CN114824656B - Separator paper, preparation method and battery - Google Patents
Separator paper, preparation method and battery Download PDFInfo
- Publication number
- CN114824656B CN114824656B CN202210490862.1A CN202210490862A CN114824656B CN 114824656 B CN114824656 B CN 114824656B CN 202210490862 A CN202210490862 A CN 202210490862A CN 114824656 B CN114824656 B CN 114824656B
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- CN
- China
- Prior art keywords
- hydrophilic
- fiber
- paper base
- aerogel
- polydopamine
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- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000835 fiber Substances 0.000 claims abstract description 158
- 239000004964 aerogel Substances 0.000 claims abstract description 90
- 229920001690 polydopamine Polymers 0.000 claims abstract description 70
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 76
- 229960003638 dopamine Drugs 0.000 claims description 38
- 238000000576 coating method Methods 0.000 claims description 30
- 239000011248 coating agent Substances 0.000 claims description 27
- 239000003607 modifier Substances 0.000 claims description 25
- 229920000728 polyester Polymers 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 19
- 239000002270 dispersing agent Substances 0.000 claims description 17
- 229920000297 Rayon Polymers 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 10
- 229920001046 Nanocellulose Polymers 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 8
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims description 6
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims description 6
- 229960003237 betaine Drugs 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 abstract description 13
- 239000000243 solution Substances 0.000 description 69
- 239000007983 Tris buffer Substances 0.000 description 45
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 34
- 238000003756 stirring Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- 238000004090 dissolution Methods 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- 238000002791 soaking Methods 0.000 description 14
- 238000001035 drying Methods 0.000 description 10
- 239000012628 flowing agent Substances 0.000 description 10
- 229920002401 polyacrylamide Polymers 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 238000004513 sizing Methods 0.000 description 9
- 229920000178 Acrylic resin Polymers 0.000 description 8
- 239000004925 Acrylic resin Substances 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 7
- 238000007606 doctor blade method Methods 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- YLGXILFCIXHCMC-JHGZEJCSSA-N methyl cellulose Chemical compound COC1C(OC)C(OC)C(COC)O[C@H]1O[C@H]1C(OC)C(OC)C(OC)OC1COC YLGXILFCIXHCMC-JHGZEJCSSA-N 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 238000000748 compression moulding Methods 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 229920002978 Vinylon Polymers 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000011002 quantification Methods 0.000 description 4
- 229920002994 synthetic fiber Polymers 0.000 description 4
- 239000012209 synthetic fiber Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000003828 vacuum filtration Methods 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 2
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LIFHMKCDDVTICL-UHFFFAOYSA-N 6-(chloromethyl)phenanthridine Chemical compound C1=CC=C2C(CCl)=NC3=CC=CC=C3C2=C1 LIFHMKCDDVTICL-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- MKHVZQXYWACUQC-UHFFFAOYSA-N bis(2-hydroxyethyl)azanium;dodecyl sulfate Chemical compound OCCNCCO.CCCCCCCCCCCCOS(O)(=O)=O MKHVZQXYWACUQC-UHFFFAOYSA-N 0.000 description 1
- MRUAUOIMASANKQ-UHFFFAOYSA-O carboxymethyl-[3-(dodecanoylamino)propyl]-dimethylazanium Chemical compound CCCCCCCCCCCC(=O)NCCC[N+](C)(C)CC(O)=O MRUAUOIMASANKQ-UHFFFAOYSA-O 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- TVACALAUIQMRDF-UHFFFAOYSA-N dodecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCOP(O)(O)=O TVACALAUIQMRDF-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- HDERJYVLTPVNRI-UHFFFAOYSA-N ethene;ethenyl acetate Chemical group C=C.CC(=O)OC=C HDERJYVLTPVNRI-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229940075468 lauramidopropyl betaine Drugs 0.000 description 1
- 229940094506 lauryl betaine Drugs 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229940037627 magnesium lauryl sulfate Drugs 0.000 description 1
- HBNDBUATLJAUQM-UHFFFAOYSA-L magnesium;dodecyl sulfate Chemical compound [Mg+2].CCCCCCCCCCCCOS([O-])(=O)=O.CCCCCCCCCCCCOS([O-])(=O)=O HBNDBUATLJAUQM-UHFFFAOYSA-L 0.000 description 1
- DVEKCXOJTLDBFE-UHFFFAOYSA-N n-dodecyl-n,n-dimethylglycinate Chemical compound CCCCCCCCCCCC[N+](C)(C)CC([O-])=O DVEKCXOJTLDBFE-UHFFFAOYSA-N 0.000 description 1
- ONLRKTIYOMZEJM-UHFFFAOYSA-N n-methylmethanamine oxide Chemical compound C[NH+](C)[O-] ONLRKTIYOMZEJM-UHFFFAOYSA-N 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- UHGIMQLJWRAPLT-UHFFFAOYSA-N octadecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCCCOP(O)(O)=O UHGIMQLJWRAPLT-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229940057950 sodium laureth sulfate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- SXHLENDCVBIJFO-UHFFFAOYSA-M sodium;2-[2-(2-dodecoxyethoxy)ethoxy]ethyl sulfate Chemical compound [Na+].CCCCCCCCCCCCOCCOCCOCCOS([O-])(=O)=O SXHLENDCVBIJFO-UHFFFAOYSA-M 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000009827 uniform distribution Methods 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
- H01M50/44—Fibrous material
-
- 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
-
- 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
- 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
- H01M50/494—Tensile strength
-
- 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 discloses diaphragm paper, a preparation method and a battery, relates to the technical field of batteries, and aims to solve the problems of high-temperature shrinkage rate, low tensile strength and low wettability to electrolyte of the conventional diaphragm paper. The diaphragm paper comprises a fiber paper base and a hydrophilic layer formed on the surface of the fiber paper base, wherein the hydrophilic layer at least comprises a hydrophilic aerogel layer, and the fiber paper base is a polydopamine modified fiber paper base. The preparation method is used for preparing the separator paper, and the battery uses the separator paper. The separator paper, the preparation method and the battery are used for improving the safety of the battery.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to diaphragm paper, a preparation method and a battery.
