CN114583389A - Co-based MOF-derived metal/carbon composite (Co/C) membrane and preparation method and application thereof - Google Patents
Co-based MOF-derived metal/carbon composite (Co/C) membrane and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 29
- 239000002184 metal Substances 0.000 title claims abstract description 29
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000012528 membrane Substances 0.000 title claims description 31
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 38
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 10
- 150000001868 cobalt Chemical class 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000011068 loading method Methods 0.000 claims description 12
- 239000012670 alkaline solution Substances 0.000 claims description 10
- 239000012266 salt solution Substances 0.000 claims description 10
- 239000002033 PVDF binder Substances 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- ZEVWQFWTGHFIDH-UHFFFAOYSA-N 1h-imidazole-4,5-dicarboxylic acid Chemical compound OC(=O)C=1N=CNC=1C(O)=O ZEVWQFWTGHFIDH-UHFFFAOYSA-N 0.000 claims description 5
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical compound C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 229910001868 water Inorganic materials 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000012300 argon atmosphere Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 229920001021 polysulfide Polymers 0.000 abstract description 16
- 239000005077 polysulfide Substances 0.000 abstract description 15
- 150000008117 polysulfides Polymers 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 8
- 230000008859 change Effects 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 15
- 239000012621 metal-organic framework Substances 0.000 description 15
- 239000004743 Polypropylene Substances 0.000 description 14
- 229920001155 polypropylene Polymers 0.000 description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 13
- 229910052744 lithium Inorganic materials 0.000 description 13
- 229910052717 sulfur Inorganic materials 0.000 description 13
- 239000011593 sulfur Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000011056 performance test Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910003003 Li-S Inorganic materials 0.000 description 1
- 239000012922 MOF pore Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000014233 sulfur utilization Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 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
- H01M50/403—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
- 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
-
- 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
- H01M50/411—Organic material
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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
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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
- H01M50/46—Separators, membranes or diaphragms characterised by their combination with 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
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Abstract
The invention belongs to the technical field of lithium-sulfur battery preparation, and discloses a Co-based MOF material derived metal/carbon composite material (Co/C) diaphragm, and a preparation method and application thereof. The diaphragm comprises a base diaphragm and Co/C @ graphene loaded on the base diaphragm. The diaphragm can inhibit the shuttle effect of polysulfide, relieve the volume change of an electrode in the charge-discharge process to a certain extent, and improve the electrochemical performance of the battery. The coating of the functional diaphragm is light and thin, and has small influence on the overall energy density of the battery; the preparation process is simple and can realize large-scale production. Has certain promotion effect on the commercialization of the lithium-sulfur battery system.
Description
Technical Field
The invention belongs to the technical field of lithium-sulfur battery preparation, and particularly relates to a Co-based MOF-derived metal/carbon composite (Co/C) membrane, and a preparation method and application thereof.
Background
Although lithium ion batteries have met with great success over the last 20 years, they have not been able to meet the significant demands of the future technology field due to their limited theoretical specific capacity. As one candidate for the next generation of power batteries, the theoretical energy density of lithium-sulfur batteries can reach 2600Wh/kg, which is much larger than the commercial lithium-ion batteries used at present. The lithium-sulfur battery is a lithium battery with sulfur as the positive electrode and metal lithium as the negative electrode. Lithium is the lightest metal and has a very low standard reduction potential (-3.04V). These characteristics make it an ideal negative electrode with low operating voltage and high specific capacity; sulfur is a solid, light and stable electronegative element, and has the advantages of abundant reserves, low price, environmental friendliness and the like. At present, the commercialization of lithium sulfur batteries faces the following problems:
(1) sulfur species have weak electron and ion conducting capabilities (about 5.0X 10 at room temperature)-30S/cm), the sulfur utilization rate of the active material is low.
(2) The shuttling effect of polysulfides leads to a loss of sulfur active species, which in turn leads to a rapid capacity decay.
(3) The volume change of the sulfur species during the charge-discharge cycle decreases the mechanical stability of the electrode.
As an important component of the lithium sulfur battery, the separator has functions of separating positive and negative electrodes, preventing short circuits, and allowing electrolyte ions to pass therethrough. Currently, a separator commonly used for a lithium sulfur battery is a polyolefin-based film including polypropylene (PP), Polyethylene (PE), and the like. They have the advantages of low cost, good chemical stability, high porosity, etc. On the other hand, its ion-selective permeability is low. The average size of long-chain lithium polysulphides is a few nanometers, whereas the pore size of the surface of a conventional PP separator is about 0.1 micrometer. Therefore, the PP separator cannot block migration of polysulfide to the negative electrode side. The construction of the functional diaphragm capable of intercepting polysulfide is of great significance for improving the performance of the lithium-sulfur battery.
