CN111974430B - Preparation method of monoatomic copper catalyst and application of monoatomic copper catalyst in positive electrode of lithium-sulfur battery - Google Patents
Preparation method of monoatomic copper catalyst and application of monoatomic copper catalyst in positive electrode of lithium-sulfur battery Download PDFInfo
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- 239000010949 copper Substances 0.000 title claims abstract description 98
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 74
- 239000003054 catalyst Substances 0.000 title claims abstract description 56
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 54
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 51
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 12
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- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 5
- 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 5
- 229910018091 Li 2 S Inorganic materials 0.000 description 4
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- 125000004429 atom Chemical group 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
-
- B01J35/58—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0213—Preparation of the impregnating solution
-
- 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
- D01F9/16—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of a single-atom copper catalyst and application of the single-atom copper catalyst in a positive electrode of a lithium-sulfur battery, and belongs to the technical field of battery materials. According to the invention, copper atoms on foam copper are captured and migrated to a carbon fiber matrix through high Wen Anqi treatment, so that the nitrogen-doped carbon fiber foam material loaded with single-atom copper is prepared, and the nitrogen-doped carbon fiber foam material is used as a carrier material of positive electrode sulfur in a lithium sulfur battery. The monoatomic copper catalyst prepared by the invention ensures that the lithium-sulfur battery has faster reaction kinetics, excellent capacity exertion and cycle stability under high sulfur loading. The preparation process is simple, and provides a wide prospect for application of the single-atom catalyst in lithium sulfur batteries.
Description
Technical field:
the invention relates to the technical field of battery materials, in particular to a preparation method of a single-atom copper catalyst and application of the single-atom copper catalyst in a positive electrode of a lithium-sulfur battery.
The background technology is as follows:
sulfur has the characteristics of rich natural reserve, environmental protection, high theoretical capacity (1675 mAh/g) and the like, and is an ideal batteryAnd a positive electrode material. Lithium sulfur batteries have high theoretical energy density (2600 Wh/kg) and can meet the energy density requirements of future energy storage devices. However, sulfur still faces significant challenges as a positive electrode material. Sulfur and discharge product Li 2 S/Li 2 S 2 Is an electronic insulator, thereby causing incomplete conversion of active substances in the electrochemical process and lower utilization rate. Furthermore, the intermediate product lithium polysulfide (Li 2 S x X is more than or equal to 3 and less than or equal to 8) can be dissolved in electrolyte, and shuttles between the anode and the cathode under the action of electric field force and concentration gradient, thereby causing a plurality of problems of rapid decay of battery capacity, low coulomb efficiency and the like. The method widely used at present is to increase the conductivity of the sulfur anode by compounding a carbon material with good conductivity with sulfur, and load a transition metal catalyst on a carbon material matrix. The catalyst accelerates the transformation kinetics of the lithium polysulfide while adsorbing the soluble lithium polysulfide, thereby inhibiting the shuttle effect. In addition, the catalyst can accelerate Li during battery charging 2 S/Li 2 S 2 Improves the utilization rate of active substances.
The size of the current supported transition metal catalysts is typically on the nanometer scale. Since the adsorption and catalysis processes mainly occur on the surface of the catalyst particles, while the surface atoms of the nano-sized particles account for only a small fraction of the total number of atoms, the catalyst utilization is low. The catalyst belongs to an inactive component in the lithium sulfur battery, and the improvement of the atomic utilization rate of the catalyst is helpful for improving the overall energy density of the lithium sulfur battery. The metal monoatomic catalyst is dispersed in an atomic level and embedded on a matrix, has the atomic utilization rate of 100% theoretically, a large number of coordination unsaturated active sites and maximized catalyst-matrix interaction. Metal monoatomic catalysts offer great advantages over nanoscale catalysts, both in terms of catalytic efficiency and battery energy density. Therefore, the metal monoatomic catalyst is loaded on the carbon material matrix by reasonably utilizing the material preparation means and is compounded with sulfur, so that the conversion reaction kinetics of the sulfur anode can be greatly improved, and the electrochemical performance of the lithium-sulfur battery is improved.
