CN115602997A - Co 3 O 4 -PVA-PPy-PP diaphragm, preparation method and application thereof, and lithium-sulfur battery containing diaphragm - Google Patents
Co 3 O 4 -PVA-PPy-PP diaphragm, preparation method and application thereof, and lithium-sulfur battery containing diaphragm Download PDFInfo
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- CN115602997A CN115602997A CN202211250838.7A CN202211250838A CN115602997A CN 115602997 A CN115602997 A CN 115602997A CN 202211250838 A CN202211250838 A CN 202211250838A CN 115602997 A CN115602997 A CN 115602997A
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- 229910020599 Co 3 O 4 Inorganic materials 0.000 title claims abstract description 57
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 17
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000725 suspension Substances 0.000 claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000012986 modification Methods 0.000 claims abstract description 9
- 230000004048 modification Effects 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 8
- 238000011065 in-situ storage Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 6
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims abstract description 5
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 4
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 4
- 238000005979 thermal decomposition reaction Methods 0.000 claims abstract description 4
- 238000004528 spin coating Methods 0.000 claims abstract description 3
- 239000012528 membrane Substances 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 15
- 239000003792 electrolyte Substances 0.000 claims description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000011888 foil Substances 0.000 claims description 3
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 3
- 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 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 12
- 230000001351 cycling effect Effects 0.000 abstract description 5
- 239000004743 Polypropylene Substances 0.000 abstract 5
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- -1 polypropylene Polymers 0.000 abstract 1
- 229920001155 polypropylene Polymers 0.000 abstract 1
- 229920001021 polysulfide Polymers 0.000 description 8
- 239000005077 polysulfide Substances 0.000 description 8
- 150000008117 polysulfides Polymers 0.000 description 8
- 239000000203 mixture Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 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
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
-
- 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
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
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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
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
-
- 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
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- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
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- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Cell Separators (AREA)
Abstract
The invention belongs to the technical field of lithium-sulfur batteries and discloses Co 3 O 4 -a PVA-PPy-PP separator comprising a substrate layer and a modification layer coated on the surface of the substrate; the basal layer is a polypropylene PP diaphragm, and the modification layer is Co 3 O 4 -PVA-PPy composite functional material; the preparation method of the diaphragm comprises the steps of S1 and Co preparation 3 O 4 Powder: preparation of Co by thermal decomposition 3 O 4 A powder; s2, synthesis of Co 3 O 4 -PVA-pyrrole suspension: PVA is mixed in deionized waterAdding Co after combination 3 O 4 Powder, then add pyrrole; s3, preparing Co 3 O 4 -PVA-PPy-PP separator: mixing Co 3 O 4 Dripping PVA-pyrrole suspension on a diaphragm for uniform spin coating, and preparing Co through in-situ oxidation polymerization 3 O 4 -a PVA-PPy-PP separator; also disclosed is the use of the separator in a lithium sulfur battery. The process flow for preparing the diaphragm is simple, and the obtained diaphragm has high wettability, high conductivity and thermal stability and has the effect of catalyzing the redox conversion of LiPS to inhibit the shuttle effect; the lithium-sulfur battery containing the diaphragm has excellent cycling stability and high specific discharge capacity.
Description
Technical Field
The invention relates to the technical field of lithium-sulfur batteries, in particular to Co 3 O 4 A PVA-PPy-PP diaphragm, a preparation method and an application thereof, and also relates to a membrane containing Co 3 O 4 -a PVA-PPy-PP separator.
Background
In recent years, with the continuous exhaustion of fossil energy and the idea of energy conservation and environmental protection, lithium-sulfur batteries are increasingly paid more attention as an advanced energy storage technology. The theoretical specific energy of the lithium-sulfur battery can reach 2600Wh/kg, which is far greater than that of the existing lithium ion battery, and meanwhile, the sulfur anode of the lithium-sulfur battery also has the characteristics of low price, environmental friendliness and the like. However, the lithium sulfur battery generates polysulfide that is dissolved in an electrolyte during charge and discharge, and repeatedly diffuses between a positive electrode and a negative electrode, i.e., a "shuttle effect" is generated. The shuttle effect can cause the discharge specific capacity of the lithium-sulfur battery to be reduced and the cycle performance to be poor. Therefore, the battery performance of the lithium-sulfur battery can be effectively improved by inhibiting the shuttle effect of polysulfide. Researches show that substances with the capacity of chemically adsorbing/catalytically converting lithium polysulfide are modified on the diaphragm, so that the shuttle effect of the lithium-sulfur battery can be obviously limited, and the utilization rate of the positive electrode sulfur is improved. Meanwhile, the good electrolyte wettability, conductivity and thermal stability of the diaphragm also have important influence on the electrochemical performance and safety performance of the lithium-sulfur battery.