The MOF-derived metal/carbon composite material is a composite material obtained by taking a porous MOF material as a precursor and calcining at high temperature in an inert atmosphere, and has the advantages of spontaneously forming a special framework structure and a porous high-conductivity carbon substrate. The MOF derived metal/carbon composites have the following advantages for lithium sulfur batteries: (1) the porous structure of the material can limit the diffusion of polysulfide through the physical confinement effect, and can relieve the volume change problem of the electrode in the charge-discharge cycle process; (2) the material has good conductivity, and is beneficial to improving the utilization rate of active substance sulfur. Based on the above, the Co/C @ graphene material with a certain loading capacity is loaded on the PP diaphragm, so that the electrochemical performance of the lithium-sulfur battery can be greatly improved.
Disclosure of Invention
In order to solve the problem that the current commercial lithium-sulfur battery separator cannot prevent polysulfide shuttling, the invention provides a separator based on a metal/carbon composite (Co/C) derived from Co-based MOF. The diaphragm can inhibit the shuttle effect of polysulfide, relieve the volume change of an electrode in the charge-discharge process to a certain extent, and improve the electrochemical performance of the battery.
Another object of the present invention is to provide a method for preparing the above separator.
Still another object of the present invention is to provide the use of the above separator in a lithium sulfur battery.
The purpose of the invention is realized by the following technical scheme:
the invention provides a Co-based MOF derived metal/carbon composite (Co/C) based membrane, which comprises a basic membrane and Co/C @ graphene loaded on the basic membrane. The Co/C @ graphene is a membrane modification layer formed after the Co/C and the graphene are loaded on a basic membrane.
Preferably, the base separator is a PP separator or a PE separator.
Preferably, the loading amount of Co/C @ graphene on the basic diaphragm is 0.08-0.32 mg/cm2(ii) a C in the Co/C @ grapheneThe specific surface area of o/C is 100 to 185m2Per g, pore volume of 0.1-0.21 cm3(ii)/g; the Co loading amount in the Co/C is 30.06-43.78%.
The invention provides a preparation method of the Co-based MOF derived metal/carbon composite (Co/C) based membrane, which comprises the following steps:
s1, dissolving a cobalt salt solution, 4, 5-imidazole dicarboxylic acid and 4, 4-bipyridine in an alkaline solution, carrying out a hydrothermal reaction at 160-200 ℃, washing the obtained solid with water, and drying at 60-120 ℃ to obtain Co-based MOF; calcining the prepared Co-based MOF in an inert atmosphere to obtain a metal/carbon (Co/C) composite material;
s2, ultrasonically mixing Co/C, graphene and PVDF in NMP, performing suction filtration by taking a basic diaphragm as a substrate, and finally drying to obtain a Co/C @ graphene modified diaphragm, namely the diaphragm of the metal/carbon composite material derived on the basis of the Co-based MOF.
Preferably, the cobalt salt in the cobalt salt solution in step S1 is Co (NO)3)2·6H2O; the concentration of the cobalt salt solution is 0.2-0.5 mol/L;
preferably, the alkaline solution in step S1 is a sodium hydroxide solution or a potassium hydroxide solution; the alkaline solution is an alkaline solution with the concentration of 0.2-0.4 mol/L.
Preferably, in step S1, the molar ratio of the cobalt salt solution, the 4, 5-imidazole dicarboxylic acid, the 4, 4-bipyridine and the alkaline substance in the alkaline solution is (0.2-0.5): 0.1-0.4): 0.15-0.6.
Preferably, the hydrothermal reaction time in step S1 is 2 to 4 days, and the drying time is 12 to 36 hours.
Preferably, the inert atmosphere in step S1 is nitrogen or argon atmosphere; the calcination temperature is 600-800 ℃; the calcination time is 1-5 hours.
Preferably, the mass ratio of Co/C to graphene in the step S2 is (1.35-5.4): (3.15-12.6).
Preferably, the volume ratio of the total mass of Co/C and graphene, the mass of PVDF and NMP in step S2 is (4.5-18.0) mg, (1.6-2.0) mg, (28.8-36.0) mL.
The invention provides application of the Co-based MOF derived metal/carbon composite (Co/C) based separator in the field of lithium-sulfur batteries.