The invention comprises the following steps:
the invention aims to provide a preparation method of a single-atom copper catalyst and application of the single-atom copper catalyst in a positive electrode of a lithium-sulfur battery, wherein the single-atom copper catalyst uniformly loaded on a nitrogen-doped carbon fiber foam substrate is prepared, so that the conversion reaction kinetics of the positive electrode of sulfur is quickened, the polarization of the battery is reduced, the utilization rate of active substances is improved, and meanwhile, inactive substance components are reduced. The prepared monoatomic copper/nitrogen-doped carbon fiber foam/sulfur composite positive electrode has excellent capacity exertion and cycle stability under high sulfur loading.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a method for preparing a monoatomic copper catalyst, the method comprising the steps of:
(1) Sequentially cleaning and drying natural cotton, putting the dried cotton and foam copper into a tube furnace, and sequentially performing high-temperature treatment under a protective atmosphere and an ammonia gas atmosphere to obtain nitrogen-doped carbon fiber foam loaded with a single-atom copper catalyst;
(2) Uniformly mixing sulfur powder, multi-wall carbon nano tubes and carbon black according to a proportion, adding the mixture into a proper amount of solvent, and obtaining active substance suspension after mixed grinding and ultrasonic dispersion; immersing the nitrogen-doped carbon fiber foam loaded with the monoatomic copper catalyst into the suspension for a period of time, taking out, and drying to obtain the monoatomic copper catalyst/nitrogen-doped carbon fiber/sulfur composite anode material.
In the step (1), cleaning natural cotton to remove impurities, wherein the cleaning process comprises the following steps: soaking natural cotton in 0.5-5mol/L dilute hydrochloric acid, dilute nitric acid or dilute sulfuric acid, magnetically stirring for 30-60 min, taking out, soaking in distilled water, magnetically stirring for 1-2 hr, finally soaking in absolute ethanol, magnetically stirring for 1-2 hr, and taking out; the cleaned cotton is put into a baking oven with the temperature of 40-80 ℃ to be dried for 24-48 hours.
In the step (1), cotton and foam copper which are put into the tube furnace are placed in a mass ratio of 1:5 to 1:20 along the axial direction of the tube body of the tube furnace, wherein the foam copper is close to the air inlet side of the tube furnace.
In the step (1), the high temperature treatment process is as follows: heating the tube furnace to 900-1100 ℃ under the protection of argon or nitrogen, wherein the heating rate is 5-20 ℃/min, and preserving the heat for 1-2 hours; then switching to ammonia gas atmosphere, preserving heat for 30-90 minutes, and then cooling to room temperature along with the furnace.
In the step (1), the nitrogen-doped carbon fiber material loaded with the monoatomic copper catalyst has copper atoms uniformly dispersed on a nitrogen-doped carbon fiber matrix, and the copper content is 1-5wt%.
In the step (2), the mass ratio of the sulfur powder to the multi-wall carbon nano tube to the carbon black is (70-90): (5-15): (5-15); the solvent is absolute ethyl alcohol or N-methyl pyrrolidone.
In the step (2), the proportioned sulfur powder, the multiwall carbon nanotube and the carbon black are mixed and ground for 30-120 minutes, then added into a proper amount of solvent, and dispersed for 30-120 minutes by ultrasonic; the ratio of the total amount of sulfur powder, multi-wall carbon nanotubes and carbon black added into the solvent to the solvent is 5-30g:1L.
In the step (2), the nitrogen-doped carbon fiber foam loaded with the monoatomic copper catalyst is immersed in the suspension for 1-5 minutes.
In the step (2), the nitrogen-doped carbon fiber foam loaded with the monoatomic copper catalyst, which is taken out after being soaked in the suspension, is put into a baking oven at the temperature of 40-80 ℃ to be dried for 24-48 hours.