Background
With the development of new energy battery technology, ion batteries are widely used in various fields. The diaphragm is a key material in the ion battery, and has the main functions of isolating the anode and the cathode of the battery, preventing short circuit, storing electrolyte, transporting ions and isolating electrons.
The currently commercialized diaphragm is mainly a polyolefin diaphragm, and because of high-temperature shrinkage, low tensile strength and poor safety performance, the diaphragm has low wettability to electrolyte in the charge and discharge process, and therefore, the diaphragm cannot meet the energy storage requirement of a high-safety large-scale ion battery. Therefore, there is a need to develop a separator paper having performance characteristics such as thermal stability, high tensile strength, and high wettability to an electrolyte.
Disclosure of Invention
The invention aims to provide a diaphragm paper, a preparation method and a battery, and the heat stability, tensile strength and wettability to electrolyte of the diaphragm paper are improved, so that the safety of the battery is improved.
In a first aspect, the invention provides a separator paper, which comprises a fiber paper base and a hydrophilic layer formed on the surface of the fiber paper base, wherein the hydrophilic layer at least comprises a hydrophilic aerogel layer, and the fiber paper base is a polydopamine modified fiber paper base.
Compared with the prior art, the diaphragm paper provided by the invention has the following advantages:
in the diaphragm paper provided by the invention, the fiber paper base is the polydopamine modified fiber paper base, and the polydopamine modified fiber paper base has good compatibility by utilizing the strong adhesiveness, good biocompatibility and excellent photo-thermal conversion property of polydopamine. The hydrophilic layer in the diaphragm paper at least contains the hydrophilic aerogel layer, and the hydrophilic aerogel layer has strong tensile strength, high flexibility and excellent heat insulation performance, so that when the hydrophilic layer is formed on the surface of the fiber paper base, the wettability to electrolyte in the charge and discharge process can be improved, and the tensile strength, the wettability to electrolyte and the thermal stability of the surface of the fiber paper base can be improved to a certain extent. Meanwhile, the polydopamine has super-strong viscosity, so that the aerogel can be tightly adhered, the slag falling phenomenon of the diaphragm paper is reduced, the hydrophilic aerogel can exist stably on the surface of the fiber paper base, and the performance stability of the surface of the fiber paper base is ensured. In addition, in the diaphragm paper provided by the invention, the hydrophilic aerogel layer is light in weight, and the quantification of the diaphragm paper can be reduced.
From the above, the diaphragm paper provided by the invention can form a hydrophilic layer on the fiber paper base, so that the wettability, tensile strength and thermal stability of the diaphragm paper to electrolyte are improved, and the quantification of the diaphragm paper is reduced.
In a second aspect, the present invention also provides a method for preparing separator paper, including:
manufacturing the polydopamine coated fiber into a fiber paper base;
a hydrophilic layer is formed on at least one surface of the fibrous paper substrate.
Compared with the prior art, the preparation method of the diaphragm paper has the same beneficial effects as those of the diaphragm paper of the first aspect, and the details are not repeated here.
In a third aspect, the present invention also provides a battery comprising the separator paper provided in the first aspect.
Compared with the prior art, the beneficial effects of the battery provided by the invention are the same as those of the separator paper in the first aspect, and the description is omitted here.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and do not constitute a limitation on the invention. In the drawings:
fig. 1 is a schematic view of a battery according to an embodiment of the present invention;
FIG. 2 is a schematic diagram of a separator paper according to an embodiment of the present invention;
FIG. 3 is a schematic flow chart of a method for preparing separator paper according to an embodiment of the present invention;
reference numerals:
100-battery, 101-separator paper, 102 a-positive electrode, 102 b-positive electrode material, 103 a-negative electrode, 103 b-negative electrode material, 200-separator paper, 201-fiber paper base, 202-hydrophilic layer.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear, the invention is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present invention, the meaning of "a plurality" is two or more, unless explicitly defined otherwise. The meaning of "a number" is one or more than one unless specifically defined otherwise.
The diaphragm paper is a key material in the ion battery, and has the main functions of isolating the anode and the cathode of the battery, preventing short circuit, storing electrolyte, transporting ions and isolating electrons.
Embodiments of the present invention provide a battery that may include the separator paper of embodiments of the present invention to improve wettability, tensile strength, and thermal stability of the separator paper to an electrolyte, it being understood that the battery may further include a positive electrode, a positive electrode material, a negative electrode, and a negative electrode material. The separator paper may be defined as having opposing first and second surfaces with a positive electrode material between the positive electrode and the first surface and a negative electrode material between the negative electrode and the second surface. Fig. 1 shows a schematic structural diagram of a battery according to an embodiment of the present invention, and as shown in fig. 1, a battery 100 according to an embodiment of the present invention includes a separator paper 101, and a positive electrode material 102b, a negative electrode material 103b, and a negative electrode 103a distributed on both sides of the separator paper 101.
