CN118156728A - Composite diaphragm with aperture gradient effect and preparation method and application thereof - Google Patents
Composite diaphragm with aperture gradient effect and preparation method and application thereof Download PDFInfo
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- CN118156728A CN118156728A CN202410564357.6A CN202410564357A CN118156728A CN 118156728 A CN118156728 A CN 118156728A CN 202410564357 A CN202410564357 A CN 202410564357A CN 118156728 A CN118156728 A CN 118156728A
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- 239000002131 composite material Substances 0.000 title claims abstract description 73
- 230000000694 effects Effects 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000011148 porous material Substances 0.000 claims abstract description 93
- 239000000919 ceramic Substances 0.000 claims abstract description 50
- 229920000098 polyolefin Polymers 0.000 claims abstract description 42
- 239000001913 cellulose Substances 0.000 claims abstract description 36
- 229920002678 cellulose Polymers 0.000 claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 16
- 239000002033 PVDF binder Substances 0.000 claims abstract description 15
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000013329 compounding Methods 0.000 claims abstract description 6
- 238000005096 rolling process Methods 0.000 claims abstract description 5
- 239000012528 membrane Substances 0.000 claims description 129
- 239000000243 solution Substances 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 18
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 18
- 229910052744 lithium Inorganic materials 0.000 claims description 14
- 239000011230 binding agent Substances 0.000 claims description 11
- 239000013310 covalent-organic framework Substances 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- 239000000853 adhesive Substances 0.000 claims description 10
- 230000001070 adhesive effect Effects 0.000 claims description 10
- 229910001507 metal halide Inorganic materials 0.000 claims description 10
- 150000005309 metal halides Chemical class 0.000 claims description 10
- 239000012621 metal-organic framework Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 4
- 238000004146 energy storage Methods 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 239000000446 fuel Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 239000000661 sodium alginate Substances 0.000 claims description 2
- 235000010413 sodium alginate Nutrition 0.000 claims description 2
- 229940005550 sodium alginate Drugs 0.000 claims description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000001764 infiltration Methods 0.000 claims 1
- 230000008595 infiltration Effects 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract description 25
- 229910001510 metal chloride Inorganic materials 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 2
- 238000004807 desolvation Methods 0.000 abstract 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 17
- 239000003792 electrolyte Substances 0.000 description 17
- 229910001416 lithium ion Inorganic materials 0.000 description 17
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 16
- 238000012986 modification Methods 0.000 description 8
- 230000004048 modification Effects 0.000 description 8
- 239000011592 zinc chloride Substances 0.000 description 8
- 235000005074 zinc chloride Nutrition 0.000 description 8
- 150000001450 anions Chemical class 0.000 description 7
- 210000004027 cell Anatomy 0.000 description 7
- 210000001787 dendrite Anatomy 0.000 description 7
- 239000000835 fiber Substances 0.000 description 7
- 239000013207 UiO-66 Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 2
- 238000004873 anchoring Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000005077 polysulfide Substances 0.000 description 2
- 229920001021 polysulfide Polymers 0.000 description 2
- 150000008117 polysulfides Polymers 0.000 description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ICXAPFWGVRTEKV-UHFFFAOYSA-N 2-[4-(1,3-benzoxazol-2-yl)phenyl]-1,3-benzoxazole Chemical compound C1=CC=C2OC(C3=CC=C(C=C3)C=3OC4=CC=CC=C4N=3)=NC2=C1 ICXAPFWGVRTEKV-UHFFFAOYSA-N 0.000 description 1
- 229920006310 Asahi-Kasei Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229940096017 silver fluoride Drugs 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
- H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
-
- 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
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Cell Separators (AREA)
Abstract
The invention discloses a composite diaphragm with aperture gradient effect, a preparation method and application thereof, wherein the diaphragm is a diaphragm formed by sequentially compounding a cellulose diaphragm, a polyolefin diaphragm, a ceramic diaphragm and a nano aperture material, the polyolefin diaphragm, the cellulose diaphragm and the ceramic diaphragm are soaked in polyvinylidene fluoride and metal chloride solution according to the order of the aperture from large to small, and then the three are compounded into a film by simple rolling. Because the pore diameters of various diaphragms and materials are distributed from large to small, gradient change in pore diameter is formed, more ions can enter the diaphragm at the larger side of the pore diameter, the ion flow can be more homogenized at the side of the gradually reduced pore diameter, and the desolvation process is accelerated, so that the whole composite diaphragm has higher ion mobility.
