CN114204208A - Preparation method of PVDF-CTFE-based lithium-sulfur battery composite diaphragm - Google Patents
Preparation method of PVDF-CTFE-based lithium-sulfur battery composite diaphragm Download PDFInfo
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- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000012528 membrane Substances 0.000 claims abstract description 34
- 238000009987 spinning Methods 0.000 claims abstract description 19
- 239000002243 precursor Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 9
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 239000002244 precipitate Substances 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 17
- 239000003960 organic solvent Substances 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 14
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 239000002105 nanoparticle Substances 0.000 claims description 13
- 238000001291 vacuum drying Methods 0.000 claims description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000006255 coating slurry Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
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- PIWMYUGNZBJTID-UHFFFAOYSA-N 2,5-dihydroxyterephthalaldehyde Chemical compound OC1=CC(C=O)=C(O)C=C1C=O PIWMYUGNZBJTID-UHFFFAOYSA-N 0.000 claims description 7
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 239000005297 pyrex Substances 0.000 claims description 7
- 229910016287 MxOy Inorganic materials 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
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- 210000002469 basement membrane Anatomy 0.000 claims description 5
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- 238000007710 freezing Methods 0.000 claims description 5
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- 239000007924 injection Substances 0.000 claims description 5
- 239000002048 multi walled nanotube Substances 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000003828 vacuum filtration Methods 0.000 claims description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 4
- 108010010803 Gelatin Proteins 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 4
- 229920000159 gelatin Polymers 0.000 claims description 4
- 239000008273 gelatin Substances 0.000 claims description 4
- 235000019322 gelatine Nutrition 0.000 claims description 4
- 235000011852 gelatine desserts Nutrition 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- 229920000609 methyl cellulose Polymers 0.000 claims description 4
- 239000001923 methylcellulose Substances 0.000 claims description 4
- 235000010981 methylcellulose Nutrition 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 229920002635 polyurethane Polymers 0.000 claims description 4
- 239000004814 polyurethane Substances 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- CFJRPNFOLVDFMJ-UHFFFAOYSA-N titanium disulfide Chemical compound S=[Ti]=S CFJRPNFOLVDFMJ-UHFFFAOYSA-N 0.000 claims description 4
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 3
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 3
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 239000000661 sodium alginate Substances 0.000 claims description 3
- 235000010413 sodium alginate Nutrition 0.000 claims description 3
- 229940005550 sodium alginate Drugs 0.000 claims description 3
- 229920006159 sulfonated polyamide Polymers 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004697 Polyetherimide Substances 0.000 claims description 2
- 239000006230 acetylene black Substances 0.000 claims description 2
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N dimethylacetone Natural products CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 229920001601 polyetherimide Polymers 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims 1
- 230000032683 aging Effects 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 238000007789 sealing Methods 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 9
- 238000013508 migration Methods 0.000 abstract description 7
- 230000005012 migration Effects 0.000 abstract description 7
- 229920001021 polysulfide Polymers 0.000 abstract description 5
- 239000005077 polysulfide Substances 0.000 abstract description 5
- 150000008117 polysulfides Polymers 0.000 abstract description 5
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 230000014759 maintenance of location Effects 0.000 abstract description 2
- 239000004743 Polypropylene Substances 0.000 description 20
- 238000012360 testing method Methods 0.000 description 12
- 239000004698 Polyethylene Substances 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 230000001351 cycling effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 239000012456 homogeneous solution Substances 0.000 description 3
- 238000005213 imbibition Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000010041 electrostatic spinning Methods 0.000 description 2
- 239000012982 microporous membrane Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
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- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
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- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Cell Separators (AREA)
Abstract
The invention relates to a preparation method of a PVDF-CTFE-based lithium-sulfur battery composite diaphragm. The method comprises the following steps: firstly, preparing oxide @ covalent organic framework powder, mixing the oxide @ covalent organic framework powder with PVDF-CTFE in proportion, curing, stirring and defoaming to obtain a spinning precursor solution; spinning the spinning precursor solution under certain spinning conditions to obtain a fiber membrane, and then coating a carbon material/metal compound coating on the surface of the dried fiber membrane to obtain the modified PVDF-CTFE lithium-sulfur battery composite membrane. The prepared composite diaphragm can obviously improve the capacity retention rate and the rate capability of the battery; the lithium ion battery has high liquid absorption rate, high lithium ion migration rate and high safety performance; meanwhile, the migration of polysulfide can be inhibited to a certain extent, and the diaphragm is simple in preparation condition and low in process cost.