In practical applications, the battery of the embodiment of the present invention may be a lithium ion battery, a sodium ion battery, or other ion batteries, which are not described in detail herein.
The separator paper provided by the embodiment of the invention can be applied to the battery. Fig. 2 shows a schematic structural view of a separator paper according to an embodiment of the present invention. As shown in fig. 2, the separator paper 200 according to the embodiment of the present invention includes a fibrous paper base 201 and a hydrophilic layer 202 formed on the surface of the fibrous paper base, the hydrophilic layer 202 containing at least a hydrophilic aerogel layer. The fiber paper base is a polydopamine modified fiber paper base.
Compared with the prior diaphragm paper which is mainly polyolefin diaphragm paper, the diaphragm paper has the advantages of large high-temperature shrinkage, low tensile strength, poor safety performance and low wettability to electrolyte in the charge and discharge process, and can not meet the energy storage requirement of high-safety large-scale sodium ion batteries. In the diaphragm paper provided by the invention, the fiber paper base is the polydopamine modified fiber paper base, and the polydopamine modified fiber paper base has good compatibility due to strong adhesiveness, good biocompatibility and excellent photo-thermal conversion. The hydrophilic layer in the diaphragm paper at least contains the hydrophilic aerogel layer, and the hydrophilic aerogel layer has strong tensile strength, high flexibility and excellent heat insulation performance, so that after the hydrophilic layer is formed on the surface of the fiber paper base by using the hydrophilic aerogel, the wettability of the hydrophilic layer to electrolyte in the charge and discharge process can be improved, and the tensile strength, the wettability and the thermal stability of the surface of the fiber paper base can be improved to a certain extent. Meanwhile, the polydopamine has super-strong viscosity, so that the aerogel can be tightly adhered, the slag falling phenomenon of the diaphragm paper is reduced, and the hydrophilic aerogel can stably exist on the surface of the fiber paper base. Further, since the hydrophilic aerogel layer is light in weight, the basis weight of the separator paper can be reduced.
From the above, the membrane paper provided by the invention can form a hydrophilic layer on the fiber paper base, so that the liquid absorption and retention rate, the tensile strength and the thermal stability of the membrane paper are improved, and the quantification of the membrane paper is reduced.
In one implementation, the fiber paper base of the embodiment of the invention contains fibers modified by polydopamine, and the polydopamine coats the fibers. Because polydopamine has strong adhesiveness, good biocompatibility and excellent light-heat conversion, the polydopamine modified fiber has good compatibility.
In practical applications, the fibers contained in the fiber paper base may be defined as synthetic fibers including at least one of polyester fibers, polyamide fibers, polypropylene fibers, polyvinyl chloride, and polyurethane.
The hydrophilic aerogel layer may have a nanoporous network structure. The hydrophilic aerogel contained in the hydrophilic aerogel layer is a surface-modified aerogel, or may be a hydrophilic aerogel mixed with a surface-modifying agent.
In practical application, the mass ratio of aerogel to surface modifier is (4-6): 1, the surface and the pores of the aerogel are modified to the maximum extent, so that the formed hydrophilic aerogel layer has good wettability to the electrolyte.
The hydrophilic aerogel of the embodiment of the invention is the aerogel mixed with the surface modifier, and the surface modifier can be adsorbed on the surface of the aerogel, so that the surface can be effectively protected. Meanwhile, the mass ratio of the aerogel to the surface modifier is (4-6): 1, the surface modifier can be uniformly adsorbed on the surface of the aerogel.
The aerogel may be a nano aerogel, a micro-porous aerogel, or a mesoporous aerogel, for example. When the aerogel is a nano aerogel, it may be specifically a nanofiber aerogel.
Illustratively, the surface modifier may be defined as at least one of a quaternary ammonium salt type surface modifier, a sulfate type surface modifier, and a betaine type surface modifier,
the quaternary ammonium salt surface modifier may be lauryl dimethyl ammonium oxide, cocoamidopropyl dimethyl ammonium oxide or other ammonium surface modifiers, the sulfate surface modifier may be sodium lauryl sulfate, sodium laureth sulfate, diethanolamine lauryl sulfate, magnesium lauryl sulfate, triethanolamine lauryl sulfate or other sulfate surface modifiers, and the betaine surface modifier may be stearyl phosphate betaine, lauryl phosphate betaine, lauramidopropyl betaine, lauryl betaine or other betaine surface modifiers.
In an alternative, the hydrophilic layer further comprises an auxiliary agent. The auxiliary agent may include at least one of a dissolving agent, a dispersing agent, a flow agent, and a binder. When the auxiliary agent comprises a dissolving agent, a dispersing agent, a flowing agent and a binding agent, the hydrophilic layer comprises 5-30 parts of hydrophilic aerogel layer, 50-85 parts of dissolving agent, 0.5-1 part of dispersing agent, 0-0.03 part of flowing agent and 0.5-3 parts of binding agent according to parts by mass.
