CN113363668A - Graphene-loaded glass fiber membrane with excimer ultraviolet irradiation modification and preparation method thereof - Google Patents
Graphene-loaded glass fiber membrane with excimer ultraviolet irradiation modification and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 135
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 130
- 239000003365 glass fiber Substances 0.000 title claims abstract description 55
- 239000012528 membrane Substances 0.000 title claims abstract description 53
- 230000004048 modification Effects 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000002715 modification method Methods 0.000 title description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 34
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 34
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 34
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002356 single layer Substances 0.000 claims abstract description 25
- 238000012986 modification Methods 0.000 claims abstract description 22
- 239000010410 layer Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 12
- 238000009210 therapy by ultrasound Methods 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000000835 fiber Substances 0.000 claims description 14
- 238000011068 loading method Methods 0.000 claims description 13
- 238000003828 vacuum filtration Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 5
- 230000001678 irradiating effect Effects 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 229920001021 polysulfide Polymers 0.000 abstract description 12
- 239000005077 polysulfide Substances 0.000 abstract description 12
- 150000008117 polysulfides Polymers 0.000 abstract description 12
- 125000000524 functional group Chemical group 0.000 abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
- 239000003792 electrolyte Substances 0.000 abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 abstract description 6
- 239000001301 oxygen Substances 0.000 abstract description 6
- 238000004146 energy storage Methods 0.000 abstract description 5
- 239000013543 active substance Substances 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- 239000011259 mixed solution Substances 0.000 description 24
- 239000002344 surface layer Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 3
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- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910014033 C-OH Inorganic materials 0.000 description 2
- 229910014570 C—OH Inorganic materials 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
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- 235000019441 ethanol Nutrition 0.000 description 2
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- 239000010439 graphite Substances 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 description 1
- 241000764238 Isis Species 0.000 description 1
- 229910003003 Li-S Inorganic materials 0.000 description 1
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- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
- H01M50/434—Ceramics
- H01M50/437—Glass
-
- 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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
- H01M50/454—Separators, membranes or diaphragms characterised by the material having a layered structure comprising a non-fibrous layer and a fibrous layer superimposed on one another
-
- 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 relates to an energy storage system device material, in particular to a graphene loaded glass fiber membrane with excimer ultraviolet irradiation modification and a preparation method thereof, and belongs to the technical field of energy storage system device materials. According to the invention, excimer ultraviolet irradiation is adopted to form partial oxygen-containing functional groups on the surface of the single-layer graphene, and the wettability of the graphene to the electrolyte of the lithium-sulfur battery is improved, so that the irradiation operation is simple and convenient, and the method is clean and efficient; the graphene is loaded on the glass fiber diaphragm, and the proportion of the graphene solution to polyvinylpyrrolidone, the thickness of the graphene loaded on the diaphragm, and the irradiation time and power are all technical difficulties when the graphene solution is prepared. The glass fiber loaded with the graphene layer is irradiated by the excimer ultraviolet lamp prepared by the invention and used as the diaphragm of the lithium-sulfur battery, and the diaphragm can not only physically block polysulfide but also fix the polysulfide through efficient and powerful chemical adsorption, so that active substances can be efficiently utilized, and the electrochemical performance of the lithium-sulfur battery is improved.
Description
Technical Field
The invention relates to an energy storage system device material, in particular to an EUV (extreme ultraviolet radiation) -graphene-loaded glass fiber membrane (or EUV/graphene-separator) with excimer ultraviolet irradiation modification and a preparation method thereof, and belongs to the technical field of energy storage system device materials.