Description
Technical Field
The invention belongs to the field of lithium-sulfur battery materials, and particularly relates to a preparation method of a PVDF-CTFE-based lithium-sulfur battery composite diaphragm.
Background
At present, lithium ion batteries are widely applied to various portable electronic devices and electric automobiles, but with the continuous development of society, the theoretical specific capacity of the lithium ion batteries is limited, so that the lithium ion batteries cannot meet the requirements of technical development. In order to further expand the application prospect of the lithium ion battery, batteries of various systems are paid attention by researchers. The lithium-sulfur battery has high theoretical specific capacity and energy density, and the active substance elemental sulfur has rich resources, low cost and environmental protection, and has great potential to become a next generation new energy storage body. However, polysulfide, an intermediate product in the charging and discharging processes of the lithium-sulfur battery, is dissolved in electrolyte, so that the loss of positive active substances is caused, and the capacity of the battery is attenuated; meanwhile, polysulfide can generate redox reaction with metal lithium after reaching the negative electrode to form shuttle effect, and the coulomb efficiency of the system is reduced. In addition, during the charge and discharge cycle, the interface layer between the lithium metal and the electrolyte is unstable, which causes problems such as lithium dendrite growth, and the like, and thus, the potential safety hazard of the battery system is increased.
In the lithium-sulfur battery diaphragm, a microporous polyethylene or polypropylene diaphragm prepared by a melt-stretching method is commonly used at present, and a polypropylene microporous membrane, a polyethylene microporous membrane and a multi-layer composite diaphragm produced by Celgard are mainly used. Because the shuttle effect in the charging and discharging processes of the lithium-sulfur battery cannot be effectively inhibited, the lithium-sulfur battery adopting the traditional polyolefin diaphragm often has lower discharge capacity and coulombic efficiency, and meanwhile, because the melting point of the polyolefin diaphragm material is low, the safety performance of the battery is also urgently required to be improved.
The PVDF-CTFE/oxide @ covalent organic framework particle blend membrane is prepared by an electrostatic spinning method, and the polysulfide inhibition coating is coated on the surface of the PVDF-CTFE/oxide @ covalent organic framework particle blend membrane, so that the mechanical strength and the thermal stability of the membrane are improved, the lithium ion migration efficiency is improved, and the battery assembled by adopting the composite membrane has better cycle stability and rate capability.
Disclosure of Invention
The invention aims to provide a preparation method of a PVDF-CTFE-based lithium-sulfur battery composite diaphragm, and the prepared diaphragm has good lithium ion selective permeability and high safety performance, and can effectively improve the cycle performance and the coulombic efficiency of a lithium-sulfur battery.
