammetry tests were performed by assembling symmetric cells and evaluated against peak current and area. The positive and negative poles are all 1cm 2 The same spinning material Ni @ NCDs-CNF has electrolyte of 40 mu L and 0.2M Li 2 S 6 And (3) an electrolyte. CV (cyclic voltammetry) test conditions were: the voltage test range is-1-1V at room temperature (25 ℃), and the sweep rates are 20mV/s and 1mV/s respectively.
Li 2 S 6 The electrolyte was prepared as follows: mixing S powder and Li 2 S powder in a glove box, 10mL of 1M LiTFSI + DOL/DME (1:1) v/v + 2% LiNO was added in a molar ratio of 5:1 3 Heating and stirring the solution in the electrolyte at 40 ℃ until the solution is completely reacted and dissolved to obtain a brown yellow solution, namely 0.2M Li 2 S 6 And (3) an electrolyte.
(1) Comparison of electrochemical Properties of Ni @ NCDs-CNF, Ni-CNF, CNF
The Ni-CNF and CNF of comparative examples 1-2 were used as comparative electrode materials, and the test results of the test were shown in fig. 6 and 7 by assembling the symmetrical cell according to the above method.
As can be seen from FIGS. 6 and 7, when the sweep rate of the cyclic voltammetry test on the symmetric battery is 20mV/s, the peak currents of Ni @ NCDs-CNF, Ni-CNF and CNF are 17.5mA, 15.5mA and 4.5mA in sequence; when the sweep rate is 1mV/s, the peak currents of Ni @ NCDs-CNF, Ni-CNF and CNF are 2.8mA, 2.4mA and 1.3mA in sequence.
(2) Comparison of electrochemical properties of Ni @ NCDs-CNF at different calcination temperatures
The preparation method of the Ni @ NCDs-CNF spinning material is basically the same as that of the example 1, and the differences are only that: and roasting the materials for 3 hours at 500 ℃, 600 ℃, 700 ℃ and 800 ℃ respectively under the argon atmosphere to obtain the Ni @ NCDs-CNF electrode materials with different roasting temperatures. Assembling the electrode materials into a symmetrical battery to carry out cyclic voltammetry tests with sweep rates of 20mV/s and 2mV/s respectively; wherein, 0.2M Li 2 S 6 The amount of electrolyte was 20. mu.L.
Test results show that when the sweep rate is 20mV/s, the peak currents of the electrode materials processed by the Ni @ NCDs-CNF at 500 ℃, 600 ℃, 700 ℃ and 800 ℃ are 1mA, 2.5mA, 9mA and 0.2mA in sequence; when the sweep rate is 2mV/s, the peak currents of the electrode materials processed by the Ni @ NCDs-CNF at 500 ℃, 600 ℃, 700 ℃ and 800 ℃ are 0.48mA, 1.35mA, 2mA and 0.1mA respectively.
Experimental example 3
The electrode materials of example 1 and comparative examples 1-2 were assembled into asymmetric cells and subjected to cyclic voltammetry and comparative redox peak position and peak current to evaluate their catalytic activity. The positive and negative poles are 1cm respectively 2 The electrolyte solution of the spinning material and the lithium sheet was 20. mu.L of 0.2M Li 2 S 8 And (3) an electrolyte. CV (cyclic voltammetry) test conditions were: the voltage test range is 1.7-2.8V at room temperature (25 ℃), and the sweep rates are respectively 0.1 mV/s. The test results are shown in fig. 8.
As can be seen from FIG. 8, the oxidation peak positions of the electrode materials Ni @ NCDs-CNF, Ni-CNF and CNF are respectively 2.5V, 2.57V and 2.57V, and the peak currents are respectively 6.08mA, 3.57mA and 1.26 mA; the first reduction peak positions are respectively 2.297V, 2.297V and 2.2V, and the peak currents are 1.25mA, 0.55mA and 0.45 mA; the second reduction peak positions were 1.96V, 1.92V, 1.88V, respectively, and the peak currents were 3.7mA, 1.45mA, 0.7 mA.