Description
Technical Field
The invention belongs to the technical field of diaphragm modification, and particularly relates to a composite diaphragm with a pore diameter gradient effect, and a preparation method and application thereof.
Background
With the global increasing demand for clean energy, the development of new energy technologies, particularly high performance battery technologies, has become a hot spot for research. Among many battery technologies, a battery using metals such as lithium, sodium, and zinc as a negative electrode is attracting attention due to its high theoretical specific capacity and low reduction potential, and is expected to greatly increase the energy density of the battery. However, the high activity of these metals also presents significant challenges, especially in the formation of dendrites on the surface of the metal negative electrode. The continuous growth of dendrites not only can penetrate through the battery separator to cause short circuits and potential safety accidents, but also can accelerate the consumption of electrolyte, and reduce the charge and discharge efficiency and the service life of the battery. Therefore, the dendrite problem in the metal negative electrode battery is solved, the safety and the performance of the battery are improved, and the research is focused. While much research is currently focused on modification of the surface of the anode, uniform ion transport at the solid-liquid interface is also critical to prevent dendrite formation. Some current solutions, such as electrolyte additives or artificial solid electrolytes, while somewhat effective, are limited in their commercial application by the high cost and complex manufacturing processes. Therefore, it is important to find a modification method which is simple, low-cost and environment-friendly. In this regard, polyolefin separators (e.g., polyethylene) used in conventional lithium ion batteries have disadvantages in terms of affinity for lithium ions and electrolytes, uniformity of pore distribution, and mechanical strength, which may lead to dendrite formation and short circuit of the battery. Therefore, modification of the battery separator is not only necessary. However, in general, the modification of the separator is mainly directed to doping or cladding of elements, and optimization of the structure of the separator itself is rarely mentioned. While only a large porosity, large pore size separator is used, it is not highly desolvated in ion migration and its ion mobility is not efficient.
Disclosure of Invention
Based on the problems, the invention aims to provide a composite diaphragm with an aperture gradient effect, a preparation method and application thereof, and solves the problem of low ion conductivity of the existing energy storage device in high power and high multiplying power.
The composite membrane provided by the invention is formed by compositing three membranes with different pore sizes so as to form a complete pore size gradient structure, wherein the composite membrane is formed by compositing a ceramic membrane, a polyolefin membrane and a cellulose membrane through an adhesive, the pore sizes of the ceramic membrane, the polyolefin membrane and the cellulose membrane are sequentially increased, pore diameters of pore channels of the composite membrane are increased from 10nm to 5 mu m according to the compositing sequence of the ceramic membrane, the polyolefin membrane and the cellulose membrane, metal halide is further attached in the composite membrane, and the thickness of the composite membrane is 10-35 mu m.
The pore diameters of the ceramic membrane, the polyolefin membrane and the cellulose membrane are respectively 0.01-1 mu m, 0.05-2 mu m and 0.1-5 mu m. The thickness of the cellulose film is 4-30 mu m; the thickness of the polyolefin membrane is 4-20 mu m; the thickness of the ceramic diaphragm is 5-15 mu m.
And a layer of metal or covalent organic framework material with sub-nanometer pore diameter is deposited on the surface of the ceramic diaphragm and in the pore canal of the composite diaphragm. Forming four-layer aperture gradient effect.