In order to achieve the purpose, the technical scheme of the invention provides a preparation method of a PVDF-CTFE-based lithium-sulfur battery composite diaphragm, which comprises the following steps:
(1) oxide @ covalent organic framework MxOySynthesis of @ COF powder: adding a certain amount of oxide nanoparticles and 2, 5-dihydroxy terephthalaldehyde into a mixed solution of mesitylene and an organic solvent, and carrying out ultrasonic treatment for 15min to obtain a solution A, wherein the mass ratio of the oxide nanoparticles to the 2, 5-dihydroxy terephthalaldehyde to the mesitylene to the organic solvent is (7-8): 1: 0.8-0.9: 0.5-0.7; adding a certain amount of sulfonated high polymer into a mixed solution of mesitylene and an organic solvent, and carrying out ultrasonic treatment for 15min to obtain a solution B, wherein the mass ratio of the sulfonated high polymer to the oxide nanoparticles in the mesitylene, the organic solvent and the solution A is 13-16: 1: 1.2-1.5: 6-7; and mixing the solution A and the solution B, adding the mixture into a Pyrex tube, adding a certain amount of acetic acid to obtain a solution C, wherein the mass ratio of the acetic acid to the sulfonated high polymer of the solution B is 1:35-45, carrying out ultrasonic treatment on the solution C for 10min, then carrying out quick freezing under liquid nitrogen, and then carrying out degassing through three freezing-unfreezing cycles. The Pyrex tube was then sealed and heated at 110 ℃ for 72h and the precipitate obtained by vacuum filtration. Finally washing with acetone, deionized water and ethanol respectively, and vacuum drying at 120 deg.C overnight to obtain the prepared MxOy@ COF powder;
(2) preparation of PVDF-CTFE basal membrane: and (2) drying the PVDF-CTFE for 24 hours at 80 ℃, dissolving the PVDF-CTFE in an organic solvent to form a solution D, wherein the mass fraction of the PVDF-CTFE in the solution D is 20-30%, and mechanically stirring the solution D for 12 hours at 60 ℃ to obtain a uniform solution. Secondly, take a certain amount of MxOyAdding the @ COF powder into the uniform solution, performing ball milling for 3h to obtain a dispersion solution, curing the dispersion solution at 60-80 ℃ for 12-24h, performing ultrasonic stirring for 24-36h, and standing for 24-48h to form a spinning solution, wherein M isxOyThe mass ratio of the @ COF powder to PVDF-CTFE was 1: 10-15. Setting spinning voltage at 10-15KV, solution injection rate at 0.5-1.5ml/h, and receiving distance at 15-25 cm; drying the fiber membrane obtained by spinning in a vacuum drying oven at 60 ℃ for 12-18h to obtain a dry PVDF-CTFE basement membrane;
(3) preparing a PVDF-CTFE-based lithium-sulfur battery composite diaphragm: the carbon material was activated in 68% concentrated nitric acid for 6h, after which multiple washes were performed until the pH of the wash solution was 7. Filtering, washing and drying to obtain an activated carbon material, adding a certain amount of the activated carbon material into absolute ethyl alcohol, and carrying out ultrasonic treatment for 2 hours to obtain a precursor solution A, wherein the mass ratio of the activated carbon material to the absolute ethyl alcohol is 1: 4-5; adding a certain amount of metal compound into deionized water to form a suspension, wherein the mass ratio of the metal compound to the deionized water is 1: 0.5-0.7, then adding the suspension into the precursor solution A for ultrasonic treatment for 1h, and vigorously stirring for 4h to obtain a precursor solution B. Wherein the mass ratio of the activated carbon material to the metal compound is 1: 5-8, filtering and washing for multiple times, drying the collected precipitate MC in a vacuum oven at 70 ℃ for 12h, and placing the precipitate MC in a dryer for later use. And mixing the precipitate MC, the binder and the organic solvent, stirring for 10 hours at 65 ℃ to prepare coating slurry, wherein the mass ratio of the precipitate MC to the binder to the organic solvent is 2-3:1:7-8, uniformly coating the obtained coating slurry on a dried PVDF-CTFE basal membrane by using a scraper, and performing vacuum drying for 12 hours at 60 ℃ to obtain the PVDF-CTFE-based lithium-sulfur battery composite membrane.
The oxide nano-particles are one of aluminum oxide, silicon dioxide, titanium dioxide, zirconium oxide, antimony trioxide and manganese dioxide.
The particle size of the oxide nanoparticles is 40-100 nm.
The organic solvent is one or more of dimethylacetamide, dimethyl sulfoxide, acetone and N-methylpyrrolidone.
The sulfonated high polymer is one of sulfonated polyamide, sulfonated polyetherimide and sulfonated polyurethane.
The carbon material is one of Super P, graphene oxide, a multi-walled carbon nanotube and acetylene black.
The binder is one of polyvinylidene fluoride, carboxymethyl cellulose, methyl cellulose, gelatin and sodium alginate.
The metal compound is one or more of titanium disulfide, molybdenum disulfide, copper sulfide, titanium nitride and ferrous sulfide.
The binder is one of carboxymethyl cellulose, methyl cellulose, gelatin, sodium alginate and polyvinylidene fluoride.
Compared with a commercial separator, the PVDF-CTFE-based lithium-sulfur battery composite separator has the following advantages:
1. the PVDF-CTFE-based lithium-sulfur battery composite membrane is prepared by an electrostatic spinning method, the obtained base membrane has higher porosity and liquid absorption rate, and compared with PVDF, PVDF-CTFE shows lower crystallinity, higher flexibility and better electrochemical reaction activity.