Experimental example 4
The electrode materials in example 1 and comparative examples 1-2 were assembled into asymmetric batteries and subjected to a charge-discharge rate test to compare the battery performance. The positive and negative poles are 1cm respectively 2 S @ spinning material, lithium sheet of (1.5 mg/cm) S loading 2 The electrolyte is 30 mu L of 1M LiTFSI + DOL/DME (1:1) v/v +2 percent LiNO 3 And (3) an electrolyte.
Preparation of S @ spinning material: dissolving 0.1g of sulfur powder in 10mL of toluene, heating and stirring at 40 ℃ to obtain a uniform solution (namely a sulfur-containing solution), sequentially dropwise adding 150 mu L of the solution into Ni @ NCDs-CNF, Ni-CNF and CNF electrode materials, weighing by a ten-thousandth balance and confirming that the sulfur capacity is 1.5mg/cm 2 . After drying, assembling the battery according to the steps, namely the electrolyte: active substance S was 20. mu.L: 1 mg.
And (3) testing rate performance and cycle stability: the battery was subjected to multiplying factor tests of 0.2C, 0.5C, 1C, 2C, and 0.2C, with a voltage range of 1.5-3.0V, and the results are shown in fig. 9 comparing the charge-discharge plateau potential, capacity, and coulombic efficiency.
As can be seen from FIG. 9, the specific discharge capacities of the electrode materials Ni @ NCDs-CNF, Ni-CNF and CNF at 0.2C, 0.5C, 1C, 2C and 0.2C are (1150, 1050, 970, 860, 1050mAh/g), (1000, 790, 615, 493, 850mAh/g), (800, 690, 500, 400 and 600mAh/g) in sequence.
Experimental example 5
And performing ultra-high-loading low-E/S performance tests on the Ni @ NCDs-CNF and the Ni-CNF.
1.8mL of the sulfur-containing solution obtained in Experimental example 4 was gradually added dropwise to the Ni @ NCDs-CNF electrode material, and the sulfur-containing solution was weighed by a ten-thousandth balance and confirmed to have a sulfur loading of 18mg/cm 2 (ii) a Sequentially and gradually dripping 1mL of sulfur-containing solution into the Ni-CNF electrode material, weighing by a ten-thousandth balance and confirming that the sulfur loading is 10mg/cm 2 (ii) a After drying, the battery was assembled according to the procedure of experimental example 4, in which the electrolyte was used in an amount of 90 μ L and 50 μ L, i.e., E: s is 5. mu.L: 1 mg.
And (3) testing the charge and discharge performance: the battery was charged at 0.1mA/cm 2 、0.5mA/cm 2 Charge and discharge property ofThe voltage range can be tested to be 1.5-3.0V, and the results are shown in figure 10 by comparing the actual capacity and the coulombic efficiency.
As can be seen from FIG. 10, Ni @ NCDs-CNF and Ni-CNF are at 0.1mA/cm 2 、0.5mA/cm 2 The actual discharge capacity at the current density was (18.7 mAh/cm) 2 ，14.1mAh/cm 2 )、(6.8mAh/cm 2 ，4.2mAh/cm 2 )。
From the experimental results, the self-supporting spinning sulfur cathode host material uniformly loading the small-size catalyst provided by the invention is suitable for high-sulfur-loading and electrolyte-poor lithium sulfur batteries, and has the following advantages compared with the traditional lithium sulfur battery cathode host material: 1) the catalyst has high-efficiency catalytic performance in polysulfide catalytic conversion, and effectively relieves shuttle effect; 2) the electrolyte shows excellent capacity performance and coulombic efficiency under the severe conditions of ultrahigh sulfur loading and poor electrolyte.
In addition, in patent CN109037554A, the spinning material is only used as a separator intercalation, but the spinning material is directly used as a self-supporting anode host material in the invention, and a conductive additive and a binder are not needed, so that the raw material cost and the process link are greatly saved, and the mass energy density of the battery is improved.