Illustratively, the dissolving agent may be defined as at least one of water, ethanol, acetone, methanol, propylene glycol, and the dispersing agent may be defined as at least one of methyl cellulose ether, hydroxyethyl methyl cellulose ether, polyvinyl alcohol, hydroxymethyl cellulose ether, hydroxyethyl cellulose ether, hydroxypropyl methyl cellulose ether; the flow agent may be defined as a combination of organic and inorganic materials, such as a combination of polypropylene and water, a combination of polycarbonate and water; the binder may be defined as at least one of acrylic resin, vinyl acetate-ethylene copolymer emulsion, sodium polyacrylate, and polyacrylamide.
The dissolving agent provided by the embodiment of the invention can dissolve hydrophilic aerogel, the dispersing agent can stably disperse undissolved solid matters of a hydrophilic layer, the solid matters are adsorbed on the surfaces of solid particles, the interfacial tension between liquid and liquid or between solid and liquid is reduced, so that the system is uniform, the suspension performance is increased, and no precipitation is caused. The flow agent can reduce the surface tension, increase the wettability and improve the leveling effect under dynamic or static conditions, and can avoid film coating defects such as orange peel, shrinkage cavity, brush mark and the like caused by poor leveling, so that the thickness of the whole system is uniform; the binder may link the components of the hydrophilic layer together by interfacial (surface) layer molecular (atomic) interactions, so that de-flow is prevented even in the presence of a flow agent. Under the combined action of the dissolvent, the dispersing agent, the flowing agent and the binder, the uniform distribution of solid matters of the hydrophilic layer can be ensured, the leveling effect is improved, the flow separation can be prevented, and the stability of the hydrophilic layer is improved.
The embodiment of the invention also provides a preparation method of the diaphragm paper, which can be used for preparing the diaphragm paper of the embodiment of the invention. Fig. 3 shows a schematic flow chart of a method for producing separator paper according to an embodiment of the present invention. As shown in fig. 3, the preparation method of the separator paper according to the embodiment of the invention includes:
step 301: and manufacturing the polydopamine coated fiber into a fiber paper base. For example: synthetic fibers can be added into the dopamine solution, and the mixture is stirred and mixed to enable dopamine to be self-polymerized to form polydopamine, so that polydopamine-coated fibers are obtained. At this time, the polydopamine is wrapped on the surface of the synthetic fiber, and then the fiber wrapped by polydopamine is made into paper by vacuum filtration by a wet papermaking method, so as to obtain the fiber paper base wrapped by polydopamine.
Because the polydopamine has strong adhesiveness, good biocompatibility and excellent photo-thermal conversion, the fiber paper base modified by polydopamine has good compatibility, and the synthetic fiber after being fully stirred can be uniformly wrapped by polydopamine.
Step 302: a hydrophilic layer is formed on the surface of the fibrous paper substrate. For example: coating a hydrophilic layer on the surface of a fiber paper base to obtain diaphragm paper,
meanwhile, the polydopamine has super-strong viscosity, so that aerogel can be tightly adhered, the slag falling phenomenon of diaphragm paper is reduced, and the hydrophilic layer can exist stably on the surface of the fiber paper base. Moreover, the basis weight of the separator paper can be reduced due to the low weight of the hydrophilic layer.
For example, the preparation method of the dopamine solution can be as follows: adding ionized water into the Tris for dissolution to obtain a Tris buffer solution, dissolving dopamine in the Tris solution to prepare a dopamine solution with the concentration range of 0.1g/L-5g/L, and dripping an acid solution to adjust the pH value to 8-10. It should be understood that the acid solution herein may be at least one of sulfuric acid solution, hydrochloric acid solution, acetic acid solution, or other acid solution.
In one alternative, forming a hydrophilic layer on a surface of a fibrous paper substrate comprises: and coating a hydrophilic layer on the surface of the fiber paper base to obtain the diaphragm paper. For example: and uniformly coating the slurry on the polyester fiber paper by a coating mode on the hydrophilic layer, and then drying and soft-pressing to form the diaphragm paper. The coating mode may be a roll coating method, a doctor blade coating method or a casting coating method, or may be other coating methods, which will not be described herein.
Illustratively, the hydrophilic layer further comprises a hydrophilic aerogel layer, the hydrophilic aerogel contained in the hydrophilic aerogel layer is aerogel mixed with a surface modifier, and the aerogel and the surface modifier are ground and dispersed by a grinder for 15-40 min after being mixed, so that the hydrophilic aerogel layer is obtained. The grinding machine can be a disc type grinding machine, a rotating shaft type grinding machine, a three-roller grinding machine or an automatic grinding machine, and can also be other types of grinding machines, and the description is omitted here. According to the embodiment of the invention, aerogel and the surface modifier are mixed and ground for dispersion, so that the aerogel and the surface modifier can be better mixed.
From the above, the diaphragm paper provided by the invention has strong adhesiveness, good biocompatibility and excellent photo-thermal conversion property, so that the diaphragm paper has good compatibility when the fiber paper base is a fiber paper base modified by polydopamine. The hydrophilic layer in the diaphragm paper at least contains the hydrophilic aerogel layer, and the tensile strength, flexibility and heat insulation performance of the hydrophilic aerogel layer are high, and the hydrophilic aerogel layer is light in weight, so that after the hydrophilic layer is formed on the fiber paper base, the liquid absorption and retention rate, tensile strength and thermal stability of the diaphragm paper can be improved, and the quantification of the diaphragm paper can be reduced.
