CN115347322B - Preparation method and application of porous polyolefin composite membrane - Google Patents
Preparation method and application of porous polyolefin composite membrane Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 69
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 7
- 239000002002 slurry Substances 0.000 claims description 20
- 229920000642 polymer Polymers 0.000 claims description 18
- 239000000835 fiber Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 229910003002 lithium salt Inorganic materials 0.000 claims description 10
- 159000000002 lithium salts Chemical class 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000007493 shaping process Methods 0.000 claims description 8
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 238000009423 ventilation Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000005279 LLTO - Lithium Lanthanum Titanium Oxide Substances 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229920006231 aramid fiber Polymers 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 claims description 3
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 3
- 238000009832 plasma treatment Methods 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 2
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 claims description 2
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 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 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 229920005672 polyolefin resin Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 claims description 2
- 238000004804 winding Methods 0.000 claims description 2
- 239000002657 fibrous material Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 8
- 239000012535 impurity Substances 0.000 abstract description 4
- 239000007787 solid Substances 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 3
- 229920000620 organic polymer Polymers 0.000 abstract description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 2
- 239000005518 polymer electrolyte Substances 0.000 abstract description 2
- 230000000536 complexating effect Effects 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 230000005012 migration Effects 0.000 abstract 1
- 238000013508 migration Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 8
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000003517 fume Substances 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- VWYHCWVXCWCOPV-UHFFFAOYSA-L dilithium trifluoromethanesulfonate Chemical compound [Li+].[Li+].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F VWYHCWVXCWCOPV-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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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
- 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
-
- 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
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
-
- 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
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
-
- 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
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/494—Tensile strength
-
- 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
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/497—Ionic conductivity
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the technical field of microporous composite films, and particularly relates to a preparation method and application of a porous polyolefin composite film; then, the solid electrolyte material is subjected to mixed acid pretreatment and secondary ultrasonic dispersion to eliminate impurities on the surface of the solid electrolyte and provide more active functional groups, so that the complexing action of the solid electrolyte material with a solvent, an organic polymer and a polyolefin-based film is enhanced, the dispersibility of the solid electrolyte is greatly improved, the use amount of the solvent is reduced, and Li in the composite solid polymer electrolyte is realized + The transmission performance is improved, and the obtained porous polyolefin composite membrane product is used as a lithium battery diaphragm and a (semi) solid electrolyte membrane, and has the characteristics of high conductivity at room temperature, good compatibility with a metal lithium interface, high migration number of lithium ions, high mechanical strength and the like.
Description
Technical Field
The invention belongs to the technical field of microporous composite membranes, and particularly relates to a preparation method and application of a porous polyolefin composite membrane.
Background
Polyolefin microporous membranes are polymeric membranes and have been widely used in the preparation of lithium battery separator membranes and separation membranes. However, with the progress of technology, in the process of using as a lithium battery diaphragm, more and more problems are exposed, mainly including poor heat resistance, frequent safety accidents, low energy density and the like, patent CN201620045629 describes a ceramic coating diaphragm, but only mechanical and physical compounding is adopted, the coating is easy to fall off, a large amount of electrolyte is still required, and safety accidents are easy to be caused, so that safer lithium ion batteries are urgently needed. The (semi) solid electrolyte membrane is born in such a demand background. The solid electrolyte membrane has a certain research result in the industry, basically is solid-liquid mixed electrolyte, has better properties than liquid electrolyte and solid electrolyte, and the theoretical room-temperature ionic conductivity can reach 10 -4 S/cm or more, and has excellent chemical and mechanical properties. However, in the current use, the interface impedance ion conductivity is far insufficient, so that a large lifting space exists, the compatibility of the solid electrolyte, the solvent and the base material is poor, the cost is high, and the manufacturing process is complicated and long in period.