At present, those skilled in the art introduce porous carbon materials, transition metal oxides, nitrides, sulfides, etc. into the separator to capture and convert lithium sulfur compounds in the electrolyte to improve battery capacity and long cycle performance. But generally, wettability, conductivity and thermal stability are difficult to satisfy simultaneously; moreover, the existing diaphragm has complex preparation process and higher cost.
Disclosure of Invention
The invention aims to provide Co 3 O 4 A PVA-PPy-PP diaphragm, a preparation method and an application thereof, aiming at solving the problem of the absorption of the lithium polysulfide of the prior lithium-sulfur battery diaphragmPoor catalytic conversion performance, difficult simultaneous satisfaction of wettability, conductivity and thermal stability, complex preparation process and higher cost. Also provides a catalyst containing Co 3 O 4 The lithium-sulfur battery with the PVA-PPy-PP diaphragm has the diaphragm with high wettability and thermal stability, lower electrochemical impedance and higher ionic conductivity, and can improve the redox activity of lithium polysulfide, so that the battery has excellent cycling stability and high specific discharge capacity.
In order to achieve the above purpose, the invention provides the following technical scheme:
co 3 O 4 -a PVA-PPy-PP membrane comprising a substrate layer and a finishing layer coated on the surface of the substrate; the basal layer is a PP diaphragm, and the modification layer is Co 3 O 4 -PVA-PPy composite functional material.
A Co as described above 3 O 4 The preparation method of the PVA-PPy-PP diaphragm comprises the following steps:
s1, preparing Co 3 O 4 Powder:
preparation of Co by thermal decomposition 3 O 4 Powder of Co (NO) 3 ) 2 ·6H 2 Placing O powder into a tube furnace, heating to 550 ℃ in air at a heating rate of 3 ℃/min, and keeping the temperature for 2h to obtain Co 3 O 4 Powder;
s2, synthesis of Co 3 O 4 -PVA-pyrrole suspension:
dissolving PVA in deionized water, and stirring in an oil bath kettle at 90 deg.C for 0.5h until the solution is fully mixed; subsequently, co prepared in S1 was added to the PVA solution 3 O 4 Stirring the powder vigorously at room temperature for 1h; then adding pyrrole into the mixed solution to obtain Co 3 O 4 -a PVA-pyrrole suspension;
s3, preparing Co 3 O 4 -PVA-PPy-PP separator:
mixing the Co obtained in S2 3 O 4 Dripping the PVA-pyrrole suspension on a PP diaphragm, and uniformly and rotatably coating the suspension on the PP diaphragm by using a spin coater at the rotating speed of 1000r-minOn the film; preparation of Co by in situ oxidative polymerization of pyrrole 3 O 4 -a PVA-PPy-PP separator.
Further, in S3, by Co 3 O 4 Co preparation by in-situ oxidative polymerization of pyrrole in-PVA-pyrrole-PP 3 O 4 The specific method of the PVA-PPy-PP diaphragm comprises the following steps: will be coated with Co 3 O 4 Impregnation of PP Membrane into FeCl of PVA-pyrrole 3 Removing the membrane after the solution is washed twice by deionized water, rinsed once by absolute ethyl alcohol and air-dried to obtain Co 3 O 4 -a PVA-PPy-PP separator; finally, mixing Co 3 O 4 The PVA-PPy-PP membrane is dried for 12h at 25 ℃.
Further, in S3, the Co prepared 3 O 4 Thickness of the PVA-PPy modification layer is about 1 μm, co 3 O 4 The diameter of the PVA-PPy-PP membrane was 1.9cm.
A Co as described above 3 O 4 -use of a PVA-PPy-PP separator in a lithium sulphur battery.