Background
Lithium sulfur batteries constructed with positive and negative electrode lithium metal due to their high theoretical energy density (2600 Wh kg)−1) And high theoretical specific capacity (1675 mA h g)-1) And the sulfur material is widely existed in a geological structure, so that the novel advanced battery system with great application prospect is formed. And through more than ten years of research on lithium-sulfur batteries, some basic problems existing in the lithium-sulfur batteries are initially solved and improved. For example, the self-insulation property of sulfur can be realized by doping and adding different conductive materials into a sulfur positive electrode to form a sulfur-limiting structure, such as adding a composite carbon material, graphene and the like; the problems that polysulfide existing in a lithium-sulfur battery is easy to diffuse and active substances are greatly lost can be solved by adding a catalyst into electrolyte, adding an interlayer and the like to prevent the polysulfide from diffusing; and in case of the problem that sulfur has a large volume expansion during charge and discharge, the volume change thereof can be limited by using a solid electrolyte, adding a transition metal material, and the like. The modified diaphragm obtained by modifying the glass fiber is applied to the lithium sulfur battery, and can effectively prevent polysulfide from diffusing, so that the method is a simple, convenient and efficient method for improving the performance of the lithium sulfur battery on the basis of not reducing the volume energy density of the battery.
The graphene material has a good adsorption effect on polysulfide, and simultaneously, the graphene is processed in some physical and chemical modes to form the modified graphene, so that the wettability of the modified graphene to electrolyte can be greatly improved, and the modified graphene can have a more prominent anchoring and bonding effect on the bonded polysulfide. The method is characterized in that graphene is loaded on a glass fiber diaphragm by combining the characteristics of high conductivity of a graphene material and high efficiency, green and environment friendliness of an excimer ultraviolet lamp irradiation technology, and the modified graphene diaphragm EUV/graphene-separator is obtained by irradiation of the excimer ultraviolet lamp and applied to a lithium sulfur battery, so that polysulfide can be effectively adsorbed and anchored, the utilization rate of active substances in the battery is improved, and the lithium sulfur battery can obtain good electrochemical performance. Such ideal separators can simultaneously adsorb/capture and convert to LiPS, contributing to long cycle stability with high sulfur loading and to practical application of Li-S batteries.
Disclosure of Invention
The invention provides a graphene loaded glass fiber membrane with excimer ultraviolet irradiation modification.
The invention also provides a preparation method of the graphene loaded glass fiber membrane with the excimer ultraviolet irradiation modification.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of a graphene loaded glass fiber membrane with excimer ultraviolet irradiation modification comprises the following steps:
(1) preparing a graphene solution: dissolving single-layer graphene in absolute ethyl alcohol, adding polyvinylpyrrolidone (PVP) and ultrasonically stirring, wherein the mass ratio of the single-layer graphene to the polyvinylpyrrolidone is 1: 1-10;
(2) graphene-supported glass fiber film: loading the graphene solution obtained in the step (1) on a glass fiber diaphragm in a vacuum filtration mode, and drying;
(3) irradiating and modifying the graphene film by an excimer ultraviolet lamp: and (3) in the air, placing the fiber film obtained in the step (2) under an excimer ultraviolet lamp for irradiation, and then drying in vacuum to obtain the graphene-loaded glass fiber film with excimer ultraviolet irradiation modification.
According to the invention, excimer ultraviolet irradiation is adopted to form partial oxygen-containing functional groups on the surface of single-layer graphene (as shown in figure 8), and the wettability of graphene to the electrolyte of a lithium-sulfur battery is improved, so that the irradiation operation is simple and convenient, and the method is clean and efficient; the graphene is loaded on the glass fiber diaphragm, and the proportion of the graphene solution to polyvinylpyrrolidone, the thickness of the graphene loaded on the diaphragm, and the irradiation time and power are all technical difficulties when the graphene solution is prepared.
Under the condition of no excimer ultraviolet lamp irradiation, the diaphragm made by pure graphene loading cannot provide good guarantee for high performance and high safety and stability of the lithium-sulfur battery. The high-energy irradiation of the excimer ultraviolet lamp enables the surface layer of the graphene to have a character similar to that after micro-oxidation, partial oxygen-containing functional groups are loaded on the single-layer graphene, and then the functional groups can play a role in chemically adsorbing polysulfide in the charging and discharging of the lithium-sulfur battery.