The invention belongs to the development type, and the above is only the preferable embodiment of the invention, and does not limit the protection scope of the invention. Many variations and/or modifications in the specific implementation of the invention may occur to those skilled in the art. Any other substitutions, combinations, modifications, changes and substitutions which are equivalent to one another without departing from the principles of the invention are intended to be included within the scope of the invention.
Claims (10)
1. A self-supporting spinning sulfur anode host material of a uniform load catalyst, which is characterized in that: the sulfur anode host material comprises self-supporting spinning carbon nano-fibers and nickel-loaded nitrogen-doped carbon quantum dots uniformly distributed in the self-supporting spinning carbon nano-fibers; in the nickel-loaded nitrogen-doped carbon quantum dot, a Ni-N bond exists between the nickel and the nitrogen-doped carbon quantum dot.
2. The homogeneously catalyst-supported, self-supporting, spun sulfur positive host material of claim 1, characterized in that: the mass ratio of the nickel-loaded nitrogen-doped carbon quantum dots to the self-supporting spinning carbon nanofiber is 0.1-1: 1.2.
3. The homogeneously catalyst-supported, self-supporting, spun sulfur positive host material of claim 1, characterized in that: in the nickel-loaded nitrogen-doped carbon quantum dot, the mass ratio of nickel to the nitrogen-doped carbon quantum dot is 1: 1-5.
4. The homogeneously catalyst-supported, self-supporting, spun sulfur positive host material of claim 1, characterized in that: the size of the nickel-loaded nitrogen-doped carbon quantum dot is less than 20 nm; the nitrogen-doped carbon quantum dots at least comprise N, C, O elements.
5. A method for preparing the uniformly catalyst-supported self-supporting spun sulfur positive host material of any one of claims 1 to 4, wherein: the method comprises the following steps:
(1) preparation of nitrogen-doped carbon quantum dots
Preparing nitrogen-doped carbon quantum dots by using citric acid as a carbon source and ethylenediamine as a nitrogen source by adopting a hydrothermal method;
(2) preparation of nitrogen-doped carbon quantum dots loaded with nickel
Dissolving nitrogen-doped carbon quantum dots and soluble nickel salt in water, and preparing the nickel-loaded nitrogen-doped carbon quantum dots by adopting a hydrothermal method;
(3) preparation of self-supporting spinning sulfur anode host material
Mixing the nickel-loaded nitrogen-doped carbon quantum dots, polyvinylpyrrolidone and a solvent to prepare a spinning solution, and then preparing the composite nanofiber by adopting an electrostatic spinning technology;
and carrying out pre-oxidation stabilization treatment on the composite nanofiber tabletting, and then carrying out heat treatment to obtain the composite nanofiber.
6. The method of preparing the homogeneously catalyst-supported self-supporting spun sulfur positive electrode host material according to claim 5, characterized in that: in the step (1), preparing the nitrogen-doped carbon quantum dots by a hydrothermal method from bottom to top, wherein the reaction temperature of the hydrothermal method is 180-220 ℃, and the hydrothermal time is 3-8 h; and/or the mass ratio of the citric acid to the ethylenediamine is 2-4: 1.
7. The method of preparing the homogeneously catalyst-supported self-supporting spun sulfur positive electrode host material according to claim 5, characterized in that: in the step (2), the mass ratio of the nitrogen-doped carbon quantum dots to the soluble nickel salt is 1-5: 1; and/or the soluble nickel salt is one or more of nickel chloride, nickel nitrate, nickel acetate and nickel sulfate; and/or the reaction temperature of the hydrothermal method is 180-220 ℃, and the hydrothermal time is 5-10 h.