2. This patent PVDF-CTFE base lithium sulphur battery composite membrane mix high strength oxide and the modified granule of valence organic frame, this modified granule has high porosity, advantages such as good solvent and electrochemical stability can improve the electrochemical performance of battery to a certain extent, and the inside orderly pore structure of granule provides probably for high ion mobility simultaneously.
3. The PVDF-CTFE-based lithium-sulfur battery composite diaphragm surface metal oxide/carbon material coating can effectively improve the puncture strength of the diaphragm, and has a certain degree of restriction effect on polysulfide migration.
4. Compared with the existing method for preparing the lithium-sulfur battery diaphragm, the method has the advantages of simple process, low production cost and excellent product performance.
Drawings
FIG. 1 is a surface SEM image of a PVDF-CTFE-based composite membrane of a lithium-sulfur battery prepared by the invention.
Detailed Description
The following examples are provided to further illustrate the present invention and are not intended to limit the scope of the present invention.
Example 1: adding 1.7g of titanium dioxide nanoparticles with the particle size of 50nm and 0.22g of 2, 5-dihydroxy terephthalaldehyde into a solution containing 0.18g of mesitylene and 0.15g of dimethylacetamide, and carrying out ultrasonic treatment for 15min to obtain a solution A; adding 3.9g of sulfonated polyamide into 0.26g of mesitylene and 0.34g of dimethylacetamide, carrying out ultrasonic treatment for 15min to obtain a solution B, mixing the solution A and the solution B, adding the mixture into a Pyrex tube, and adding 0.092g of ethyleneAcid, then sonicated for 10min followed by flash freezing under liquid nitrogen, followed by degassing through three freeze-thaw cycles. The tube was then sealed and heated at 110 ℃ for 72h and the precipitate was obtained by filtration with vacuum filtration. And finally washing with acetone, deionized water and ethanol respectively. Vacuum drying at 120 deg.C overnight to obtain the prepared TiO2@ COF powder.
1g of PVDF-CTFE was dried at 80 ℃ for 24 hours and then dissolved in 4g of dimethylacetamide to form a solution D, which was mechanically stirred at 60 ℃ for 12 hours to obtain a homogeneous solution. Secondly, 0.1g of TiO was taken2Adding the @ COF powder into the uniform solution, carrying out ball milling for 3h to obtain a dispersion solution, curing the dispersion solution at 65 ℃ for 12-24h, carrying out ultrasonic stirring for 30h, and standing for 24h to form a spinning solution. Setting spinning voltage of 12KV, solution injection rate of 1ml/h and receiving distance of 19 cm; and (3) drying the fiber membrane obtained by spinning in a vacuum drying oven at 60 ℃ for 12h to obtain a dried PVDF-CTFE basement membrane.
5g of Super P were activated in 68% concentrated nitric acid for 6h, after which several washes were carried out until the pH of the wash solution was 7. Filtered, washed and dried to obtain activated Super P. Adding 0.8g of activated Super P into 4g of absolute ethyl alcohol, carrying out ultrasonic treatment for 2h to obtain a precursor solution A, adding 4g of titanium disulfide into 2.8g of deionized water to form a suspension, then adding the suspension into the precursor solution A, carrying out ultrasonic treatment for 1h, and carrying out vigorous stirring for 4h to obtain a precursor solution B. After filtration and multiple washings, the collected precipitate MC is dried in a vacuum oven at 70 ℃ for 12h and placed in a dryer for standby. 1.8g of precipitated MC, 0.8g of gelatin and 6g of dimethylacetamide were mixed, stirred at 65 ℃ for 10 hours to prepare a coating slurry, the obtained coating slurry was uniformly coated on a dried PVDF-CTFE-based film using a doctor blade, and vacuum-dried at 60 ℃ for 12 hours to obtain a PVDF-CTFE-based lithium-sulfur battery composite separator.