Preferably, the mass ratio of the single-layer graphene to the polyvinylpyrrolidone is 1: 2-6, and the optimal ratio is 1: 5. When a graphene ethanol solution is prepared, it is particularly important to control the ratio of graphene to polyvinylpyrrolidone, and since polyvinylpyrrolidone plays a dispersing role, the dispersion of graphene in ethanol is poor due to too low concentration of polyvinylpyrrolidone, so that the finally obtained graphene thin layer loaded on glass fiber is broken; when the concentration is too high, the final conductivity of the graphene thin layer is deteriorated due to the non-conductivity of the polyvinylpyrrolidone, thereby affecting the conductivity and internal resistance of the lithium-sulfur battery. Therefore, it is one of the technical difficulties to control the quality of polyvinylpyrrolidone and graphene. In addition, the thickness of the graphene suction filtration also influences whether the graphene thin layer is uniform on the glass fiber diaphragm.
Finally, the irradiation time and irradiation power of the excimer ultraviolet lamp can influence the micro-oxidation degree of the graphene. When the irradiation time is too short, the graphene thin layer is not changed basically due to too small power, and the polysulfide can not be well adsorbed due to too small number of oxygen-containing functional groups; when the irradiation time is too long, the irradiation power is too high, which not only wastes energy, but also causes the water oxygen in the air to be combined with the graphene surface layer to excessively influence the conductivity of the graphene thin layer.
The ultrasonic stirring in the step (1) is divided into two steps, firstly ultrasonic treatment is carried out by an ultrasonic machine for 10-40 min, and then ultrasonic treatment is carried out for 5-30 min by an ultrasonic cell disruptor.
Preferably, in the step (1), the content of the single-layer graphene in the absolute ethyl alcohol isIs 0.01-0.25 mg/mL-1In the meantime.
Preferably, in the step (2), the thickness of the graphene thin layer on the glass fiber membrane after drying is controlled to be 3 to 10 μm.
Preferably, the drying time in step (2) is 3 to 12 hours.
Preferably, in the step (3), the fiber film is irradiated under an excimer ultraviolet lamp, and the distance between the fiber film and the tube of the excimer ultraviolet lamp is 1-15 mm.
Preferably, the irradiation power of the excimer ultraviolet lamp in the step (3) is 70-100%, and the irradiation time is 10-40 min.
Preferably, the temperature of vacuum drying in the step (3) is 60-100 ℃ and the time is 5-12 h.
The graphene loaded glass fiber membrane with the excimer ultraviolet irradiation modification function is prepared by the preparation method.
The application of the graphene loaded glass fiber membrane with excimer ultraviolet irradiation modification in a lithium-sulfur battery diaphragm material is provided.
Firstly, dissolving monolayer graphite and polyvinylpyrrolidone in absolute ethyl alcohol according to a certain proportion, placing a graphene solution on a glass fiber diaphragm after uniformly stirring by ultrasonic waves, and loading the graphene solution on the surface of glass fiber in a vacuum filtration mode; and after drying, placing the membrane in excimer ultraviolet light for irradiation to obtain the graphene loaded glass fiber membrane with excimer ultraviolet light irradiation modification. The material prepared by the method can be applied to the field of energy storage of lithium-sulfur batteries, and has the following characteristics:
1. the preparation method is simple, the used reaction materials are clean and environment-friendly, and the preparation process is simple and green;
2. a certain amount of oxygen-containing functional groups are loaded on the prepared graphene thin layer, and the functional groups can play a role in chemically adsorbing polysulfide in the charge and discharge of the lithium-sulfur battery, so that the wettability of the graphene on the electrolyte of the lithium-sulfur battery is improved;
3. the prepared graphene thin layer is uniformly loaded on the glass fiber;