According to the invention, a membrane modification layer based on a Co-based MOF derived metal/carbon composite material (Co/C) is constructed and loaded on a commercial membrane to inhibit the shuttle effect of polysulfide, so that the electrochemical performance of a lithium-sulfur battery is improved. The diaphragm modification layer is a film with high conductivity and multiple adsorption sites, which is obtained by mixing Co/C and graphene and then performing suction filtration. The modification layer applied to the lithium-sulfur battery has multiple advantages: (1) co atoms in the Co/C material have strong affinity to lithium polysulfide and have strong catalytic acceleration effect on the kinetics of the redox reaction of sulfur; (2) lithium polysulfide can be effectively adsorbed and fixed by the nano porous structure and the polar surface of the Co/C composite material, rapid ion migration is obtained, and volume change in the charge-discharge process of a sulfur anode is relieved to a certain extent; (3) the high conductivity of the Co/C composite material is beneficial to improving the utilization rate of active substance sulfur; (4) the preparation method of the diaphragm is simple. Electrochemical performance test results show that the diaphragm modification layer can effectively improve the specific capacity and the cycling stability of the lithium-sulfur battery.
Compared with the prior art, the invention has the following advantages:
1. the loading amount of metal Co in the Co/C material is 30.06-43.78%. The high-load metal Co atoms are beneficial to the adsorption of polysulfide and accelerate the redox reaction kinetics of sulfur. The nano porous structure and the polar surface of the Co/C composite material can effectively adsorb and fix lithium polysulfide, obtain rapid ion migration, and relieve the volume change of a sulfur anode in the charge-discharge process to a certain extent.
2. The Co/C @ graphene can serve as a second current collector, an additional conductive network is provided, and the utilization rate of active substance sulfur is improved.
3. The coating of the functional diaphragm is light and thin, and has small influence on the overall energy density of the battery; the preparation process is simple and can realize large-scale production. Has certain promotion effect on the commercialization of the lithium-sulfur battery system.
Drawings
FIG. 1 is the XRD spectrum of Co/C obtained in example 2.
FIG. 2 is a photograph of the nitrogen desorption isotherm of Co/C obtained in example 2.
FIG. 3 is an SEM photograph of the Co/C obtained in example 2.
Fig. 4 is a graph comparing the cycle performance of the batteries prepared in example 2, comparative example 1 and comparative example 2.
Fig. 5 is a graph of the long cycle performance of the battery prepared in example 2.
Fig. 6 is a graph of the cycling performance of the cells prepared in example 2 at different membrane loadings.
FIG. 7 is an XPS plot of Co/C vs. lithium polysulfide adsorbed as obtained in example 2.
Detailed Description
The following examples are presented to further illustrate the present invention and should not be construed as limiting the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
The invention adopts XRD (equipment model: JCPDS No.01-070-2Adsorption-desorption performance test (equipment model: BELSORP-mini), SEM (equipment model: German-Zeiss-ZEISS sigma500), XPS (equipment model: Nexsa).
Example 1
Physically mixing S and CNT according to the mass ratio of 8:2, heating to 155 ℃ in an inert atmosphere, and keeping for 12 hours to ensure that sulfur fully enters CNT pore channels to form an S/CNT composite material; mixing the S/CNT (S: CNT is 8:2) composite material, CNT and PVDF according to the mass ratio of 7: 2: 1, adding a proper amount of NMP as a solvent to prepare adhesive slurry, coating the adhesive slurry on a clean aluminum foil, and controlling the surface loading of S to be 1.0mg/cm2Left and right. And drying the aluminum foil coated with the slurry in an oven at 80 ℃ for 12h, taking out, and cutting into round pieces with the diameter of 14mm by using a tablet machine to serve as positive plates of the button cells for later use.
Button cell groupLoading: the battery case model: CR2032, model of PP separator: celgard2400, negative electrode: lithium sheet (purity is more than or equal to 99.5%), electrolyte components: 1MLiTFSI, DOL/DME (1: 1, v/v), 1% LiNO3(wt), amount of electrolyte used: 10-20 μ L, glove box: ar gas (O)2＜0.1ppm，H2O＜0.1ppm)。
Example 2
Synthesis of Co/C:
(1) mixing Co (NO)3)2·6H2O (0.4365g, 1.5mmol) was dissolved in 5mL water and stirred for 0.5h to form cobalt salt solution A;
(2) sodium hydroxide (0.0601g, 1.5mmol), 5mL of water, 4, 5-imidazole dicarboxylic acid (0.1581g, 1mmol) and 4, 4-bipyridine (0.1562g, 1mmol) were stirred for 0.5h to form solution B;
(3) adding the cobalt salt solution A into the solution B, transferring the solution B into a reaction kettle, sealing, and heating at 180 ℃ for 3 days. Washing the obtained solid by deionized water, finally drying in a 60 ℃ oven to obtain Co-based MOF, and calcining the Co-based MOF for 1 hour at 800 ℃ in an inert atmosphere to obtain the Co/C material.