8. The method for preparing the uniformly catalyst-supported self-supporting spun sulfur positive host material according to claim 5, wherein: in the step (3), the mass ratio of the nickel-loaded nitrogen-doped carbon quantum dots to the polyvinylpyrrolidone is 0.1-1: 1.2; and/or the solvent is a mixed solution of absolute ethyl alcohol and water, and the concentration of polyvinylpyrrolidone in the spinning solution is 0.1-0.2 g/mL; and/or the technical parameters for preparing the composite nanofiber by adopting the electrostatic spinning technology are as follows: the environmental humidity is 35-45%, and the temperature is 30-40 ℃; the voltage is 10-20kV, the pushing speed is 0.5-1.0mL/h, the receiving distance is 10-20cm, and the receiving rotating speed is 20-40 rpm; and/or, the pre-oxidation stabilizing treatment is as follows: under the air atmosphere, the temperature is raised to 130-170 ℃ from the room temperature at the heating rate of 0.5-2 ℃/min, and the temperature is kept for 2-4 h; then raising the temperature to 200-300 ℃ at the heating rate of 0.5-2 ℃/min, and keeping the temperature for 20-50 min; and/or, the heat treatment is: under the protection of Ar atmosphere, the temperature is raised to 600-750 ℃ at the heating rate of 3-10 ℃/min, and the temperature is maintained for 2-5 h.
9. Use of the homogeneously catalyst-loaded self-supporting spun sulfur positive host material according to any one of claims 1 to 4, or the homogeneously catalyst-loaded self-supporting spun sulfur positive host material prepared by the preparation method according to any one of claims 5 to 8, for the preparation of a lithium sulfur battery.
10. Use according to claim 9, characterized in that: when the lithium-sulfur battery is prepared, firstly, sulfur and the self-supporting spinning sulfur anode host material uniformly loaded with the catalyst are compounded, and then the lithium-sulfur battery is assembled.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111107866.9A CN113839024B (en) | 2021-09-22 | 2021-09-22 | Self-supporting spinning sulfur anode host material uniformly loaded with small-size catalyst, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111107866.9A CN113839024B (en) | 2021-09-22 | 2021-09-22 | Self-supporting spinning sulfur anode host material uniformly loaded with small-size catalyst, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113839024A CN113839024A (en) | 2021-12-24 |
| CN113839024B true CN113839024B (en) | 2022-09-09 |
Family
ID=78960228
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111107866.9A Active CN113839024B (en) | 2021-09-22 | 2021-09-22 | Self-supporting spinning sulfur anode host material uniformly loaded with small-size catalyst, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113839024B (en) |
Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104549407A (en) * | 2015-02-03 | 2015-04-29 | 哈尔滨工业大学 | Preparation method of platinum based/nitrogen doped carbon quantum dot-carbon nanotube catalyst |
| CN104846486A (en) * | 2015-03-27 | 2015-08-19 | 江西师范大学 | Preparation of carbon nano fiber composite material coated by nitrogen-doped carbon nanotube and application thereof |
| CN105810963A (en) * | 2016-04-26 | 2016-07-27 | 中国科学院合肥物质科学研究院 | Preparation method and application of transition metal-nitrogen-carbon-based electrocatalyst |
| CN106219513A (en) * | 2016-07-22 | 2016-12-14 | 郑州大学 | A kind of method utilizing solid-phase pyrolysis to prepare nitrogen-doped carbon quantum dot and application thereof |
| CN108615865A (en) * | 2018-05-02 | 2018-10-02 | 上海理工大学 | A kind of lithium sulfur battery anode material and preparation method thereof |
| CN110098394A (en) * | 2019-04-28 | 2019-08-06 | 格林美（无锡）能源材料有限公司 | Nitrogen, boron codope carbon quantum dot cladding nickel cobalt aluminium acid lithium battery positive electrode and preparation method |
| CN110518285A (en) * | 2019-07-22 | 2019-11-29 | 中南大学 | Modified carbon quantum dot of a kind of ammonia and preparation method thereof and the application in lithium-sulfur cell electrolyte |