Containing one of the above-mentioned Co 3 O 4 -PVA-PPy-PP diaphragm lithium sulfur battery, the anode of the lithium sulfur battery is carbon nano tube-sulfur composite material, the cathode of the lithium sulfur battery is lithium foil, and the diaphragm of the lithium sulfur battery is Co 3 O 4 -a PVA-PPy-PP separator, the electrolyte of the lithium sulfur battery being a DOL + DME solution containing 1.0M LiTFSI in a volume ratio of 1.
Further, the positive electrode of the lithium-sulfur battery is a CNT-S composite material, and the preparation method comprises the following steps: mixing sulfur powder and carbon nano tubes in a ratio of 7:3, adding CS while stirring 2 Sealing the sample in a reaction kettle, heating at 155 deg.C for 12 hr, and drying at 60 deg.C for 12 hr.
The beneficial effects of the technical scheme are that:
1. preparation of Co by the invention 3 O 4 The PVA-PPy-PP diaphragm has simple process flow, does not need other adhesives, dispersants, thickeners and other auxiliary agents, has rich, cheap and easily obtained raw material resources and low cost;
2、co obtained by the invention 3 O 4 The PVA-PPy-PP diaphragm has good electrolyte wettability and thermal stability, has lower electrochemical impedance and higher ionic conductivity, can improve the redox activity of lithium polysulfide and inhibit the shuttle effect of the lithium polysulfide;
3. the invention provides a catalyst containing Co 3 O 4 The lithium-sulfur battery with the PVA-PPy-PP diaphragm has the advantages that the diaphragm has the effects of inhibiting the shuttle effect of lithium polysulfide, good electrolyte wettability and thermal stability, the safety problems of self discharge, two-pole short circuit and the like of the battery are avoided, and the battery has excellent cycling stability and high specific discharge capacity.
Drawings
FIG. 1 shows a Co of the present invention 3 O 4 -sem and photo images of PVA-PPy-PP membranes;
FIG. 2 shows a Co composition according to the present invention 3 O 4 Preparation method of-PVA-PPy-PP membrane and Co obtained in S1 3 O 4 Nanoparticle XRD pattern;
FIG. 3 shows a Co composition according to the present invention 3 O 4 -PVA-PPy-PP separator Co 3 O 4 -ir spectrum of PVA-PPy coating;
FIG. 4 shows a Co film according to the present invention 3 O 4 -graph comparing thermal stability of PVA-PPy-PP membranes with pure PP membranes;
FIG. 5 shows a Co film according to the present invention 3 O 4 -contact angle test contrast of PVA-PPy-PP separator with pure PP separator;
FIG. 6 shows a composition of the present invention containing Co 3 O 4 Electrochemical impedance spectra of lithium-sulfur batteries with PVA-PPy-PP separator and control;
FIG. 7 shows a composition of the present invention containing Co 3 O 4 Cycling performance at 0.2C for lithium-sulfur batteries with PVA-PPy-PP separator versus control;
FIG. 8 shows a composition of the present invention containing Co 3 O 4 Long-term cycling stability at 1C and 2C for lithium-sulfur batteries with PVA-PPy-PP separator.
Detailed Description
The invention is described in further detail below with reference to the following figures and embodiments:
as shown in FIGS. 1 to 5, a Co 3 O 4 -a PVA-PPy-PP membrane comprising a substrate layer and a finishing layer coated on the surface of the substrate; the basal layer is a PP diaphragm, and the modification layer is Co 3 O 4 -PVA-PPy composite functional material.