In order to verify the effect of the separator paper provided in the examples of the present invention, the examples of the present invention were demonstrated by comparing the examples with comparative examples.
Example 1
The embodiment of the invention provides diaphragm paper, which comprises a fiber paper base and a hydrophilic layer formed on the surface of the fiber paper base, wherein the hydrophilic layer at least comprises a hydrophilic aerogel layer, and the fiber paper base is a polydopamine modified fiber paper base.
The preparation method of the diaphragm paper provided by the embodiment of the invention comprises the following steps:
firstly, preparing a dopamine solution: adding ionized water into Tris for dissolution to obtain a Tris buffer solution, namely, a Tris buffer solution, weighing 0.01mol of Tris solution, adding deionized water into a volumetric flask for dissolution to obtain a 12mmol/L Tris buffer solution, adding a plurality of drops of hydrochloric acid for regulating the pH value to about 8, and preparing a 1g/L dopamine solution by using the Tris buffer solution.
Secondly, preparing a fiber paper base: soaking the polyester fiber in the dopamine solution, fully stirring, mixing and soaking for 12 hours, washing a reaction product with deionized water for a plurality of times until filtrate is colorless and clear, and mixing the polyester fiber coated with polydopamine with viscose fiber according to a ratio of 9:1, adding a proper amount of polyacrylamide dispersing agent, uniformly stirring, and vacuum filtering to prepare the fiber paper base coated with polydopamine.
Thirdly, preparing a hydrophilic layer: 25g of nano cellulose aerogel and 5g of lauryl dimethyl ammonium oxide are mixed, then the mixture is ground and dispersed for 15min by a grinder to obtain hydrophilic aerogel, and then 25.5 parts of hydrophilic aerogel, 70 parts of water, 1 part of methyl cellulose ether, 0.5 part of flowing agent and 3 parts of acrylic resin are mixed and stirred uniformly to obtain a hydrophilic layer.
Fourth step, coating sizing: and uniformly coating the slurry on a fiber paper base coated with polydopamine through a doctor blade coating mode, and then drying and soft compression molding to obtain the diaphragm paper, wherein the ration of the diaphragm paper is 35g/cm < 2 >.
Example two
The embodiment of the invention provides diaphragm paper, which comprises a fiber paper base and a hydrophilic layer formed on the surface of the fiber paper base, wherein the hydrophilic layer at least comprises a hydrophilic aerogel layer, and the fiber paper base is a polydopamine modified fiber paper base.
The preparation method of the diaphragm paper provided by the second embodiment of the invention comprises the following steps:
firstly, preparing a dopamine solution: adding ionized water into Tris for dissolution to obtain a Tris buffer solution, namely a Tris buffer solution, weighing 0.02mol of the Tris buffer solution, adding deionized water into a volumetric flask for dissolution to obtain a Tris buffer solution with the concentration of 14mmol/L, adding a plurality of drops of hydrochloric acid to adjust the pH value to about 8.5, and preparing a dopamine solution with the concentration of 1.5g/L by using the Tris buffer solution.
Secondly, preparing a fiber paper base: soaking the polyester fiber in the dopamine solution, fully stirring, mixing and soaking for 15 hours, washing a reaction product with deionized water for a plurality of times until filtrate is colorless and clear, and mixing the polyester fiber coated with polydopamine with viscose fiber according to a ratio of 9:1, adding a proper amount of polyacrylamide dispersing agent, uniformly stirring, and vacuum filtering to prepare the fiber paper base coated with polydopamine.
Thirdly, preparing a hydrophilic layer: 30g of nano cellulose aerogel and 5g of lauryl dimethyl ammonium oxide are mixed, then the mixture is ground and dispersed for 18min by a grinder to obtain hydrophilic aerogel, and then 30 parts of hydrophilic aerogel, 67 parts of water, 0.5 part of methyl cellulose ether, 0.5 part of flowing agent and 2 parts of acrylic resin are mixed and stirred uniformly to obtain a hydrophilic layer.
Fourth step, coating sizing: and uniformly coating the slurry on a fiber paper base coated with polydopamine through a doctor blade coating mode, and then drying and soft compression molding to obtain the diaphragm paper, wherein the ration of the diaphragm paper is 40g/cm < 2 >.
Example III
The embodiment of the invention provides diaphragm paper, which comprises a fiber paper base and a hydrophilic layer formed on the surface of the fiber paper base, wherein the hydrophilic layer at least comprises a hydrophilic aerogel layer, and the fiber paper base is a polydopamine modified fiber paper base.
The preparation method of the diaphragm paper provided by the third embodiment of the invention comprises the following steps:
firstly, preparing a dopamine solution: adding ionized water into Tris for dissolution to obtain a Tris buffer solution, namely, a Tris buffer solution, weighing 0.02mol of the Tris buffer solution, adding deionized water into a volumetric flask for dissolution to obtain a Tris buffer solution with the concentration of 14mmol/L, adding a plurality of drops of hydrochloric acid to adjust the pH value to about 9, and preparing a dopamine solution with the concentration of 1.5g/L by using the Tris buffer solution.
Secondly, preparing a fiber paper base: soaking the polyester fiber in the dopamine solution, fully stirring, mixing and soaking for 17 hours, washing a reaction product with deionized water for a plurality of times until filtrate is colorless and clear, and mixing the polyester fiber coated with polydopamine with viscose fiber and vinylon according to a ratio of 8:1:1, adding a proper amount of polyacrylamide dispersing agent, uniformly stirring, and vacuum filtering to prepare the fiber paper base coated with polydopamine.