| CN110624582A (en) * | 2019-08-27 | 2019-12-31 | 浙江工业大学 | Catalyst for depositing metal particles in carbon nano tube and preparation and application thereof |
| CN111229215A (en) * | 2020-03-09 | 2020-06-05 | 华东理工大学 | Metal high-dispersion supported catalyst based on carbon quantum dot induction and preparation method and application thereof |
| WO2020171074A1 (en) * | 2019-02-21 | 2020-08-27 | 日産化学株式会社 | Battery material and electrode material |
| CN111939930A (en) * | 2020-09-14 | 2020-11-17 | 郑州大学 | Carbon quantum dot-loaded cobalt-ruthenium alloy composite material and preparation method and application thereof |
| CN112481638A (en) * | 2020-11-27 | 2021-03-12 | 常州大学 | Bio-based carbon material loaded inorganic compound electrocatalyst and preparation method thereof |
| CN113013391A (en) * | 2021-02-23 | 2021-06-22 | 北京工业大学 | Method for preparing nitrogen-doped multidimensional and hierarchical porous carbon material adaptive to sulfur anode carrier of aluminum-sulfur battery |
| KR20210101448A (en) * | 2020-02-10 | 2021-08-19 | 서울과학기술대학교 산학협력단 | Method for manufacturing carbon material-coated current collector and carbon material-coated current collector thereby |
| CN113293406A (en) * | 2021-06-03 | 2021-08-24 | 中国科学技术大学 | Nano electro-catalyst, synthesis method, test electrode and preparation method |
-
2021
- 2021-09-22 CN CN202111107866.9A patent/CN113839024B/en active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104549407A (en) * | 2015-02-03 | 2015-04-29 | 哈尔滨工业大学 | Preparation method of platinum based/nitrogen doped carbon quantum dot-carbon nanotube catalyst |
| CN104846486A (en) * | 2015-03-27 | 2015-08-19 | 江西师范大学 | Preparation of carbon nano fiber composite material coated by nitrogen-doped carbon nanotube and application thereof |
| CN105810963A (en) * | 2016-04-26 | 2016-07-27 | 中国科学院合肥物质科学研究院 | Preparation method and application of transition metal-nitrogen-carbon-based electrocatalyst |
| CN106219513A (en) * | 2016-07-22 | 2016-12-14 | 郑州大学 | A kind of method utilizing solid-phase pyrolysis to prepare nitrogen-doped carbon quantum dot and application thereof |
| CN108615865A (en) * | 2018-05-02 | 2018-10-02 | 上海理工大学 | A kind of lithium sulfur battery anode material and preparation method thereof |
| WO2020171074A1 (en) * | 2019-02-21 | 2020-08-27 | 日産化学株式会社 | Battery material and electrode material |
| CN110098394A (en) * | 2019-04-28 | 2019-08-06 | 格林美（无锡）能源材料有限公司 | Nitrogen, boron codope carbon quantum dot cladding nickel cobalt aluminium acid lithium battery positive electrode and preparation method |
| CN110518285A (en) * | 2019-07-22 | 2019-11-29 | 中南大学 | Modified carbon quantum dot of a kind of ammonia and preparation method thereof and the application in lithium-sulfur cell electrolyte |
| CN110624582A (en) * | 2019-08-27 | 2019-12-31 | 浙江工业大学 | Catalyst for depositing metal particles in carbon nano tube and preparation and application thereof |
| KR20210101448A (en) * | 2020-02-10 | 2021-08-19 | 서울과학기술대학교 산학협력단 | Method for manufacturing carbon material-coated current collector and carbon material-coated current collector thereby |
| CN111229215A (en) * | 2020-03-09 | 2020-06-05 | 华东理工大学 | Metal high-dispersion supported catalyst based on carbon quantum dot induction and preparation method and application thereof |
| CN111939930A (en) * | 2020-09-14 | 2020-11-17 | 郑州大学 | Carbon quantum dot-loaded cobalt-ruthenium alloy composite material and preparation method and application thereof |
| CN112481638A (en) * | 2020-11-27 | 2021-03-12 | 常州大学 | Bio-based carbon material loaded inorganic compound electrocatalyst and preparation method thereof |
| CN113013391A (en) * | 2021-02-23 | 2021-06-22 | 北京工业大学 | Method for preparing nitrogen-doped multidimensional and hierarchical porous carbon material adaptive to sulfur anode carrier of aluminum-sulfur battery |
| CN113293406A (en) * | 2021-06-03 | 2021-08-24 | 中国科学技术大学 | Nano electro-catalyst, synthesis method, test electrode and preparation method |
Non-Patent Citations (4)