The metal or covalent organic framework material comprises but is not limited to ZIF-8, uiO-66 and COF-Go, wherein the aperture range of the ZIF-8 is 0.34-1.16 nm, the aperture range of the COF-GO is 0.5-1.4 nm, and the aperture range of the UiO-66 is 0.8-1.1 nm.
The method for preparing the composite membrane with the three-layer aperture gradient effect comprises the following steps,
Step 1, respectively preparing a binder and a metal halide solution, and mixing and uniformly stirring the binder and the metal halide solution to obtain a mixed solution;
step 2, adding the polyolefin membrane, the cellulose membrane and the ceramic membrane into the mixed solution prepared in the step 1, and fully soaking;
And 3, rolling the fully-infiltrated diaphragm mixture in the step 2, controlling the thickness of the composite diaphragm to be 10-35 mu m, and then standing the prepared composite diaphragm and drying in vacuum.
Further, the solute of the binder is one or more of polyvinylidene fluoride, sodium alginate, sodium polyacrylate, polyacrylic acid, polyvinyl alcohol, sodium carboxymethylcellulose, polyvinylpyrrolidone and styrene butadiene rubber, the solvent of the binder is one or more of absolute ethyl alcohol, N-methylpyrrolidone, dimethylformamide, dimethyl sulfoxide, acetone, tetrahydrofuran and cyclohexanone, and the concentration of the binder is 1-5mg/ml.
Further, the concentration of the metal halide solution is 0.1-1mg/ml, and the metal element in the metal halide is at least one selected from Ni, al, zn, sn, cu, cr, ti, mg.
Further, the step 2 is to soak the polyolefin membrane, the cellulose membrane and the ceramic membrane in a mixed solution of a binder and a metal chloride solution at room temperature, wherein the soaking time is 4-8h.
Further, the thickness of the cellulose film in the step 2 is 4-30 μm, and the pore size is 0.1-5 μm; the thickness of the polyolefin diaphragm is 4-20 mu m, and the pore size is 0.05-2 mu m; the thickness of the ceramic diaphragm is 5-15 mu m, and the pore size is 0.01-0.1 mu m.
Further, the prepared composite membrane is placed for 12 hours in the step 3, and then placed under a vacuum environment of 60 o ℃ for 12: 12h to be completely dried.
The preparation method of the composite membrane with the four-layer aperture gradient effect is characterized by further comprising the step of depositing a metal or covalent organic framework material with sub-nanometer aperture on the surface and in a pore canal of the ceramic membrane through suction filtration or spraying on the obtained dry composite membrane.
The metal or covalent organic framework material comprises but is not limited to ZIF-8, uiO-66 and COF-Go, wherein the aperture range of the ZIF-8 is 0.34-1.16 nm, the aperture range of the COF-GO is 0.5-1.4 nm, and the aperture range of the UiO-66 is 0.8-1.1 nm.
The composite diaphragm with the complete aperture gradient effect can be applied to an energy storage device of a metal battery, a fuel battery or a super capacitor comprising lithium/sodium/zinc, and the energy storage device operates under high power and not lower than 3C multiplying power.
Compared with the prior art, the invention has the advantages and beneficial effects that:
1. The composite diaphragm takes a polyolefin diaphragm, is compounded with a cellulose diaphragm and a ceramic diaphragm as a main body, is soaked in metal chloride, introduces metal elements, chlorine elements and fluorine elements, wherein in the adopted metal chloride, chloride ions can anchor anions existing in electrolyte to a great extent, and lithium-philic element fluorine elements can reduce migration energy barriers of lithium ions.
2. The composite membrane contains abundant metal elements and gradient pore diameters (the pore diameters of the ceramic membrane, the polyolefin membrane, the cellulose membrane and the nano-pore metal organic frame material are different, so that a pore diameter gradient effect is formed), and the design of the gradient pore diameter can homogenize the flow of lithium ions and can play a great advantage under the high-power condition. Ions can be conducted rapidly while ensuring that a large amount of ions are contained.