4. the obtained graphene-loaded glass fiber material can be used as a diaphragm of a lithium-sulfur battery, has a good adsorption effect on polysulfide so as to improve the electrochemical performance of the lithium-sulfur battery, and can be circulated under a current density of 0.2C, and the first-circle discharge specific capacity can reach 1164 mAh g-1。
Drawings
FIG. 1 is a SEM scanning electron micrograph of the surface layer of the graphene-separator prepared in example 1;
FIG. 2 is a SEM scanning electron micrograph of the surface layer of the EUV/graphene-separator obtained in example 2;
FIG. 3 is a SEM scanning electron micrograph of the surface layer of the EUV/graphene-separator obtained in example 3;
FIG. 4 is an XRD spectrum of the graphene-segarator obtained in example 1 and an XRD spectrum of the graphene-segarator obtained in example 4;
FIG. 5 is a TEM image of the surface layer of the EUV/graphene-separator prepared in example 5;
FIG. 6 is a TEM image of the surface layer of the EUV/graphene-separator prepared in example 6;
FIG. 7 is an electrochemical performance diagram of EUV/graphene-separator obtained by different irradiation times obtained in application example, wherein the irradiation times are 5 min,10 min, 15 min, 20min and 25 min respectively;
FIG. 8 is a FT-IR spectrum of the graphene-separator obtained in example 1 and the EUV/graphene-separator obtained in example 2;
FIG. 9 is the charge-discharge specific capacity and coulombic efficiency results for EUV/graphene-separator and graphene-separator in 300 cycles at 0.2C.
Detailed Description
The technical solution of the present invention will be further specifically described below by way of specific examples. It is to be understood that the practice of the invention is not limited to the following examples, and that any variations and/or modifications may be made thereto without departing from the scope of the invention.
In the invention, all parts and percentages are weight units, and all equipment, raw materials and the like can be purchased from the market or are commonly used in the industry, if not specified.
The instrument adopted by the embodiment of the invention is as follows:
a common ultrasonic machine: a numerical control ultrasonic cleaner, model number KQ2200DB, ultrasonic instruments ltd, kunshan;
ultrasonic cell disruptor: model L0-JY92-IIN, Ningbo Li Cheng instruments, Inc.
Example 1
A preparation method of a graphene loaded glass fiber membrane with excimer ultraviolet irradiation modification comprises the following specific steps:
(1) dissolving 8 mg of single-layer graphene in 80 mL of absolute ethyl alcohol at room temperature, adding 40 mg of polyvinylpyrrolidone (PVP), performing ultrasonic treatment on the mixed solution at room temperature for 30 min by using a common ultrasonic machine, and performing ultrasonic treatment in an ultrasonic cell crusher for 5 min to obtain a uniformly mixed solution.
(2) And loading the graphene mixed solution subjected to ultrasonic treatment on a glass fiber diaphragm in a vacuum filtration mode to enable the thickness of a graphene thin layer to be 7 microns, drying at room temperature for 12 hours, and drying in a vacuum oven at 100 ℃ for 6 hours to obtain the modified fiber diaphragm which is graphene-separator.
Example 2
A preparation method of a graphene loaded glass fiber membrane with excimer ultraviolet irradiation modification comprises the following specific steps:
(1) dissolving 8 mg of single-layer graphene in 80 mL of absolute ethyl alcohol at room temperature, adding 40 mg of polyvinylpyrrolidone (PVP), performing ultrasonic treatment on the mixed solution at room temperature for 30 min by using a common ultrasonic machine, and performing ultrasonic treatment in an ultrasonic cell crusher for 5 min to obtain a uniformly mixed solution.
(2) And loading the graphene mixed solution subjected to ultrasonic treatment on a glass fiber diaphragm in a vacuum filtration mode to enable the thickness of the graphene thin layer to be 7 microns, and drying at room temperature for 12 hours.
(3) And (3) placing the dried membrane loaded with the graphene in the air under an excimer ultraviolet lamp for irradiation, adjusting the irradiation power of the irradiation to be 95% for 15 minutes, and drying the obtained modified membrane in a vacuum oven at 100 ℃ for 6 hours after the irradiation to obtain the modified fiber membrane which is EUV/graphene-separator.