Disclosure of Invention
The invention aims to provide a preparation method and application of a porous polyolefin composite membrane.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a method for preparing a porous polyolefin composite film, comprising the steps of:
(1) Preparation of high porosity base film: the modified fiber and polyolefin resin are mixed according to the mass ratio of 0.1-10: blending and extruding the composite raw material with an extruder according to the proportion of 90-99.9 to obtain a composite raw material, and preparing the composite raw material and a pore-forming agent into a large-aperture (aperture is more than or equal to 300 nm) high-porosity (porosity is more than or equal to 55%) polyolefin film through melt extrusion, preheating, longitudinal drawing, shaping, transverse drawing and shaping and winding;
(2) The preparation of the solid electrolyte slurry comprises the following steps:
a. pretreatment of solid electrolyte: preparing a mixed acid solution in a ventilation kitchen, adding a solid electrolyte, stirring at room temperature for 5s-20min, and then cleaning and drying to obtain a pretreated solid electrolyte;
b. carrying out ultrasonic dispersion and mixing on the pretreated solid electrolyte and the polymer and the solvent twice to prepare high-solid-content solid electrolyte slurry;
(3) Coating the solid electrolyte slurry obtained in the step (2) on the base film obtained in the step (1), preparing a mixed solution of a polymer, lithium salt and a solvent in a kitchen, placing the base film coated with the solid electrolyte slurry in the mixed solution for 1-30min, taking out and drying to obtain the porous polyolefin composite film.
Further, the modified fiber in the step (1) is obtained after plasma modification, the plasma treatment time is 2-20 min, the power is 200-800W, the temperature is 50-100 ℃, the treatment atmosphere is at least one of aramid fiber, polyamide fiber, polyacrylonitrile fiber and ultra-high molecular weight polyethylene under the oxygen or air atmosphere, the longitudinal draw ratio is not lower than 10, and the transverse draw ratio is not lower than 8.
Further, in the step (2), the solid electrolyte is at least one of LLZO, LLZTO, LATP, LAGP, LLTO, and the solid electrolyte D50 is 500-2000nm; the mixed acid solution is sulfuric acid with the mass ratio of 1 mol/L to hydrochloric acid or concentrated phosphoric acid of 6-8:1-4, wherein the mass ratio of the mixed acid solution to the solid electrolyte is 6-9:1-3.
Further, the mass ratio of the pretreated solid electrolyte, the polymer and the solvent in the step (2) is 3-6:0.3-2:4-7, the two ultrasonic dispersions comprising a first ultrasonic dispersion: the temperature is 30-50 ℃, the frequency is 10000-25000 Hz, the circulating stirring speed is 1000-2000 r/min, and the ultrasonic dispersion time is 0.5-2.0 h; and (3) performing ultrasonic dispersion for the second time: the temperature is 60-90 ℃, the frequency is 50000-100000 Hz, the circulating stirring speed is 5000-10000 r/min, and the ultrasonic dispersion time is 2-5 h.
Further, the lithium salt in the step (3) is at least one of lithium bis (fluorosulfonyl) imide, lithium bis (trifluoromethylsulfonyl) imide, lithium dioxalate borate, lithium hexafluorophosphate and lithium perchlorate; the mass ratio of the polymer, the lithium salt and the solvent is 0.1-5:0.05-3:90-99.
Further, the polymer is at least one of PEO, PAN, PVA, PVP, PMMA, PVDF, and the molecular weight of the polymer is 10-100 ten thousand; the solvent is at least one of acetone, acetonitrile, N-methyl pyrrolidone, DMF, DMAC, dimethyl sulfoxide and tetrahydrofuran.
The porous polyolefin composite membrane prepared by the preparation method is used in a lithium battery diaphragm, (semi) solid electrolyte membrane, or a separation membrane and a water treatment membrane.