3. Under the synergistic effect, the lithium ion distribution can be effectively regulated, the lithium metal negative electrode can be promoted to realize uniform deposition and stripping processes, the growth of lithium dendrites is inhibited, the ion conductivity and the high-rate performance of the lithium dendrites are obviously improved, and the lithium metal negative electrode is also obviously improved in flame resistance and high temperature resistance.
4. In the composite diaphragm, the metal chloride and the metal fluoride of the inner layer and the outer layer can bring great improvement on mechanical strength and flame resistance, and the composition of beneficial components of the SEI film is greatly enhanced along with the introduction of polyvinylidene fluoride, so that the integral liquid level modification is presented.
5. The preparation process of the composite diaphragm is simple, the preparation cost is low, and the influence on the energy density of the battery is small.
6. The modified preparation method of the composite membrane can effectively solve the challenges in cost and environment, and provides a new way for improving the performance and safety of the battery.
Drawings
FIG. 1 is a schematic structural view of a composite separator in example 1;
FIG. 2 is a graph of cycling performance at 0.5C of Li-NCM811 cells prepared with different films in example 8;
Fig. 3 is a graph of performance at different magnifications for some of the examples in example 9.
Detailed Description
In order to better understand the technical solutions of the present application, the foregoing technical solutions of the present application will be described in detail below with reference to specific embodiments and accompanying drawings, and it should be understood that specific features in the embodiments and examples of the present application are detailed descriptions of the technical solutions of the present application, and not limiting the technical solutions of the present application, and the technical features in the embodiments and examples of the present application may be combined with each other without conflict.
The results of the product detection will be described below by means of specific embodiments.
The ceramic separator used in the following examples was obtained from the company of energy technologies, inc. of Hebei Jin Lixin, and it was composed mainly of alumina, and the other components included silicon oxide and magnesium oxide. The thickness of the ceramic diaphragm is 5-15 mu m, the average pore diameter of the ceramic diaphragm is 0.01-1 mu m, and the porosity is 40-50%.
The polyolefin separator used in the following examples was derived from ASAHIKASEI company and had a thickness of 9 to 20 μm. Has a porous structure, the pore size is 0.05-2 mu m, and the connectivity between pores is good. Further, the porosity of the polyolefin separator was 40%.
The cellulose membrane (CN 201911416124.7) used in the following examples is self-grinding by Ningbo soft wound nanotechnology, and is made by selecting high temperature resistant and electrochemical stable materials such as cellulose natural fiber, aramid fiber, polyimide fiber, poly-p-Phenylene Benzobisoxazole (PBO) fiber, polyacrylonitrile and the like, radially stripping the fiber by processing modes such as chemical enzyme catalysis, high pressure homogenization, mechanical grinding and the like, realizing nanocrystallization of the fiber in fineness, and simultaneously maintaining good length-diameter ratio, thickness and pore characteristics, porosity and other parameters. Then dispersing the fibers into water to manufacture a wet film, and introducing a cross-linking agent on the wet film formed by the porous nano fibers to polymerize the cross-linking agent in situ, so that the strength of the fiber nodes of the base film is further improved, and the mechanical property of the diaphragm is further improved. Meanwhile, solvent volatilization induces self-assembly of the cross-linking agent, and a three-dimensional net-shaped uniform pore structure is generated inside the diaphragm, so that the porosity and pore uniformity of the diaphragm are further improved. Finally, lithium ion conductivity is enhanced by coating or impregnating the cellulose membrane with a polymer solid electrolyte and an inorganic ceramic solid electrolyte. The thickness of the cellulose film is 5-30 mu m, the porosity is 40% -75%, and the pore size is 0.1-5 mu m.
One or more technical solutions provided in the embodiments of the present application at least have the following technical effects or advantages:
example 1
And (5) preparing a gradient battery diaphragm and assembling a battery.