And (3) carrying out physical and electrochemical performance tests on the obtained diaphragm: mainly comprises the tests of porosity, puncture strength, melting temperature, imbibition rate, ionic conductivity, ion migration number and the like. The resulting separator sheet was then loaded into a lithium sulfur battery for battery performance testing. The cycling performance of the cells was tested at room temperature at a current density of 0.2C (1C =1675 mA/g). And comparing the test result with the performance of a PP/PE/PP diaphragm provided by Celgard company which is advanced and commonly applied in the market at present, and testing the rate performance of the battery under different current densities of 0.5C, 1C, 2C and the like.
Example 2: adding 1.9g of silicon dioxide nano-particles with the particle size of 40nm and 0.27g of 2, 5-dihydroxy terephthalaldehyde into a solution containing 0.24g of mesitylene and 0.135g of dimethyl sulfoxide, and carrying out ultrasonic treatment for 15min to obtain a solution A; adding 4.23g of sulfonated polyurethane into 0.28g of mesitylene and 0.36g of dimethyl sulfoxide, carrying out ultrasonic treatment for 15min to obtain a solution B, mixing the solution A and the solution B, adding the mixture into a Pyrex tube, adding 0.12g of acetic acid, carrying out ultrasonic treatment for 10min, carrying out quick freezing under liquid nitrogen, and then carrying out degassing through three freezing-unfreezing cycles. The tube was then sealed and heated at 110 ℃ for 72h and the precipitate was obtained by filtration with vacuum filtration. And finally washing with acetone, deionized water and ethanol respectively. After vacuum drying at 120 ℃ overnight, the SiO prepared is obtained2@ COF powder.
2g of PVDF-CTFE was dried at 80 ℃ for 24 hours and then dissolved in 7.5g of dimethyl sulfoxide to form a solution D, which was mechanically stirred at 60 ℃ for 12 hours to obtain a homogeneous solution. Next, 0.22g of SiO was taken2Adding the @ COF powder into the uniform solution, carrying out ball milling for 3h to obtain a dispersion solution, curing the dispersion solution at 65 ℃ for 20h, carrying out ultrasonic stirring for 36h, and standing for 12h to form a spinning solution. Setting spinning voltage of 15KV, solution injection rate of 0.8ml/h and receiving distance of 20 cm; and (3) drying the fiber membrane obtained by spinning in a vacuum drying oven at 60 ℃ for 15h to obtain a dried PVDF-CTFE basement membrane.
4g of multi-walled carbon nanotubes were activated in 68% concentrated nitric acid for 6h, after which several washes were carried out until the pH of the washing solution was 7. Filtering, washing and drying to obtain the activated multi-wall carbon nano tube. Adding 1.5g of activated multi-walled carbon nano-tube into 7g of absolute ethyl alcohol, carrying out ultrasonic treatment for 2h to obtain a precursor solution A, adding 11g of titanium disulfide and 12g of molybdenum disulfide into 13g of deionized water to form a suspension, then adding the suspension into the precursor solution A, carrying out ultrasonic treatment for 1h, and carrying out vigorous stirring for 4h to obtain a precursor solution B. After filtration and multiple washings, the collected precipitate MC is dried in a vacuum oven at 70 ℃ for 12h and placed in a dryer for standby. Mixing 2g of precipitated MC, 0.7g of carboxymethyl cellulose and 5g of dimethyl sulfoxide, stirring for 10h at 65 ℃ to prepare coating slurry, uniformly coating the obtained coating slurry on a dried PVDF-CTFE basal membrane by using a scraper, and performing vacuum drying for 12 hours at 60 ℃ to obtain the PVDF-CTFE-based lithium-sulfur battery composite membrane.
And (3) carrying out physical and electrochemical performance tests on the obtained diaphragm: mainly comprises the tests of porosity, puncture strength, melting temperature, imbibition rate, ionic conductivity, ion migration number and the like. The resulting separator sheet was then loaded into a lithium sulfur battery for battery performance testing. The cycling performance of the cells was tested at room temperature at a current density of 0.2C (1C =1675 mA/g). And comparing the test result with the performance of a PP/PE/PP diaphragm provided by Celgard company which is advanced and commonly applied in the market at present, and testing the rate performance of the battery under different current densities of 0.5C, 1C, 2C and the like.