The monoatomic copper catalyst/nitrogen-doped carbon fiber/sulfur composite positive electrode material is used as a lithium-sulfur battery positive electrode material, and the unit area sulfur loading of the lithium-sulfur battery positive electrode material is 3-15mg/cm 2 。
The design principle of the invention is as follows:
according to the invention, the natural cotton is carbonized at high temperature under the protection of inert gas to form carbon fiber foam. And then ammonia gas treatment is carried out under the same temperature condition, nitrogen atoms are doped on the carbon fiber matrix, and ammonia molecules capture and migrate copper atoms on the foam copper to the nitrogen-doped carbon fiber matrix, so that the nitrogen-doped carbon fiber foam loaded with the monoatomic copper catalyst is prepared. Mixing sulfur powder and a small amount of conductive additive (multi-wall carbon nano tube and carbon black), adding into a proper amount of solvent to obtain active substance suspension, and carrying out impregnation treatment to obtain the monoatomic copper catalyst/nitrogen-doped carbon fiber/sulfur composite positive electrode material.
The self-supporting carbon fiber foam matrix is conducive to achieving high sulfur loading per unit area; the nitrogen atoms doped on the surface can adsorb lithium polysulfide and inhibit the shuttle effect; the uniformly dispersed monoatomic copper can catalyze the conversion reaction of the sulfur anode, reduce the polarization of the battery and improve the utilization rate of active substances. The monoatomic copper catalysts exhibit more significant catalytic performance while reducing inactive species components compared to nano-copper particle catalysts. The advantages of the components of the monoatomic copper/nitrogen-doped carbon fiber foam/sulfur composite positive electrode material are combined, and the assembled lithium-sulfur battery realizes excellent electrochemical capacity exertion and cycle performance.
The invention has the advantages and beneficial effects as follows:
1. the single-atom copper/nitrogen-doped carbon fiber foam/sulfur self-supporting composite anode prepared by the invention can realize high sulfur loading.
2. The monoatomic copper catalyst prepared by the invention can accelerate the conversion process of anode sulfur, reduce battery polarization, and enable the lithium-sulfur battery to have higher capacity and cycle performance.
3. The catalyst content in the monoatomic copper/nitrogen-doped carbon fiber foam/sulfur self-supporting composite positive electrode prepared by the method is low, and a binder and an aluminum foil current collector are not needed for preparing the electrode, so that the realization of high battery energy density is facilitated.
4. The preparation method has the advantages of simple preparation process, wide sources of raw materials required by preparation and low cost, and can be used for mass production.
Description of the drawings:
FIG. 1 is a graph of electrochemical performance of a carbon fiber/sulfur (CNF/S) electrode; in the figure: (a) a first-turn charge-discharge curve at a current density of 0.1C; (b) Specific capacity versus number of cycles for cycling at 0.1C current density versus coulombic efficiency versus number of cycles curve.
FIG. 2 is a graph of electrochemical performance of a nitrogen doped carbon fiber/sulfur (NCNF/S) electrode; in the figure: (a) a first-turn charge-discharge curve at a current density of 0.1C; (b) Specific capacity versus number of cycles for cycling at 0.1C current density versus coulombic efficiency versus number of cycles curve.
FIG. 3 is a schematic view of a high temperature process and a temperature profile for preparing nano-copper particles/nitrogen doped carbon fibers (NP-Cu/NCNF) and monoatomic copper/nitrogen doped carbon fibers (SA-Cu/NCNF); wherein: (a) a high temperature treatment schematic; (b) preparing a temperature profile of NP-Cu/NCNF; (c) preparing a temperature profile of SA-Cu/NCNF.
FIG. 4 is a view of NP-Cu/NCNF transmission electron microscopy.
FIG. 5 is a graph of electrochemical performance of a nano-copper particle/nitrogen doped carbon fiber/sulfur (NP-Cu/NCNF/S) electrode; in the figure: (a) a first-turn charge-discharge curve at a current density of 0.1C; (b) Specific capacity versus number of cycles for cycling at 0.1C current density versus coulombic efficiency versus number of cycles curve.