According to the sequence of the ceramic diaphragm, the polyolefin diaphragm and the cellulose diaphragm, the three diaphragms are sequentially immersed into a mixed solution composed of zinc chloride and PVDF, wherein the concentration of the zinc chloride solution is 1mg/ml, and the concentration of the PVDF solution is 2mg/ml. After soaking for 8 hours, the cellulose diaphragm, the ceramic diaphragm and the polyolefin diaphragm are compounded together layer by layer according to the sequence of the pore diameters from large to small, and then rolling is carried out until the thickness of the composite diaphragm is within 35 um. And then standing the rolled diaphragm undisturbed for 12h to obtain a modified diaphragm, and putting the modified diaphragm into a 60 ℃ oven for standby.
And then respectively combining the modified diaphragm with different battery electrodes to form a half battery, a symmetrical battery and a full battery for electrochemical performance test.
A schematic diagram of a gradient pore size battery separator design battery separator in example 1 of fig. 1, the pore size order of each layer of separator is: cellulose separator > polyolefin separator > ceramic separator.
Example 2
The ceramic diaphragm, the polyolefin diaphragm and the cellulose diaphragm are immersed in a mixed solution composed of zinc chloride and PVDF, wherein the concentration of the zinc chloride solution is 1mg/ml, and the concentration of the PVDF solution is 2mg/ml. After soaking for 8 hours, compounding the cellulose membrane, the ceramic membrane and the polyolefin membrane layer by layer according to the pore size sequence, and then rolling until the thickness of the composite membrane is within 35 um. And then standing the rolled diaphragm undisturbed for 12h, and putting the diaphragm into a 60 ℃ oven for standby.
And then depositing a layer of metal organic frame material with nanometer aperture such as ZIF-8 on the ceramic diaphragm side with smaller aperture of the composite diaphragm by suction filtration or spraying and other modes. Four layers of gradient effect are formed: cellulose membranes, polyolefin membranes, ceramic membranes, ZIF-8. The ZIF-8 pore diameter is as follows: 0.34 to 1.16nm.
After the ceramic diaphragm, the polyolefin diaphragm and the cellulose diaphragm are immersed in the mixed solution composed of zinc chloride and PVDF, the pore size range is not changed obviously, the PVDF mainly plays a role of a binder, and the zinc chloride is introduced to play roles of anchoring anions and flame retardance. For example, when polysulfide is added to the electrolyte, chloride ions can inhibit the shuttle effect of polysulfide. The ZIF-8 coating on the modified diaphragm is combined with the gradient pore canal of the modified diaphragm, the solution environments with different ends are isolated, one end of the two ends of the ZIF-8 pore canal is an external solution with a large space dimension, and the other end is a composite diaphragm pore canal with a micrometer-nanometer dimension and zinc chloride and metal oxide on the surface.
Example 3-example 4
The procedure of example 2 was essentially the same except that the halides used were fluoride-silver fluoride, bromide-magnesium bromide, respectively.
Example 5-example 6
The procedure is also substantially the same as in example 2, except that the nanomaterial deposited on the side of the ceramic membrane where the composite membrane pore size is smaller is different. In example 5, a layer of COF-GO covalent organic framework composite graphene oxide with sub-nanometer pore diameter is deposited, and the pore diameter of the COF-GO is 0.5-1.4 nm. In example 6, a layer of UiO-66 (metal organic framework-Zr) with sub-nanometer pore size was deposited, and the UiO-66 pore size was 0.8-1.1 nm.
Only some examples were tested here, other modifications with nano-pore size composite to gradient membrane are also protected by this patent.
Example 7
This example tested composite membranes designed based on pore size gradients prepared in examples 1 and 2 (preparation methods refer to summary of the invention), composite membranes prepared in examples 3 to 6, and cellulose membranes, polyolefin membranes, ceramic membranes, composite membranes of cellulose membranes and polyolefin membranes, composite membranes of polyolefin membranes and ceramic membranes, and modified membranes of polyolefin membranes and ceramic membranes coated with metal or covalent organic framework materials on one side of the ceramic membrane after compositing of the polyolefin membranes and ceramic membranes, lithium ion mobility reflected by lithium symmetric batteries assembled from a total of 12 membranes, and ion conductivity reflected by steel to steel batteries.