Preparing a Co/C @ graphene diaphragm:
the loading capacity is 0.32mg/cm2The preparation method of the Co/C @ graphene diaphragm comprises the steps of adding 36.0mL of NMP into 5.4mg of Co/C, 12.6mg of graphene and 2.0mg of PVDF, carrying out ultrasonic treatment for 1h, carrying out suction filtration by taking a PP diaphragm as a substrate, and finally drying at room temperature for 24h to obtain the Co/C @ graphene modified diaphragm, namely the diaphragm based on the Co-based MOF derived metal/carbon composite material (Co/C).
The loading capacity is 0.16mg/cm2The preparation method of the Co/C @ graphene diaphragm comprises the steps of adding 2.7mg of Co/C, 6.3mg of graphene and 2.0mg of PVDF into 36.0mL of NMP, carrying out ultrasonic treatment for 1 hour, carrying out suction filtration by taking a PP diaphragm as a substrate, and finally drying at room temperature for 24 hours.
The loading capacity is 0.08mg/cm2The preparation method of the Co/C @ graphene diaphragm comprises the steps of adding 36.0mL of NMP into 1.35mg of Co/C, 3.15mg of graphene and 2.0mg of PVDF, performing ultrasonic treatment for 1 hour, performing suction filtration by taking a PP diaphragm as a substrate, and finally drying at room temperature for 24 hours.
3. Assembling the button cell:
assembling the positive pole piece, the Co/C @ graphene modified diaphragm and the lithium piece into a button cell in a glove box, and carrying out electrochemical performance test in a cell test system.
Comparative example 1
1. Adding 18.0mg of graphene and 2.0mg of PVDF into 36.0mL of NMP, carrying out ultrasonic treatment for 1h, carrying out suction filtration by taking a PP diaphragm as a substrate, drying for 24h at room temperature, and cutting into round pieces by using a die for later use.
2. Assembling the positive pole piece, the graphene modified diaphragm and the lithium piece into a button cell in a glove box, and carrying out electrochemical performance test in a cell test system.
Comparative example 2
And assembling the positive pole piece, the PP diaphragm and the lithium piece into a button cell in a glove box, and carrying out electrochemical performance test in a cell test system.
Example 3
Adding a mixture of DOL and DME in a molar ratio of 5: 1, stirring vigorously for 12h under the argon atmosphere to prepare brownish red Li2S6Solution (0.2M).
Mixing Li2S6The solution was diluted to 2 mM. 50mg Co/C was added to 6mL Li2S6The solution was placed in a glove box filled with argon for 12 hours. And finally, naturally airing, and taking the solid powder for XPS test. At the same time, 50mg of Co/C was taken under the same conditions for XPS test.
FIG. 1 is the XRD spectrum of Co/C obtained in example 2. As can be seen from FIG. 1, the Co/C material shows a broad peak at about 26 ℃ and a weak peak at about 44 ℃, both of which are characteristic peaks of amorphous carbon. The crystalline peaks appearing at about 43 °, 52 °, 76 ° are all characteristic of cobalt, indicating that this is a Co/C material. FIG. 2 is a nitrogen desorption isotherm image of the Co/C material obtained in example 2, which can prove the porous structure thereof. The specific surface area of the material is 185m calculated through the results of nitrogen adsorption and desorption experiments2Per g, pore volume 0.21cm3(ii) in terms of/g. FIG. 3 is an SEM photograph of Co/C obtained in example 2. As can be seen from fig. 3, the micro-morphology of the material is in the form of regular nano-blocks. FIG. 4 is a diagram of the batteries prepared in example 2, comparative example 1 and comparative example 2Cycle performance is compared. As can be seen from fig. 4, under the same test conditions, the first-turn discharge specific capacity of the Co/C @ graphene modified diaphragm is up to 1355.7mAh/g, the first-turn discharge capacities of the graphene modified diaphragm and the PP diaphragm are 1146.9 and 1089.8mAh/g respectively, which are lower than those of the Co/C @ graphene modified diaphragm, which also indicates that the Co/C @ graphene modified diaphragm improves the utilization rate of active materials; when the membrane is circulated to 300 circles, the reversible capacity of the Co/C @ graphene modified membrane is 705.9mAh/g, which is much higher than that of a graphene modified membrane (575.1mAh/g) and a PP membrane (439.6 mAh/g). Fig. 5 is a graph of the long cycle performance of the battery prepared in example 2. As can be seen from fig. 5, the capacity fade