Example 3: adding 3.2g of antimony trioxide nano-particles with the particle size of 60nm and 0.44g of 2, 5-dihydroxy terephthalaldehyde into a solution containing 0.36g of mesitylene and 0.26g N-methyl pyrrolidone for ultrasonic treatment for 15min to obtain a solution A; adding 6.45g of sulfonated polyurethane into 0.48g of mesitylene and 0.65g N-methyl pyrrolidone for ultrasonic treatment for 15min to obtain a solution B, mixing the solution A and the solution B, adding the mixture into a Pyrex tube, adding 0.16g of acetic acid for ultrasonic treatment for 10min, then performing quick freezing under liquid nitrogen, and then performing degassing through three freezing-unfreezing cycles. The tube was then sealed and heated at 110 ℃ for 72h and the precipitate was obtained by filtration with vacuum filtration. And finally washing with acetone, deionized water and ethanol respectively. After vacuum drying at 120 ℃ overnight, the prepared Sb was obtained2O3@ COF powder.
4g of PVDF-CTFE were dried at 80 ℃ for 24 hours and then dissolved in 15.2g N-methylpyrrolidone to form a solution D, which was mechanically stirred at 60 ℃ for 12 hours to obtain a homogeneous solution. Secondly, 0.4g of Sb is taken2O3Adding the @ COF powder into the uniform solution, ball-milling for 3h to obtain a dispersion solution, curing the dispersion solution at 70 ℃ for 24h, ultrasonically stirring for 48h, and standingStanding for 24h to form a spinning solution. Setting spinning voltage of 16KV, solution injection rate of 1.2ml/h and receiving distance of 22 cm; and (3) drying the fiber membrane obtained by spinning in a vacuum drying oven at 60 ℃ for 15h to obtain a dried PVDF-CTFE basement membrane.
4g of graphene oxide was activated in 68% concentrated nitric acid for 6h, followed by multiple washes until the pH of the wash solution was 7. And filtering, washing and drying to obtain the activated graphene oxide. Adding 1.8g of graphene oxide into 9g of absolute ethyl alcohol, carrying out ultrasonic treatment for 2h to obtain a precursor solution A, adding 12.6g of titanium nitride into 6.5g of deionized water to form a suspension, then adding the suspension into the precursor solution A, carrying out ultrasonic treatment for 1h, and carrying out vigorous stirring for 4h to obtain a precursor solution B. After filtration and multiple washings, the collected precipitate MC is dried in a vacuum oven at 70 ℃ for 12h and placed in a dryer for standby. 3g of precipitated MC, 1.2g of methylcellulose and 9g N-methyl pyrrolidone are mixed, stirred for 10 hours at 65 ℃ to prepare coating slurry, the obtained coating slurry is uniformly coated on a dried PVDF-CTFE basal membrane by a scraper, and the dried PVDF-CTFE basal membrane is dried in vacuum for 12 hours at 60 ℃ to obtain the PVDF-CTFE lithium-sulfur battery composite membrane.
And (3) carrying out physical and electrochemical performance tests on the obtained diaphragm: mainly comprises the tests of porosity, puncture strength, melting temperature, imbibition rate, ionic conductivity, ion migration number and the like. The resulting separator sheet was then loaded into a lithium sulfur battery for battery performance testing. The cycling performance of the cells was tested at room temperature at a current density of 0.2C (1C =1675 mA/g). And comparing the test result with the performance of a PP/PE/PP diaphragm provided by Celgard company which is advanced and commonly applied in the market at present, and testing the rate performance of the battery under different current densities of 0.5C, 1C, 2C and the like.