The composite membrane of the cellulose membrane and the polyolefin membrane and the composite membrane of the polyolefin membrane and the ceramic membrane are compounded by adopting an adhesive. In this example, the adhesive was SBR latex, an organosilicon defoamer, a sodium dodecyl sulfate wetting agent, and deionized water in a ratio of 100:1:1:1000, and the mixture was stirred and dispersed uniformly, and after standing, an adhesive solution was obtained, and the above test results are shown in table 1.
TABLE 1
Ion mobility measures the ability of ions to move in an electrolyte. Lower ion mobility not only reduces the ion conductivity of the electrolyte, but can also lead to severe concentration polarization effects. In order to be able to accommodate large amounts of ions while maintaining high ionic conductivity, high ion mobility is critical to accommodate high power and high rate battery operating conditions. As can be seen from table 1, the modified composite separator prepared in examples 1 to 6 exhibited better ion conductivity and ion mobility than the cellulose separator polyolefin separator ceramic separator. Particularly, after a metal or covalent organic framework structure with smaller pore diameter is introduced, the ion conductivity effect of the battery prepared by the composite diaphragm with the pore diameter gradient effect is more remarkable.
Example 8
This example tests the cycling performance of NCM811 batteries based on different separators.
The NCM811 battery was assembled in a glove box using lithium metal as the negative electrode, NCM811 as the positive electrode, and 1m LiPF6 EC/DEC (volume ratio of 1:1) as the electrolyte, using different separators. When the NCM811 battery was assembled, the separator of examples 1 to 6 had a smaller pore diameter and a larger pore diameter and a positive electrode, respectively.
The preparation method of the NCM811 positive electrode plate comprises the following steps: nickel Cobalt Manganese (NCM), superP (conductive carbon black) and polyvinylidene fluoride (PVDF) binder are mixed according to the mass ratio of 8:1:1, uniformly ground and then dispersed in polymethyl pyrrolidone (NMP), then the mixture is placed in a homogenizer for homogenization for 20min to obtain uniform slurry, the slurry is scraped on an aluminum foil by a preparation machine, and the aluminum foil is placed in a vacuum drying oven at 80 ℃ for drying for 12h.
Taking a CR2025 type button cell made of the polyolefin diaphragm, the ceramic diaphragm and the composite diaphragm of the embodiment 2 as an example, the diameter of the type cell is 20mm, the thickness is 2.5mm, and the CR2025 type button cell is assembled according to the sequence of a cathode shell, a lithium sheet, dropwise adding electrolyte, the diaphragm, dropwise adding electrolyte, an anode electrode sheet, a gasket and an elastic sheet, and the cell pressure is 0.85 megapascal.
The cycle performance of the Li-NCM811 cell prepared from the above 3 separators at 0.5C is shown in FIG. 2.
Example 9
This example tests the cycle rate performance of NCM811 batteries prepared based on different separators in example 7.
The NCM811 battery was assembled in a glove box using lithium metal as the negative electrode, NCM811 as the positive electrode, and 1m LiPF6 EC/DEC (volume ratio of 1:1) as the electrolyte, using different separators. When the NCM811 battery was assembled, the side of the separator of example 1 or example 2 having the smaller pore diameter faced the negative electrode, and the side having the larger pore diameter faced the positive electrode.
The preparation method of the positive electrode slice comprises the following steps: nickel Cobalt Manganese (NCM), superP (conductive carbon black) and polyvinylidene fluoride (polyvinylidene fluoride) binder are mixed according to the mass ratio of 8:1:1, uniformly ground and then dispersed in polymethyl pyrrolidone (NMP), then the mixture is placed in a refiner for 20min to obtain uniform slurry, the slurry is scraped on an aluminum foil by a preparation machine, and the aluminum foil is placed in a vacuum drying oven at 80 ℃ for 12h to be dried.