rate at 300 cycles was only 0.18% at a high rate of 2C, indicating that the battery based on the Co/C @ graphene modified separator had good cycle stability. FIG. 6 is a graph showing the cycle characteristics of the separator at various loadings for the cell prepared in example 2, and it can be seen from FIG. 6 that the cycle characteristics were even at 0.08mg/cm2Under the ultralow load, the Li-S battery still shows excellent cycle performance, the initial discharge capacity is 1457mAh/g, and the reversible capacity of the Co/C @ graphene modified diaphragm is 769mAh/g after 100 cycles of circulation. FIG. 7 is an XPS map obtained in example 3. As can be seen from FIG. 7, the Co2p XPS peak has Co2p1/2sat.(804.800、801.854eV)、Co2p1/2(796.365、793.680eV)、Co2p3/2sat. (785.559, 782.140eV) and Co2p3/2(780.138, 778.406 eV). After the Co/C material adsorbs lithium polysulfide, Co2p1/2(796.280eV) and Co2p3/2The (779.520, 778.362eV) peaks shifted to lower binding energies, with offsets of-0.085 eV, -0.618eV, and-0.044 eV, respectively. Co2p1/2And Co2p3/2Red-shift of the XPS peak indicates an electron from S6 2-Transfer to Co ion to make S6 2-Forms an interactive chemical interaction with Co, illustrating the adsorption of polysulfides by the Co/C material.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A Co-based MOF derived metal/carbon composite based membrane comprising a base membrane and Co/C @ graphene supported on the base membrane.
2. The Co-based MOF derived metal/carbon composite based membrane according to claim 1, wherein the base membrane is a PP membrane or a PE membrane.
3. The Co-based MOF derived metal/carbon composite based membrane according to claim 1, wherein the loading of Co/C @ graphene on the base membrane is 0.08-0.32 mg/cm2(ii) a The specific surface area of Co/C in the Co/C @ graphene is 100-185 m2Per g, pore volume of 0.1-0.21 cm3(ii)/g; the Co loading amount in the Co/C is 30.06-43.78%.
4. A method for preparing a Co-based MOF derived metal/carbon composite based membrane according to any one of claims 1 to 3, comprising the steps of:
s1, dissolving a cobalt salt solution, 4, 5-imidazole dicarboxylic acid and 4, 4-bipyridine in an alkaline solution, carrying out a hydrothermal reaction at 160-200 ℃, washing the obtained solid with water, and drying at 60-120 ℃ to obtain a Co-based MOF material; calcining the prepared Co-based MOF material in an inert atmosphere to obtain a Co/C material;
s2, ultrasonically mixing Co/C, graphene and PVDF in NMP, performing suction filtration by taking a basic diaphragm as a substrate, and finally drying to obtain a Co/C @ graphene modified diaphragm, namely the diaphragm of the metal/carbon composite material derived based on the Co-based MOF.
5. The method for preparing the Co-based MOF-derived metal/carbon composite membrane according to claim 4, wherein the cobalt salt in the cobalt salt solution is Co (NO) in step S13)2·6H2O; the concentration of the cobalt salt solution is 0.2-0.5 mol/L; step S1, the alkaline solution is a sodium hydroxide solution or a potassium hydroxide solution; the alkaline solution is an alkaline solution with the concentration of 0.2-0.4 mol/L.
6. The method for preparing a Co-based MOF-derived metal/carbon composite membrane according to claim 4, wherein the molar ratio of the cobalt salt solution, the 4, 5-imidazole dicarboxylic acid, the 4, 4-bipyridine and the alkaline substance in the alkaline solution in step S1 is (0.2-0.5): (0.1-0.4): (0.15-0.6).
7. The preparation method of the Co-based MOF-derived metal/carbon composite membrane according to claim 4, wherein the hydrothermal reaction time in the step S1 is 2-4 days; the drying time is 12-36 h; the inert atmosphere is nitrogen or argon atmosphere; the calcination temperature is 600-800 ℃; the calcination time is 1-5 hours.
8. The preparation method of the Co-based MOF-derived metal/carbon composite membrane is characterized in that the mass ratio of Co/C to graphene in the step S2 is (1.35-5.4) to (3.15-12.6).
9. The preparation method of the Co-based MOF-derived metal/carbon composite material membrane is characterized in that the volume ratio of the total mass of Co/C and graphene, the mass of PVDF and NMP in the step S2 is (4.5-18.0) mg, namely (1.6-2.0) mg, namely (28.8-36.0) mL.
10. Use of a Co-based MOF derived metal/carbon composite based separator according to any one of claims 1 to 3 in the field of lithium sulphur batteries.
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