FIG. 6 is a scanning transmission electron microscope image of SA-Cu/NCNF; wherein: (a) scanning transmission electron microscopy images; (b) X-ray energy scattering spectra of the corresponding carbon, oxygen, nitrogen, copper elements.
FIG. 7 is a graph of electrochemical performance of a monoatomic copper/nitrogen doped carbon fiber/sulfur (SA-Cu/NCNF/S) electrode; in the figure: (a) a first-turn charge-discharge curve at a current density of 0.1C; (b) Specific capacity versus number of cycles for cycling at 0.1C current density versus coulombic efficiency versus number of cycles curve.
The specific embodiment is as follows:
the present invention will be described with reference to comparative examples and examples, but the present patent protection is not limited to the following examples.
Comparative example 1
Comparative example 1 is the preparation of carbon fiber (CNF) and its use in positive electrodes of lithium sulfur batteries. The natural cotton is washed by 10 percent of dilute hydrochloric acid (about 3.1 mol/L), distilled water and ethanol, and the washed cotton is put into a 60 ℃ oven for drying for 24 hours. And (3) placing the dried cotton into a tube furnace, preserving heat for 30 minutes at 25 ℃ under the argon atmosphere, heating to 1000 ℃ at a speed of 5 ℃/min, preserving heat for 2 hours, and cooling to room temperature along with the furnace, thus obtaining the CNF foam. 450mg of sulfur powder, 25mg of multi-walled carbon nanotubes and 25mg of carbon black were mixed and ground in a mortar for 30 minutes, added to 35mL of absolute ethanol, and ultrasonically dispersed for 1 hour to obtain an active material suspension. Immersing the CNF foam into the suspension for 1 minute, taking out, and putting into a 60 ℃ oven for drying for 24 hours to obtain the CNF/S composite anode material. The sulfur loading per unit area of CNF/S is 6mg/cm 2 。
2032 button cell was used for electrochemical performance testing of electrode materials. CNF/S foam was cut to a length of 5mm by 2mm in height as a working electrode, a lithium sheet (diameter 16mm, thickness 0.45 mm) as a counter electrode, and Celgard 2400 polypropylene film (diameter 19mm, thickness 25 μm) as a separator. The electrolyte is a lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) electrolyte containing 1M and 0.2M lithium nitrate (LiNO) 3 ) 1,3 Dioxolane (DOL) and ethylene glycol dimethyl ether (DME) mixed solution (volume ratio 1:1) of the additive. During discharge test, the potential interval is 1.8-2.8V (vs. Li/Li) + ). As shown in fig. 1 (a), the CNF/S electrode has a first-turn discharge capacity of 950mAh/g at a current density of 0.1C (1c=1675 mA/g), and the polarization voltage, i.e., the difference between the charge voltage plateau and the discharge voltage plateau, is large, about 0.3V. As shown in FIG. 1 (b), the CNF/S electrode maintained a specific capacity of 773mAh/g after 50 cycles, the capacity retention was 75%, and the capacity decay was faster.