Example 3
A preparation method of a graphene loaded glass fiber membrane with excimer ultraviolet irradiation modification comprises the following specific steps:
(1) dissolving 10 mg of single-layer graphene in 80 mL of absolute ethyl alcohol at room temperature, adding 40 mg of polyvinylpyrrolidone (PVP), performing ultrasonic treatment on the mixed solution at room temperature for 30 min by using a common ultrasonic machine, and performing ultrasonic treatment in an ultrasonic cell crusher for 5 min to obtain a uniformly mixed solution.
(2) And loading the graphene mixed solution subjected to ultrasonic treatment on a glass fiber diaphragm in a vacuum filtration mode to enable the thickness of the graphene thin layer to be 10 microns, and drying at room temperature for 12 hours.
(3) And (3) placing the dried membrane loaded with the graphene in the air under an excimer ultraviolet lamp for irradiation, adjusting the irradiation power of the irradiation to be 95% for 15 minutes, and drying the obtained modified membrane in a vacuum oven at 100 ℃ for 6 hours after the irradiation to obtain the modified fiber membrane which is EUV/graphene-separator.
Example 4
A preparation method of a graphene loaded glass fiber membrane with excimer ultraviolet irradiation modification comprises the following specific steps:
(1) dissolving 5 mg of single-layer graphene in 80 mL of absolute ethyl alcohol at room temperature, adding 40 mg of polyvinylpyrrolidone (PVP), performing ultrasonic treatment on the mixed solution at room temperature for 30 min by using a common ultrasonic machine, and performing ultrasonic treatment in an ultrasonic cell crusher for 5 min to obtain a uniformly mixed solution.
(2) And loading the graphene mixed solution subjected to ultrasonic treatment on a glass fiber diaphragm in a vacuum filtration mode to enable the thickness of the graphene thin layer to be 5 microns, and drying at room temperature for 12 hours.
(3) And (3) placing the dried membrane loaded with the graphene in the air under an excimer ultraviolet lamp for irradiation, adjusting the irradiation power of the irradiation to be 95% for 15 minutes, and drying the obtained modified membrane in a vacuum oven at 100 ℃ for 6 hours after the irradiation to obtain the modified fiber membrane which is EUV/graphene-separator.
Example 5
A preparation method of a graphene loaded glass fiber membrane with excimer ultraviolet irradiation modification comprises the following specific steps:
(1) dissolving 8 mg of single-layer graphene in 80 mL of absolute ethyl alcohol at room temperature, adding 40 mg of polyvinylpyrrolidone (PVP), performing ultrasonic treatment on the mixed solution at room temperature for 30 min by using a common ultrasonic machine, and performing ultrasonic treatment in an ultrasonic cell crusher for 5 min to obtain a uniformly mixed solution.
(2) And loading the graphene mixed solution subjected to ultrasonic treatment on a glass fiber diaphragm in a vacuum filtration mode to enable the thickness of the graphene thin layer to be 7 microns, and drying at room temperature for 12 hours.
(3) And (3) placing the dried membrane loaded with the graphene in the air under an excimer ultraviolet lamp for irradiation, adjusting the irradiation power of the irradiation to be 90% for 10 minutes, and drying the obtained modified membrane in a vacuum oven at 100 ℃ for 6 hours after the irradiation to obtain the modified fiber membrane which is EUV/graphene-separator.
Example 6
A preparation method of a graphene loaded glass fiber membrane with excimer ultraviolet irradiation modification comprises the following specific steps:
(1) dissolving 8 mg of single-layer graphene in 80 mL of absolute ethyl alcohol at room temperature, adding 40 mg of polyvinylpyrrolidone (PVP), performing ultrasonic treatment on the mixed solution at room temperature for 30 min by using a common ultrasonic machine, and performing ultrasonic treatment in an ultrasonic cell crusher for 5 min to obtain a uniformly mixed solution.
(2) And loading the graphene mixed solution subjected to ultrasonic treatment on a glass fiber diaphragm in a vacuum filtration mode to enable the thickness of the graphene thin layer to be 7 microns, and drying at room temperature for 12 hours.