The mechanism of the invention: aiming at the problems of the existing (semi) solid electrolyte membrane, the invention provides a method for preparing a high-porosity and large-aperture base membrane by reinforcing and modifying a polyolefin material, then, preprocessing the solid electrolyte by using a mixed acid solution to eliminate impurities on the surface of the solid electrolyte and provide more active functional groups so as to strengthen the complexation of the solid electrolyte, a solvent, an organic polymer and the polyolefin base membrane, then, performing secondary ultrasonic dispersion on the preprocessed solid electrolyte, the solvent and the polymer to prepare a high-solid-content solid electrolyte slurry, and coating the slurry on the high-porosity base membrane to prepare a first coating; finally preparing a polymer-lithium salt solution, immersing the membrane coated with the solid electrolyte therein, and drying to prepare the porous polyolefin composite membrane. By enhancing polyolefin properties with the modified fibers, a high porosity polyolefin-based film having a large pore size can be produced with an improved draw ratio; the solid electrolyte is pretreated by the mixed acid solution, so that the surface impurities of the solid electrolyte can be quickly eliminated, the interfacial compatibility of the solid electrolyte with the polymer and the base film is enhanced, and the solid electrolyte slurry with high solid content is prepared by secondary ultrasonic dispersion. The acid treatment does not change the three-dimensional structure of the solid electrolyte, but can obtain a porous structure with high specific surface area, thereby realizing the improvement of Li+ transmission performance in the composite solid polymer electrolyte. The interfacial resistance of the electrolyte membrane is reduced and the ionic conductivity of the electrolyte membrane is improved by the synergistic effect of the enhanced modification and the modified coating on the base membrane.
The invention has the advantages that:
1. the invention firstly carries out fiber reinforcement modification on the raw material of the base film, and the fiber can generate free radical reaction and increase the number of active groups under the condition of plasma treatment, thereby enhancing the affinity strength of the interface between the fiber and resin; in addition, the fiber modification also improves the mechanical property of the material, so that the tensile ratio of the material can be greatly improved to obtain a high-porosity large-aperture polyolefin-based membrane without losing the mechanical strength of the base membrane;
2. the solid electrolyte is treated by mixed acid, the macroscopic three-dimensional structure of the solid electrolyte is not damaged, but impurities on the surface of the solid electrolyte are eliminated, the internal pore diameter of the solid electrolyte is expanded to a certain extent, the porous structure with high specific surface area and active functional groups is obtained, and the solid electrolyte is directly mixed and crosslinked with an organic polymer by taking a solvent as a dispersing agent through secondary ultrasonic dispersion to prepare slurry with high solid content (the mass fraction is more than 30 percent) which is uniform in dispersion and stable in performance, so that the solvent consumption is reduced, the solvent volatilization time is shortened, and the production efficiency is improved;
3. the high-solid-content slurry with stable performance prepared by the invention can be directly coated on a high-porosity base film, and a solid electrolyte slightly larger than the pore diameter of the base film is selected, so that the short circuit cannot be caused by a through hole, and more Li can be dissociated by the interaction of the solid electrolyte with high specific surface area and lithium salt + Fast realizing Li inside the composite film + The transmission performance is improved, and the ionic conductivity is greatly improved;
4. the porous polyolefin composite membrane prepared by the invention is prepared by double modification of a base membrane and a coating material, and the interface impedance of an electrolyte membrane is reduced and the ion conductivity of the electrolyte membrane is improved due to the synergistic effect of the enhancement modification of the base membrane and the pretreatment of a solid electrolyte, the prepared porous polyolefin composite membrane is placed in a microwave ultrasonic bath for ultrasonic treatment for 1h (the temperature is 30-50 ℃ and the frequency is 10000-25000 Hz), the coating is not dropped, the mechanical property and the conductivity are not reduced as found by the test, and the porous polyolefin composite membrane with stable performance is obtained through the synergistic effect of the improvement of the base membrane and the coating material, so that the porous polyolefin composite membrane can be used as a lithium battery diaphragm, (semi) solid electrolyte membrane, various separation membranes, water treatment membranes and the like.