Comparative example 2
Comparative example 2 is the preparation of nitrogen doped carbon fiber (NCNF) and its use in positive electrodes of lithium sulfur batteries. Washing natural cotton with 10% diluted hydrochloric acid, distilled water and ethanol, and oven drying at 60deg.C for 24 hr. And (3) placing the dried cotton into a tubular furnace, preserving heat for 30 minutes at 25 ℃ under an argon atmosphere, heating to 1000 ℃ at a speed of 5 ℃/minute, preserving heat for 2 hours, switching to an ammonia atmosphere, preserving heat for 1 hour, and cooling to room temperature along with the furnace under the argon atmosphere to obtain NCNF foam. 450mg of sulfur powder, 25mg of multi-wall carbon nano tube and 25mg of carbon black are mixed and ground in a mortar for 30 minutes, added into 35mL of absolute ethyl alcohol, and dispersed for 1 hour by ultrasonic to obtain an active substance suspension. And immersing NCNF foam into the suspension for 1 minute, taking out, and putting into a 60 ℃ oven for drying for 24 hours to obtain the NCNF/S composite anode material. The sulfur loading per unit area of NCNF/S obtained by weighing is 4.3mg/cm 2 。
2032 button cell was used for electrochemical performance testing of electrode materials. NCNF/S foam was cut to a length of 5mm by 2mm in height as a working electrode, a lithium sheet (diameter 16mm, thickness 0.45 mm) as a counter electrode, and Celgard 2400 polypropylene film (diameter 19mm, thickness 25 μm) as a separator.The electrolyte is 1M LiTFSI-containing electrolyte and 0.2M LiNO 3 The DOL and DME of the additive were mixed (volume ratio 1:1). During discharge test, the potential interval is 1.8-2.8V (vs. Li/Li) + ). As shown in FIG. 2 (a), the NCNF/S electrode had a first-turn discharge capacity of 1073mAh/g at a current density of 0.1C, and the difference between the polarization voltage, i.e., the charge voltage plateau and the discharge voltage plateau, was about 0.32V. The adsorption of the doped nitrogen atoms on the carbon fibers to the lithium polysulfide suppresses the shuttle effect of the lithium polysulfide, thereby improving the specific capacity of the electrode. As shown in FIG. 2 (b), the NCNF/S electrode maintained a specific capacity of 920mAh/g after 50 cycles, with a capacity retention of 81%.
Comparative example 3
Comparative example 3 is the preparation of NP-Cu/NCNF and its use in the positive electrode of lithium-sulfur batteries. Washing natural cotton with 10% diluted hydrochloric acid, distilled water and ethanol, and oven drying at 60deg.C for 24 hr. As shown in fig. 3 (a), the dried cotton was placed in a tube furnace together with copper foam. As shown in fig. 3 (b), the temperature is kept for 30 minutes at 25 ℃ under argon atmosphere, the temperature is raised to 1000 ℃ at a speed of 5 ℃/minute, the temperature is kept for 2 hours, the temperature is switched to ammonia atmosphere, the temperature is kept for 3 hours, and then the temperature is cooled to room temperature along with the furnace under argon atmosphere, so as to obtain the NP-Cu/NCNF foam. As shown in fig. 4, dispersed nano copper particles are loaded on the carbon fiber matrix. The copper content was 0.32at% (atomic%) as measured by X-ray photoelectron spectroscopy.
450mg of sulfur powder, 25mg of multi-wall carbon nano tube and 25mg of carbon black are mixed and ground in a mortar for 30 minutes, added into 35mL of absolute ethyl alcohol, and dispersed for 1 hour by ultrasonic to obtain an active substance suspension. And immersing the NP-Cu/NCNF foam into the suspension for 1 minute, taking out, and putting into a 60 ℃ oven for drying for 24 hours to obtain the NP-Cu/NCNF/S composite anode material. The sulfur loading per unit area of NP-Cu/NCNF/S is 5mg/cm 2 。
2032 button cell was used for electrochemical performance testing of electrode materials. The NP-Cu/NCNF/S foam was cut to a length of 5mm by 2mm in height as a working electrode, a lithium sheet (diameter 16mm, thickness 0.45 mm) as a counter electrode, and Celgard 2400 polypropylene film (diameter 19mm, thickness 25 μm) as a separator. The electrolyte is LiTFSI containing 1mol/LMass sum 0.2mol/L LiNO 3 The DOL and DME of the additive were mixed (volume ratio 1:1). During discharge test, the potential interval is 1.8-2.8V (vs. Li/Li) + ). As shown in FIG. 5 (a), the NP-Cu/NCNF/S electrode had a first-turn discharge capacity of 1062mAh/g at a current density of 0.1C, and the difference between the polarization voltage, i.e., the charge voltage plateau and the discharge voltage plateau, was about 0.24V. The adsorption effect of the nano copper particles loaded on the carbon fiber on lithium polysulfide and the catalysis effect on sulfur species conversion reaction improve the utilization rate and specific capacity of active substances of the electrode and reduce the polarization of the battery. As shown in FIG. 5 (b), the electrode maintains the specific capacity of 994mAh/g after 50 circles of circulation, the capacity retention rate is 87%, the irreversible consumption of lithium polysulfide is reduced by the catalysis of the electrode reaction by the nano copper particles, and the circulation performance is improved.