(3) And (3) placing the dried membrane loaded with the graphene in the air under an excimer ultraviolet lamp for irradiation, adjusting the irradiation power of the irradiation to be 100% for 25 minutes, and drying the obtained modified membrane in a vacuum oven at 100 ℃ for 6 hours after the irradiation to obtain the modified fiber membrane which is EUV/graphene-separator.
FIG. 1 is a SEM image of the surface layer of the graphene-separator prepared in example 1. FIGS. 2 and 3 are SEM micrographs of the surface layers of the EUV/graphene-separator obtained in examples 2 and 3. The irradiation of the excimer ultraviolet lamp can not generate macroscopic influence on the surface layer structure of the graphene, the surfaces of the excimer ultraviolet lamp, the ultraviolet lamp and the graphene still present the specific lamellar structure of the single-layer graphene, and the size and the area of the graphene thin layer are basically not obviously changed before and after the irradiation of the excimer ultraviolet lamp, which shows that the structure of the graphene can not be damaged by the irradiation of the excimer ultraviolet lamp.
FIG. 4 is an XRD spectrum of the graphene-segarator obtained in example 1 and an XRD spectrum of the graphene-segarator obtained in example 4. As can be seen from the figure: diffraction broad peaks exist at 2 theta =26.6 degrees of the graphene-loaded glass fiber membrane and the graphene-loaded glass fiber membrane irradiated by the excimer ultraviolet lamp, and correspond to a graphite carbon structure (JCPDF No. 26-1076), which shows that the graphene can still maintain the crystallinity and the structure after irradiation by the excimer ultraviolet lamp.
FIGS. 5 and 6 are TEM images of the surface layer of the EUV/graphene-separator obtained in examples 5 and 6, respectively. It can be seen that the internal macrostructure of the EUV/graphene-separator after excimer ultraviolet irradiation is basically unchanged.
FIG. 8 is a FT-IR spectrum of the graphene-separator obtained in example 1 and the EUV/graphene-separator obtained in example 2. In the figure, the membrane is located at 1640cm on both diaphragms-1The bending vibration stretching peak of the left and right C-OH, but the peak on the EUV/graphene-separator is enhanced compared with the stretching vibration on the graphene-separator, which shows that the C-OH content of the graphene surface layer irradiated by an excimer ultraviolet lamp is increased to a certain extent, and the increase of the functional group is greatly helpful for improving the wettability of the graphene in the electrolyte. Meanwhile, 1420cm can be obtained from FIG. 8-1Both nearby membranes have an absorption peak, which is a bending vibration absorption peak corresponding to CO-H, respectively, andthe stretching vibration of the peak in the EUV/graphene-separator is obviously stronger than that of the peak in the graphene-separator, CO-H exists on both diaphragms, part of the untreated graphene diaphragm surface also contains oxygen groups, and the content of CO-H on the graphene surface layer is increased through irradiation of an excimer ultraviolet lamp.
Example 7 Single-layer graphene to polyvinylpyrrolidone proportional relationship Single-factor test
(1) Taking 8 mg of single-layer graphene, dissolving the single-layer graphene in 80 mL of absolute ethyl alcohol at room temperature, and adding a certain amount of PVP to ensure that the mass ratio of the single-layer graphene to the absolute ethyl alcohol is respectively as follows: 1: 0 (PVP amount at this time: 0), 1: 1. 1: 3. 1: 5. 1: 7. 1: and 10, performing ultrasonic treatment on the mixed solution for 30 min by using a common ultrasonic machine at room temperature, and performing ultrasonic treatment in an ultrasonic cell disruption instrument for 5 min to obtain a uniformly mixed solution.
(2) And loading the graphene mixed solution subjected to ultrasonic treatment on a glass fiber diaphragm in a vacuum filtration mode to enable the thickness of the graphene thin layer to be 7 microns, and drying at room temperature for 12 hours.