Co 3 O 4 The preparation method of the PVA-PPy-PP diaphragm comprises the following steps:
s1, preparation of Co 3 O 4 Powder:
preparation of Co by thermal decomposition 3 O 4 Powder of Co (NO) 3 ) 2 ·6H 2 Putting O into a tube furnace, heating to 550 ℃ in air at a heating rate of 3-min, and keeping the temperature for 2h to obtain Co 3 O 4 Powder;
s2, synthesis of Co 3 O 4 -PVA-pyrrole suspension:
dissolving PVA in deionized water, and stirring in an oil bath kettle at 90 deg.C for 0.5 hr until the solution is fully mixed; subsequently, co prepared in S1 was added to the PVA solution 3 O 4 Stirring the powder vigorously at room temperature for 1h; then adding pyrrole into the mixed solution to obtain Co 3 O 4 -a PVA-pyrrole suspension;
s3, preparing Co 3 O 4 -PVA-PPy-PP separator:
mixing the Co obtained in S2 3 O 4 Dripping the PVA-pyrrole suspension on a PP diaphragm, and uniformly spin-coating the suspension on the PP diaphragm by using a spin coater at the rotating speed of 1000 r/min; by Co 3 O 4 Co prepared by in-situ oxidative polymerization of pyrrole in-PVA-pyrrole-PP 3 O 4 The PVA-PPy-PP diaphragm is prepared by the following specific method: will be coated with Co 3 O 4 Membrane immersion in PVA-pyrrole in FeCl 3 Removing the membrane after the solution is washed twice by deionized water, rinsed once by absolute ethyl alcohol and air-dried to obtain Co 3 O 4 -a PVA-PPy-PP separator; finally, mixing Co 3 O 4 Drying a-PVA-PPy-PP diaphragm for 12h at the temperature of 25 ℃ to obtain Co 3 O 4 The thickness and diameter of the PVA-PPy-PP separator were 1 μm and 1.9cm, respectively.
A Co as described above 3 O 4 -use of a PVA-PPy-PP separator in a lithium sulphur battery.
Containing one of the above-mentioned Co 3 O 4 A lithium-sulfur battery with a PVA-PPy-PP diaphragm, wherein the positive electrode of the lithium-sulfur battery is a carbon nano tube-sulfur composite material, the negative electrode of the lithium-sulfur battery is a lithium foil, and the diaphragm of the lithium-sulfur battery is Co 3 O 4 -a PVA-PPy-PP separator, the electrolyte of the lithium sulphur battery being a DOL + DME solution containing 1.0M LiTFSI in a volume ratio of 1; the preparation method of the CNT-S composite material comprises the following steps: sulfur powder and carbon nanotubes were mixed at 7:3, adding CS while stirring 2 Sealing the sample in a reaction kettle, heating at 155 deg.C for 12 hr, and drying at 60 deg.C in vacuum environment for 12 hr.
For the above-mentioned material containing Co 3 O 4 Electrochemical performance test of lithium-sulfur batteries with PVA-PPy-PP separator:
as shown in fig. 6 to 8, the electrochemical test was performed in a glove box filled with argon (oxygen and water content less than 0.1 ppm). The 2032 coin-type half cell was assembled in a glove box at different C-rates (1C =1672mAh g) within a voltage window of 1.7-2.8V on New Wei CT2001A system -1 ) Electrochemical charge-discharge tests were performed. CV and Electrochemical Impedance Spectroscopy (EIS) tests were performed using a Cowster electrochemical workstation (BT 2000) with EIS testing frequencies ranging from 0.01 to 10 5 Hz. All electrochemical experiments were performed at room temperature (25 ℃). The specific capacity of the lithium-sulfur battery was calculated based on the mass of sulfur. For each cell, for a typical electrode (2.0-2.2 mg cm) -2 ) The ratio of electrolyte/sulfur (E/S) used was controlled to about 10. Mu.L/mg. The electrolyte was a mixed solution of DME and DOL (v: v = 1. The electrolyte addition was 10 μ L for all symmetric and asymmetric cells.
The above description is only an example of the present invention, and the common general knowledge of the technical solutions or characteristics known in the solutions is not described herein too much. It should be noted that, for those skilled in the art, without departing from the technical solution of the present invention, several variations and modifications can be made, and these should also be considered as the protection scope of the present invention, which will not affect the effect of the implementation of the present invention and the practicability of the patent. The scope of the claims of the present application shall be determined by the contents of the claims, and the description of the embodiments and the like in the specification shall be used to explain the contents of the claims.
Claims (7)
1. Co 3 O 4 -a PVA-PPy-PP separator characterized in that: the diaphragm comprises a substrate layer and a modification layer coated on the surface of the substrate layer; the basal layer is a PP diaphragm, and the modification layer is Co 3 O 4 -PVA-PPy composite functional material.