Detailed Description
Example 1
(1) Preparation of high porosity base film:
2g of polyamide fiber (5 ten thousand molecular weight) is treated by oxygen plasma with power of 200W and temperature of 50 ℃ for 2min; and then fully mixing with 98g of polypropylene resin, transferring the mixture into a double-screw extruder, and carrying out melt blending extrusion granulation to obtain the modified fiber reinforced polypropylene master batch. Then preparing the high-porosity large-aperture base film by melt extrusion, preheating, longitudinal drawing, shaping, transverse drawing and shaping rolling, wherein the longitudinal drawing ratio is adjusted to 10, the transverse drawing ratio is adjusted to 8, the film is not broken, and the aperture is about 300 nm.
(2) Preparing solid electrolyte slurry:
pretreatment of solid electrolyte: firstly preparing 1 mol/L sulfuric acid and hydrochloric acid in a ventilation kitchen according to a mass ratio of 4:1, then taking 50g of solid electrolyte of LATP (D50 is 500 nm), pretreating for 2min under the stirring condition, and then cleaning and drying to obtain pretreated solid electrolyte;
taking 30g of pretreated solid electrolyte, adding 40g of acetonitrile, adding 3g of PEO (molecular weight of 15 ten thousand) while performing ultrasonic dispersion for the first time, wherein the ultrasonic dispersion temperature is 30 ℃, the frequency is 10000Hz, the circulating stirring speed is 1000r/min, and the time is 0.5 h; then carrying out the second ultrasonic dispersion, wherein the temperature is 60 ℃, the frequency is 50000 Hz, the circulation stirring speed is 5000 r/min, and the time is 2 h, thus obtaining the 50% solid electrolyte slurry with stable performance.
(3) And coating the slurry on a high-porosity base film, and drying to obtain the polyolefin composite film.
(4) 2g of PEO (molecular weight: 50 ten thousand) and 1g of lithium bis (fluorosulfonyl) imide are taken out in a fume hood, dissolved in acetonitrile under stirring (wherein the total weight of polymer, lithium salt and solvent is 100 g), and after the solution is made into a transparent solution, the composite film obtained in the step (3) is immersed in the transparent solution for 10s, taken out, and dried at 60 ℃ for 6h to obtain the porous polyolefin composite film.
Example 2
(1) Preparation of high porosity base film:
10g of meta-aramid fiber (3 ten thousand molecular weight) is treated by oxygen plasma with the power of 800W and the temperature of 100 ℃ for 20min; and then fully mixing with 90g of polypropylene resin, transferring the mixture into a double-screw extruder, and carrying out melt blending extrusion granulation to obtain the modified fiber reinforced polypropylene master batch. Then adding 1g of pore-forming agent, preparing a high-porosity large-aperture base film by melt extrusion, preheating, longitudinal stretching, shaping, transverse stretching and shaping rolling, wherein the longitudinal stretching ratio is adjusted to 12, the transverse stretching ratio is adjusted to 10, the film is not broken, and the aperture is about 400 nm.
(2) Preparing solid electrolyte slurry:
pretreatment of solid electrolyte: firstly preparing 1 mol/L sulfuric acid and phosphoric acid in a ventilation kitchen according to a mass ratio of 4:1, mixing 200g of the obtained mixed acid solution in proportion, then taking 50g of solid electrolyte of LLTO (D50 is 600 nm), pretreating for 2min under the stirring condition, and then cleaning and drying to obtain pretreated solid electrolyte;
60g of pretreated solid electrolyte is taken and 70g of NMP is added, 20g of PVDF (molecular weight 15 ten thousand) is added while carrying out the first ultrasonic dispersion, the ultrasonic dispersion temperature is 40 ℃, the frequency is 15000Hz, the circulating stirring speed is 1500r/min, and the time is 1 h; then, the second ultrasonic dispersion is carried out, the temperature is 70 ℃, the frequency is 70000 and Hz, the circulation stirring speed is 7000 and r/min, and the time is 3 and h, and the 40% solid electrolyte slurry with stable performance is obtained.