(3) And (3) placing the dried membrane loaded with the graphene in the air under an excimer ultraviolet lamp for irradiation, adjusting the irradiation power of the irradiation to be 95% for 15 minutes, and drying the obtained modified membrane in a vacuum oven at 100 ℃ for 6 hours after the irradiation to obtain the modified fiber membrane which is EUV/graphene-separator.
And preparing the prepared different films into a diaphragm with the diameter of 16 mm and a sulfur positive electrode, assembling a lithium negative electrode into a lithium-sulfur button cell, and performing charge-discharge test at the current density of 0.2C to obtain the discharge specific capacity in the first charge-discharge and the average coulomb efficiency in 80-turn charge-discharge behaviors (see table 1).
TABLE 1
| Mass ratio of single layer graphene to PVP | 1：0 | 1：1 | 1：3 | 1：5 | 1：7 | 1：10 |
| Specific discharge capacity of first coil (mAh g) at 0.2C-1） | 785 | 790 | 800 | 1164 | 987.5 | 950.4 |
| Coulombic efficiency (%) | 94 | 97.5 | 99 | 99.4 | 99.5 | 98.7 |
And (4) conclusion: the data in table 1 illustrate a mass ratio of 1: the separator cell of 5 has the best electrochemical performance and good cycle stability.
Investigation test of different irradiation powers during irradiation of application example
A preparation method of a graphene loaded glass fiber membrane with excimer ultraviolet irradiation modification comprises the following specific steps:
(1) dissolving 8 mg of single-layer graphene in 80 mL of absolute ethyl alcohol at room temperature, adding 40 mg of polyvinylpyrrolidone (PVP), performing ultrasonic treatment on the mixed solution at room temperature for 30 min by using a common ultrasonic machine, and performing ultrasonic treatment in an ultrasonic cell crusher for 5 min to obtain a uniformly mixed solution.
(2) And loading the graphene mixed solution subjected to ultrasonic treatment on a glass fiber diaphragm in a vacuum filtration mode to enable the thickness of the graphene thin layer to be 7 microns, and drying at room temperature for 12 hours.
(3) And (3) placing the dried membrane loaded with the graphene in the air under an excimer ultraviolet lamp for irradiation, adjusting the irradiation power of the irradiation to 95%, and irradiating for 5 min,10 min, 15 min, 20min and 25 min respectively, and then drying the obtained modified membrane in a vacuum oven at 100 ℃ for 6 h to obtain the modified fiber membrane which is EUV/graphene-separator.
The obtained electrochemical performance data of EUV/graphene-separator with different irradiation times are shown in FIG. 7, wherein the irradiation times are 10 min, 15 min, 20min, 25 min and 5 min, respectively. The specific capacities of the five batteries in the first circle of discharge are 918.5, 1164, 747, 931.9 and 795.4 mAh g respectively-1The specific discharge capacities of the lithium-sulfur batteries with the five separators after 80 charge-discharge cycles are 696.2, 914.8, 642.5 and 718.2,463 mAh g-1Fig. 7 shows that the specific discharge capacity of the lithium-sulfur battery loaded with the graphene diaphragm irradiated by the excimer ultraviolet lamp for 15 min is higher than that of the lithium-sulfur battery loaded with the graphene diaphragm and the common glass fiber diaphragm which are not irradiated for 5 min,10 min, 20min and 25 min, regardless of the specific discharge capacity of the first circle or the specific discharge capacity maintained after 80 cycles.
The test result shows that: the excimer ultraviolet irradiation modified graphene loaded glass fiber diaphragm battery prepared in the example 2 shows the best electrochemical performance.
Application example charging Point and coulombic efficiency experiment
The prepared EUV/graphene-separator (example 2) and graphene-separator (example 1) and ordinary glass fibers were cut into small 16 mm diameter disks, and all three different membranes were dried overnight in a vacuum oven at 100 ℃ and transferred to a glove box for use as lithium-sulfur battery membranes. The anode is S, the cathode is Li metal, and the mixing volume ratio is 1: electrochemical testing of a lithium sulfur cell assembled from 1, 3-Dioxolane (DOL) and 1, 2-Dimethoxyethane (DME) in 1.0M lithium bistrifluoromethanesulfonylimide (LiTFSI) solution as the working electrolyte and 2.0% LiNO3 added was performed on a model lan d-CT2001A cell test system.