2. Co according to claim 1 3 O 4 The preparation method of the PVA-PPy-PP membrane is characterized by comprising the following steps: the method comprises the following steps:
s1, preparation of Co 3 O 4 Powder:
preparation of Co by thermal decomposition 3 O 4 Powder of Co (NO) 3 ) 2 ·6H 2 Placing O powder into a tube furnace, heating to 550 ℃ in air at a heating rate of 3 ℃/min, and keeping the temperature for 2h to obtain Co 3 O 4 Powder;
s2, synthesis of Co 3 O 4 -PVA-pyrrole suspension:
dissolving PVA in deionized water, and stirring in an oil bath kettle at 90 deg.C for 0.5h until the solution is fully mixed; subsequently, co prepared in S1 was added to the PVA solution 3 O 4 Stirring the powder vigorously at room temperature for 1h; then adding pyrrole into the mixed solution to obtain Co 3 O 4 -a PVA-pyrrole suspension;
s3, preparing Co 3 O 4 -PVA-PPy-PP separator:
mixing the Co obtained in S2 3 O 4 -dripping the PVA-pyrrole suspension onto a PP membrane, and then spin-coating the suspension uniformly onto the PP membrane with a spin coater at a rotation speed of 1000 r/min; in situ oxidative polymerization by pyrroleCo is prepared to obtain Co 3 O 4 -a PVA-PPy-PP separator.
3. Co according to claim 2 3 O 4 The preparation method of the PVA-PPy-PP diaphragm is characterized by comprising the following steps: in S3, by Co 3 O 4 Co preparation by in-situ oxidative polymerization of pyrrole in-PVA-pyrrole-PP 3 O 4 The specific method of the PVA-PPy-PP diaphragm comprises the following steps: will be coated with Co 3 O 4 Impregnation of PP separator of PVA-pyrrole into FeCl 3 Removing the membrane after the solution is washed twice by deionized water, rinsed once by absolute ethyl alcohol and air-dried to obtain Co 3 O 4 -a PVA-PPy-PP separator; finally, mixing Co 3 O 4 Drying the PVA-PPy-PP membrane for 12h at 25 ℃.
4. Co according to claim 2 3 O 4 The preparation method of the PVA-PPy-PP membrane is characterized by comprising the following steps: in S3, the obtained Co is prepared 3 O 4 The thickness of the PVA-PPy modification layer is about 1 μm, co 3 O 4 The diameter of the PVA-PPy-PP separator was 1.9cm.
5. Co according to claim 1 3 O 4 -use of a PVA-PPy-PP separator in a lithium sulphur battery.
6. Comprising a Co compound as defined in claim 1 3 O 4 -a lithium-sulphur battery with a PVA-PPy-PP separator, characterized in that: the positive electrode of the lithium-sulfur battery is a carbon nano tube-sulfur composite material, the negative electrode of the lithium-sulfur battery is a lithium foil, and the diaphragm of the lithium-sulfur battery is Co 3 O 4 -a PVA-PPy-PP separator, the electrolyte of the lithium sulfur battery being a DOL + DME solution containing 1.0M LiTFSI in a volume ratio of 1.
7. Comprising a Co as claimed in claim 6 3 O 4 -a lithium-sulphur battery with a PVA-PPy-PP separator, characterized in that: the positive electrode of the lithium-sulfur battery is a CNT-S composite material, and the preparation method thereof comprises the following steps: mixing sulfur powder and carbon nano tubes in a weight ratio of 7:3, adding CS while stirring 2 Sealing the sample in a reaction kettle, heating at 155 deg.C for 12 hr, and drying at 60 deg.C for 12 hr.
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| CN202211250838.7A CN115602997A (en) | 2022-10-13 | 2022-10-13 | Co 3 O 4 -PVA-PPy-PP diaphragm, preparation method and application thereof, and lithium-sulfur battery containing diaphragm |
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| CN202211250838.7A CN115602997A (en) | 2022-10-13 | 2022-10-13 | Co 3 O 4 -PVA-PPy-PP diaphragm, preparation method and application thereof, and lithium-sulfur battery containing diaphragm |
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| CN202211250838.7A Pending CN115602997A (en) | 2022-10-13 | 2022-10-13 | Co 3 O 4 -PVA-PPy-PP diaphragm, preparation method and application thereof, and lithium-sulfur battery containing diaphragm |
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