Thirdly, preparing a hydrophilic layer: 30g of nano cellulose aerogel and 8g of lauryl dimethyl ammonium oxide are mixed, then the mixture is ground and dispersed for 20min by a grinder to obtain hydrophilic aerogel, and then 30 parts of hydrophilic aerogel, 66.5 parts of water, 1 part of hydroxymethyl cellulose ether, 0.5 part of flowing agent and 2 parts of acrylic resin are mixed and stirred uniformly to obtain a hydrophilic layer.
Fourth step, coating sizing: and uniformly coating the slurry on a fiber paper base coated with polydopamine through a doctor blade coating mode, and then drying and soft compression molding to obtain the diaphragm paper, wherein the ration of the diaphragm paper is 38g/cm < 2 >.
Example IV
The embodiment of the invention provides diaphragm paper, which comprises a fiber paper base and a hydrophilic layer formed on the surface of the fiber paper base, wherein the hydrophilic layer at least comprises a hydrophilic aerogel layer, and the fiber paper base is a polydopamine modified fiber paper base.
The preparation method of the diaphragm paper provided by the fourth embodiment of the invention comprises the following steps:
firstly, preparing a dopamine solution: adding ionized water into Tris for dissolution to obtain a Tris buffer solution, namely, a Tris buffer solution, weighing 0.02mol of the Tris buffer solution, adding deionized water into a volumetric flask for dissolution to obtain a Tris buffer solution with the concentration of 14mmol/L, adding a plurality of drops of hydrochloric acid to adjust the pH value to about 9, and preparing a dopamine solution with the concentration of 1.5g/L by using the Tris buffer solution.
Secondly, preparing a fiber paper base: soaking the polyester fiber in the dopamine solution, fully stirring, mixing and soaking for 17 hours, washing a reaction product with deionized water for a plurality of times until filtrate is colorless and clear, and mixing the polyester fiber coated with polydopamine with viscose fiber and vinylon according to a ratio of 8:1:1, adding a proper amount of polyacrylamide dispersing agent, uniformly stirring, and vacuum filtering to prepare the fiber paper base coated with polydopamine.
Thirdly, preparing a hydrophilic layer: 30g of nano cellulose aerogel and 9g of lauryl dimethyl ammonium oxide are mixed, then the mixture is ground and dispersed for 27min by a grinder to obtain hydrophilic aerogel, 31 parts of hydrophilic aerogel, 66.5 parts of water, 1 part of methyl cellulose ether, 0.5 part of flowing agent and 2 parts of acrylic resin are mixed and stirred uniformly to obtain a hydrophilic layer.
Fourth step, coating sizing: and uniformly coating the slurry on a fiber paper base coated with polydopamine through a doctor blade coating mode, and then drying and soft compression molding to obtain the diaphragm paper, wherein the ration of the diaphragm paper is 39g/cm < 2 >.
Example five
The embodiment of the invention provides a diaphragm paper, which comprises the following components: the hydrophilic layer at least contains a hydrophilic aerogel layer, and the fiber paper base is a polydopamine modified fiber paper base.
The preparation method of the diaphragm paper provided by the fifth embodiment of the invention comprises the following steps:
firstly, preparing a dopamine solution: adding ionized water into Tris for dissolution to obtain a Tris buffer solution, namely, a Tris buffer solution, weighing 0.02mol of the Tris buffer solution, adding deionized water into a volumetric flask for dissolution to obtain a Tris buffer solution with the concentration of 14mmol/L, adding a plurality of drops of hydrochloric acid to adjust the pH value to about 9, and preparing a dopamine solution with the concentration of 1.5g/L by using the Tris buffer solution.
Secondly, preparing a fiber paper base: soaking the polyester fiber in the dopamine solution, fully stirring, mixing and soaking for 17 hours, washing a reaction product with deionized water for a plurality of times until filtrate is colorless and clear, and mixing the polyester fiber coated with polydopamine with viscose fiber and vinylon to obtain a mixture of 7:2:1, adding a proper amount of polyacrylamide dispersing agent, uniformly stirring, and vacuum filtering to prepare the fiber paper base coated with polydopamine.
Thirdly, preparing a hydrophilic layer: 30g of nano cellulose aerogel and 8g of lauryl dimethyl ammonium oxide are mixed, then the mixture is ground and dispersed for 25min by a grinder to obtain hydrophilic aerogel, and then 35 parts of hydrophilic aerogel, 61.5 parts of water, 1 part of methyl cellulose ether, 0.5 part of flowing agent and 2 parts of acrylic resin are mixed and stirred uniformly to obtain a hydrophilic layer.
Fourth step, coating sizing: and uniformly coating the slurry on a fiber paper base coated with polydopamine through a doctor blade coating mode, and then drying and soft compression molding to obtain the diaphragm paper, wherein the ration of the diaphragm paper is 38g/cm < 2 >.
Example six
The embodiment of the invention provides diaphragm paper, which comprises a fiber paper base and a hydrophilic layer formed on the surface of the fiber paper base, wherein the hydrophilic layer at least comprises a hydrophilic aerogel layer, and the fiber paper base is a polydopamine modified fiber paper base.