Example 1
Example 1 is the preparation of SA-Cu/NCNF and its use in the positive electrode of lithium sulfur batteries. Washing natural cotton with 10% diluted hydrochloric acid, distilled water and ethanol, and oven drying at 60deg.C for 24 hr. As shown in fig. 3 (a), the dried cotton was placed in a tube furnace together with copper foam. As shown in fig. 3 (c), the temperature is kept for 30 minutes at 25 ℃ under argon atmosphere, the temperature is raised to 1000 ℃ at a speed of 5 ℃/minute, the temperature is kept for 2 hours, the temperature is switched to ammonia atmosphere, the temperature is kept for 1 hour, and the temperature is cooled to room temperature along with the furnace under argon atmosphere, so that SA-Cu/NCNF foam is obtained. As shown in fig. 6, no distinct particles were observed locally in the carbon fiber, but the X-ray energy scattering spectrum showed a uniformly dispersed copper signal, with copper uniformly dispersed in a monoatomic form on the nitrogen-doped carbon fiber matrix. The copper content was 0.25at% (atomic%) as measured by X-ray photoelectron spectroscopy.
450mg of sulfur powder, 25mg of multi-wall carbon nano tube and 25mg of carbon black are mixed and ground in a mortar for 30 minutes, added into 35mL of absolute ethyl alcohol, and dispersed for 1 hour by ultrasonic to obtain an active substance suspension. And immersing the SA-Cu/NCNF foam into the suspension for 1 minute, taking out, and putting into a 60 ℃ oven for drying for 24 hours to obtain the SA-Cu/NCNF/S composite anode material. The sulfur loading per unit area of SA-Cu/NCNF/S is 5mg/cm 2 。
2032 button cellAnd testing the electrochemical performance of the electrode material. SA-Cu/NCNF/S foam was cut to a length of 5mm by 2mm in height as a working electrode, a lithium sheet (diameter 16mm, thickness 0.45 mm) as a counter electrode, and Celgard 2400 polypropylene film (diameter 19mm, thickness 25 μm) as a separator. The electrolyte is electrolyte containing 1mol/L LiTFSI and 0.2mol/L LiNO 3 The DOL and DME of the additive were mixed (volume ratio 1:1). During discharge test, the potential interval is 1.8-2.8V (vs. Li/Li) + ). As shown in FIG. 7 (a), the SA-Cu/NCNF/S electrode had a first-turn discharge capacity of 1312mAh/g at a current density of 0.1C, and the polarization voltage, i.e., the difference between the charge voltage plateau and the discharge voltage plateau, was only 0.12V. Compared with CNF/S, NCNF/S and NP-Cu/NCNF/S electrodes, SA-Cu/NCNF/S electrodes have the fastest electrochemical kinetics, the lowest cell polarization and the highest capacity performance due to the remarkable catalytic effect of the single-atom copper catalyst on the sulfur anode conversion reaction. As shown in FIG. 7 (b), the electrode maintained a specific capacity of 1254mAh/g after 50 cycles, a capacity retention of 88%, and had excellent cycle stability.
Therefore, based on the above description, the invention provides a preparation method of a single-atom copper catalyst, which can effectively improve the electrochemical kinetics of a positive electrode of a lithium-sulfur battery. The prepared monoatomic copper/nitrogen-doped carbon fiber foam/sulfur composite positive electrode material has higher capacity exertion and cycle performance under high sulfur carrying capacity. The preparation method is simple, the raw materials are cheap, the expansion production is facilitated, and the method has a wide commercialization prospect.
Furthermore, the above-described embodiments are illustrative of the present patent only, and should not be construed as limiting the present patent. Any modifications or adaptations to be made based on the principles and techniques of this patent should and are intended to be comprehended within the meaning of this patent.