(3) And coating the slurry on a high-porosity base film, and drying to obtain the polyolefin composite film.
(4) 2g of PVDF (molecular weight 40 ten thousand) and 1g of lithium bis (trifluoromethylsulfonate) are taken out in a fume hood, dissolved in NMP (wherein the total weight of polymer, lithium salt and solvent is 100 g) under stirring, and the composite membrane obtained in the step (3) is immersed in the transparent solution for 15s and then taken out, and dried at 60 ℃ for 6h to obtain the porous polyolefin composite membrane.
Example 3
Example 3 differs from example 1 in that:
(1) The preparation condition of the high-porosity base film is that 0.1g of polyacrylonitrile fiber is treated by oxygen plasma, the power is 300W, and the temperature is 60 ℃ for 5min; then fully mixing with 99.9g of polypropylene resin, and transferring the mixture into a double-screw extruder, wherein the pore diameter of the base film obtained under the condition is 350nm;
comparative example 1: high porosity base film prepared in example 1
Comparative example 2: the high porosity base film prepared in example 1 was then coated with a ceramic composite film prepared by adding 50g of alumina ceramic slurry to 50g of water, then adding 1g of polyacrylic acid dispersant, 2g of polyether auxiliary agent and 5g of polyurethane binder, magnetically stirring and mixing uniformly, coating the high porosity base film prepared in example 1, and drying to prepare the ceramic composite film.
The ion conductivity test method is as follows: the conductivity of the porous polyolefin composite film was measured by an ac impedance method. Before measurement, a block-type battery (generally a stainless steel sheet) was assembled in a glove box filled with argon, a porous polyolefin composite membrane was punched into a disc with a diameter of 10mm, and then sandwiched between two Stainless Steel (SS) electrodes to assemble a stainless steel/composite membrane/stainless steel measurement system. The alternating current impedance spectrum test is carried out by adopting a biological-VMP 300 electrochemical workstation, the EIS test is carried out after the symmetrical battery is placed under the condition of 1h at the specific temperature (30 ℃, 40 ℃, 50 ℃, 60 ℃ and 80 ℃), the frequency range is set to be 7 MHz-0.1 Hz, and the amplitude is set to be 10 mV.
The tensile strength rate test method is as follows: the tensile properties of the porous polyolefin composite film were measured using Shanghai titled Q210a equipment. Before measurement, determining the sampling direction of a sample, cutting the porous membrane into 15 x 150mm sample strips by using a sampler, then placing the sample strips into a clamp of stretching equipment, opening software to select a stretching test, setting parameters according to thickness types, gradually stretching until the sample strips are broken, and reading corresponding stretching strength.
In order to verify the stability of the prepared porous polyolefin composite film, the prepared porous polyolefin composite film is placed in a microwave ultrasonic bath for ultrasonic treatment for 1h (the temperature is 30-50 ℃ and the frequency is 10000-25000 Hz), and the performance is tested according to the tensile strength and conductivity test method, wherein the tensile strength and the conductivity of the porous polyolefin composite film are not obviously reduced, but the conductivity of comparative example 2 is obviously reduced, the mechanical strength is low, and the conductivity of comparative example 1 is lower because the modification is not performed.