Table 2 is a table of the cycling performance of the Li-NCM811 battery of example 7 at different rates. Batteries using composite separators have significantly higher rate performance than batteries using commercial separators. The positive electrode full cell voltage was 3V-4.3V, the test temperature was 25 ℃, and fig. 3 is a cycle performance magnification chart of a part of the separator in this example.
TABLE 2
As can be seen from Table 1, the groups such as-OH on the surfaces of the ceramic particles in the individual ceramic separators are relatively strong in lyophilicity, so that the wettability of the separators to the electrolyte is improved. However, the polyolefin+ceramic composite membrane has a limited contact between the surface and the electrolyte after the adhesive is coated, so that the improvement of the ion conductivity of the polyolefin+ceramic composite membrane is not obvious. And the metal chloride is coated on the surface of the cellulose membrane, the polyolefin membrane and the ceramic membrane through PVDF, as in the embodiment 1, the zinc chloride is introduced to play a role of anchoring anions, so that positively charged Li + can shuttle in the anions more easily, and the mobility of lithium ions is improved. The composite membrane pore canal has better affinity with electrolyte, and metal oxide in the composite membrane pore canal has affinity to lithium ions in lithium electrolyte, so that the lithium ions can uniformly pass through the composite membrane pore canal, the lithium electrolyte in each pore canal in the composite membrane is uniformly distributed, and the problem that the rate of the lithium ions passing through the membrane under high current is reduced due to the fact that the lithium ions only pass through the membrane from the local area of the composite membrane is avoided.
The more complete the aperture size gradient effect of the composite membrane pore canal, the more excellent the performance in high rate performance. In example 1, the porous membrane is formed by compounding a ceramic membrane, a polyolefin membrane and a cellulose membrane with sequentially increased pore diameters, in example 2, the porous membrane is formed by compounding a nano ZIF-8 material, a ceramic membrane, a polyolefin membrane and a cellulose membrane with sequentially increased pore diameters, in comparison with example 1, the pore diameter gradient of a pore channel of the composite membrane is more perfect, and the ion migration rate of the porous membrane of example 2 is improved under high current. This is because of the unique gradient pore size design, since the micron-nanometer size pore size on one side of the composite membrane is larger and can accommodate more ions, the pore diameter is continuously reduced to the nanometer level along with the composite order of the membrane, the radius of lithium ions (0.2 nm-0.3 nm) and the radius of lithium hydrated ions (0.76 nm) in the electrolyte, and the radius of anions hydrated ions (several angstroms-tens of angstroms) are freely shuttled by the nanometer level.
The pore size of the ZIF-8 layer is reduced to be sub-nanometer, anions such as chloride ions in the composite membrane pore can inhibit the anion shuttle membrane in the electrolyte, so that the composite membrane pore can shuttle more lithium ions, the sub-nanometer pore diameter of the ZIF-8 pore is smaller than the molecular size of a solvent and larger than the radius of the lithium ions, the ZIF-8 layer with the sub-nanometer pore diameter can play a role in removing solvent molecules around the lithium ions, lithium ions can freely migrate in the ZIF-8 pore structure, the migration rate of the ions is greatly accelerated, and the gradient pore diameter structure has ideal effects in the application of high-power equipment. Other materials with a nano-pore size are the same.
Finally, it should be noted that the above-mentioned embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same, and although the present invention has been described in detail with reference to examples, it should be understood by those skilled in the art that modifications and equivalents may be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention, and all such modifications and equivalents are intended to be encompassed in the scope of the claims of the present invention.
Claims (13)
1. The composite membrane is characterized in that the composite membrane is formed by compounding a ceramic membrane, a polyolefin membrane and a cellulose membrane through an adhesive, pore diameters of pore passages of the ceramic membrane, the polyolefin membrane and the cellulose membrane are sequentially increased, the pore diameters of the pore passages of the composite membrane are increased from 10nm to 5 mu m according to the compounding sequence of the ceramic membrane, the polyolefin membrane and the cellulose membrane, metal halide is further attached in the composite membrane, and the thickness of the composite membrane is 10-35 mu m.