Cycling Performance of various examples and PP/PE/PP separator lithium-sulfur batteries
| Serial number | Specific capacity of first discharge (mAh/g) | Specific discharge capacity (mAh/g) after 100 times of charge and discharge | Capacity retention ratio/%) |
| Example 1 | 1465 | 1176 | 81 |
| Example 2 | 1244 | 974 | 78 |
| Example 3 | 1359 | 1045 | 77 |
| PP/PE/PP diaphragm | 1100 | 780 | 71 |
Rate capability of various examples and PP/PE/PP diaphragm lithium-sulfur battery
| Serial number | 0.5C | 1C | 2C |
| Example 1 | 1034mAh/g | 733 mAh/g | 613mAh/g |
| Example 2 | 987mAh/g | 722 mAh/g | 601 mAh/g |
| Example 3 | 979 mAh/g | 695 mAh/g | 556 mAh/g |
| PP/PE/PP diaphragm | 900 mAh/g | 640 mAh/g | 508 mAh/g |
The physicochemical properties of the various examples and the PP/PE/PP separator were tested as follows:
| performance index name | PP/PE/PP diaphragm | Example 1 | Example 2 | Example 3 |
| Porosity (%) | 43 | 85 | 84 | 80 |
| Liquid absorption Rate (%) | 85 | 233 | 257 | 289 |
| Melting temperature (. degree.C.) | 145 | 303 | 312 | 298 |
| Puncture strength (N) | 2.4 | 2.8 | 2.7 | 2.7 |
| Ion conductivity (mS cm)-1） | 0.75 | 2.77 | 2.54 | 2.39 |
| Transference number of lithium ion | 0.30 | 0.54 | 0.42 | 0.51 |
Claims (8)
1. A preparation method of a PVDF-CTFE-based lithium-sulfur battery composite diaphragm is characterized by comprising the following steps:
(1) oxide @ covalent organic framework MxOySynthesis of @ COF powder: adding a certain amount of oxide nanoparticles and 2, 5-dihydroxy terephthalaldehyde into a mixed solution of mesitylene and an organic solvent, and carrying out ultrasonic treatment for 15min to obtain a solution A, wherein the mass ratio of the oxide nanoparticles to the 2, 5-dihydroxy terephthalaldehyde to the mesitylene to the organic solvent is (7-8): 1: 0.8-0.9: 0.5-0.7; adding a certain amount of sulfonated high polymer into a mixed solution of mesitylene and an organic solvent, and carrying out ultrasonic treatment for 15min to obtain a solution B, wherein the mass ratio of the sulfonated high polymer to the oxide nanoparticles in the mesitylene, the organic solvent and the solution A is 13-16: 1: 1.2-1.5: 6-7; mixing the solution A and the solution B, adding the mixture into a Pyrex tube, adding a certain amount of acetic acid to obtain a solution C, wherein the mass ratio of the acetic acid to the sulfonated high polymer of the solution B is 1:35-45, carrying out ultrasonic treatment on the solution C for 10min, then carrying out rapid freezing under liquid nitrogen, then carrying out degassing through three freezing-unfreezing cycles, then sealing the Pyrex tube, heating at 110 ℃ for 72h, obtaining precipitates through vacuum filtration, finally washing with acetone, deionized water and ethanol respectively, and carrying out vacuum drying at 120 ℃ overnight to obtain the prepared MxOy@ COF powder;
(2) preparation of dried PVDF-CTFE-based Membrane: drying PVDF-CTFE for 24 hours at 80 ℃, dissolving the PVDF-CTFE in an organic solvent to form a solution D, wherein the mass fraction of the PVDF-CTFE in the solution D is 20-30%, mechanically stirring the solution D for 12 hours at 60 ℃ to obtain a uniform solution, and then taking a certain amount of MxOyAdding the @ COF powder into the uniform solution and ball-milling for 3h to obtain the productDispersing the solution, aging the dispersed solution at 60-80 deg.C for 12-24 hr, ultrasonically stirring for 24-36 hr, standing for 24-48 hr to obtain spinning solution, wherein M isxOyThe mass ratio of the @ COF powder to PVDF-CTFE was 1: 10-15, setting the spinning voltage to be 10-15KV, the solution injection rate to be 0.5-1.5ml/h, and the receiving distance to be 15-25 cm; drying the fiber membrane obtained by spinning in a vacuum drying oven at 60 ℃ for 12-18h to obtain a dry PVDF-CTFE basement membrane;
(3) preparing a PVDF-CTFE-based lithium-sulfur battery composite diaphragm: activating a carbon material in 68% concentrated nitric acid for 6 hours, then washing for multiple times until the pH value of a washing solution is 7, filtering, washing and drying to obtain an activated carbon material, adding a certain amount of the activated carbon material into absolute ethyl alcohol, and carrying out ultrasonic treatment for 2 hours to obtain a precursor solution A, wherein the mass ratio of the activated carbon material to the absolute ethyl alcohol is 1: 4-5; adding a certain amount of metal compound into deionized water to form a suspension, wherein the mass ratio of the metal compound to the deionized water is 1: 0.5-0.7, then adding the suspension into the precursor solution A for ultrasonic treatment for 1h, and violently stirring for 4h to obtain a precursor solution B, wherein the mass ratio of the activated carbon material to the metal compound is 1: 5-8, filtering and washing the precipitate MC for multiple times, drying the precipitate MC in a vacuum oven at 70 ℃ for 12 hours, and placing the dried precipitate MC in a dryer for later use; and mixing the precipitate MC, the binder and the organic solvent, stirring for 10 hours at 65 ℃ to prepare coating slurry, wherein the mass ratio of the precipitate MC to the binder to the organic solvent is 2-3:1:7-8, uniformly coating the obtained coating slurry on a dried PVDF-CTFE basal membrane by using a scraper, and performing vacuum drying for 12 hours at 60 ℃ to obtain the PVDF-CTFE-based lithium-sulfur battery composite membrane.