The porous polyolefin composite membrane prepared in the examples and the comparative examples is subjected to mechanical property test, ion conductivity test and ultrasonic test results after 1 hour of composite membrane, and the test results are shown as follows:
Claims (7)
1. a method for preparing a porous polyolefin composite film, comprising the steps of:
(1) Preparation of high porosity base film: the modified fiber and polyolefin resin are mixed according to the mass ratio of 0.1-10: blending and extruding the composite raw material with an extruder according to the proportion of 90-99.9, preparing a polyolefin film with the aperture of not less than 300nm and the porosity of not less than 55% by melt extrusion, preheating, longitudinal drawing, shaping, transverse drawing and shaping and winding the composite raw material and a pore-forming agent, and modifying the modified fiber by plasma;
(2) The preparation of the solid electrolyte slurry comprises the following steps:
a. pretreatment of solid electrolyte: preparing a mixed acid solution in a ventilation kitchen, adding the solid electrolyte, stirring at room temperature for 5s-20min, and then cleaning and drying to obtain a pretreated solid electrolyte, wherein the mixed acid solution is prepared from 1 mol/L sulfuric acid and hydrochloric acid or concentrated phosphoric acid according to a mass ratio of 6-8:1-4, wherein the mass ratio of the mixed acid solution to the solid electrolyte is 6-9:1-3;
b. carrying out ultrasonic dispersion and mixing on the pretreated solid electrolyte and the polymer and the solvent twice to prepare high-solid-content solid electrolyte slurry;
(3) Coating the solid electrolyte slurry obtained in the step (2) on the base film obtained in the step (1), preparing a mixed solution of a polymer, lithium salt and a solvent in a kitchen, then placing the base film coated with the solid electrolyte slurry in the mixed solution for 1-30min, taking out and drying to obtain a porous polyolefin composite film;
the polymer in the step (2) and the polymer in the step (3) are the same, the polymer is at least one of PEO, PAN, PVA, PVP, PMMA, PVDF, and the molecular weight of the polymer is 10-100 ten thousand.
2. The method for preparing a porous polyolefin composite membrane according to claim 1, wherein: the plasma treatment time in the step (1) is 2-20 min, the power is 200-800W, the temperature is 50-100 ℃, the treatment atmosphere is oxygen or air atmosphere, the fiber material is at least one of aramid fiber, polyamide fiber, polyacrylonitrile fiber and ultra-high molecular weight polyethylene, the longitudinal draw ratio is not lower than 10, and the transverse draw ratio is not lower than 8.
3. The method for producing a porous polyolefin composite film according to claim 2, wherein: the solid electrolyte in the step (2) is at least one of LLZO, LLZTO, LATP, LAGP, LLTO, and the solid electrolyte D50 is 500-2000nm.
4. A method of preparing a porous polyolefin composite membrane according to claim 3, wherein: the mass ratio of the pretreated solid electrolyte, the polymer and the solvent in the step (2) is 3-6:0.3-2:4-7, the two ultrasonic dispersions comprising a first ultrasonic dispersion: the temperature is 30-50 ℃, the frequency is 10000-25000 Hz, the circulating stirring speed is 1000-2000 r/min, and the ultrasonic dispersion time is 0.5-2.0 h; and (3) performing ultrasonic dispersion for the second time: the temperature is 60-90 ℃, the frequency is 50000-100000 Hz, the circulating stirring speed is 5000-10000 r/min, and the ultrasonic dispersion time is 2-5 h.
5. The method for preparing a porous polyolefin composite membrane according to claim 4, wherein: the lithium salt in the step (3) is at least one of lithium bis (fluorosulfonyl) imide, lithium bis (trifluoromethylsulfonyl) imide, lithium dioxalate borate, lithium hexafluorophosphate and lithium perchlorate; the mass ratio of the polymer, the lithium salt and the solvent is 0.1-5:0.05-3:90-99.
6. The method of preparing a porous polyolefin composite membrane according to claim 5, wherein: the solvent is at least one of acetone, acetonitrile, N-methyl pyrrolidone, DMF, DMAC, dimethyl sulfoxide and tetrahydrofuran.
7. The use of the porous polyolefin composite membrane produced by the production method according to any one of claims 1 to 6, wherein the porous polyolefin composite membrane is used in a lithium battery separator, a semi-solid electrolyte membrane or a solid electrolyte membrane, or a separation membrane, a water treatment membrane.
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