The charge-discharge specific capacity and coulombic efficiency results of EUV/graphene-separator and graphene-separator in 300 cycles of 0.2C are shown in FIG. 9.
In fig. 9, the first strip from top to bottom is a membrane with loaded graphene and irradiated for 15 min, the second strip is a membrane with loaded graphene and not irradiated, the third strip is the electrochemical performance of a common glass fiber membrane battery, the EUV/graphene-separator irradiated for 15 min by an excimer ultraviolet lamp, the graphene-separator not irradiated and the common glass fiber membrane are subjected to 0.2C and 80 cycles, and the specific capacities of the five batteries in the first discharge cycle are 1164, 931.9, 795.4 mAh g-1The specific discharge capacities of the lithium-sulfur battery with the five separators after 80 charge-discharge cycles are 914.8, 718.2 and 463 mAh g respectively-1Fig. 9 shows that the graphene diaphragm-loaded lithium sulfur battery subjected to excimer ultraviolet lamp irradiation for 15 min has a higher specific discharge capacity than the non-irradiated lithium sulfur battery loaded with the graphene diaphragm and the common glass fiber diaphragm regardless of the specific discharge capacity of the first cycle or the specific discharge capacity maintained after 80 cycles.
The above-described embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.
Claims (10)
1. A preparation method of a graphene loaded glass fiber membrane with excimer ultraviolet irradiation modification is characterized by comprising the following steps:
(1) preparing a graphene solution: dissolving single-layer graphene in absolute ethyl alcohol, adding polyvinylpyrrolidone (PVP) and ultrasonically stirring, wherein the mass ratio of the single-layer graphene to the polyvinylpyrrolidone is 1: 1-10;
(2) graphene-supported glass fiber film: loading the graphene solution obtained in the step (1) on a glass fiber diaphragm in a vacuum filtration mode, and drying;
(3) irradiating and modifying the graphene film by an excimer ultraviolet lamp: and (3) in the air, placing the fiber film obtained in the step (2) under an excimer ultraviolet lamp for irradiation, and then drying in vacuum to obtain the graphene-loaded glass fiber film with excimer ultraviolet irradiation modification.
2. The method of claim 1, wherein: the ultrasonic stirring in the step (1) is divided into two steps, firstly ultrasonic treatment is carried out by an ultrasonic machine for 10-40 min, and then ultrasonic treatment is carried out for 5-30 min by an ultrasonic cell disruptor.
3. The method of claim 1, wherein: the content of the single-layer graphene in the absolute ethyl alcohol in the step (1) is 0.01-0.25 mg/mL-1To (c) to (d); the mass ratio of the single-layer graphene to the polyvinylpyrrolidone is 1: 2-6.
4. The method of claim 1, wherein: in the step (2), the thickness of the graphene thin layer on the glass fiber diaphragm after drying is controlled to be 3-10 μm.
5. The method of claim 1, wherein: the drying time in the step (2) is 3-12 h.
6. The method of claim 1, wherein: and (3) irradiating the fiber film under an excimer ultraviolet lamp, wherein the distance between the fiber film and a lamp tube of the excimer ultraviolet lamp is 1-15 mm.
7. The method of claim 1, wherein: in the step (3), the irradiation power of the excimer ultraviolet lamp is 70-100%, and the irradiation time is 10-40 min.
8. The method of claim 1, wherein: the temperature of vacuum drying in the step (3) is 60-100 ℃, and the time is 5-12 h.
9. The graphene-loaded glass fiber membrane with excimer ultraviolet irradiation modification is prepared by the preparation method of claim 1.
10. The application of the graphene loaded glass fiber membrane with the excimer ultraviolet irradiation modification function in the lithium-sulfur battery separator material according to claim 9.
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