Claims (8)
1. A preparation method of a monoatomic copper catalyst is characterized by comprising the following steps: the method comprises the following steps:
(1) Sequentially cleaning and drying natural cotton, putting the dried cotton and foam copper into a tube furnace, and sequentially performing high-temperature treatment under a protective atmosphere and an ammonia gas atmosphere to obtain nitrogen-doped carbon fiber foam loaded with a single-atom copper catalyst; wherein: the mass ratio of cotton to foam copper put into the tube furnace is 1:5 to 1:20, and the cotton and the foam copper are put separately along the axial direction of the tube body of the tube furnace, wherein the foam copper is close to the air inlet side of the tube furnace; the high-temperature treatment process comprises the following steps: heating the tube furnace to 900-1100 ℃ under the protection of argon or nitrogen, wherein the heating rate is 5-20 ℃/min, and preserving the heat for 1-2 hours; then switching to ammonia gas atmosphere, preserving heat for 30-90 minutes, and then cooling to room temperature along with a furnace;
(2) Uniformly mixing sulfur powder, multi-wall carbon nano tubes and carbon black according to a proportion, adding the mixture into a proper amount of solvent, and obtaining active substance suspension after mixed grinding and ultrasonic dispersion; immersing the nitrogen-doped carbon fiber foam loaded with the monoatomic copper catalyst into the suspension for a period of time, taking out, and drying to obtain the monoatomic copper catalyst/nitrogen-doped carbon fiber/sulfur composite anode material.
2. The method for preparing the monoatomic copper catalyst according to claim 1, wherein: in the step (1), cleaning natural cotton to remove impurities, wherein the cleaning process comprises the following steps: soaking natural cotton in 0.5-5mol/L dilute hydrochloric acid, dilute nitric acid or dilute sulfuric acid, magnetically stirring for 30-60 min, taking out, soaking in distilled water, magnetically stirring for 1-2 hr, finally soaking in absolute ethanol, magnetically stirring for 1-2 hr, and taking out; the cleaned cotton is put into a baking oven with the temperature of 40-80 ℃ to be dried for 24-48 hours.
3. The method for preparing the monoatomic copper catalyst according to claim 1, wherein: in the step (1), the nitrogen-doped carbon fiber material loaded with the monoatomic copper catalyst has copper atoms uniformly dispersed on a nitrogen-doped carbon fiber matrix, and the copper content is 1-5wt%.
4. The method for preparing the monoatomic copper catalyst according to claim 1, wherein: in the step (2), the mass ratio of the sulfur powder to the multi-wall carbon nano tube to the carbon black is (70-90): (5-15): (5-15); the solvent is absolute ethyl alcohol or N-methyl pyrrolidone.
5. The method for preparing the monoatomic copper catalyst according to claim 1, wherein: in the step (2), the proportioned sulfur powder, the multiwall carbon nanotube and the carbon black are mixed and ground for 30-120 minutes, then added into a proper amount of solvent, and dispersed for 30-120 minutes by ultrasonic; the ratio of the total amount of sulfur powder, multi-walled carbon nanotubes and carbon black added to the solvent is (5-30) g:1L.
6. The method for preparing the monoatomic copper catalyst according to claim 1, wherein: in the step (2), the nitrogen-doped carbon fiber foam loaded with the monoatomic copper catalyst is immersed in the suspension for 1-5 minutes.
7. The method for preparing the monoatomic copper catalyst according to claim 1, wherein: in the step (2), the nitrogen-doped carbon fiber foam loaded with the monoatomic copper catalyst, which is taken out after being soaked in the suspension, is put into a baking oven at the temperature of 40-80 ℃ to be dried for 24-48 hours.
8. Use of the monoatomic copper catalyst prepared by the method of claim 1 in a positive electrode of a lithium-sulfur battery, characterized in that: the monoatomic copper catalyst/nitrogen-doped carbon fiber/sulfur composite positive electrode material is used as a lithium-sulfur battery positive electrode material, and the unit area sulfur loading of the lithium-sulfur battery positive electrode material is 3-15mg/cm 2 。
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