The preparation method of the diaphragm paper provided by the sixth embodiment of the invention comprises the following steps:
firstly, preparing a dopamine solution: adding ionized water into Tris for dissolution to obtain a Tris buffer solution, namely, a Tris buffer solution, weighing 0.02mol of the Tris buffer solution, adding deionized water into a volumetric flask for dissolution to obtain a 16mmol/L Tris buffer solution, adding a plurality of drops of hydrochloric acid to adjust the pH value to about 9, and preparing a 2g/L dopamine solution by using the Tris buffer solution.
Secondly, preparing a fiber paper base: taking two parts of the dopamine solution, respectively soaking polyester fiber and viscose fiber in the two parts of the dopamine solution, fully stirring, mixing and soaking for 17 hours, washing a reaction product with deionized water for a plurality of times until filtrate is colorless and clear, and mixing the polyester fiber coated with polydopamine with the viscose fiber according to a ratio of 8:2, mixing, adding a proper amount of polyacrylamide dispersing agent, uniformly stirring, and vacuum filtering to prepare the fiber paper base coated with polydopamine.
Thirdly, preparing a hydrophilic layer: 32g of nano cellulose aerogel and 8g of lauryl dimethyl ammonium oxide are mixed, then the mixture is ground and dispersed for 20min by a grinder to obtain hydrophilic aerogel, and then 33 parts of hydrophilic aerogel, 63.5 parts of water, 1 part of methyl cellulose ether, 0.5 part of flowing agent and 2 parts of acrylic resin are mixed and stirred uniformly to obtain a hydrophilic layer.
Fourth step, coating sizing: and uniformly coating the slurry on a fiber paper base coated with polydopamine through a doctor blade coating mode, and then drying and soft compression molding to obtain the diaphragm paper, wherein the ration of the diaphragm paper is 37g/cm < 2 >.
Comparative example one
The first comparative example of the present invention provides a separator paper comprising a fibrous paper base and a hydrophilic layer formed on the surface of the fibrous paper base, the hydrophilic layer containing at least a hydrophilic aerogel layer, the separator paper not containing dopamine or polydopamine.
The preparation method of the diaphragm paper provided by the first comparative example of the invention comprises the following steps:
first, preparing a fiber paper base: polyester fiber, viscose fiber and vinylon were respectively mixed in 8:1:1, adding a proper amount of polyacrylamide dispersing agent, uniformly stirring, and making into a fiber paper base through vacuum filtration.
Second, preparing hydrophilic layer: 30g of nano cellulose aerogel and 8g of lauryl dimethyl ammonium oxide are mixed, then the mixture is ground and dispersed for 20min by a grinder to obtain hydrophilic aerogel, and then 30 parts of hydrophilic aerogel, 66.5 parts of water, 1 part of methyl cellulose ether, 0.5 part of flowing agent and 2 parts of acrylic resin are mixed and stirred uniformly to obtain a hydrophilic layer.
Thirdly, coating sizing: and uniformly coating the slurry on the fiber paper base through a scraper coating mode by using a hydrophilic layer, and then drying and soft-press forming to obtain the diaphragm paper, wherein the ration of the diaphragm paper is 38g/cm < 2 >.
Comparative example two
The second comparative example of the present invention provides a separator paper comprising a fibrous paper base, which does not contain dopamine or polydopamine nor the hydrophilic layer of the examples.
The preparation method of the diaphragm paper provided by the second comparative example comprises the following steps:
first, preparing a fiber paper base: polyester fiber and viscose fiber were mixed in a ratio of 9:1, adding a proper amount of polyacrylamide dispersing agent, uniformly stirring, and making into a fiber paper base through vacuum filtration.
Second, coating sizing: mixing 10 parts of polyvinyl alcohol, 10 parts of sodium polyacrylate and 80 parts of water, uniformly stirring, uniformly coating on the fiber paper base, and then drying and soft-pressing to obtain the diaphragm paper with the ration of 40g/cm < 2 >.
Comparative example three
The third comparative example of the present invention provides a separator paper comprising a fibrous paper base, the fibrous paper base being a polydopamine modified fibrous paper base, the separator paper not comprising the hydrophilic layer of the present invention.
The preparation method of the diaphragm paper provided by the third comparative example comprises the following steps:
firstly, preparing a dopamine solution: adding ionized water into Tris for dissolution to obtain a Tris buffer solution, namely, a Tris buffer solution, weighing 0.02mol of the Tris buffer solution, adding deionized water into a volumetric flask for dissolution to obtain a 16mmol/L Tris buffer solution, adding a plurality of drops of hydrochloric acid to adjust the pH value to about 9, and preparing a 2g/L dopamine solution by using the Tris buffer solution.
Secondly, preparing a fiber paper base: taking two parts of the dopamine solution, respectively soaking polyester fiber and viscose fiber in the two parts of the dopamine solution, fully stirring, mixing and soaking for 17 hours, washing a reaction product with deionized water for a plurality of times until filtrate is colorless and clear, and mixing the polyester fiber coated with polydopamine with the viscose fiber according to a ratio of 9:1, adding a proper amount of polyacrylamide dispersing agent, uniformly stirring, and vacuum filtering to prepare the fiber paper base coated with polydopamine.