| Title |
|---|
| Printable 3D Carbon Nanofiber Networks with Embedded Metal Nanocatalysts;Marcel Simsek等;《ACS Appl. Mater.》;20200804;第12卷(第35期);39533-39540 * |
| 基于纳米碳点复合材料化学修饰电极的制备及应用;郑笑晨;《中国优秀硕士学位论文全文数据库（工程科技I辑）》;20160315(第03期);B014-936 * |
| 掺杂型石墨烯量子点的可控制备及其光致发光与电催化研究;龙滨莉;《中国优秀硕士学位论文全文数据库（工程科技I辑）》;20180115(第01期);B014-26 * |
| 高分散钴氮共掺杂碳纳米纤维氧还原催化剂;周扬等;《物理化学学报》;20170715;第30卷(第7期);1429-1435 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113839024A (en) | 2021-12-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111211300A (en) | Metallic nickel/nitrogen doped carbon nanotube and lithium-sulfur battery composite positive electrode material thereof | |
| CN111153448B (en) | Preparation method and application of bamboo/wood-based nano-cellulose limited transition metal oxide electrode material | |
| CN113113681B (en) | Composite sodium supplement additive and application thereof in sodium ion battery | |
| CN109888219A (en) | A kind of Cu oxide/carbon nano-fiber/sulfur electrode material and its preparation and application | |
| CN109713257A (en) | A kind of high-performance Si@SnO2@C composite and its preparation method and application | |
| CN104752702A (en) | Cathode material of lithium sulphur battery, preparation method of cathode material, cathode of lithium sulphur battery and lithium sulphur battery | |
| CN112599777A (en) | Preparation method and application of transition metal sulfide/nitrogen and sulfur co-doped carbon composite fiber electrode material | |
| CN112599770A (en) | Lithium/sodium ion battery negative electrode material and preparation method thereof | |
| CN114497549B (en) | Method for electrochemically preparing positive electrode lithium supplement material, lithium supplement material and lithium supplement slurry | |
| CN110854373B (en) | Composite negative electrode material and preparation method thereof | |
| CN109950503B (en) | CoMoOxPreparation method of/carbon/sulfur composite nano material, lithium ion battery cathode and lithium ion half battery | |
| He et al. | Perovskite transition metal oxide of nanofibers as catalytic hosts for lithium–sulfur battery | |
| CN112736221B (en) | Novel Fe3Preparation method of C/N-CNF @ RGO integrated electrode | |
| CN110970606B (en) | Nitrogen-doped hollow spherical carbon-coated sulfur positive electrode material and preparation method and application thereof | |
| CN113839024B (en) | Self-supporting spinning sulfur anode host material uniformly loaded with small-size catalyst, preparation method and application thereof | |
| CN116885184A (en) | Composite lithium supplementing material, lithium supplementing positive electrode and lithium ion battery | |
| CN110586104A (en) | Titanium dioxide, copper oxide and cobalt titanate composite nanofiber and preparation method thereof | |
| CN113972375B (en) | Preparation method and application of porous carbon fiber/tungsten oxide self-supporting lithium-sulfur battery positive electrode material | |
| CN113506862B (en) | Nano carbon fiber composite material for lithium-sulfur battery anode and preparation method and application thereof | |
| CN113611866B (en) | Flexible self-supporting sodium ion battery negative electrode material and preparation method thereof | |
| CN115425209A (en) | Preparation method and application of myrica-shaped iron-doped cobalt-based chalcogenide nitrogen-doped carbon porous composite material | |
| CN116960281A (en) | Composite polyanion type sodium ferrous sulfate positive electrode material, preparation method thereof and sodium ion battery containing positive electrode material | |
| CN114864939A (en) | Lithium-sulfur battery anode catalytic material and preparation method and application thereof | |
| CN113753962A (en) | Cobalt sulfide/carbon composite negative electrode material for sodium ion battery and preparation method thereof | |
| CN114937760B (en) | Nitrogen-sulfur-selenium co-doped SnS 0.5 Se 0.5 Preparation method of @ CNF self-supporting electrode material |
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 |