2. The composite membrane according to claim 1, wherein the pore diameters of the ceramic membrane, the polyolefin membrane and the cellulose membrane are respectively 0.01-0.1 μm, 0.05-2 μm and 0.1-5 μm.
3. The composite membrane of claim 2 wherein a layer of metal or covalent organic framework material having sub-nanometer pore size is deposited on the surface and within the pores of the ceramic membrane of the composite membrane.
4. A composite membrane according to claim 3, wherein the metallic or covalent organic framework material includes, but is not limited to, ZIF-8, uio-66, COF-Go, wherein ZIF-8 has a pore size in the range of 0.34 to 1.16nm, COF-Go has a pore size in the range of 0.5 to 1.4nm, uio-66 has a pore size in the range of 0.8 to 1.1nm.
5. A method of preparing a composite separator according to claim 1, wherein the preparation of the composite separator comprises the steps of,
Step 1, respectively preparing a binder and a metal halide solution, and mixing and uniformly stirring the binder and the metal halide solution to obtain a mixed solution;
step 2, adding the polyolefin membrane, the cellulose membrane and the ceramic membrane into the mixed solution prepared in the step 1, and fully soaking;
And 3, rolling the fully-infiltrated diaphragm mixture in the step 2, controlling the thickness of the composite diaphragm to be 10-35 mu m, and then standing the prepared composite diaphragm and drying in vacuum.
6. The preparation method of the adhesive according to claim 5, wherein the solute of the adhesive is one or more of polyvinylidene fluoride, sodium alginate, sodium polyacrylate, polyacrylic acid, polyvinyl alcohol, sodium carboxymethyl cellulose, polyvinylpyrrolidone and styrene butadiene rubber, the solvent of the adhesive is one or more of absolute ethyl alcohol, N-methyl pyrrolidone, dimethylformamide, dimethyl sulfoxide, acetone, tetrahydrofuran and cyclohexanone, and the concentration of the adhesive is 1-5mg/ml.
7. The method according to claim 5, wherein the concentration of the metal halide solution is 0.1 to 1mg/ml, and the metal element in the metal halide is at least one selected from Ni, al, zn, sn, cu, cr, ti, mg.
8. The method according to claim 5, wherein the infiltration time in step 2 is 4-8 hours.
9. The method according to claim 5, wherein the cellulose film in step 2 has a thickness of 4 to 30 μm and a pore size of 0.1 to 5 μm; the thickness of the polyolefin diaphragm is 4-20 mu m, and the pore size is 0.05-2 mu m; the thickness of the ceramic diaphragm is 5-15 mu m, and the pore size is 0.01-0.1 mu m.
10. The method according to claim 5, wherein the prepared composite membrane is left to stand for 12 hours in the step 3, and then is left to stand for 12h to be completely dried in a vacuum environment of 60 o ℃.
11. A method of preparing a composite membrane according to claim 3, further comprising, after step 3 of the preparation method according to claim 3, depositing a sub-nano-pore size metal or covalent organic framework material on the ceramic membrane surface and in the pores by suction filtration or spray coating on the resulting dried composite membrane.
12. The method of preparing a composite membrane according to claim 11, wherein the metallic or covalent organic framework material includes, but is not limited to, ZIF-8, uio-66, COF-Go, wherein the ZIF-8 pore size ranges from 0.34 to 1.16nm, COF-Go pore size ranges from 0.5 to 1.4nm, uio-66 pore size ranges from 0.8 to 1.1nm.
13. An energy storage device employing the composite separator with pore size gradient effect of any one of claims 1 to 4 in a metal battery, fuel cell or supercapacitor comprising lithium/sodium/zinc.
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