Fourth step, coating sizing: mixing 10 parts of polyvinyl alcohol, 10 parts of sodium polyacrylate and 80 parts of water, uniformly stirring, uniformly coating on the fiber paper base coated with polydopamine, and then drying and soft-pressing to obtain the diaphragm paper with the ration of 41g/cm < 2 >.
The invention tests the related data of the diaphragm paper prepared by the embodiment and the comparative example, wherein the first embodiment to the sixth embodiment use a fiber paper base modified by polydopamine and a hydrophilic layer is formed on the fiber paper base, the first comparative example does not contain dopamine or polydopamine in the embodiment of the invention compared with the embodiment of the invention, the second comparative example does not contain dopamine or polydopamine in the embodiment of the invention, the hydrophilic layer in the embodiment of the invention does not contain the hydrophilic layer in the embodiment of the invention, and the third comparative example does not contain the hydrophilic layer in the embodiment of the invention. The test results of examples and comparative examples are shown in the following table:
as can be seen from the above table, the separator papers prepared in examples one to six of the present invention, which used the polydopamine-modified fibrous paper base and formed the hydrophilic layer on the fibrous paper base, the separator papers prepared in comparative example one also formed the hydrophilic layer on the fibrous paper base, and the separator papers of the present invention were smaller in basis weight and smaller than 40g/m each as compared with comparative examples two and three without hydrophilic layer 2 Thus, it is possible to obtain a separator paper having a lighter weight after forming a hydrophilic layer on a fibrous paper base. The separator paper prepared in the first to sixth embodiments of the present invention uses a fiber paper base modified by polydopamine and has a hydrophilic layer, and compared with the separator paper in the first to third embodiments, the separator paper of the present invention has a higher tensile strength under the combined action of polydopamine and hydrophilic layer, a higher liquid absorption speed, a higher liquid absorption amount, a higher air permeability and a lower heat shrinkage under the same temperature conditions in the same time.
The foregoing is merely a specific embodiment of the invention, and it will be apparent that various modifications and combinations thereof can be made without departing from the spirit and scope of the invention. Accordingly, the specification and drawings are merely exemplary illustrations of the present invention as defined in the appended claims and are considered to cover any and all modifications, variations, combinations, or equivalents that fall within the scope of the invention. It will be apparent to those skilled in the art that various modifications and variations can be made to the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents. Any person skilled in the art can easily think of changes or substitutions within the technical scope of the present disclosure, and the present disclosure is intended to be covered by the present disclosure. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (9)
1. The diaphragm paper is characterized by comprising a fiber paper base and a hydrophilic layer formed on the surface of the fiber paper base, wherein the hydrophilic layer at least comprises a hydrophilic aerogel layer, the fiber paper base is a polydopamine modified fiber paper base, the hydrophilic aerogel contained in the hydrophilic aerogel layer is nano cellulose aerogel, and the fibers contained in the fiber paper base are polyester fibers and/or viscose fibers;
the preparation method of the diaphragm paper comprises the following steps:
mixing polyester fibers and/or viscose fibers with a dopamine solution until dopamine contained in the dopamine solution is self-polymerized on the surfaces of the polyester fibers and/or viscose fibers to obtain polydopamine-coated fibers;
making the fiber coated by polydopamine into a fiber paper base;
and coating the nano cellulose aerogel on the surface of the fiber paper base to obtain the diaphragm paper.
2. The separator paper according to claim 1, wherein the fibers contained in the fiber paper base are modified with polydopamine, the polydopamine coating the fibers; and/or the number of the groups of groups,
the hydrophilic aerogel layer has a nanoporous network structure.
3. The separator paper according to claim 1 or 2, wherein the hydrophilic aerogel contained in the hydrophilic aerogel layer is a surface-modified aerogel; and/or the number of the groups of groups,
the hydrophilic aerogel contained in the hydrophilic aerogel layer is aerogel mixed with a surface modifier.
4. A separator paper according to claim 3, characterized in that the mass ratio of aerogel to surface modifier is (4-6): 1, a step of; and/or the number of the groups of groups,
the surface modifier is at least one of quaternary ammonium salt surface modifier, sulfate surface modifier and betaine surface modifier.
5. The separator paper according to claim 1 or 2, wherein the hydrophilic layer further contains an auxiliary agent comprising a dissolving agent, a dispersing agent, a flow agent and a binder, and the hydrophilic layer comprises 5 to 30 parts by mass of the hydrophilic aerogel layer, 50 to 85 parts by mass of the dissolving agent, 0.5 to 1 part by mass of the dispersing agent, 0 to 0.03 part by mass of the flow agent and 0.5 to 3 parts by mass of the binder.
6. A method for producing the separator paper according to any one of claims 1 to 5, comprising:
manufacturing the polydopamine coated fiber into a fiber paper base;
a hydrophilic layer is formed on the surface of the fiber paper base.
7. The method for preparing the separator paper according to claim 6, wherein the making the polydopamine coated fiber into a fiber paper base comprises:
mixing fibers with a dopamine solution until dopamine contained in the dopamine solution is self-polymerized on the surface of the fibers to form polydopamine;
and manufacturing the fiber coated by polydopamine into a fiber paper base.
8. The method of producing a separator paper according to claim 7, wherein the forming a hydrophilic layer on the surface of the fibrous paper base comprises:
and coating a hydrophilic layer on the surface of the fiber paper base to obtain the diaphragm paper.
9. A battery comprising the separator paper according to any one of claims 1 to 5.
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