2. The preparation method of the PVDF-CTFE-based lithium-sulfur battery composite membrane according to claim 1, which is characterized by comprising the following steps: the oxide nano-particles are one of aluminum oxide, silicon dioxide, titanium dioxide, zirconium oxide, antimony trioxide and manganese dioxide.
3. The method for preparing the PVDF-CTFE-based lithium-sulfur battery composite membrane as claimed in claim 1, wherein: the particle size of the oxide nanoparticles is 40-100 nm.
4. The method for preparing the PVDF-CTFE-based lithium-sulfur battery composite membrane as claimed in claim 1, wherein: the organic solvent is one or more of dimethylacetamide, dimethyl sulfoxide, acetone and N-methylpyrrolidone.
5. The method for preparing the PVDF-CTFE-based lithium-sulfur battery composite membrane as claimed in claim 1, wherein: the sulfonated high polymer is one of sulfonated polyamide, sulfonated polyetherimide and sulfonated polyurethane.
6. The method for preparing the PVDF-CTFE-based lithium-sulfur battery composite membrane as claimed in claim 1, wherein: the carbon material is one of Super P, graphene oxide, a multi-walled carbon nanotube and acetylene black.
7. The method for preparing the PVDF-CTFE-based lithium-sulfur battery composite membrane as claimed in claim 1, wherein: the metal compound is one or more of titanium disulfide, molybdenum disulfide, copper sulfide, titanium nitride and ferrous sulfide.
8. The method for preparing the PVDF-CTFE-based lithium-sulfur battery composite membrane as claimed in claim 1, wherein: the binder is one of carboxymethyl cellulose, methyl cellulose, gelatin, sodium alginate and polyvinylidene fluoride.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114865226A (en) * | 2022-05-25 | 2022-08-05 | 齐齐哈尔大学 | Preparation method and application of MXene-based inorganic particle/PVDF-based polymer composite diaphragm |
| CN115483505A (en) * | 2022-10-08 | 2022-12-16 | 华南理工大学 | Functional diaphragm of lithium metal battery and preparation method and application thereof |
| CN115498357A (en) * | 2022-07-07 | 2022-12-20 | 陕西科技大学 | Functional composite diaphragm based on tantalum-based MXene derivative and preparation method and application thereof |
| CN115483505B (en) * | 2022-10-08 | 2024-05-31 | 华南理工大学 | Lithium metal battery functional diaphragm and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114865226A (en) * | 2022-05-25 | 2022-08-05 | 齐齐哈尔大学 | Preparation method and application of MXene-based inorganic particle/PVDF-based polymer composite diaphragm |
| CN115498357A (en) * | 2022-07-07 | 2022-12-20 | 陕西科技大学 | Functional composite diaphragm based on tantalum-based MXene derivative and preparation method and application thereof |
| CN115483505A (en) * | 2022-10-08 | 2022-12-16 | 华南理工大学 | Functional diaphragm of lithium metal battery and preparation method and application thereof |
| CN115483505B (en) * | 2022-10-08 | 2024-05-31 | 华南理工大学 | Lithium metal battery functional diaphragm and preparation method and application thereof |
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